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

Abstract

The present invention addresses the problem of providing: an epoxy resin composition which exhibits good low temperature curability even if a specific trithiol compound is contained therein; and an adhesive, a sealing material, a cured product, a semiconductor device and an electronic component that contain the epoxy resin composition.　Provided are: an epoxy resin composition that contains (A) a thiol compound represented by chemical formula (I), (B) a thiol compound having an isocyanuric acid skeleton, (C) an epoxy resin and (D) a latent thermal curing catalyst; and an adhesive, a sealing material, a cured product, a semiconductor device and an electronic component that contain the epoxy resin composition.

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, the adhesive strength with an adherend, which has been a conventional problem, can be improved. The present inventors have found that an epoxy resin composition containing this trithiol compound as a curing agent has insufficient curing properties at low temperatures (e.g., 70°C). In particular, in the case of semiconductor devices and electronic components that include components that deteriorate under high-temperature conditions, all of the manufacturing processes must be carried out under low-temperature conditions. Therefore, adhesives and sealants used in the manufacture of such devices and components are required to exhibit sufficient curing properties even under low-temperature conditions.

[0006] An object of the present invention is to provide an epoxy resin composition that has good low-temperature curing properties 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) a compound represented by chemical formula (I): (2) The epoxy resin composition according to aspect (1), wherein the molar ratio of component (A) to component (B) ([component (A)] / [component (B)]) is 0.01 to 100. (3) The epoxy resin composition according to aspect (1), wherein the (B) thiol compound having an isocyanuric acid skeleton is represented by formula (II): (In the formula, R １ , R ２ and R ３ are each independently C １～６ Alkylene group or -R ４ -Z-(CO) ｎ -R ５ - and R ４ and R ５ are each independently C １～６ is an alkylene group, Z is a sulfur atom or an oxygen atom, n is 0 or 1, and R ４ is bonded to a nitrogen atom of the isocyanuric acid skeleton.) The epoxy resin composition according to aspect (1) or (2), wherein the epoxy resin composition is a compound represented by the formula: (4) The epoxy resin composition according to any one of aspects (1) to (3), wherein components (A) to (D) are contained in a single container. (5) The epoxy resin composition according to any one of aspects (1) to (3), wherein components (A) to (D) are separated 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) A cured product obtained by curing the epoxy resin composition according to any one of aspects (1) to (5) or the adhesive or sealant according to aspect (6). (8) A semiconductor device or electronic component comprising the cured product according to aspect (7).

[0008] According to an embodiment of the present invention, there are provided an epoxy resin composition having good low-temperature curing properties even when a specific trithiol compound is contained, an adhesive or sealant containing the same, a cured product obtained by curing the composition or the sealant, and a semiconductor device or electronic component containing the cured product.

[0009] 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.

[0010] [Epoxy Resin Composition] An epoxy resin composition according to one embodiment of the present invention comprises: (A) a compound represented by the chemical formula (I): (B) a thiol compound having an isocyanuric acid skeleton, (C) an epoxy resin, and (D) a thermal latent curing catalyst. According to this embodiment, an epoxy resin composition having good low-temperature curing properties can be provided even when the epoxy resin composition contains a thiol compound represented by chemical formula (I).

[0011] (A) Thiol Compound Represented by Chemical Formula (I) The epoxy resin composition of the present embodiment comprises (A) 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.

[0012] (A) The thiol compound represented by chemical formula (I) acts as a curing agent for epoxy resins, 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.

[0013]

[0014]

[0015] 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.

[0016] Component (A) contains a by-product of the thiol compound represented by the chemical formula (I), for example, the compounds represented by (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.

[0017] In the present embodiment, the content of component (A) in the epoxy resin composition is preferably 1 to 60% by weight, more preferably 5 to 60% by weight, even more preferably 5 to 55% by weight, and particularly preferably 5 to 50% by weight, relative to the total weight of the epoxy resin composition.

[0018] (B) Thiol Compound Having an Isocyanuric Acid Skeleton The epoxy resin composition of the present embodiment contains (B) a thiol compound having an isocyanuric acid skeleton (hereinafter also referred to as "component (B)"). By using a combination of (A) the thiol compound represented by chemical formula (I) and (B) the thiol compound having an isocyanuric acid skeleton as a curing agent for an epoxy resin, the low-temperature curing properties of the epoxy resin composition are improved.

[0019] As described in Patent Document 3, when a resin composition containing a thiol compound represented by chemical formula (I) was used as an adhesive, the adhesive strength with the adherend, which was a problem when conventional thiol compounds were used as curing agents, was improved. This is thought to be because the thiol compound represented by chemical formula (I) has very few polar moieties other than the thiol group in its structure. Therefore, when it comes into contact with a highly polar surface such as a metal surface, the thiol group relatively easily approaches the metal surface, resulting in a strong adhesive force between the thiol group and the metal. However, the present inventors have found that epoxy resin compositions containing this thiol compound represented by chemical formula (I) as a curing agent have insufficient curing properties at low temperatures (e.g., 70°C). The present inventors hypothesized that thiol compounds represented by chemical formula (I), which have very few polar moieties in their structure, have difficulty extracting protons from the thiol group, especially at low temperatures. For example, ester thiols such as pentaerythritol tetrakis(3-mercaptopropionate), tend to form a six-membered ring structure, which facilitates the extraction of protons (H). Furthermore, in OH group-containing thiols, OH facilitates proton abstraction from the thiol. Therefore, we investigated the improvement of the activation of the thiol compound represented by chemical formula (I) at low temperatures and found that, in particular, by using it in combination with (B) a thiol compound having an isocyanuric acid skeleton, low-temperature curing properties are significantly improved. The reason for this is thought to be, but is not limited to, that due to the rigidity and polarity of (B) the thiol compound having an isocyanuric acid skeleton, the thiol compound having an isocyanuric acid skeleton serves as a reaction field that facilitates proton abstraction from the thiol group of the thiol compound represented by chemical formula (I).

[0020] Furthermore, by using a combination of (A) a thiol compound represented by chemical formula (I) and (B) a thiol compound having an isocyanuric acid skeleton as an epoxy resin curing agent, the resulting cured epoxy resin exhibited better elongation than a cured epoxy resin containing only (B) a thiol compound having an isocyanuric acid skeleton as a curing agent.More interestingly, a cured resin of a resin composition containing component (A) and (B) a thiol compound having an isocyanuric acid skeleton in a specific mixing ratio exhibited better elongation than a cured resin of a resin composition containing only component (A) as a curing agent.

[0021] In this embodiment, the thiol compound (B) having an isocyanuric acid skeleton is preferably a trithiol having an isocyanuric acid skeleton, and is represented by the formula (II): (In the formula, R １ , R ２ and R ３ are each independently C １～６ Alkylene group or -R ４ -Z-(CO) ｎ -R ５ - and R ４ and R ５ are each independently C １～６ is an alkylene group, Z is a sulfur atom or an oxygen atom, n is 0 or 1, and R ４ is bonded to a nitrogen atom of the isocyanuric acid skeleton. １～６ The alkylene group may be either straight-chain or branched.

[0022] Specific examples of thiol compounds having an isocyanuric acid skeleton 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, 1,3,5-tris[3-(2-mercaptoethoxy)propyl]isocyanurate, Examples of the thiol compound having an isocyanuric acid skeleton include, but are not limited to, 1,3,5-tris(2-(3-sulfanylbutanoyloxy)ethyl)-1,3,5-triazinane-2,4,6-trione, tris(mercaptomethyl)isocyanurate, tris(2-mercaptoethyl)isocyanurate, tris(3-mercaptopropyl)isocyanurate, tris(4-mercaptobutyl)isocyanurate, and tris(5-mercaptopentyl)isocyanurate. These thiol compounds having an isocyanuric acid skeleton may be used alone or in combination of two or more.

[0023] In this embodiment, the molar ratio of component (A) to component (B) ([component (A)] / [component (B)]) is preferably 0.01 to 100, more preferably 0.05 to 100, even more preferably 0.1 to 95, and particularly preferably 0.4 to 95. In this embodiment, the weight ratio of component (A) to component (B) ([component (A)] / [component (B)]) is preferably 0.01 to 100, more preferably 0.05 to 90, even more preferably 0.1 to 80, and particularly preferably 0.3 to 70. In this embodiment, the molar ratio of component (A) to the total amount of component (A) and component (B) ([component (A)] / {[component (A)]+[component (B)]}) is preferably 0.01 to 0.99, more preferably 0.02 to 0.99, and even more preferably 0.04 to 0.99. In the present embodiment, the weight ratio of component (A) to the total amount of component (A) and component (B) ([component (A)] / {[component (A)]+[component (B)]}) is preferably 0.01 to 0.99, more preferably 0.02 to 0.99, and even more preferably 0.03 to 0.99.

[0024] (C) Epoxy Resin The epoxy resin composition of this embodiment contains (C) an epoxy resin (hereinafter also referred to as "component (C)"). The epoxy resin is not particularly limited as long as it has 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. In consideration of ensuring heat resistance, epoxy resins having 2 to 6 epoxy groups are more preferred, and those having 2 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 divided into aromatic epoxy resins and epoxy resins without aromatic rings.

[0025] Aromatic epoxy resins are epoxy resins having a structure containing an aromatic ring such as a benzene ring. 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.

[0026] 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.

[0027] Epoxy resins without an aromatic ring include, for example, aliphatic epoxy resins and epoxy resins with a heterocycle.

[0028] 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.

[0029] 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.

[0030] The epoxy resins may be used alone or in combination of two or more.

[0031] In the present embodiment, the content of the epoxy resin (C) in the epoxy resin composition is preferably 30 to 75 wt %, more preferably 30 to 60 wt %, and even more preferably 35 to 60 wt %, relative to the total weight of the epoxy resin composition.

[0032] In the present embodiment, the total content of component (A) and component (B) in the epoxy resin composition is preferably 1 to 70 wt %, more preferably 10 to 65 wt %, and even more preferably 20 to 60 wt %, relative to the total weight of the epoxy resin composition. In the present embodiment, the ratio of the number of epoxy group equivalents of the epoxy resin to the sum of the number of thiol group equivalents of component (A) and the number of thiol group equivalents of component (B) ([number of epoxy group equivalents of epoxy resin] / ([number of thiol group equivalents of component (A)]+[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.

[0033] 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.

[0034] 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).

[0035] 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).

[0036] (D) Thermal Latent Curing Catalyst The epoxy resin composition of this embodiment contains (D) a thermal latent curing catalyst (hereinafter also referred to as "component (D)"). A thermal 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 (D).

[0037] 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.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] Examples of urea compounds include, but are not limited to, urea and thiourea.

[0043] 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.

[0044] 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 (D) include, but are not limited to, "Fujicure FXR-1020" (T&K TOKA Corporation), "Fujicure FXR-1030" (T&K TOKA Corporation), "Fujicure FXR-1121" (T&K TOKA Corporation), "Fujicure FXR-1081" (T&K TOKA Corporation), "Fujicure FXR-1061" (T&K TOKA Corporation), and "Fujicure FXR-1171" (T&K TOKA Corporation). Component (D) may be used singly or in combination of two or more.

[0045] The content of component (D) 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 0.5 to 10% by weight, relative to the total weight of the resin composition.

[0046] Incidentally, component (D) may be provided in the form of a dispersion in an epoxy resin. When component (D) 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 components (A) and (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 (C) ([number of epoxy group equivalents of the entire epoxy resin] / [number of thiol group equivalents of component (B)]). 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 components (A) and (B) ([number of epoxy group equivalents of the entire epoxy resin] / [number of thiol group equivalents of components (A) and (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.

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

[0048] Thiol Compound Other than Component (A) and Component (B) The epoxy resin composition of the present embodiment may contain a thiol compound other than component (A) and 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; Examples include 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril and 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril.

[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 the present embodiment, the weight ratio of component (A) to other thiol compounds ([component (A)]:[other thiol compounds]) in the epoxy resin composition is preferably set to be 100:0 to 1:99.

[0052] When other thiol compounds are contained, 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 all thiol compounds by adding the number of thiol equivalents of components (A) and (B) and the number of thiol equivalents of the other thiol compounds ([number of epoxy group equivalents of the entire epoxy resin] / [number of thiol group equivalents of all thiol compounds]). 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 all thiol compounds ([number of epoxy group equivalents of the entire epoxy resin] / [number of thiol group equivalents of all 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 (d５０ ) 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 (D), 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 combination.

[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 (D) and other optional components as needed 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 (D) and other optional components as needed 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 (D) and other optional components as needed. Alternatively, the components (A) to (D) and other optional components as needed may be contained in a single component. Alternatively, a component may contain only the components (A) to (D) and / or other optional components as needed. 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) and component (D), or liquid A: component (A) and component (B), liquid B: component (C) and component (D), or liquid A: component (A) and component (C), liquid B: component (B) and component (D), or liquid A: component (A) and component (D), liquid B: component (B) and component (C), or liquid A: component (B), liquid B: component (A) and component (D). The liquid mixture may be liquid A: component (A), component (B), and component (C), liquid B: component (A) and component (D), liquid A: component (A), component (B), and component (C), liquid B: component (B) and component (D), liquid A: component (A), component (B), and component (C), liquid B: component (B) and component (D), liquid A: component (A), component (B), and component (C), liquid B: component (C) and component (D), liquid A: component (A), component (B), and component (D), or liquid B: component (C) and component (D). When components (A) to (D) are contained in liquid A, liquid B may contain one or more selected from components (A) to (D). In addition, components other than components (A) to (D) (e.g., other thiol compounds) may be contained in both or either liquid A and liquid B in the above combinations.When components (A) to (D) are contained in liquid A and the other components are contained in liquid B, only liquid A or a combination of liquid A and liquid B can be considered to be the resin composition of this embodiment. On the other hand, when components (A) to (D) are each contained in a separate liquid, the respective liquids can be considered to be the resin composition of this embodiment. An example of a case where components (A) to (D) are each contained in a separate liquid is a resin composition in which components (A) to (D) are separated into two or more containers, specifically a kit composed of multiple liquids containing any of components (A) to (D).

[0068] The epoxy resin composition thus obtained is thermosetting, and at a temperature of 100°C, it preferably cures within 5 hours, more preferably within 3 hours, and even more preferably within 1 hour. When the epoxy resin composition of this 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. The epoxy resin composition of this embodiment has excellent curing properties, particularly at low temperatures (for example, 70°C).

[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 separated 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 (D) 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 (D) 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 (D) 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 of only the components (A) to (C) and / or other optional components as required. For example, when the mixture is separated into liquids A and B, the separation may be as follows: liquid A: component (A), liquid B: component (B), component (C), and component (D), or liquid A: component (A) and component (B), liquid B: component (C) and component (D), or liquid A: component (A) and component (C), liquid B: component (B) and component (D), or liquid A: component (A) and component (C), liquid B: component (B) and component (D), or liquid A: component (A) and component (D), liquid B: component (B) and component (C), or liquid A: component (B), component (A), and component (C). The liquid mixture may be liquid A: component (A), component (B), and component (C), liquid B: component (A) and component (D), liquid A: component (A), component (B), and component (C), liquid B: component (B) and component (D), liquid A: component (A), component (B), and component (C), liquid B: component (B) and component (D), liquid A: component (A), component (B), and component (C), liquid B: component (C) and component (D), liquid A: component (A), component (B), and component (D), or liquid B: component (C) and component (D). When components (A) to (D) are contained in liquid A, liquid B may contain one or more selected from components (A) to (D). In addition, components other than components (A) to (D) (e.g., other thiol compounds) may be contained in both or either liquid A and liquid B in the above combinations.When components (A) to (D) are contained in liquid A and the other components are contained in liquid B, liquid A alone, or liquid A and liquid B together, can be considered to be the adhesive or sealant of this embodiment. On the other hand, when components (A) to (D) are each contained in a separate liquid, the respective liquids together can be considered to be the adhesive or sealant of this embodiment. An example of a case where components (A) to (D) are each contained in a separate liquid is an adhesive or sealant in which components (A) to (D) are separated into two or more containers, specifically a kit composed of multiple liquids containing any of components (A) to (D).

[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. The cured product according to this embodiment has good elongation.

[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 to 6, Comparative Examples 1 to 4] 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) Thiol compound represented by chemical formula (I) (A-1): Thiol compound represented by chemical formula (I) (1,2,3-(3-mercaptopropyloxy)propane) (obtained from Shikoku Chemicals Corporation, 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.

[0077] (B) Thiol compound having an isocyanuric acid skeleton (B-1): 2-{2,4,6-trioxo-3,5-bis[2-(3-sulfanylpropanoyloxy)ethyl]-1,3,5-triazinan-1-yl}ethyl 3-sulfanylpropionate represented by the following formula (product name: TEMPIC, manufactured by SC Organic Chemical Co., Ltd., thiol equivalent: 175 g / eq) (B-2): 1,3,5-tris[3-(2-mercaptoethylsulfanyl)propyl]isocyanurate represented by the following formula (product name: ACTOCURE (registered trademark) SS32, manufactured by Kawaguchi Chemical Industry Co., Ltd., thiol equivalent: 183 g / eq)

[0078] (C) Epoxy Resin (C-1): Bisphenol F epoxy resin / bisphenol A epoxy resin mixture (product name: EXA-835LV, manufactured by DIC Corporation, epoxy equivalent: 163 g / eq)

[0079] (D) Thermal Latent Curing Catalysts (D-1): Amine-epoxy adduct latent curing catalyst (product name: Novacure HXA9322HP, manufactured by Asahi Kasei Corporation). The latent curing catalyst (D-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 a fine particle latent curing catalyst is dispersed in an epoxy resin (a mixture of bisphenol A epoxy resin and bisphenol F epoxy resin (epoxy equivalent: 180 g / eq)). (D-2): Modified amine compound that is solid at room temperature (product name: Fujicure FXR-1020, manufactured by T&K TOKA Corporation).

[0080] In Table 1, "molar ratio (A / (A+B))" is the molar ratio of component (A) to the total amount of component (A) and component (B) ([component (A)] / {[component (A)]+[component (B)]}). "Weight ratio (A / (A+B))" is the weight ratio of component (A) to the total amount of component (A) and component (B) ([component (A)] / {[component (A)]+[component (B)]}). "Molar ratio (A / B)" is the molar ratio of component (A) to component (B) ([component (A)] / [component (B)]). "Weight ratio (A / B)" is the weight ratio of component (A) to component (B) ([component (A)] / [component (B)]).

[0081] In the examples and comparative examples, the properties of the resin compositions and the cured products obtained by curing the resin compositions were measured as follows.

[0082] [Evaluation of 70°C curability] Each resin composition was dropped onto a hot plate at 70±2°C to a size of approximately 5 mmφ, and while stirring in a circular motion with a stirring rod, the stirring rod was lifted and pulled away. The time until the stringiness disappeared was measured with a stopwatch. The results are shown in Table 1.

[0083] [Evaluation of 120°C curability] Each resin composition was dropped onto a hot plate at 120±2°C to a size of approximately 5 mmφ, and while stirring in a circular motion with a stirring rod, the stirring rod was lifted and pulled away. The time until the stringiness disappeared was measured with a stopwatch. The results are shown in Table 1.

[0084] [Evaluation of elongation of cured product] Each resin composition was applied to a Teflon (registered trademark) sheet in a thickness of 0.3 mm and subjected to a heat curing treatment by heating at 120°C for 60 minutes in an air dryer to produce a cured product sheet. Dumbbells for tensile tests were made from the resulting cured product sheets, and the breaking elongation (unit: %) was measured at room temperature (22°C) and a tensile speed of 5 mm / min using a tensile tester (Autograph AGS-J, manufactured by Shimadzu Corporation). The measurement results are shown in Table 1.

[0085] Similar evaluations were also carried out on a two-component resin composition in which the composition of Example 1 was such that component A was component (C) and component B was component (A), component (B), and component (D).

[0086]

[0087] The epoxy resin compositions of Comparative Examples 1 and 2, which contained only the thiol compound represented by chemical formula (I) of component (A) as the epoxy resin curing agent, exhibited good curing properties at 120°C but poor curing properties at 70°C. The epoxy resin compositions of Examples 1 to 6, which contained a combination of the thiol compound represented by chemical formula (I) of component (A) and the thiol compound having an isocyanuric acid skeleton of component (B) as the epoxy resin curing agent, exhibited good curing properties at 70°C. Furthermore, the cured products obtained by curing the resin compositions of these Examples exhibited better elongation than the cured products obtained by curing the resin compositions of Comparative Examples 3 and 4, which contained only the thiol compound having an isocyanuric acid skeleton of component (B) as the epoxy resin curing agent. In particular, the cured products of Examples 3 to 6 exhibited better elongation than the cured products of the resin compositions of Comparative Examples 1 and 2, which contained only the thiol compound having an isocyanuric acid skeleton of component (A) as the curing agent. Although not shown in Table 1, similar evaluations were also performed on a two-component resin composition in which the composition of Example 1 was changed so that Liquid A was the component (C) and Liquid B was the component (A), component (B), and component (D), and similar results were obtained.

[0088] 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.

[0089] The disclosure of Japanese Patent Application No. 2023-119049 (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) Chemical formula (I): (B) a thiol compound having an isocyanuric acid skeleton; (C) an epoxy resin; and (D) a thermal latent curing catalyst.

2. The epoxy resin composition according to claim 1, wherein the molar ratio of component (A) to component (B) ([component (A)] / [component (B)]) is 0.01 to 100.

3. The thiol compound (B) having an isocyanuric acid skeleton is represented by the formula (II): (In the formula, R １ , R ２ and R ３ are each independently １～６ Alkylene group or -R ４ -Z-(CO) ｎ -R ５ - and R ４ and R ５ are each independently １～６ is an alkylene group, Z is a sulfur atom or an oxygen atom, n is 0 or 1, R ４ is bonded to a nitrogen atom of the isocyanuric acid skeleton.

4. The epoxy resin composition according to any one of claims 1 to 3, wherein components (A) to (D) 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 (D) 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. 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.

8. A semiconductor device or electronic part comprising the cured product according to claim 7.

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