WO2025187449A1 - Resin composition, adhesive agent, sealing material, cured product, semiconductor device, and electronic component - Google Patents

Abstract

The present invention provides: a resin composition that has excellent low gloss properties even when a specific trithiol compound is contained therein; and an adhesive or sealing material, a cured product, and a semiconductor device or electronic component which contain said resin composition.　Provided are: a resin composition containing (A) a (meth)acrylate compound, (B) a thiol compound represented by chemical formula (I), and (C) a thermally latent curing catalyst that is solid at room temperature; and an adhesive or sealing material, a cured product, and a semiconductor device or electronic component which contain said resin composition.

Description

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

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

Currently, adhesives, sealants, etc. containing curable resin compositions are often used to assemble and mount components used in semiconductor devices, such as semiconductor chips, in order to maintain reliability. Known examples of such resin compositions include curable compositions that use an epoxy compound or (meth)acrylate compound as the base compound and a thiol compound as the curing agent (see, for example, Patent Documents 1 and 2).

Patent Document 3 discloses a compound having the following structural formula:

Disclosed is a trithiol compound having the formula:

Japanese Patent Application Publication No. 6-211969 JP 2009-51954 A Japanese Patent Application Laid-Open No. 2022-180364

The present inventors have studied curable compositions that use a (meth)acrylate compound as a base and the trithiol compound described in Patent Document 3 as a curing agent, and have found that when cured with light or heat, the resulting cured product tends to have a high gloss. Curable compositions that produce high-gloss cured products have the problem of being prone to causing optical defects due to light reflection, etc., when applied near optical components such as optical sensor modules, including image sensor modules and TOF sensor modules. Therefore, resin compositions used to fix, bond, or protect components that make up optical sensor modules, including image sensor modules and TOF sensor modules, are required to have low gloss to prevent optical defects.

The present invention aims to provide a resin composition that exhibits excellent low gloss even when it contains a specific trithiol compound, as well as an adhesive or sealant containing the same, a cured product, and a semiconductor device or electronic component.

Specific means for solving the above problems are as follows.
The present invention encompasses a resin composition, an adhesive or sealant, a cured product, and a semiconductor device or electronic component according to the following embodiments.
[1] (A) a (meth)acrylate compound,
(B) Chemical formula (I):

and (C) a thermal latent curing catalyst that is solid at room temperature.
[2] The resin composition according to the above [1], further comprising (D) a photopolymerization initiator.
[3] The resin composition according to the above [1] or [2], wherein the (C) thermally latent curing catalyst that is solid at room temperature includes at least one selected from the group consisting of an amine adduct-based thermally latent curing catalyst and a microcapsule-type thermally latent curing catalyst.
[4] The resin composition according to the above [3], wherein the (C) thermal latent curing catalyst that is solid at room temperature contains a compound having at least one urea bond in its structure.
[5] The resin composition according to any one of the above [1] to [4], further comprising (B') a thiol compound other than component (B), wherein the ratio of the number of (meth)acryloyl group equivalents of component (A) to the sum of the number of thiol group equivalents of component (B) and the number of thiol group equivalents of component (B') ([number of (meth)acryloyl group equivalents of component (A)]/([number of thiol group equivalents of component (B)]+[number of thiol group equivalents of component (B')])) is 0.1 to 10.
[6] The resin composition according to any one of [1] to [5] above, wherein the gloss of a 300 μm thick cured product obtained by curing the resin composition under the curing conditions of 80°C for 60 minutes is less than 90 at an incident angle of 60°.
[7] The resin composition according to any one of the above [1] to [6], wherein the components (A) to (C) are contained in a single container.
[8] The resin composition according to any one of the above [1] to [6], wherein the components (A) to (C) are separated into two or more containers.
[9] An adhesive or sealant comprising the resin composition according to any one of [1] to [8] above.
[10] The adhesive or sealant according to [9] above, which is for use in a semiconductor device or electronic component.
[11] A cured product obtained by curing the resin composition according to any one of [1] to [8] above, or the adhesive or sealant according to [9] or [10] above.
[12] A semiconductor device or electronic component comprising the cured product according to [11] above.

According to an aspect of the present invention, there are provided a resin composition that exhibits excellent low gloss even when it contains a specific trithiol compound, an adhesive or sealant containing the resin, a cured product obtained by curing the resin composition or the adhesive or sealant, and a semiconductor device or electronic component containing the cured product.

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.
In this specification, a resin composition "having excellent low gloss" refers to a resin composition that can provide a cured product with sufficiently low gloss. A cured product with a "sufficiently low gloss" refers to a cured product having a gloss of less than 90 at an incident angle of 60°, as measured according to JIS Z 8741, for example.

[Resin composition]
The resin composition according to one embodiment of the present invention comprises:
(A) a (meth)acrylate compound,
(B) Chemical formula (I):

and (C) a thermal latent curing catalyst that is solid at room temperature. According to this aspect, even when the trithiol compound of formula (I) is contained, a resin composition having excellent low gloss can be provided.

(A) (Meth)acrylate Compound The resin composition of this embodiment contains (A) a (meth)acrylate compound (hereinafter also referred to as "component (A)"). The (A) (meth)acrylate compound imparts curability and adhesiveness to the resin composition. The (meth)acrylate compound as component (A) is not particularly limited as long as it contains a polyfunctional (meth)acrylate compound having at least two (meth)acryloyl groups. From the viewpoints of adhesion and reactivity, the polyfunctional (meth)acrylate compound is preferably a compound having 2 to 6 (meth)acryloyl groups, and more preferably a compound having two (meth)acryloyl groups. In this specification, "(meth)acryloyl group" includes both a methacryloyl group and an acryloyl group. Furthermore, "(meth)acrylate compound" includes both an acrylate compound and a methacrylate compound.

Examples of the (meth)acrylate compound include di(meth)acrylate of tris(2-hydroxyethyl)isocyanurate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, or an oligomer thereof; pentaerythritol tri(meth)acrylate, or an oligomer thereof; poly(meth)acrylate of dipentaerythritol; tris(acryloxyethyl)isocyanurate; caprolactone-modified tris((meth)acryloxyethyl)isocyanurate; poly(meth)acrylate of alkyl-modified dipentaerythritol; poly(meth)acrylate of caprolactone-modified dipentaerythritol; ethoxylated bisphenol A di(meth)acrylate; dihydroxy Examples of the acrylate include, but are not limited to, dicyclopentadiethyl (meth)acrylate, polyester (meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, poly(meth)acrylate of ditrimethylolpropane, polyurethane having two or more (meth)acryloyl groups in one molecule, polyester having two or more (meth)acryloyl groups in one molecule, phenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, epoxy resin half (meth)acrylate, and (meth)acrylate having an allyloxymethyl group (see JP 2024-009452 A).
Examples of commercially available (meth)acrylate compounds include, but are not limited to, polyester acrylate (product name: EBECRYL810) manufactured by Daicel-Allnex Corporation, ditrimethylolpropane tetraacrylate (product name: EBECRYL140) manufactured by Daicel-Allnex Corporation, polyester acrylate (product name: M7100) manufactured by Toagosei Co., Ltd., dimethylol-tricyclodecane diacrylate (product name: Light Acrylate DCP-A) manufactured by Kyoeisha Chemical Co., Ltd., and neopentyl glycol-modified trimethylolpropane diacrylate (product name: Kayarad R-604) manufactured by Nippon Kayaku Co., Ltd.

(A) The (meth)acrylate compound may be used alone or in combination with two or more types.

In this embodiment, the content of the (A) (meth)acrylate compound in the resin composition is preferably 10 to 90% by weight, more preferably 15 to 85% by weight, even more preferably 20 to 80% by weight, and particularly preferably 25 to 70% by weight, relative to the total weight of the resin composition.

(B) Thiol Compound Represented by Chemical Formula (I) The resin composition of this embodiment comprises (B) a thiol compound represented by chemical formula (I):

The trithiol compound represented by chemical formula (I) functions as a curing agent for (meth)acrylate compounds. 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 2022-180364 A) or JP 2023-126883 A.

(B) The thiol compound represented by chemical formula (I) acts as a curing agent for the (meth)acrylate compound, 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.

Further examples of by-products include, but are not limited to, (0) thiol compounds represented by chemical formulas (I-1) to (I-45), (1) multimers of these thiol compounds (e.g., dimers, trimers, etc.), (2) condensates of two or more selected from these thiol compounds, and (3) condensates of one or more selected from these thiol compounds with one or more selected from the thiol compounds represented by chemical formulas (IV-1) to (IV-6) described in JP 2023-126883 A.

When component (B) contains a by-product of the compound represented by 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 ratio of the content of the by-product of the compound represented by chemical formula (I) to the content of the compound represented by 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, and 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 peak area of each component when the curing agent is analyzed by liquid chromatography.

In this embodiment, the content of component (B) in the resin composition is preferably 1 to 70% by weight, more preferably 5 to 60% by weight, and even more preferably 10 to 50% by weight, relative to the total weight of the resin composition.

In this embodiment, the ratio of the number of (meth)acryloyl group equivalents of component (A) to the number of thiol group equivalents of component (B) ([number of (meth)acryloyl 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, and even more preferably 0.2 to 5.0.

In this specification, functional group equivalents such as thiol equivalent and (meth)acryloyl equivalent refer to the molecular weight of the compound per functional group, and functional group equivalents such as thiol group equivalent number and (meth)acryloyl group equivalent number refer to the number of functional groups (equivalent number) per compound weight (charge amount).

Theoretically, the (meth)acryloyl equivalent of a (meth)acrylate compound is the molecular weight of the (meth)acrylate compound divided by the number of (meth)acryloyl groups in one molecule. The actual (meth)acryloyl equivalent can be measured, for example, by NMR. The (meth)acryloyl group equivalent of a (meth)acrylate compound is the number of (meth)acryloyl groups (equivalents) per weight (charged amount) of (meth)acrylate compound, and is the quotient obtained by dividing the weight (g) of the (meth)acrylate compound by the (meth)acryloyl equivalent of that (meth)acrylate compound (if multiple (meth)acrylate compounds are contained, the sum of such quotients for each (meth)acrylate compound).

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 using 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 thiol compound, and is the quotient obtained by dividing the weight (g) of the thiol compound by the thiol equivalent of that thiol compound (if multiple thiol compounds are included, the sum of such quotients for each thiol compound).

(C) Thermally Latent Curing Catalyst That Is Solid at Room Temperature The resin composition of this embodiment contains (C) a thermally latent curing catalyst that is solid at room temperature (hereinafter also referred to as "component (C)"). A thermally latent curing catalyst is a compound or substance that is inactive at room temperature but is activated by heating to function as a curing catalyst. The thermally latent curing catalyst of this embodiment is solid at room temperature. Examples of thermally latent curing catalysts that are solid at room temperature include dicyandiamide; urea compounds that are solid at room temperature; amine compounds that are solid at room temperature; amine adduct-based thermally latent curing catalysts such as reaction products of amine compounds and epoxy compounds (amine-epoxy adducts), reaction products of amine compounds and isocyanate compounds or urea compounds (amine-urea adducts), and combinations thereof; microencapsulated thermally latent curing catalysts; and solid-dispersed thermally latent curing catalysts such as inclusion-type thermally latent curing catalysts. Examples of amine compounds include aliphatic amines, aromatic amines, and heterocyclic amines.

The present inventors have investigated curable compositions containing a (meth)acrylate compound as a base compound and a trithiol compound represented by chemical formula (I) as a curing agent, and have found that the gloss of the cured product tends to be high when thermally cured. The reasons for this are thought to be, but are not limited to, the following: When curing a (meth)acrylate compound with a trithiol compound represented by formula (I), the viscosity of the curable composition is low due to the (meth)acrylate compound, which has many relatively low viscosity compounds, and the trithiol compound represented by chemical formula (I), which has a very low viscosity. This is thought to result in a cured product with high surface smoothness and a high level of gloss. Furthermore, when thermally curing a (meth)acrylate compound-thiol compound, a basic catalyst such as an amine can be used to promote the curing reaction in an anionic polymerization system. While the crosslink density is low due to the low number of functional groups in the trithiol compound represented by formula (I), the low steric hindrance structure reduces unevenness in curing, which is thought to result in a smooth surface and a high level of gloss.
In this embodiment, by including a thermally latent curing catalyst that is solid at room temperature in the resin composition, excellent low gloss can be achieved even in a curable composition that contains a (meth)acrylate compound as a main component and a trithiol compound represented by formula (I) as a curing agent. The reasons for this include, but are not limited to, the following:
(1) A slight difference in the degree of cure occurs between the high-basicity area around the thermal latent curing catalyst particles, which are solid at room temperature, and the thin-basic area away from them, resulting in a moderate unevenness in the cure, which can suppress the gloss level.
This is thought to be due to several mechanisms, such as: (2) the soft bulk of the trithiol compound represented by formula (I) cures by following the periphery of the heat-latent curing catalyst particles that are solid at room temperature, causing minute irregularities on the surface and suppressing surface gloss; and (3) the low viscosity of the trithiol compound represented by formula (I) makes it easy for the heat-latent curing catalyst that is solid at room temperature to rise to the surface of the polymerization system, causing minute irregularities on the surface of the resulting cured product.

Examples of urea compounds that are solid at room temperature include, but are not limited to, 1,1'-(4-methyl-1,3-phenylene)bis(3,3-dimethylurea) (product name: U-CAT 3512T, manufactured by San-Apro Co., Ltd.) and 3-{3-[(3,3-dimethylureido)methyl]-3,5,5-trimethylcyclohexyl}-1,1-dimethylurea (product name: U-CAT 3513N, manufactured by San-Apro Co., Ltd.).

Amine compounds that are solid at room temperature include, for example, 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 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.

Amine compounds used as one of the raw materials for producing amine adduct-based thermal latent curing catalysts are those that contain one or more active hydrogen atoms in the molecule capable of addition reacting with epoxy or isocyanate groups, and at least one functional group selected from primary, secondary, and tertiary amino groups. Examples of such amine compounds include, but are not limited to, the amine compounds that are solid at room temperature listed above, as well as 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 heterocyclic amine compounds containing nitrogen atoms such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, and piperazine.

Among these, compounds containing a tertiary amino group in the molecule and imidazole derivatives are particularly useful raw materials for producing 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, 2-phenylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and 2-phenyl-4,5-dihydroxymethylimidazole. imidazole compounds such as phenyl-4-methylimidazole and 1-(2-aminoethyl)-2-methylimidazole; 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-methylimidazole, 1-(2-hydroxy 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, benzimidazole, 2 Examples of such amines include, but are not limited to, alcohols, phenols, thiols, carboxylic acids, and hydrazides having a tertiary amino group or an imidazole skeleton in the molecule, such as 1-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.

Examples of epoxy compounds used as one of the raw materials for producing amine-epoxy adduct thermal latent curing catalysts include, but are not limited to, 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; polyglycidyl esters obtained by reacting epichlorohydrin with polycarboxylic acids such as phthalic acid and terephthalic acid; glycidyl amine compounds obtained by reacting epichlorohydrin with 4,4'-diaminodiphenylmethane or m-aminophenol; 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, various phenylphenol glycidyl ethers, and glycidyl methacrylate.

Examples of isocyanate compounds used as one of the raw materials for manufacturing amine-urea adduct latent curing catalysts 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 compounds containing terminal isocyanate groups obtained by reacting these polyfunctional isocyanate compounds with active hydrogen compounds. Examples of such compounds containing terminal isocyanate groups include, but are not limited to, an adduct having a terminal isocyanate group obtained by reacting toluylene diisocyanate with trimethylolpropane, and an adduct having a terminal isocyanate group obtained by reacting toluylene diisocyanate with pentaerythritol.

Urea compounds used as one of the raw materials for manufacturing amine-urea adduct latent curing catalysts include, but are not limited to, urea and thiourea.

Amine adduct-based thermally latent curing catalysts are, for example, combinations of the above-mentioned two components: (a) an amine compound and an epoxy compound; (b) a three-component combination of these two components and an active hydrogen compound; or (c) a two- or three-component combination of an amine compound and an isocyanate compound and/or a urea compound. These can be easily prepared by mixing the components and reacting them at temperatures between room temperature and 200°C, then cooling and solidifying them and pulverizing them, or by reacting them in a solvent such as methyl ethyl ketone, dioxane, or tetrahydrofuran, removing the solvent, and pulverizing the solids. Amine adduct-based thermally latent curing catalysts include combinations of an amine-epoxy adduct-based curing catalyst and an amine-urea adduct-based curing catalyst.

A microencapsulated thermally latent curing catalyst is a curing catalyst with a core made of an amine compound or an amine adduct compound obtained by reacting an amine compound with an epoxy compound, an isocyanate compound, or a urea compound, coated with a shell made of a synthetic resin or an inorganic oxide. Examples of amine compounds include the amine compounds listed above. Imidazole derivatives are preferred as the amine compound because they exhibit favorable latency. Examples of imidazole derivatives include 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole. Examples of synthetic resins that form the shell include phenolic resins, melamine resins, epoxy resins, urethane resins, and urea resins, and these resins can also be used in combination. Examples of inorganic oxides that form the shell include silica, alumina, titania, and magnesia.

An inclusion-type thermal latent curing catalyst is a curing catalyst that has a structure in which guest molecules such as amine compounds are trapped at the molecular level within the crystalline space formed by the host molecule.

In this embodiment, from the viewpoint of achieving superior low gloss, (C) the thermally latent curing catalyst that is solid at room temperature preferably includes at least one selected from the group consisting of amine adduct-based thermally latent curing catalysts and microencapsulated thermally latent curing catalysts. Amine adduct-based thermally latent curing catalysts and microencapsulated thermally latent curing catalysts are thought to facilitate the formation of micro-irregularities on the surface of the cured product because the destruction and/or dissolution of the thermally latent curing catalyst particles is appropriately controlled during heating for thermal curing. Among these, those containing a compound with at least one urea bond in its structure (e.g., those containing the reaction product of an amine compound and an isocyanate compound or a urea compound (amine-urea adduct system)) are more preferred. Because urea bonds are relatively highly polar, they are thought to facilitate the formation of segments in the curing reaction system of a resin composition using the trithiol compound represented by formula (I) as a curing agent, making it easier to form micro-irregularities on the surface of the cured product.

Typical examples of commercially available thermal latent curing catalysts that are solid at room temperature include, but are not limited to, the following: Amine-epoxy adduct curing catalysts include "Amicure PN-23" (product name of Ajinomoto Fine-Techno Co., Ltd.), "Amicure PN-40" (product name of Ajinomoto Fine-Techno Co., Ltd.), "Amicure PN-50" (product name of Ajinomoto Fine-Techno Co., Ltd.), "Hardener X-3661S" (product name of ACR Co., Ltd.), "Hardener X-3670S" (product name of ACR Co., Ltd.), "Novacure HX-3742" (product name of Asahi Kasei Corporation), and "Novacure Examples of such catalysts include, but are not limited to, "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). The "Novacure" series is also a microcapsule-type thermal latent curing catalyst. Furthermore, examples of amine-urea adduct curing catalysts include, but are not limited to, "Fujicure FXE-1000" (product name of T&K TOKA Corporation), "Fujicure FXR1020" (product name of T&K TOKA Corporation), "Fujicure FXR-1030" (product name of T&K TOKA Corporation), "Fujicure FXR-1110" (product name of T&K TOKA Corporation), "Fujicure FXR1121" (product name of T&K TOKA Corporation), "Fujicure FXR1081" (product name of T&K TOKA Corporation), "Fujicure FXR1061" (product name of T&K TOKA Corporation), and "Fujicure FXR1171" (product name of T&K TOKA Corporation). An example of a commercially available clathrate-type thermal latent curing catalyst is "NISSOCURE TIC-188" (product name: Nippon Soda Co., Ltd.).

(C) The thermally latent curing catalysts that are solid at room temperature may be used alone or in combination of two or more.

The content of component (C) in the resin composition is preferably 0.1 to 30% by weight, more preferably 0.5 to 20% by weight, and even more preferably 1 to 15% by weight, based on the total weight of the resin composition.

Furthermore, component (C) may be provided in the form of a dispersion in which particles of a thermally latent curing catalyst that is solid at room temperature are dispersed in an epoxy resin. The resin composition of this embodiment may contain such an epoxy resin.

If desired, the resin composition of this embodiment may contain optional components other than the above components (A) to (C), such as those described below.

(D) Photopolymerization Initiator The resin composition of this embodiment may contain (D) a photopolymerization initiator (hereinafter also referred to as "component (D)") to the extent that the effects of the present invention are not impaired. In this specification, a photopolymerization initiator refers to a reactant that absorbs light, generates radicals, and promotes polymerization. The inclusion of a photopolymerization initiator promotes photocuring (e.g., UV curing) of the resin composition. For example, the resin composition can be further cured by heat after curing with light (UV) or during light irradiation. Interestingly, a resin composition containing the photopolymerization initiator of this embodiment can exhibit low gloss even when subjected to photocuring. The reason for this is thought to be, but is not limited to, that the thermal latent curing catalyst (C), which is solid at room temperature, does not dissolve during photocuring, maintaining its particle shape. The type of photopolymerization initiator is not particularly limited, and known materials can be used. Examples of the photopolymerization initiator include, but are not limited to, alkylphenone compounds, acylphosphine oxide compounds, oxime ester compounds, and compounds having a photosensitive moiety and a peroxide structure.

Examples of alkylphenone compounds include benzyl dimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethan-1-one (commercially available as Omnirad 651, manufactured by IGM Resins B.V.); α-aminoalkylphenones such as 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one (commercially available as Omnirad 907, manufactured by IGM Resins B.V.); 1-hydroxy-cyclohexyl-phenyl-ketone (commercially available as IGM Resins B.V.); Examples of suitable hydroxyalkylphenones include, but are not limited to, α-hydroxyalkylphenones such as Omnirad 184 (manufactured by IGM Resins B.V.); 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one (commercially available as Omnirad 379EG, manufactured by IGM Resins B.V.), and 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone (commercially available as Omnirad 369, manufactured by IGM Resins B.V.).

Examples of acylphosphine oxide compounds include, but are not limited to, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (commercially available as Omnirad TPO H, manufactured by IGM Resins B.V.) and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (commercially available as Omnirad 819, manufactured by IGM Resins B.V.).

Examples of oxime ester compounds include, but are not limited to, 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)] (trade name: Irgacure OXE-01, manufactured by BASF), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (trade name: Irgacure OXE-02, manufactured by BASF), methanone, ethanone, 1-[9-ethyl-6-(1,3-dioxolane, 4-(2-methoxyphenoxy)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (trade name: ADEKA OPT-N-1919, manufactured by ADEKA Corporation).

Examples of compounds having a photosensitive moiety and a peroxide structure, or commercially available products thereof, include, but are not limited to, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone (BTTB), Perdual TA, and Perdual TX (all manufactured by NOF Corporation).

Other examples of photopolymerization initiators include 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, benzil dimethyl ketal, benzophenone, Non, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenyl glyoxylate, benzyl, camphorquinone, and the like, but are not limited to these.

As the photopolymerization initiator, various photopolymerization initiators may be used alone or in combination of two or more types.

From the viewpoint of the photocuring speed and storage stability of the resin composition, the content of the photopolymerization initiator is preferably 0.01 to 10% by weight, and more preferably 0.04 to 8% by weight, relative to the total weight of the resin composition.

(E) Filler The resin composition of this embodiment may contain a filler (hereinafter also referred to as "component (E)") within a range that does not impair the effects of the present invention. By containing a filler in the resin composition, the linear expansion coefficient of the cured product obtained by curing the resin composition can be reduced, and thermal cycle resistance can be improved. Furthermore, if the filler has a low elastic modulus, it can alleviate stress generated in the cured product, improving long-term reliability. Fillers are broadly classified into inorganic fillers and organic fillers.

The inorganic filler is not particularly limited as long as it is made of granular 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. Silica filler is preferred as the inorganic filler, as it allows for a high loading. Amorphous silica is preferred as the silica. The surface of the inorganic filler may be treated with a coupling agent such as a silane coupling agent.

Examples of organic fillers include polytetrafluoroethylene (PTFE) fillers, silicone fillers, acrylic fillers, fillers with a urethane skeleton, fillers with a butadiene skeleton, and styrene fillers. The organic fillers may be surface-treated.

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

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 ) measured by laser diffraction in accordance with ISO-13320 (2009). 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, thereby preventing wear on the jet dispenser nozzle and preventing the resin composition ejected from the jet dispenser nozzle from scattering 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 0.001 μm or more, and more preferably 0.1 μm or more. In some embodiments of this aspect, the average particle size of the filler is preferably 0.01 μm to 5.0 μm, 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 0.001 μm or more and less than 0.1 μm and a filler having an average particle size of 0.1 μm to 6.0 μm may be used in combination.

The filler content in the resin composition of this embodiment is preferably 10 to 50% by weight, more preferably 15 to 45% by weight, and even more preferably 15 to 40% by weight, relative to the total weight of the resin composition.

(F) Stabilizer The resin composition of this embodiment may contain (F) a stabilizer (hereinafter also referred to as "component (F)"), if desired, to the extent that the effects of the present invention are not impaired. The stabilizer can further improve the storage stability of the 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 boric acid ester compounds, aluminum chelates, and organic acids is preferred because of its high effect of improving storage stability.

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 boric acid ester compounds are preferred because they are liquid at room temperature (25°C), and therefore the viscosity of the resin composition can be kept 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.
The stabilizers may be used alone or in combination of two or more.

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 resin composition.

(B') Thiol Compound Other Than Component (B) The resin composition of this embodiment may contain (B') a thiol compound other than component (B) (hereinafter also referred to as "component (B')", "(B') other thiol compound" or "other thiol compound"). Examples of the other thiol compound include:
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 compound;
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 the thiols include triazine thiols such as 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.

Other examples of 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) 1,3,4,6-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-methylglycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a-dimethylglycoluril, 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-sulfanylpropoxy)propoxy]propane-1-thiol, pentaerythritol tetrapropanethiol, 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptomethylthio)propane tris(3-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(mercaptomethyl) 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 ...mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl) 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)-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) 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-dithianylthio]-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-7,9,13,15-tetra 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(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]-1,3-dithiolane, 4-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]-5-mercaptomethylthio-1,3-dithiolane, 4-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]-5-mercaptomethylthio methylthio-1,3-dithiolane, 2-{bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]methyl}-1,3-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]mercapto Examples include mercaptomethylthiomethyl-1,3-dithietane, 2-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]mercaptomethylthiomethyl-1,3-dithietane, and 4-{1-[2-(1,3-dithietanyl)]-3-mercapto-2-thiapropylthio}-5-[1,2-bis(mercaptomethylthio)-4-mercapto-3-thiabutylthio]-1,3-dithiolane.

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

When a thiol compound other than component (B) is contained, it is preferable to add the number of thiol group equivalents of component (B) and the number of thiol group equivalents of the thiol compounds other than component (B) together and calculate the ratio of the number of (meth)acryloyl group equivalents of component (A) to the number of thiol group equivalents of all thiol compounds ([number of (meth)acryloyl group equivalents of component (A)] / [number of thiol group equivalents of all thiol compounds]). In this embodiment, the ratio of the number of (meth)acryloyl group equivalents of component (A) to the sum of the number of thiol group equivalents of component (B) and the number of thiol group equivalents of component (B') ([number of (meth)acryloyl group equivalents of component (A)]/([number of thiol group equivalents of component (B)]+[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.

Reactive Diluent: If desired, the resin composition of this embodiment may contain a reactive diluent 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 a group reactive with the thiol group of the thiol compound and has a relatively low viscosity at room temperature. Examples of reactive diluents include monofunctional maleimide compounds, monofunctional (meth)acrylate compounds, monofunctional acrylamide compounds, and monofunctional epoxy compounds.

Monofunctional maleimide compounds are compounds that have one maleimide group as a group reactive with a thiol group. Examples include maleimides; aliphatic hydrocarbon group-containing maleimides such as methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, and cyclohexylmaleimide; aromatic ring-containing maleimides such as phenylmaleimide; and the like.

Monofunctional (meth)acrylate compounds are compounds that have one (meth)acryloyl group as a group reactive with a thiol group. Examples of monofunctional (meth)acrylate compounds include ethyl (meth)acrylate, trifluoroethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and isodecyl (meth)acrylate. acrylate, isobornyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, butoxydiethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, 2-ethylhexyldiethylene glycol (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, m-phenoxybenzyl (meth)acrylate, and other esters of monohydric alcohols and (meth)acrylic acid; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, octyl acrylate, nonyl acrylate, isononyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, cyclic trimethylolpropane formal acrylate, 1-naphthalenemethyl (meth)acrylate, 1-ethylcyclohexyl (meth)acrylate, 1-methylcyclohexyl (meth)acrylate, 1-ethylcyclopentyl (meth)acrylate, 1-methyl Cyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, tetrahydrodicyclopentadienyl (meth)acrylate, 2-(o-phenylphenoxy)ethyl (meth)acrylate, isobornylcyclohexyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth) Acrylate, 1-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, 2-methyl-2-adamantanyl (meth)acrylate, 2-ethyl-2-adamantanyl (meth)acrylate, 2-isopropyladamantan-2-yl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, (adamantan-1-yloxy)methyl (meth)acrylate, 2-isopropyl-2-adamantyl (meth)acrylate, 1-methyl-1-ethyl -1-adamantylmethanol (meth)acrylate, 1,1-diethyl-1-adamantylmethanol (meth)acrylate, 2-cyclohexylpropan-2-yl (meth)acrylate, 1-isopropylcyclohexyl (meth)acrylate, 1-methylcyclohexyl (meth)acrylate, 1-ethylcyclopentyl (meth)acrylate, 1-methylcyclohexyl (meth)acrylate, tetrahydropyranyl (meth)acrylate, tetrahydro-2-furanyl (meth)acrylate, 2-octyl Examples include mono(meth)acrylates of polyhydric alcohols or esters of monohydric alcohols and (meth)acrylic acid, such as (5-oxotetrahydrofuran-3-yl(meth)acrylate, (5-oxotetrahydrofuran-2-yl)methyl(meth)acrylate, (2-oxo-1,3-dioxolan-4-yl)methyl(meth)acrylate, N-acryloyloxyethylhexahydrophthalimide, α-acryloyl-ω-methoxypoly(oxyethylene), and 1-ethoxyethyl(meth)acrylate.

Monofunctional epoxy compounds are compounds that have one epoxy group as a reactive group with thiol groups. Examples of monofunctional epoxy compounds 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 with other functional groups such as allyl glycidyl ether, glycidyl methacrylate, and 1-vinyl-3,4-epoxycyclohexane.

(G) Other Additives The resin composition of this embodiment may, if desired, 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. The type and amount of each additive are as per usual, provided that the gist of this embodiment is not impaired.

In order to prevent a reduction in curing strength and adhesion and to prevent outgassing and bleeding, the resin composition of this embodiment is substantially free of liquid components such as water, solvents, ionic liquids, etc. (excluding liquid components (A) and (B)). For example, the content of liquid components is preferably 3% by weight or less, and more preferably 1% by weight or less, relative to the total weight of the resin composition. Examples of solvents include organic solvents commonly used in the field of curable compositions, such as hydrocarbons (benzene, toluene, xylene, cyclohexane, etc.), aprotic polar solvents (N,N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, etc.), nitriles (acetonitrile, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (ethyl acetate, butyl acetate, etc.), ethers (cyclopentyl methyl ether, diethyl ether, tetrahydrofuran, dimethoxyethane, etc.), alcohols (methanol, ethanol, propanol, butanol, etc.), terpenes (turpentine, terpineol, isobornyl acetate, etc.), and halogenated solvents (dichloromethane, chloroform, etc.).

The method for producing the resin composition of this embodiment is not particularly limited. For example, the 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 melting them by heating if necessary, to form a uniform composition. The mixer is not particularly limited, but examples that can be used include a Raikai mixer, Henschel mixer, three-roll mill, ball mill, planetary mixer, and bead mill, all of which are equipped with a stirring device and a heating device. Appropriate combinations of these devices may also be used.

Depending on the intended use, the 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. When a two-component (or multi-component) resin composition is used, the components (A) to (C) and other optional components as needed can be selected in the same way 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 needed can be divided into two or multiple components in any manner without particular restrictions. 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 needed. Components (A) to (C) may be contained in a single component, or a component may be composed solely of the components (A) to (C) and/or other optional components as needed. For example, when separating into liquid A and liquid B, the separation may be liquid A: component (A), liquid B: component (B) and component (C), or liquid A: component (A) and component (C), or liquid B: component (B), or liquid A: component (A) and component (D), or liquid B: component (B) and component (C), or liquid A: component (A), component (B) and component (C), or liquid B: component (B'), or liquid A: component (A), liquid B: component (B), component (C), and component (D). When components (A) to (C) are contained in liquid A and 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 (C) are contained in separate liquids, the liquids can be considered together to be the resin composition of this embodiment. An example of a case in which components (A) to (C) are contained in separate liquids is a resin composition in which components (A) to (C) are separated into two or more containers, specifically a kit composed of multiple liquids containing any of components (A) to (C).

The resin composition obtained in this manner is thermosetting and can be cured, for example, by heat treatment at 40 to 200°C for 0.1 to 300 minutes. At a temperature of 100°C, curing preferably occurs within 5 hours, more preferably within 3 hours, and even more preferably within 1 hour. When the resin composition of this embodiment is used to manufacture semiconductor devices containing components that deteriorate under high-temperature conditions, it is preferable to thermally cure the composition at a temperature of 40 to 90°C for 30 to 120 minutes. The resin composition of this embodiment can achieve low gloss whether cured at a relatively low temperature (e.g., 60 to 100°C) or at a relatively high temperature (e.g., above 100°C).

When the resin composition of this embodiment contains (D) a photopolymerization initiator, the resin composition can also be cured with light (UV). For example, after curing with light (UV), or during light irradiation, the resin composition can be further cured with heat. A resin composition containing the photopolymerization initiator of this embodiment can exhibit low gloss even when subjected to photocuring.

In one embodiment, the resin composition of this aspect has a gloss at an incident angle of 60° of a 300 μm thick cured product obtained by curing the resin composition at 80°C for 60 minutes, which gloss is preferably less than 90, more preferably 85 or less, and even more preferably 80 or less. The gloss at an incident angle of 60° can be measured in accordance with JIS Z 8741. Note that in this specification, the gloss of a cured product of a resin composition is a value measured for a cured product of the resin composition prepared on a sample low-gloss substrate to prevent the gloss of the substrate from affecting the measurement results.

The resin composition of this embodiment can be used, for example, as an adhesive or sealant for fixing, joining, or protecting semiconductor devices or electronic components, or the components that make them up, or as a raw material for such adhesives or sealants.

[Adhesive or sealant]
Another embodiment of the present invention is an adhesive or sealant that includes the resin composition of the above-described embodiment. This adhesive or sealant provides excellent fixation, bonding, or protection for general-purpose plastics (e.g., PE, PS, PP, etc.), 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 that make up semiconductor devices or electronic components. 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, other semiconductor modules, and integrated circuits.

Depending on the intended use, 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. 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-component types in any way without particular restriction. When the composition 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) 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 the liquid is divided into liquid A and liquid B, the division may be liquid A: component (A), liquid B: component (B) and component (C), or liquid A: component (A) and component (C), liquid B: component (B), or liquid A: component (A) and component (D), liquid B: component (B) and component (C), or liquid A: component (A), component (B) and component (C), or liquid B: component (B'), or liquid A: component (A), liquid B: component (B), component (C), and component (D). When components (A) to (C) are contained in liquid A and other components are contained in liquid B, only liquid A, or a combination of liquid A and liquid B, can be considered as the adhesive or sealant of this embodiment. On the other hand, when components (A) to (C) are contained in separate liquids, the liquids can be considered together to be the adhesive or sealant of this embodiment. An example of a case in which components (A) to (C) are contained in separate liquids is an adhesive or sealant in which components (A) to (C) are separated into two or more containers, specifically a kit composed of multiple liquids containing any of components (A) to (C).

[Cured product of resin composition, adhesive, or sealant]
A cured product according to another embodiment of the present invention is a cured product obtained by curing the resin composition, adhesive, or sealant according to the above-described embodiment.

[Semiconductor devices, electronic components]
Another aspect of the present invention is a semiconductor device or electronic component that includes the cured product of the above-described aspect. 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.

The present invention will be explained 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.

[Production of resin composition]
Resin compositions of Examples, Comparative Examples, and Reference Examples 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:

(A) (Meth)acrylate Compound (A-1): Dimethylol-tricyclodecane diacrylate (product name: Light Acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd., (meth)acryloyl equivalent: 152 g/eq, molecular weight: 304 g/mol)
(A-2): Difunctional alkoxylated bisphenol A acrylate (product name: ABE-300, manufactured by Shin-Nakamura Chemical Co., Ltd., (meth)acryloyl equivalent: 236 g/eq, molecular weight: 472 g/mol)
(A-3): Dipropylene glycol diacrylate (product name: M-408, manufactured by Toagosei Co., Ltd., (meth)acryloyl equivalent: 117 g/eq, molecular weight: 468 g/mol)

(B) Thiol compound represented by formula (I) (B-1): Thiol compound represented by 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.
(B') 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 Chemicals Corporation, thiol equivalent: 110 g/eq)

(C) Thermally Latent Curing Catalyst that is Solid at Room Temperature (C-1): Amine adduct-based thermally latent curing catalyst (product name: Fujicure FXR-1121, a mixture of epoxy compound-modified imidazoles and urea-modified amines, solid at room temperature, manufactured by T&K TOKA Corporation)
(C-2): Amine-epoxy adduct-based thermal latent curing catalyst (product name: Novacure HXA9322HP, core-shell type, manufactured by Asahi Kasei Corporation)
This thermal latent curing catalyst (C-2) 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 latent curing catalyst in the form of fine particles that is solid at room temperature is dispersed in an epoxy resin (a mixture of bisphenol A epoxy resin and bisphenol F epoxy resin (epoxy group equivalent: 180 g/eq)).
(C-3): Amine-urea adduct-based thermal latent curing catalyst (product name: Fujicure FXR-1030, solid at room temperature, manufactured by T&K TOKA Corporation)
(C-4): 2-undecylimidazole (solid at room temperature, manufactured by Tokyo Chemical Industry Co., Ltd.)
(C-5): 2-heptadecylimidazole (solid at room temperature, manufactured by Tokyo Chemical Industry Co., Ltd.)

(C') Thermally latent curing catalyst that is liquid at room temperature (C'-1): N,N-dimethylbenzylamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
(C'-2): 1-ethylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
(C'-3): 2-ethyl-4-methylimidazole (Tokyo Chemical Industry Co., Ltd.)

(D) Photopolymerization initiator (D-1): 1-hydroxycyclohexylphenyl ketone (product name: Omnirad 184, manufactured by IGM Resins B.V.)

(E) Filler (E-1): Silica filler (product name: SE2300, manufactured by Admatechs Co., Ltd., specific surface area: 4.4 m ² /g)
(F) Stabilizer (F-1): Triisopropyl borate (G) Other additives (G-1): Silane coupling agent (3-glycidoxypropyltrimethoxysilane) (product name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)

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

[Evaluation of storage stability]
The resin compositions of the Examples, Comparative Examples, and Reference Examples were placed in syringes with a tip diameter of 5 mm and stored frozen at -20°C for 24 hours. After frozen storage, the resin compositions were allowed to stand at room temperature (25°C) for 1 hour, and then the storage stability of the resin compositions was confirmed by checking whether they could be manually extruded from the tip of the syringe. Evaluation was performed according to the following criteria. The measurement results are shown in Table 1.
◎: Can be discharged stably as before. ○: Can be discharged, but some viscosity increase and stringiness is observed. △: Difficult to discharge and viscosity increase is observed. ×: Cannot be discharged and hardens inside the syringe.

[Evaluation of Glossiness]
The resin compositions of the Examples, Comparative Examples, and Reference Examples were printed onto a 25 mm x 75 mm x 1.5 mm polyamide plate by stencil printing to form a 25 mm x 50 mm (0.3 mm thick) rectangle. The printed resin compositions were cured under the following four curing conditions. The cured products on the polyamide plate were used as test pieces.
Curing condition 1: Curing was carried out in a fan dryer at 80° C. for 60 minutes.
Curing condition 2: Pre-curing was performed by UV irradiation using a UV LED irradiation device AC475 manufactured by Excelitas Technologies, with an integrated light intensity of 2000 mJ/cm ² (measured with a UIT-250 (connected to a UVD-365 receiver) manufactured by Ushio Inc.) The pre-cured curable resin composition was then fully cured in an air dryer at 80°C for 60 minutes.
Curing condition 3: Curing was carried out in a blower dryer at 150° C. for 60 minutes.
Curing condition 4: Pre-curing was performed by UV irradiation using a UV LED irradiation device AC475 manufactured by Excelitas Technologies, with an integrated light intensity of 2000 mJ/cm ² (measured with a UIT-250 (connected to a UVD-365 receiver) manufactured by Ushio Inc.) The pre-cured curable resin composition was then fully cured in an air dryer at 150°C for 60 minutes.
The specular gloss (%) of the surface of the test piece was measured in accordance with JIS Z 8741 using a Gloss Checker IG-331 (light source: LED (wavelength 890 nm)) manufactured by Horiba, Ltd., under conditions of an incident angle of 20° and an acceptance angle of 20°, and an incident angle of 60° and an acceptance angle of 60°. The results are shown in Table 1. The same evaluation was also carried out on a two-component resin composition in which, in the composition of Example 1, Liquid A was the component (A), and Liquid B was the component (B), component (C), and component (D).

In the table,
"Glossiness UV+80℃/60min(20°)" means the glossiness of the cured resin composition cured under curing condition 2 at an incident angle of 20°,
"Glossiness UV+80℃/60min (60°)" means the glossiness of the cured resin composition cured under curing condition 2 at an incident angle of 60°,
"Gloss 80°C/60 min (20°)" means the gloss at an incident angle of 20° of the cured resin composition cured under curing condition 1,
"Gloss 80°C/60 min (60°)" means the gloss at an incident angle of 60° of the cured resin composition cured under curing condition 1,
"Glossiness UV+150°C/60min (20°)" means the glossiness of the cured resin composition cured under curing condition 4 at an incident angle of 20°,
"Glossiness UV+150°C/60min (60°)" means the glossiness of the cured resin composition cured under curing condition 4 at an incident angle of 60°,
"Gloss 150°C/60min (20°)" means the gloss at an incident angle of 20° of the cured resin composition cured under curing condition 3,
"Glossiness 150°C/60min (60°)" means the glossiness of the cured resin composition cured under curing condition 3 at an incident angle of 60°.

The resin compositions of Comparative Examples 1 to 3, which contained (A) a (meth)acrylate compound, (B) a trithiol compound of formula (I), and (C') a thermally latent curing catalyst that was liquid at room temperature, produced cured products with high gloss under all curing conditions.
On the other hand, the resin compositions of Examples 1 to 10, which contained (A) a (meth)acrylate compound, (B) a trithiol compound of formula (I), and (C) a thermally latent curing catalyst that is solid at room temperature, showed lower gloss levels compared to the resin compositions of Comparative Examples 1 to 3, which contained (C') a thermally latent curing catalyst that is liquid at room temperature instead of (C) the thermally latent curing catalyst that is solid at room temperature. Furthermore, the resin compositions of Examples 1 to 8, which contained a thermally latent curing catalyst having a urea bond in its structure, showed lower gloss levels when cured at either 80°C or 150°C.
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), component (C), and component (D), and the composition showed excellent low gloss.

The resin composition of the present invention is extremely useful, and can be used, for example, as an adhesive or sealant for fixing, joining, or protecting semiconductor devices or electronic components or the components that make them up, or as a raw material for such adhesives or sealants.

The disclosure of Japanese Patent Application No. 2024-032374 (filing date: March 4, 2024) is incorporated herein by reference in its entirety.
All publications, patent applications, and technical standards mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent application, or technical standard was specifically and individually indicated to be incorporated by reference.

Claims (12)

(A) a (meth)acrylate compound,
(B) Chemical formula (I):

and (C) a thermal latent curing catalyst that is solid at room temperature. The resin composition according to claim 1, further comprising (D) a photopolymerization initiator. The resin composition according to claim 1 or 2, wherein the (C) thermally latent curing catalyst that is solid at room temperature includes at least one selected from the group consisting of amine adduct-based thermally latent curing catalysts and microcapsule-type thermally latent curing catalysts. The resin composition according to claim 3, wherein the (C) thermal latent curing catalyst that is solid at room temperature includes a compound having at least one urea bond in its structure. The resin composition according to any one of claims 1 to 4, further comprising (B') a thiol compound other than component (B), wherein the ratio of the number of (meth)acryloyl group equivalents of component (A) to the sum of the number of thiol group equivalents of component (B) and the number of thiol group equivalents of component (B') ([number of (meth)acryloyl group equivalents of component (A)]/([number of thiol group equivalents of component (B)]+[number of thiol group equivalents of component (B')])) is 0.1 to 10. The resin composition according to any one of claims 1 to 5, wherein the gloss of a 300 μm-thick cured product obtained by curing the resin composition at 80°C for 60 minutes is less than 90 at an incident angle of 60°. The resin composition described in any one of claims 1 to 6, wherein components (A) to (C) are contained in a single container. The resin composition described in any one of claims 1 to 6, wherein components (A) to (C) are separated into two or more containers. An adhesive or sealant containing the resin composition described in any one of claims 1 to 8. The adhesive or sealant according to claim 9, which is for use in semiconductor devices or electronic components. A cured product obtained by curing the resin composition described in any one of claims 1 to 8, or the adhesive or sealant described in claim 9 or 10. A semiconductor device or electronic component comprising the cured product described in claim 11.