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

Abstract

The present invention addresses the problem of providing: a resin composition having favorable storage stability and low-temperature curability even when a specific trithiol compound is contained; an adhesive or sealing material comprising the same; a cured product; and a semiconductor device or electronic component.　Provided are: a resin composition comprising (A) a (meth)acrylate compound, (B) a thiol compound represented by chemical formula (I), (C) a thermally latent curing catalyst, and (D) an inorganic filler having a specific surface area of at least 4 m2 / g; an adhesive or sealing material comprising the same; a cured product; and a semiconductor device or electronic component.

Description

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

[0001] The present invention relates to a resin composition, an adhesive or sealing material 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 are often used for assembling and mounting components used in semiconductor devices, such as semiconductor chips, in order to maintain reliability, etc. Known examples of such resin compositions include curable compositions containing an epoxy compound or a (meth)acrylate compound as a base compound and a thiol compound as a curing agent (see, for example, 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 A JP 2009-51954 A JP 2022-180364 A

[0005] The present inventors have studied curable compositions containing 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 a thermally latent curing catalyst is used as a curing catalyst from the viewpoint of storage stability, the curing property is insufficient, particularly at low temperatures (e.g., 80°C). 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 property even under low-temperature conditions.

[0006] An object of the present invention is to provide a resin composition that has good storage stability and 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: The present invention encompasses a resin composition, an adhesive or sealant, a cured product, and a semiconductor device or electronic component, each having the following aspects: [1] (A) a (meth)acrylate compound, (B) a compound represented by chemical formula (I): (C) a thermal latent curing catalyst; and (D) a thiol compound having a specific surface area of ​​4 m ２ / g or more of an inorganic filler. [2] The resin composition according to the above item [1], further comprising (E) a photopolymerization initiator. [3] The resin composition according to the above item [1] or [2], wherein the content of the (D) inorganic filler is 1 to 90 wt % based on the total weight of the resin composition. [4] The resin composition according to the above item [1] or [2], wherein the ratio of the total surface area of ​​the (D) inorganic filler in the resin composition to the content of the (C) thermal latent curing catalyst in the resin composition is 7 to 400 m ２ / g. [5] The resin composition according to any one of [1] to [4] above, wherein the content of the (meth)acrylate compound having an average molecular weight of less than 250 in the resin composition is 0 to 90% by weight relative to the content of component (B) in the resin composition. [6] The resin composition according to any one of [1] to [5] above, 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. [7] The resin composition according to any one of [1] to [6] above, wherein components (A) to (D) are contained in a single container. [8] The resin composition according to any one of [1] to [6] above, wherein components (A) to (D) are separated into two or more containers. [9] An adhesive or encapsulant comprising the resin composition according to any one of [1] to [8] above.

[10] The adhesive or encapsulant 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 encapsulant according to [9] or

[10] above.

[12] A semiconductor device or electronic component comprising the cured product according to

[11] above.

[0008] According to aspects of the present invention, there are provided a resin composition having good storage stability and 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 like, 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] [Resin Composition] The resin composition according to one embodiment of the present invention comprises: (A) a (meth)acrylate compound; (B) a compound represented by the chemical formula (I): (C) a thermal latent curing catalyst; and (D) a thiol compound having a specific surface area of ​​4 m ２ / g or more of an inorganic filler. According to this aspect, even when the trithiol compound of formula (I) is contained, a resin composition having good storage stability and low-temperature curing property can be provided.

[0011] (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" refers to both a methacryloyl group and an acryloyl group. Furthermore, "(meth)acrylate compound" refers to both an acrylate compound and a methacrylate compound.

[0012] 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.

[0013] The (A) (meth)acrylate compound may be used alone or in combination of two or more kinds.

[0014] In this embodiment, the content of the (meth)acrylate compound (A) in the resin composition is preferably 10 to 90 wt %, more preferably 15 to 85 wt %, even more preferably 20 to 80 wt %, and particularly preferably 25 to 70 wt %, relative to the total weight of the resin composition.

[0015] The content of the (meth)acrylate compound having an average molecular weight of less than 250 in the resin composition may be 0 to 150% by weight relative to the content of the thiol compound (B) represented by chemical formula (I) in the resin composition. From the viewpoint of suppressing aggregation of the (C) thermal latent curing catalyst described below and from the viewpoint of the adhesive strength of the resulting cured resin composition, the content of the (meth)acrylate compound having an average molecular weight of less than 250 in the resin composition is preferably 0 to 90% by weight, more preferably 0 to 50% by weight, even more preferably 0 to 30% by weight, and particularly preferably 0 to 10% by weight, relative to the content of the thiol compound (B) represented by chemical formula (I) in the resin composition. Furthermore, the total content of the (meth)acrylate compound having an average molecular weight of less than 250 in the resin composition and the content of the thiol compound (B) represented by chemical formula (I) is preferably 5 to 90% by weight, more preferably 10 to 80% by weight, and even more preferably 15 to 70% by weight, relative to the entire resin composition. From the viewpoint of more easily achieving the above-mentioned effects, it is most preferable that the resin composition does not substantially contain any (meth)acrylate compound having an average molecular weight of less than 250.

[0016] (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.

[0017] (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 of 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-A-2022-180364.

[0018]

[0019]

[0020] 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.

[0021] When component (B) contains a by-product of the compound represented by the chemical formula (I), for example, the compounds represented by (I-1) to (I-9) described in JP-A-2022-180364 or the compounds described in JP-A-2023-126883, the ratio of the content of the by-product of the compound represented by the chemical formula (I) to the content of the 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, 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 size of the peak area of ​​each component when the curing agent is analyzed by liquid chromatography.

[0022] In this embodiment, the content of component (B) in the resin composition is preferably 1 to 70 wt %, more preferably 5 to 60 wt %, and even more preferably 10 to 50 wt %, relative to the total weight of the resin composition.

[0023] 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.

[0024] In this specification, functional group equivalents such as thiol equivalent and (meth)acryloyl equivalent refer to the molecular weight of a 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 weight (charged amount) of a compound.

[0025] 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 (equivalent number) per weight (charged amount) of the (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 (when multiple (meth)acrylate compounds are contained, the sum of such quotients for each (meth)acrylate compound).

[0026] 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).

[0027] (C) Thermal Latent Curing Catalyst The resin composition of this embodiment contains (C) a thermal latent curing catalyst (hereinafter also referred to as "component (C)"). A thermal 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. Examples of thermal latent curing catalysts include dicyandiamide; amine compounds that are solid at room temperature; amine adduct-based thermal 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 thermal latent curing catalysts; and solid-dispersed thermal latent curing catalysts such as inclusion-type thermal latent curing catalysts. From the viewpoint of the storage stability and curability of the resin composition, amine adduct-based thermal latent curing catalysts, microencapsulated thermal latent curing catalysts, and inclusion-type thermal latent curing catalysts are preferred as component (C). Amine compounds include aliphatic amines, aromatic amines, and heterocyclic amines.

[0028] Examples of amine 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.

[0029] The amine compound used as one of the raw materials for producing the amine adduct-based thermal 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 or an isocyanate 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, in addition to the above-mentioned amine compounds that are solid at room temperature, 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 amine compounds such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, and piperazine. However, the present invention is not limited to these.

[0030] Among these, compounds having a tertiary amino group in the molecule and imidazole derivatives are particularly useful as raw materials that provide 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 the tertiary amino acid 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 N,N-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.

[0031] Examples of epoxy compounds used as one of the raw materials for producing the amine-epoxy adduct thermal latent curing catalyst 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 resins, epoxidized cresol novolac resins, and epoxidized polyolefins; and monofunctional epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, various phenylphenol glycidyl ethers, and glycidyl methacrylate.

[0032] Examples of the isocyanate compound used as one of the raw materials for producing the amine-urea 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.

[0033] Examples of urea compounds used as one of the raw materials for producing the amine-urea adduct latent curing catalyst include, but are not limited to, urea and thiourea.

[0034] 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-component 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, reacting them at a temperature between room temperature and 200°C, cooling to solidify, and then pulverizing the mixture; or by reacting them in a solvent such as methyl ethyl ketone, dioxane, or tetrahydrofuran, removing the solvent, and then pulverizing the solid content. 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.

[0035] A microencapsulated thermally latent curing catalyst is a curing catalyst having 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, and coated with a shell made of a synthetic resin or an inorganic oxide. Examples of the amine compound include the amine compounds described 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.

[0036] Representative examples of commercially available thermal latent curing catalysts 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. Examples of the amine-urea adduct curing catalyst 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).

[0037] An inclusion-type thermally latent curing catalyst is a curing catalyst having a structure in which guest molecules such as amine compounds are confined at the molecular level in crystalline spaces formed by host molecules. An example of a commercially available inclusion-type thermally latent curing catalyst is "NISSOCURE TIC-188" (product name of Nippon Soda Co., Ltd.).

[0038] The thermal latent curing catalyst (C) may be used alone or in combination of two or more.

[0039] 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 10% by weight, based on the total weight of the resin composition.

[0040] Component (C) may be provided in the form of a dispersion in which particles of a thermal latent curing catalyst are dispersed in an epoxy resin, and the resin composition of this embodiment may contain such an epoxy resin.

[0041] (D) A specific surface area of ​​4 m ２ / g or more of an inorganic filler. ２ / g or more (hereinafter also referred to as "component (D)"). In a resin composition containing (A) a (meth)acrylate compound, (B) a thiol compound represented by chemical formula (I), and (C) a thermal latent curing catalyst, (D) a specific surface area of ​​4 m ２ / g or more of an inorganic filler, the low-temperature curing property of the resin composition is improved. In this specification, the specific surface area is the BET specific surface area measured by the BET method, unless otherwise specified.

[0042] The present inventors have investigated curable compositions containing a (meth)acrylate compound as a base and a trithiol compound represented by chemical formula (I) as a curing agent, and have found that when a thermally latent curing catalyst is used as the curing catalyst, the curing properties are insufficient, particularly at low temperatures (e.g., 80°C), compared to when a non-latent curing catalyst is used. The reasons for this include, but are not limited to, the following: In thermal curing of 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. From the perspective of storage stability, there are many types of powder-type thermally latent curing catalysts (including dispersions in epoxy resins) that are solid at room temperature. When such a powder-type thermally latent curing catalyst is used in a polymerization system of a (meth)acrylate compound, which contains many compounds with relatively low viscosity, and a trithiol compound represented by chemical formula (I), which has a very low viscosity, the viscosity of the curable composition is low, which is thought to result in aggregation of the powder-type thermally latent curing catalyst, or re-aggregation of the thermally latent curing catalyst once dispersed, resulting in reduced curability. In addition, it is thought that the trithiol compound of formula (I), which has very few polar moieties in its structure, has difficulty in extracting the protons from the thiol group, especially at low temperatures. For example, in the case of an ester-based thiol such as pentaerythritol tetrakis(3-mercaptopropionate), it is easy to form a six-membered ring structure, so that the proton (H) is easily extracted. In addition, in the case of an OH group-containing thiol, the OH group facilitates the extraction of protons from the thiol. In this embodiment, ２ By including an inorganic filler of 1 / g or more in the resin composition, the thermal curing property of the (meth)acrylate compound-trithiol compound represented by chemical formula (I) is improved even when a thermal latent curing catalyst is used as the curing catalyst. The reasons for this include, but are not limited to, (1) a specific surface area of ​​4 m ２ / g or more of the inorganic filler inhibits aggregation or re-aggregation of the thermal latent curing catalyst, and (2) the inorganic filler having polar groups on its surface serves as a reaction field that facilitates abstraction of protons from the thiol groups of the trithiol compound of formula (I).

[0043] From the viewpoint of being able to suppress aggregation or re-aggregation of the latent curing catalyst and from the viewpoint that the surface of the inorganic filler having a polar group can serve as a reaction field that facilitates abstraction of protons from the thiol group of the trithiol compound of formula (I), it is important that the inorganic particles have a specific surface area of ​​a certain level or more. ２ The upper limit of the specific surface area of ​​the inorganic filler of 400 m / g or more is not particularly limited, but from the viewpoint of appropriate viscosity increase and fluidity of the obtained resin composition, it is preferable that the upper limit be 400 m / g or more. ２ / g or less, and ２ It is more preferable that the SiO2 content is 1 / g or less.

[0044] The inorganic filler is made of granular material formed from an inorganic material, and its specific surface area is 4 m ２ / g or more. Examples of inorganic materials 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. The inorganic filler may be surface-treated with a coupling agent such as a silane coupling agent, as long as the effects of the present invention are not impaired. Even when the inorganic filler is surface-treated, the effect of inhibiting aggregation or re-agglomeration of the thermal latent curing catalyst by the inorganic filler described in (1) of paragraph 0042 above can be achieved. Furthermore, even when the inorganic filler is surface-treated, polar groups often remain on the surface of the surface-treated particles, and therefore, the effect of the inorganic filler serving as a reaction field that facilitates the abstraction of protons from the thiol groups of the trithiol compound of formula (I), described in (2) of paragraph 0042 above, can be achieved.

[0045] The shape of the inorganic filler is not particularly limited, and may be any of spherical, flaky, needle-like, irregular, and the like.

[0046] Specific surface area is 4m ２ The inorganic filler having a specific surface area of ​​4 m / g or more may be used alone or in combination of two or more. ２(C) From the viewpoint of suppressing aggregation or re-aggregation of the thermal latent curing catalyst, an inorganic filler having a specific surface area of ​​4 m ２ / g, (D) the content of inorganic filler is less than 4 m ２ The content of the inorganic filler is preferably 0 to 90% by weight, more preferably 0 to 50% by weight, even more preferably 0 to 30% by weight, and particularly preferably 0 to 10% by weight, based on the content of the inorganic filler of 1000 ppm or more per 1000 ppm of the resin composition. ２ It is most preferable that the composition is substantially free of inorganic fillers having a molecular weight of less than 1 / g.

[0047] The content of the inorganic filler (D) in the resin composition of this embodiment is preferably 1 to 90 wt %, more preferably 1 to 80 wt %, and even more preferably 3 to 70 wt %, relative to the total weight of the resin composition.

[0048] In this embodiment, the ratio of the total surface area of ​​the inorganic filler (D) in the resin composition to the content of the thermal latent curing catalyst (C) in the resin composition is 7 to 400 m ２ / g, and 10 to 400m ２ / g is more preferable.

[0049] In this embodiment, the ratio of the total surface area of ​​the inorganic filler (D) in the resin composition to the content of the (meth)acrylate compound (A) in the resin composition is 0.7 to 50 m ２ / g, and 1 to 50m ２ / g is more preferable.

[0050] If desired, the resin composition of this embodiment may contain optional components other than the above components (A) to (D), such as those described below, as needed.

[0051] (E) Photopolymerization Initiator The resin composition of this embodiment may contain (E) a photopolymerization initiator (hereinafter also referred to as "component (E)") 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 to generate radicals and promote polymerization. By including a photopolymerization initiator, photocuring (e.g., UV curing) of the resin composition is promoted, and for example, the resin composition can be further cured by heat after curing with light (UV) or during light irradiation. The type of photopolymerization initiator is not particularly limited, and known materials can be used. Examples of photopolymerization initiators include, but are not limited to, alkylphenone-based compounds, acylphosphine oxide-based compounds, oxime ester-based compounds, and compounds having a photosensitive moiety and a peroxide structure.

[0052] Examples of alkylphenone compounds include benzyl dimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethan-1-one (commercially available as Omnirad 651 from IGM Resins B.V.); α-aminoalkylphenones such as 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one (commercially available as Omnirad 907 from IGM Resins B.V.); α-hydroxyalkylphenones such as 1-hydroxy-cyclohexyl-phenyl-ketone (commercially available as Omnirad 184 from IGM Resins B.V.); 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one (commercially available as Omnirad 184 from IGM Resins B.V.); 379EG), 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone (commercially available as Omnirad 369, manufactured by IGM Resins BV), and the like.

[0053] Examples of the acylphosphine oxide compound 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.), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (commercially available as Omnirad 819 manufactured by IGM Resins B.V.), and the like.

[0054] Examples of the oxime ester compound 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).

[0055] Examples of compounds having a photosensitive moiety and a peroxide structure or commercially available products thereof include 3,3′,4,4′-tetrakis(tert-butylperoxycarbonyl)benzophenone (BTTB), Perdual TA, and Perdual TX (all manufactured by NOF Corporation), but are not limited to these.

[0056] Other examples of the photopolymerization initiator 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, and the like. 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, benzil, camphorquinone, and the like.

[0057] As the photopolymerization initiator, various photopolymerization initiators may be used alone or in combination of two or more kinds.

[0058] 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, more preferably 0.04 to 8% by weight, relative to the total weight of the resin composition.

[0059] (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.

[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 boric acid ester compounds are preferred because they are liquid at room temperature (25°C), and therefore can keep the viscosity of the 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 resin composition.

[0062] (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"). Other thiol compounds include, for example, aliphatic thiol compounds such as ethanedithiol, propanedithiol, hexamethylenedithiol, decamethylenedithiol, tolylene-2,4-dithiol, 2,2-bis(mercaptomethyl)-1,3-propanedithiol, 2-(mercaptomethyl)-2-methyl-1,3-propanedithiol, and 2-ethyl-2-(mercaptomethyl)-1,3-propanedithiol; aromatic thiol compounds such as benzenedithiol, toluenedithiol, and xylenedithiol (p-xylenedithiol); cyclic sulfide compounds such as 1,4-dithiane ring-containing polythiol compounds; mercaptoalkyl sulfide compounds such as 3-thiapentane-1,5-dithiol and 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol; Mercaptopropionic acid esters such as pentaerythritol tetrakis(3-mercaptopropionate); epoxy resin terminal mercapto compounds; 3,6-dioxa-1,8-octanedithiol, mercaptoalkyl ether disulfide compounds, mercaptoalkyl ether compounds such as 2,2'-[[2,2-bis[(2-mercaptoethoxy)methyl]-1,3-propanediyl]bis(oxy)]bisethanethiol, 3,3'-[[2,2-bis[(3-mercaptopropoxy)methyl]-1,3-propanediyl]bis(oxy)]bis-1-propanethiol, 3-[2,2-bis[(3-mercaptopropoxy)methyl]butoxy]-1-propanethiol, 3-(3-mercaptopropoxy)-2,2-bis[(3-mercaptopropoxy)methyl]-1-propanol, and 2,2-bis[(3-mercaptopropoxy)methyl]-1-butanol; Glycoluril-type thiols such as 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril and 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril;Examples of triazine thiols include 2-{2,4,6-trioxo-3,5-bis[2-(3-sulfanylpropanoyloxy)ethyl]-1,3,5-triazinan-1-yl}ethyl 3-sulfanylpropionate, 1,3,5-tris[3-(2-mercaptoethylsulfanyl)propyl]isocyanurate, and tris(3-mercaptopropyl)isocyanurate;

[0063] 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.

[0064] These other thiol compounds may be used alone or in combination of two or more.

[0065] 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) to calculate the ratio of the number of (meth)acryloyl group equivalents of component (A) to the number of thiol group equivalents of all the thiol compounds ([number of (meth)acryloyl group equivalents of component (A)] / [number of thiol group equivalents of all the 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.

[0066] 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.

[0067] The monofunctional maleimide compound is a compound having one maleimide group as a group reactive with a thiol group, and examples thereof include maleimide; aliphatic hydrocarbon group-containing maleimides such as methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, and cyclohexylmaleimide; and aromatic ring-containing maleimides such as phenylmaleimide.

[0068] The monofunctional (meth)acrylate compound is a compound having 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, isodecyl (meth)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, Esters of monohydric alcohols and (meth)acrylic acid such as 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, and m-phenoxybenzyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)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-methylcyclopentyl (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-cyclohexylpropane-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-oxotetrahydrofuran-3-yl (meth)acrylate, (5-oxotetrahydrofuran-2-yl)methyl (meth)acrylate, (2-oxo-1,Examples of the acrylate include mono(meth)acrylates of polyhydric alcohols or esters of monohydric alcohols and (meth)acrylic acid, such as (3-dioxolan-4-yl)methyl(meth)acrylate, N-acryloyloxyethylhexahydrophthalimide, α-acryloyl-ω-methoxypoly(oxyethylene), and 1-ethoxyethyl(meth)acrylate.

[0069] A monofunctional epoxy compound is a compound having one epoxy group as a group reactive with a thiol group. Examples of the monofunctional epoxy compound 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.

[0070] Other Additives If desired, the resin composition of this embodiment may further contain other additives, such as a coupling agent, carbon black, titanium black, an ion trapping agent, a leveling agent, an antioxidant, an antifoaming agent, a viscosity modifier, a flame retardant, a colorant, a solvent, etc. The type and amount of each additive are as per usual, provided that the addition does not impair the spirit and scope of this embodiment.

[0071] From the viewpoint of preventing a reduction in curing strength and adhesion and preventing outgassing and bleeding, the resin composition of this embodiment is substantially free of liquid components such as water, solvents, ionic liquids, etc. (excluding the liquid components (A) to (C)). For example, the content of liquid components relative to the total weight of the resin composition is preferably 3 wt % or less, and more preferably 1 wt % or less. Examples of the solvent 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.).

[0072] 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 (D), and other optional components as needed, into an appropriate mixer, and stirring and mixing while melting by heating if necessary to form a homogeneous composition. The mixer is not particularly limited, but examples 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 equipped with a stirrer and a heater. These devices may also be used in appropriate combinations.

[0073] 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, 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. The components (A) to (D) may be contained in a single component, or 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 liquid A: component (A), liquid B: component (B) and 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), or liquid B: component (B) and component (C), or liquid A: component (B), liquid B: component (A) and component (C) and component (D), or liquid A: component (A) and component (B) and component (D), or liquid B: component (A) and component (C) and component (D), or liquid A: component (A) and component (B) and component (C) and component (D), or liquid B: component (B'). When components (A) to (D) 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 resin composition of this embodiment. On the other hand, when the components (A) to (D) are contained in separate liquids, the liquids can be considered as a combination of the resin composition of this embodiment. Examples of the case where the components (A) to (D) are contained in separate liquids include a resin composition in which the components (A) to (D) are separated into two or more containers, specifically a kit composed of multiple liquids containing any of the components (A) to (D).

[0074] The resin composition thus obtained is thermosetting, and preferably cures within 5 hours, more preferably within 3 hours, and even more preferably within 1 hour at a temperature of 100°C. When the resin composition of this embodiment is used to manufacture a semiconductor device 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 is particularly excellent in curing properties at low temperatures (e.g., 80°C).

[0075] When the resin composition of this embodiment contains a photopolymerization initiator (E), the resin composition can also be cured by light (UV). For example, after curing by light (UV), or during light irradiation, the resin composition can be further cured by heat.

[0076] 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 components constituting them, or as a raw material thereof.

[0077] [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 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 (TOF) sensor modules, other semiconductor modules, and integrated circuits.

[0078] 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 (D) and other optional components as needed can be selected in the same manner 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 manner without particular limitation. When divided into two or multi-components in any manner, one or more components selected from the components (A) to (D) and other optional components as needed may be contained in each component, or the components (A) to (D) may be contained in a single component, or a component consisting solely of the components (A) to (D) and / or other optional components as needed may be present. 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) 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), component (C) and component (D), or liquid A: component (A), component (B) and component (D), or liquid B: component (A), component (C) and component (D), or liquid A: component (A), component (B), component (C) and component (D), or liquid B: component (B'). When components (A) to (D) 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 the components (A) to (D) are contained in separate liquids, the liquids together can be regarded as the adhesive or sealant of this embodiment.Examples of the case where the components (A) to (D) are contained in separate liquids include an adhesive or sealant in which the components (A) to (D) are separated into two or more containers, and specifically, a kit composed of multiple liquids containing any of the components (A) to (D).

[0079] [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.

[0080] [Semiconductor Device, Electronic Component] 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 TOF sensor modules, other semiconductor modules, and integrated circuits.

[0081] 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.

[0082] [Production of Resin Compositions] 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 Tables 1 and 2. In Tables 1 and 2, 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:

[0083] (A) (Meth)acrylate Compounds (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: DPGDA, manufactured by Daicel-Allnex Corporation, (meth)acryloyl equivalent: 121 g / eq, molecular weight: 242 g / mol) (A-4): Dipropylene glycol diacrylate (product name: M-408, manufactured by Toagosei Co., Ltd., (meth)acryloyl equivalent: 117 g / eq, molecular weight: 468 g / mol)

[0084] (B) Thiol compound represented by formula (I) (B-1): Thiol compound represented by formula (I) (1,2,3-(3-mercaptopropyloxy)propane) (obtained from Shikoku Chemical Industry Co., Ltd., thiol equivalent: 106 g / eq). Note that this thiol equivalent is an average value of values ​​measured by a known method, for example, the method disclosed in paragraph

[0079] of JP-A No. 2012-153794. (B') Other thiol compound other than component (B) (B'-1): Pentaerythritol trippropanethiol represented by the following formula (trade name: Multiol Y-3, manufactured by SC Organic Chemical Co., Ltd., thiol equivalent: 124 g / eq). (B'-2): 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)

[0085] (C) Thermal Latent Curing Catalysts (C-1): Amine adduct thermal 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 thermal latent curing catalyst (product name: Novacure HXA9322HP, 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 fine particle latent curing catalyst is dispersed in epoxy resin (a mixture of bisphenol A epoxy resin and bisphenol F epoxy resin (epoxy equivalent: 180 g / eq)). (C-3): Amine-urea adduct-based thermal latent curing catalyst (product name: Fujicure FXR-1020, solid at room temperature, manufactured by T&K TOKA Corporation)

[0086] (D) Specific surface area is 4 m ２ / g or more inorganic filler (D-1): Silica filler 1 (product name: Seahoster (registered trademark) KE-S-30HG, amorphous silica, manufactured by Nippon Shokubai Co., Ltd., specific surface area: 12 m ２ / g) (D-2): Silica filler 2 (product name: SE2300, manufactured by Admatechs Co., Ltd., specific surface area: 4.4 m ２ / g) (D-3): Silica filler 3 (product name: CAB-O-SIL (registered trademark) TS-720, polydimethylsiloxane surface-treated fumed silica, manufactured by Cabot Corporation, specific surface area: 200 m ２ / g) (D-4): Aluminum oxide filler (product name: ASFP-03S, manufactured by Denka Co., Ltd., specific surface area: 6.0 m ２ / g) (D-5): Magnesium oxide filler (product name: Starmag PSF-150, manufactured by Konoshima Chemical Co., Ltd., specific surface area: 145 m ２ / g) (D') specific surface area is 4 m ２ / g or less inorganic filler (D'-1): Silica filler 5 (product name: FB-7SDX, manufactured by Denka Co., Ltd., specific surface area: 2.4 m ２ / g) (D'-2): Silica filler 6 (product name: KYKLOS (registered trademark) MSV 25, manufactured by Tatsumori Co., Ltd., specific surface area: 0.11 m ２ / g, average particle size: 25 μm) The specific surface area of ​​component (D'-2) was calculated by the following formula: S = 6 / Dρ, where S is the specific surface area (m ２ / g), D is the particle size (diameter) (μm), and ρ is the density (g / cm ３ )

[0087] (E) Photopolymerization initiator (E-1): 1-hydroxy-cyclohexyl-phenyl-ketone (product name: Omnirad 184, manufactured by IGM Resins B.V.) (F) Stabilizer (F-1): triisopropyl borate

[0088] In Tables 1 and 2, the filler specific surface area (m ２ / g) represents the specific surface area of ​​the inorganic filler. ２ ) is the specific surface area (m ２ / g) by the weight parts (g) of the inorganic filler in 100 parts by weight of the resin composition. ２ / g) is the ratio of the total surface area (m ) of the inorganic filler in the resin composition to the content (g) of the thermal latent curing catalyst (C) in the resin composition. ２ In Tables 1 and 2, the ratio of "total filler surface area / resin amount (m ２ / g) is the ratio of the total surface area (m ) of the inorganic filler in the resin composition to the content (g) of the (meth)acrylate compound (A) in the resin composition. ２ ) represents the ratio.

[0089] 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.

[0090] [Evaluation of 80°C curability] Each resin composition was dropped onto a hot plate at 80±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 (gel time, unit: seconds) was measured with a stopwatch. For Examples 1 to 5 and Comparative Examples 1 to 3, the relative gel time was determined, assuming that the gel time of the resin composition of Comparative Example 1 (which did not contain inorganic filler) was 1. The results are shown in Tables 1 and 2.

[0091] [Evaluation of storage stability] The resin compositions of Examples, Comparative Examples, and Reference Examples were placed in a syringe 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 it was confirmed whether the resin compositions could be manually extruded from the tip of the syringe, thereby confirming the storage stability of the resin compositions. Evaluation was performed according to the following criteria. The measurement results are shown in Tables 1 and 2. ◯: Can be ejected stably, just like at the beginning △: Can be ejected, but some increase in viscosity and stringiness are observed ×: Difficulty in ejection and increase in viscosity is observed XX: Cannot be ejected and hardened in the syringe

[0092] [Adhesion Strength] A resin composition was stencil-printed onto a nickel substrate with a size of φ2 mm and a thickness of 125 μm, and a 3.2 mm × 1.6 mm × 0.45 mm thick alumina chip was mounted on the printed resin composition, and a load was applied and cured to prepare a test piece (n = 10). The curing conditions at this time were 80 ° C / 60 minutes in a blower dryer. The alumina chip on this nickel substrate was poked from the side with a MODEL-1605HTP strength tester manufactured by Aiko Engineering Co., Ltd., and the shear strength (unit: N) was calculated from the value when the alumina chip peeled off, and the average value of n = 10 was used as the measurement result. The measurement results are shown in Tables 1 and 2.

[0093]

[0094]

[0095] Comparison of the resin compositions of Reference Examples 1 and 2, which contain (B') another thiol compound as a curing agent and a thermal latent curing catalyst, with Comparative Examples 1, 3, 4, and 5, which contain (B) a trithiol compound of formula (I) as a curing agent and a thermal latent curing catalyst, reveals that the problem of insufficient low-temperature curing properties when a thermal latent curing catalyst is used is a problem specific to (B) the trithiol compound of formula (I). In addition to components (A) to (C), ２ The resin compositions of Examples 1 to 10 containing an inorganic filler of 1 / g or more had good storage stability and curability at 80°C. ２ / g, and (D) a specific surface area of ​​4 m ２ The resin compositions of Comparative Examples 2 and 3, which did not contain an inorganic filler of 1 / g or more, showed no improvement in low-temperature curing properties. Although not shown in Table 1, similar evaluations were also performed on a two-component resin composition in Example 1, in which Liquid A was made up of component (A) and component (D) and Liquid B was made up of component (B), component (C), and component (E). The results showed that the storage stability and curing properties at 80°C were good.

[0096] The resin composition of the present invention is very 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.

[0097] The disclosure of Japanese Patent Application No. 2024-032373 (filing date: March 4, 2024) 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) a (meth)acrylate compound, (B) a compound of formula (I): (C) a thermal latent curing catalyst; and (D) a thiol compound having a specific surface area of ​​4 m ２ / g or more of an inorganic filler.

2. The resin composition according to claim 1, further comprising (E) a photopolymerization initiator.

3. The resin composition according to claim 1 or 2, wherein the content of the inorganic filler (D) is 1 to 90% by weight based on the total weight of the resin composition.

4. The ratio of the total surface area of ​​the inorganic filler (D) in the resin composition to the content of the thermal latent curing catalyst (C) in the resin composition is 7 to 400 m ２ The resin composition according to any one of claims 1 to 3, wherein the molecular weight of the resin composition is 1 / g.

5. A resin composition according to any one of claims 1 to 4, wherein the content of the (meth)acrylate compound having an average molecular weight of less than 250 in the resin composition is 0 to 90% by weight relative to the content of component (B) in the resin composition.

6. The resin composition according to any one of claims 1 to 5, 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.

7. The resin composition according to any one of claims 1 to 6, wherein components (A) to (D) are contained in a single container.

8. The resin composition according to any one of claims 1 to 6, wherein components (A) to (D) are separated into two or more containers.

9. An adhesive or sealant comprising the resin composition according to any one of claims 1 to 8.

10. The adhesive or sealant according to claim 9, which is for use in semiconductor devices or electronic components.

11. A cured product obtained by curing the resin composition according to any one of claims 1 to 8, or the adhesive or sealant according to claim 9 or 10.

12. A semiconductor device or electronic part comprising the cured product according to claim 11.

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