Curable resin composition

Abstract

The present invention addresses the problem of providing a UV-curable resin composition that provides a flexible cured product having a lower crosslinking density than conventional cured products. The present invention comprises the following (A) to (D): (A) a polyfunctional (meth)acrylate compound; (B) an adjusting agent containing the following (b1) and / or (b2): (b1) a monofunctional (meth)acrylate compound, and (b2) an epoxy resin having no reactive unsaturated double bond; (C) a polyfunctional thiol compound; and (D) a photo-radical initiator, wherein the total number (total amount) of (meth)acryloyloxy contained in the (A) polyfunctional (meth)acrylate compound, the total number (total amount) of (meth)acryloyloxy contained in the (B) adjusting agent, the total number (total amount) of epoxy groups contained in the (B) adjusting agent, and the total number (total amount) of thiol groups contained in the (C) polyfunctional thiol compound satisfy a predetermined relationship.

Description

[Technical Field]

[0001] The present invention relates to a curable resin composition, an adhesive containing the same, a cured product obtained by curing the same, and a semiconductor device containing the cured product. [Background technology]

[0002] Adhesives that are cured by ultraviolet (UV) irradiation (hereinafter also referred to as "UV-curable adhesives") are used in many fields. Among UV-curable adhesives, there are also adhesives that are temporarily fixed by UV irradiation and then fully cured by heating (hereinafter also referred to as "UV-thermosetting adhesives") (see, for example, Patent Document 1). Some UV-curable adhesives contain polyfunctional acrylate compounds and polyfunctional thiol compounds. These adhesives cure through an enethiol reaction (radical addition of a thiol group to the double bond in a (meth)acryloyloxy group) and homopolymerization (radical polymerization of a (meth)acryloyloxy group).

[0003] UV-curable adhesives are often used in the manufacture of semiconductor devices that require high-precision positioning during assembly, such as image sensor modules. In image sensor modules, the relative positional relationship between each component is extremely important. Therefore, when assembling image sensor modules, it is necessary to position each component with high precision. Therefore, using this adhesive, which can be cured in a short time by UV irradiation, is extremely useful in the manufacture of image sensor modules, as it improves assembly efficiency. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-077024 [Patent Document 2] International Publication No. 2018 / 181421 Summary of the Invention [Problem to be solved by the invention]

[0005] An assembly made using a UV-curable adhesive may be heated and / or cooled with significant temperature changes. For example, if the UV-curable adhesive is cured by UV irradiation and subsequent heating, the assembly may be heated and then cooled after UV curing. Furthermore, the UV-cured assembly may be placed in a hot environment, such as the inside of a car in the summer.

[0006] Assemblies made using conventional UV-curable adhesives have had the problem that the cured product may peel off from the adherend during the heating and / or cooling process described above.

[0007] In order to solve the above-mentioned problems of the conventional art, an object of the present invention is to provide a UV-curable curable resin composition that gives a cured product that is difficult to peel from an adherend even when the ambient temperature changes. Another object of the present invention is to provide a UV-curable curable resin composition that gives a cured product that is difficult to peel from an adherend even when the ambient temperature changes during the heating and / or cooling process after UV curing. [Means for solving the problem]

[0008] The present inventors have conducted extensive research to solve the above problems and have arrived at the present invention.

[0009] That is, the present invention includes, but is not limited to, the following inventions.

[0010] 1. (A) to (D) below: (A) a polyfunctional (meth)acrylate compound; (B) A regulator containing the following (b1) and / or (b2): (b1) Monofunctional (meth)acrylate compound (b2) an epoxy resin having no reactive unsaturated double bonds; (C) a polyfunctional thiol compound; and (D) Photoradical initiator Including, [the total number of (meth)acryloyloxy groups in the (A) polyfunctional (meth)acrylate compound] / [the total number of thiol groups in the (C) polyfunctional thiol compound] is 0.4 to 0.8, A curable resin composition, in which [total number of (meth)acryloyloxy groups in (B) regulator + total number of epoxy groups in (B) regulator] / [total number of thiol groups in (C) polyfunctional thiol compound] is 0.05 to 0.65.

[0011] 2. The curable resin composition according to item 1 above, further comprising (E) a heat curing accelerator.

[0012] 3. The curable resin composition according to item 1 or 2 above, wherein [total number of (meth)acryloyloxy groups in (A) the polyfunctional (meth)acrylate compound] / [total number of thiol groups in (C) the polyfunctional thiol compound] is 0.5 to 0.7.

[0013] 4. The curable resin composition according to any one of items 1 to 3 above, wherein (B) the regulator contains both (b1) a monofunctional (meth)acrylate compound and (b2) an epoxy resin having no reactive unsaturated double bond.

[0014] 5. The curable resin composition according to any one of items 1 to 4 above, wherein the polyfunctional thiol compound (C) has three or more thiol groups.

[0015] 6. The curable resin composition according to any one of items 1 to 5 above, wherein the (C) polyfunctional thiol compound includes a trifunctional thiol compound and / or a tetrafunctional thiol compound.

[0016] 7. The curable resin composition according to any one of items 1 to 6 above, wherein the (A) polyfunctional (meth)acrylate compound includes a bifunctional (meth)acrylate compound.

[0017] 8. The curable resin composition according to any one of items 1 to 7 above, wherein the (B) regulator essentially consists of a (b1) monofunctional (meth)acrylate compound, and the ratio [total number of (meth)acryloyloxy groups in the (B) regulator + total number of epoxy groups in the (B) regulator] / [total number of thiol groups in the (C) polyfunctional thiol compound] is 0.2 to 0.5.

[0018] 9. The curable resin composition according to any one of items 1 to 7 above, wherein the (B) regulator essentially consists of the (b2) epoxy resin, and the ratio [total number of (meth)acryloyloxy groups in the (B) regulator + total number of epoxy groups in the (B) regulator] / [total number of thiol groups in the (C) polyfunctional thiol compound] is 0.2 to 0.5.

[0019] 10. An adhesive comprising the curable resin composition according to any one of items 1 to 9 above.

[0020] 11. A cured product obtainable by curing the curable resin composition according to any one of items 1 to 9 above, or the adhesive according to item 10 above.

[0021] 12. A semiconductor device comprising the cured product according to item 11 above.

[0022] 13. A sensor module comprising the cured product according to item 11 above.

[0023] As described above, the curable resin composition of the present invention contains (A) a polyfunctional (meth)acrylate compound, (B) a regulator, (C) a polyfunctional thiol compound, and (D) a photoradical initiator as essential components. These components are described below. 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 to refer to a component that constitutes a curable resin composition before curing, even though the component is not a polymer.

[0024] Furthermore, in this specification, terms such as "(meth)acrylic acid," "(meth)acrylate," "(meth)acrylic," and "(meth)acryloyl" may be used as general terms for "acrylic acid" (or a derivative thereof) and "methacrylic acid" (or a derivative thereof). Each of these terms may be used as an independent term or as part of another term. For example, the term "(meth)acrylic acid" means "acrylic acid and / or methacrylic acid," and the term "(meth)acryloyloxy group" means "acryloyloxy group and / or methacryloyloxy group."

[0025] (A) Polyfunctional (meth)acrylate compound The curable resin composition of the present invention contains (A) a polyfunctional (meth)acrylate compound. The polyfunctional (meth)acrylate compound used in the present invention is a compound containing a total of two or more (meth)acryloyloxy groups that react with thiol groups in a polyfunctional thiol compound described below. In other words, the polyfunctional (meth)acrylate compound is a compound having a structure in which one molecule of a compound having two or more hydroxyl groups is esterified with a total of two or more molecules of (meth)acrylic acid (unesterified hydroxyl groups may also be present). As long as the polyfunctional (meth)acrylate compound satisfies the above structural requirements, it may contain a (meth)acryloyl group that is not in the form of a (meth)acryloyloxy group. For example, N,N'-methylenebisacrylamide does not fall under the category of polyfunctional (meth)acrylate compounds. (A) The polyfunctional (meth)acrylate compound preferably includes one having a molecular weight of 100 to 10,000, more preferably 200 to 5,000, even more preferably 200 to 3,000, and particularly preferably 200 to 800.

[0026] Examples of polyfunctional (meth)acrylate compounds include: -di(meth)acrylate of bisphenol A; -di(meth)acrylate of bisphenol F; - polyfunctional (meth)acrylates having an isocyanuric skeleton; -Dimethyloltricyclodecane di(meth)acrylate; - polyfunctional (meth)acrylates of trimethylolpropane or its oligomers; - polyfunctional (meth)acrylate of ditrimethylolpropane; - polyfunctional (meth)acrylates of pentaerythritol or its oligomers; - polyfunctional (meth)acrylates of dipentaerythritol; and - neopentyl glycol modified trimethylolpropane di(meth)acrylate; -di(meth)acrylate of polyethylene glycol; -di(meth)acrylate of polypropylene glycol; di(meth)acrylates of open-chain or cyclic alkanediols; -di(meth)acrylate of neopentyl glycol; - Polyurethanes containing two or more (meth)acryloyl groups per molecule; - polyesters containing two or more (meth)acryloyl groups in one molecule; -polyfunctional (meth)acrylate of glycerin; and the like. Among these, di(meth)acrylate of dimethyloltricyclodecane, (tri / tetra)(meth)acrylate of ditrimethylolpropane, hexa(meth)acrylate of dipentaerythritol, di(meth)acrylate of neopentyl glycol-modified trimethylolpropane, and polyurethanes having two (meth)acryloyl groups per molecule are preferred. These may be used alone or in combination of two or more. In this specification, "polyfunctional (meth)acrylate" refers to a compound containing two or more (meth)acryloyloxy groups. For example, "polyfunctional (meth)acrylate of trimethylolpropane or its oligomer" refers to an ester of one molecule of trimethylolpropane or its oligomer with two or more molecules of (meth)acrylic acid.

[0027] In the present invention, the polyfunctional (meth)acrylate compound preferably includes a bifunctional (meth)acrylate compound. A bifunctional (meth)acrylate compound is a polyfunctional (meth)acrylate compound having a total of two (meth)acryloyloxy groups. Similarly, for example, a trifunctional or tetrafunctional (meth)acrylate compound is a polyfunctional (meth)acrylate compound having three or four (meth)acryloyloxy groups. In the present invention, a silane coupling agent having a plurality of (meth)acrylate groups is not included in the polyfunctional (meth)acrylate compound. Preferably, the polyfunctional (meth)acrylate compound does not contain a silicon atom.

[0028] (B) Regulator The curable resin composition of the present invention contains a regulator (B). The regulator (B) used in the present invention is the following regulator (b1) and / or (b2): (b1) Monofunctional (meth)acrylate compound (b2) Epoxy resins that do not have reactive unsaturated double bonds Includes.

[0029] The monofunctional (meth)acrylate compound used in the present invention is a compound containing one (meth)acryloyloxy group. This (meth)acryloyloxy group reacts with a thiol group in a polyfunctional thiol compound described below. In other words, the monofunctional (meth)acrylate compound is a compound having a structure in which one molecule of a compound having one or more hydroxyl groups is esterified with one molecule of (meth)acrylic acid (although some unesterified hydroxyl groups may also be present). In the present invention, a silane coupling agent having one (meth)acrylate group is not included in the monofunctional (meth)acrylate compound. Preferably, the monofunctional (meth)acrylate compound does not contain a silicon atom.

[0030] 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 esters of monohydric alcohols and (meth)acrylic acid, such as 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, and 3-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, tetrahydrodicyclopentadiene Eni (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 -a Damantyl (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 Mono(meth)acrylates of polyhydric alcohols such as 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-1,3-dioxolan-4-yl)methyl(meth)acrylate, and 1-ethoxyethyl(meth)acrylate. These may be used alone or in combination of two or more. (b1) The monofunctional (meth)acrylate compound preferably includes one having a molecular weight of 100 to 1,000, more preferably 120 to 500, further preferably 140 to 400, and particularly preferably 160 to 300.

[0031] In one embodiment of the present invention, the monofunctional (meth)acrylate compound does not have an epoxy group in its molecule. If the monofunctional (meth)acrylate compound has an epoxy group in its molecule, the crosslink density may increase when heated after UV curing. This is because, during UV curing, the double bond in the (meth)acryloyloxy group of the monofunctional (meth)acrylate compound is homopolymerized and incorporated into a polymer chain, and the epoxy group of the monofunctional (meth)acrylate compound may react with a thiol group in another polymer chain under heat to form a new crosslink.

[0032] On the other hand, the epoxy resin (b2) without a reactive unsaturated double bond used in the present invention is a compound containing one or more epoxy groups but without a reactive unsaturated double bond. A reactive unsaturated double bond refers to a double bond that can react with a thiol group in a polyfunctional thiol compound and / or a (meth)acryloyloxy group in a polyfunctional (meth)acrylate compound (specifically, the double bond therein) under UV irradiation or heating. Normally, epoxy groups and thiol groups do not react under UV irradiation, but can react under heating. Therefore, normally, (b2) epoxy resin does not react with a polyfunctional thiol compound under UV irradiation, but when a thermal curing accelerator (especially a basic component) is present in the system or on the surface of the adherend, only the epoxy group can react with the polyfunctional thiol compound under heating. A silane coupling agent containing one or more epoxy groups but not having a reactive unsaturated double bond is not included in the epoxy resin not having a reactive unsaturated double bond. Preferably, the epoxy resin not having a reactive unsaturated double bond does not contain a silicon atom.

[0033] (b2) Epoxy resins are broadly classified into monofunctional epoxy resins and polyfunctional epoxy resins. The (b2) epoxy resin may contain only one of these, or may contain both of these. From the viewpoint of thermosetting properties, the (b2) epoxy resin preferably contains a polyfunctional epoxy resin. The (b2) epoxy resin particularly preferably contains a difunctional epoxy resin.

[0034] Monofunctional epoxy resins are compounds containing one epoxy group and no reactive unsaturated double bonds. Examples of monofunctional epoxy resins include, but are not limited to, n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, ps-butylphenyl glycidyl ether, styrene oxide, α-pinene oxide, 4-tert-butylphenyl glycidyl ether, neodecanoic acid glycidyl ester, and 2-(4,4-dimethylpentan-2-yl)-5,7,7-trimethyloctanoic acid glycidyl ester. These may be used alone or in combination of two or more.

[0035] A multifunctional epoxy resin is a compound that contains two or more epoxy groups and does not have a reactive unsaturated double bond. Multifunctional epoxy resins are broadly classified into aliphatic multifunctional epoxy resins and aromatic multifunctional epoxy resins. Aliphatic multifunctional epoxy resins are multifunctional epoxy resins that have a structure that does not contain an aromatic ring. Examples of aliphatic multifunctional epoxy resins include: diepoxy resins such as (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, polytetramethylene ether glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, 1,2-epoxy-4-(2-methyloxiranyl)-1-methylcyclohexane, cyclohexane-type diglycidyl ether, and dicyclopentadiene-type diglycidyl ether; - Triepoxy resins such as trimethylolpropane triglycidyl ether, glycerin triglycidyl ether; -alicyclic epoxy resins such as vinyl(3,4-cyclohexene) dioxide and 2-(3,4-epoxycyclohexyl)-5,1-spiro-(3,4-epoxycyclohexyl)-m-dioxane; - glycidylamine type epoxy resins such as tetraglycidylbis(aminomethyl)cyclohexane; hydantoin-type epoxy resins, such as 1,3-diglycidyl-5-methyl-5-ethylhydantoin; and Epoxy resins with a silicone backbone, such as 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane These may be used alone or in combination of two or more.

[0036] Aromatic polyfunctional epoxy resins are polyfunctional epoxy resins that have a structure containing aromatic rings. Many of the epoxy resins that have been commonly used in the past, such as bisphenol A epoxy resins, are of this type. Examples of aromatic polyfunctional epoxy resins include: -bisphenol A epoxy resin; - Branched polyfunctional bisphenol A type epoxy resins such as p-glycidyloxyphenyldimethyltrisbisphenol A diglycidyl ether; -Bisphenol F type epoxy resin; -Novolac type epoxy resins; -Tetrabromobisphenol A type epoxy resin; -fluorene-type epoxy resins; -biphenyl aralkyl epoxy resins; - diepoxy resins such as 1,4-phenyldimethanol diglycidyl ether; biphenyl-type epoxy resins such as 3,3',5,5'-tetramethyl-4,4'-diglycidyloxybiphenyl; - glycidylamine-based epoxy resins such as diglycidylaniline, diglycidyltoluidine, triglycidyl-p-aminophenol, tetraglycidyl-m-xylylenediamine; and -Naphthalene ring-containing epoxy resin These may be used alone or in combination of two or more. The epoxy equivalent of the (b2) epoxy resin is preferably 90 to 500 g / eq, more preferably 100 to 450 g / eq, and even more preferably 100 to 350 g / eq.

[0037] In one embodiment of the present invention, the epoxy resin (b2) comprises a liquid epoxy resin. As used herein, "liquid epoxy resin" refers to an epoxy resin that is in a liquid physical state at 25°C. In this case, from the viewpoint of improving the adhesive reliability (peel resistance) of the cured product obtained by UV-curing the resin composition of the present invention, it is preferable that the regulator (B) comprises both the monofunctional (meth)acrylate compound (b1) and the epoxy resin (b2).

[0038] In the present invention, the (B) regulator includes either or both of the (b1) monofunctional (meth)acrylate compound and the (b2) epoxy resin. In one embodiment, the (B) regulator includes both the (b1) monofunctional (meth)acrylate compound and the (b2) epoxy resin.

[0039] (C) Polyfunctional thiol compound The curable resin composition of the present invention contains a polyfunctional thiol compound. The polyfunctional thiol compound used in the present invention is a compound containing two or more thiol groups that react with the (meth)acryloyloxy groups (more precisely, the double bonds therein) in the polyfunctional (meth)acrylate compound and the monofunctional (meth)acrylate compound, and with the epoxy groups in the epoxy resin having no reactive unsaturated double bond. The polyfunctional thiol compound preferably contains three or more thiol groups. The polyfunctional thiol compound more preferably contains a trifunctional thiol compound and / or a tetrafunctional thiol compound. The trifunctional and tetrafunctional thiol compounds refer to thiol compounds having three and four thiol groups, respectively. The thiol equivalent of the polyfunctional thiol compound is preferably 90 to 150 g / eq, more preferably 90 to 140 g / eq, and even more preferably 90 to 130 g / eq.

[0040] Polyfunctional thiol compounds are broadly classified into thiol compounds that have a hydrolyzable partial structure such as an ester bond in the molecule (i.e., hydrolyzable) and thiol compounds that do not have such a partial structure (i.e., non-hydrolyzable). Examples of hydrolyzable polyfunctional thiol compounds include trimethylolpropane tris(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: TMMP), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate (manufactured by SC Organic Chemical Co., Ltd.: TEMPIC), pentaerythritol tetrakis(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: PEMP), and tetraethylene glycol bis(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: PEMP). Examples of suitable mercaptobutyrates include dipentaerythritol hexakis(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: EGMP-4), dipentaerythritol hexakis(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: DPMP), pentaerythritol tetrakis(3-mercaptobutyrate) (manufactured by Showa Denko K.K.: KarenzMT (registered trademark) PE1), and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by Showa Denko K.K.: KarenzMT (registered trademark) NR1). These may be used alone or in combination of two or more.

[0041] On the other hand, examples of non-hydrolyzable polyfunctional thiol compounds include 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril (manufactured by Shikoku Chemical Industry Co., Ltd.: TS-G), 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril (manufactured by Shikoku Chemical Industry Co., Ltd.: C3 TS-G), 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, and 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-dimethylglycoluril. 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 Choleuril, pentaerythritol tripropanethiol (manufactured by SC Organic Chemical Co., Ltd.: PEPT), 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)ethanethiol kis(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)-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) thio)-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-di Thietanyl)]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-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-methyl mercapto-2,4,7-trithiaoctyl]-5-mercaptomethylthio-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]mercaptomethylthiomethyl-1,Examples include 3-dithietane, 2-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]mercaptomethylthiomethyl-1,3-dithietane, 4-{1-[2-(1,3-dithietanyl)]-3-mercapto-2-thiapropylthio}-5-[1,2-bis(mercaptomethylthio)-4-mercapto-3-thiabutylthio]-1,3-dithiolane, etc. These may be used alone or in combination of two or more.

[0042] In the curable resin composition of the present invention, the total number (total amount) of (meth)acryloyloxy groups contained in the (A) polyfunctional (meth)acrylate compound, the total number (total amount) of (meth)acryloyloxy groups contained in the (B) regulator, the total number (total amount) of epoxy groups contained in the (B) regulator, and The total number (total amount) of thiol groups contained in the (C) polyfunctional thiol compound It is necessary that the following relationship be satisfied. Specifically, in the curable resin composition of the present invention, [(A) the total number of (meth)acryloyloxy groups in the polyfunctional (meth)acrylate compound] / [(C) the total number of thiol groups in the polyfunctional thiol compound] is 0.4 to 0.8, and [Total number of (meth)acryloyloxy groups in (B) regulator + Total number of epoxy groups in (B) regulator] / [Total number of thiol groups in (C) polyfunctional thiol compound] is 0.05 to 0.65.

[0043] The total number of (meth)acryloyloxy groups in the (A) polyfunctional (meth)acrylate compound is the quotient obtained by dividing the mass (g) of the polyfunctional (meth)acrylate compound contained in the (A) polyfunctional (meth)acrylate compound by the (meth)acryloyl equivalent of that polyfunctional (meth)acrylate compound (if multiple types of polyfunctional (meth)acrylate compounds are contained, the sum of such quotients for each polyfunctional (meth)acrylate compound). The (meth)acryloyl equivalent can be calculated by dividing the molecular weight of that polyfunctional (meth)acrylate compound by the number of (meth)acryloyloxy groups in one molecule of that polyfunctional (meth)acrylate compound. The total number of (meth)acryloyloxy groups in the (B) regulator can be determined in the same manner as that in the (A) polyfunctional (meth)acrylate compound.

[0044] The curable resin composition of the present invention preferably contains a polyfunctional (meth)acrylate compound having a (meth)acryloyl equivalent of 60 to 300 g / eq, more preferably a polyfunctional (meth)acrylate compound having a (meth)acryloyl equivalent of 70 to 250 g / eq, and particularly preferably a polyfunctional (meth)acrylate compound having a (meth)acryloyl equivalent of 80 to 220 g / eq. The ratio of the total number of (meth)acryloyl groups in the (A) polyfunctional (meth)acrylate compound having a (meth)acryloyl equivalent of 300 g / eq or less to the total number of (meth)acryloyl groups in all the (A) polyfunctional (meth)acrylate compounds is preferably 0.7 to 1, more preferably 0.8 to 1, even more preferably 0.9 to 1, and particularly preferably 0.95 to 1. When the (A) polyfunctional (meth)acrylate compound having a (meth)acryloyl equivalent of 300 g / eq or less accounts for the majority of the (A) polyfunctional (meth)acrylate compound, the curable resin composition of the present invention tends to have good curability, and the composition tends to provide a cured product with a strong crosslinked structure, which is preferable.

[0045] Preferably, the (A) polyfunctional (meth)acrylate compound having a (meth)acryloyl equivalent of 300 g / eq or less does not have a poly(alkylene glycol) skeleton. In one embodiment of the present invention, the curable resin composition of the present invention contains (A) a polyfunctional (meth)acrylate compound having a (meth)acryloyl equivalent of 60 to 300 g / eq and not having a poly(alkylene glycol) skeleton. In this case, the cured product obtained from this composition is more likely to be imparted with adhesion to an adherend (i.e., the cured product is less likely to peel from an adherend). In this specification, the term "poly(alkylene glycol) backbone" refers to a poly(oxyalkylene) chain consisting of two or more oxyalkylene groups, such as a poly(oxyethylene) chain that can be introduced by ethylene oxide (EO) modification, or a poly(oxypropylene) chain that can be introduced by propylene oxide (PO) modification.

[0046] It is not preferable for the above-mentioned (A) polyfunctional (meth)acrylate compound having a (meth)acryloyl equivalent of 300 g / eq or less to have a poly(alkylene glycol) skeleton. This is because if the curable resin composition of the present invention contains such a (A) polyfunctional (meth)acrylate compound, the cured product obtained from the composition will be brittle and prone to peeling from the adherend. The reason for this is presumed to be that in such (A) polyfunctional (meth)acrylate compounds, the poly(alkylene glycol) skeletons are present in a relatively dense arrangement, and therefore association of the poly(alkylene glycol) skeletons can form brittle microstructures in the cured product. The curable resin composition of the present invention may contain (A) a polyfunctional (meth)acrylate compound having a (meth)acryloyl equivalent of 60 to 300 g / eq and a poly(alkylene glycol) skeleton. However, from the viewpoint of adhesion reliability, the ratio (total number of (meth)acryloyl groups in (A) a polyfunctional (meth)acrylate compound having a (meth)acryloyl equivalent of 60 to 300 g / eq and a poly(alkylene glycol) skeleton) / (total number of (meth)acryloyl groups in all (A) a polyfunctional (meth)acrylate compounds) is preferably 0.5 or less, more preferably 0.4 or less, even more preferably 0.3 or less, particularly preferably 0.2 or less, and most preferably 0.1 or less. In one embodiment of the present invention, this ratio is 0 to 0.5, preferably 0 to 0.4, more preferably 0 to 0.3, particularly preferably 0 to 0.2, and most preferably 0 to 0.1.

[0047] The total number of epoxy groups in (B) regulator is the quotient obtained by dividing the mass (g) of the epoxy resins containing no reactive unsaturated double bonds contained in (B) regulator by the epoxy equivalent of the epoxy resins (if multiple epoxy resins containing no reactive unsaturated double bonds are contained, the sum of such quotients for each epoxy resin is used). The epoxy equivalent can be determined by the method described in JIS K7236. If the epoxy equivalent cannot be determined by this method, it can also be calculated by dividing the molecular weight of the epoxy resin by the number of epoxy groups in one molecule of the epoxy resin.

[0048] The total number of thiol groups in the (C) polyfunctional thiol compound is the quotient obtained by dividing the mass (g) of the polyfunctional thiol compound contained in the (C) polyfunctional thiol compound by the thiol equivalent of that polyfunctional thiol compound (if multiple polyfunctional thiol compounds are contained, the sum of such quotients for each polyfunctional thiol compound). The thiol equivalent can be determined by iodometric titration. This method is widely known and is disclosed, for example, in paragraph 0079 of JP 2012-153794 A. If the thiol equivalent cannot be determined by this method, it may be calculated as the quotient obtained by dividing the molecular weight of the polyfunctional thiol compound by the number of thiol groups in one molecule of the polyfunctional thiol compound.

[0049] In one embodiment of the present invention, in the curable resin composition, a portion of the (A) polyfunctional (meth)acrylate compound is substituted with the (B) regulator, and the total amount of the (A) polyfunctional (meth)acrylate compound and the (B) regulator is approximately equivalent to the amount of the (C) polyfunctional thiol compound. In one embodiment, [total number of (meth)acryloyloxy groups for the (A) polyfunctional (meth)acrylate compound + total number of (meth)acryloyloxy groups for the (B) regulator + total number of epoxy groups for the (B) regulator] / [total number of thiol groups for the (C) polyfunctional thiol compound] is 0.8 to 1.2, preferably 0.9 to 1.1, and more preferably 0.95 to 1.1. However, the curable resin composition of the present invention contains the (A) polyfunctional (meth)acrylate compound, the (B) regulator, and the (C) polyfunctional thiol compound in such quantitative ratios that the total number of (meth)acryloyloxy groups in the (A) polyfunctional (meth)acrylate compound, the total number of (meth)acryloyloxy groups in the (B) regulator, the total number of epoxy groups in the (B) regulator, and the total number of thiol groups in the (C) polyfunctional thiol compound satisfy the above conditions.

[0050] If the ratio [(A) the total number of (meth)acryloyloxy groups in the polyfunctional (meth)acrylate compound] / [(C) the total number of thiol groups in the polyfunctional thiol compound] is less than 0.4, the content of the structure resulting from the reaction of the polyfunctional (meth)acrylate compound (A) with the polyfunctional thiol compound (C) that provides adhesiveness (in other words, the structure of the cured product obtained by a conventional UV-curable adhesive) in the cured product will be too low, resulting in insufficient adhesion after UV curing. On the other hand, if the ratio [(A) the total number of (meth)acryloyloxy groups in the polyfunctional (meth)acrylate compound] / [(C) the total number of thiol groups in the polyfunctional thiol compound] is more than 0.8, the cured product after UV curing will be prone to peeling from the adherend due to expansion and / or contraction of the adherend with changes in ambient temperature (i.e., poor adhesion reliability).

[0051] In the present invention, [total number of (meth)acryloyloxy groups in (A) polyfunctional (meth)acrylate compound] / [total number of thiol groups in (C) polyfunctional thiol compound] is preferably 0.45 to 0.7, more preferably 0.5 to 0.7, and even more preferably 0.5 to 0.65.

[0052] Furthermore, if the ratio [(B) modifier (total number of (meth)acryloyloxy) groups + (B) modifier (total number of epoxy) groups] / (C) polyfunctional thiol compound (total number of thiol) groups] is less than 0.05, the cured product after UV curing is likely to peel off from the adherend due to the expansion and / or contraction of the adherend with changes in ambient temperature (i.e., poor adhesive reliability). On the other hand, if the ratio [(B) modifier (total number of (meth)acryloyloxy) groups + (B) modifier (total number of epoxy) groups] / (C) polyfunctional thiol compound (total number of thiol) groups] is more than 0.65, the content of the structure formed by the reaction of the (A) polyfunctional (meth)acrylate compound and the (C) polyfunctional thiol compound in the cured product will be too low, resulting in insufficient adhesiveness after UV curing.

[0053] In the present invention, [total number of (meth)acryloyloxy groups in the (B) regulator + total number of epoxy groups in the (B) regulator] / [total number of thiol groups in the (C) polyfunctional thiol compound] is preferably 0.2 to 0.5, and more preferably 0.30 to 0.45. In one embodiment of the present invention, the (B) regulator consists essentially of a (b1) monofunctional (meth)acrylate compound (and does not substantially contain a (b2) epoxy resin). In this case, the ratio [total number of (meth)acryloyloxy groups in the (B) regulator + total number of epoxy groups in the (B) regulator] / [total number of thiol groups in the (C) polyfunctional thiol compound] is preferably 0.2 to 0.5, more preferably 0.25 to 0.45. If this ratio is less than 0.2, the effect of the (B) regulator in reducing the crosslink density of the cured product is reduced, making the cured product more likely to peel. On the other hand, if this ratio exceeds 0.5, UV curability may be impaired. In another embodiment of the present invention, the (B) regulator consists essentially of the (b2) epoxy resin (substantially does not contain the (b1) monofunctional (meth)acrylate compound). In this case, [total number of (meth)acryloyloxy groups in the (B) regulator + total number of epoxy groups in the (B) regulator] / [total number of thiol groups in the (C) polyfunctional thiol compound] is preferably 0.2 to 0.5, more preferably 0.25 to 0.45. If this ratio is less than 0.2, the effect of the (B) regulator in imparting flexibility to the cured product is reduced, making the cured product more likely to peel. On the other hand, if this ratio exceeds 0.5, UV curability may be impaired. In a further embodiment of the present invention, the (B) regulator contains both a (b1) monofunctional (meth)acrylate compound and a (b2) epoxy resin. In this case, the ratio of the total number of (meth)acryloyloxy groups in the (B) regulator to the total number of epoxy groups in the (B) regulator is preferably 1:0.01 to 1:20, more preferably 1:0.05 to 1:15, even more preferably 1:0.1 to 1:10, particularly preferably 1:0.1 to 1:5, and most preferably 1:0.1 to 1:1. If the ratio of the total number of epoxy groups in the (B) regulator to the total number of (meth)acryloyloxy groups in the (B) regulator is too low, the adhesion after UV curing and subsequent heat curing is likely to be insufficient. On the other hand, if the ratio of the total number of epoxy groups in the (B) regulator to the total number of (meth)acryloyloxy groups in the (B) regulator is too high, the adhesion after UV curing is likely to be insufficient.

[0054] (D) Photoradical initiator The curable resin composition of the present invention contains (D) a photoradical initiator. By including (D) a photoradical initiator, the curable resin composition can be cured by short-term UV irradiation. The (D) photoradical initiator that can be used in the present invention is not particularly limited, and known initiators can be used. Examples of (D) photoradical initiators include 1-hydroxycyclohexyl phenyl ketone, 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-morpholinopropane-1-one, and the like. -on, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, benzil dimethyl ketal, benzophenone, 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, etc. These may be used alone or in combination of two or more. The amount of (D) the photoradical initiator is preferably 0.01 to 10 mass %, more preferably 0.05 to 5 mass %, and even more preferably 0.1 to 3 mass % of the curable resin composition.

[0055] As a result of extensive investigations, the present inventors have found that the use of (B) a regulator containing (b1) a monofunctional (meth)acrylate compound and / or (b2) an epoxy resin makes it possible to prevent peeling of the cured product from the adherend during the heating and / or cooling process, which has been a problem with conventional UV-curable adhesives.

[0056] When the temperature of an assembly consisting of multiple parts made of different materials bonded together with adhesive changes, each part deforms according to the thermal expansion coefficient of that material. Because the degree of this deformation varies from part to part due to differences in thermal expansion coefficients, stress is generated in the assembly due to the deformation of each part. This stress acts particularly on the joints between the parts, i.e., the cured adhesive. If the cured adhesive is moderately flexible, it will adapt to the deformation of the assembled parts, preventing peeling from the adherend. However, the cured products of conventional UV-curable adhesives lack flexibility and are therefore unable to adapt to the deformation of the assembled parts, resulting in peeling from the adherend.

[0057] Such peeling of the cured product from the adherend occurs particularly when a UV-curable adhesive is cured by a heat curing process following a UV curing process to bond multiple adherends, and the material constituting one of the adherends has a glass transition temperature (T g ) (for example, when one of the adherends is made of polyethylene terephthalate (PET) or polybutylene terephthalate (PBT)).

[0058] This peeling of the cured product from the adherend is believed to be due to the cured product's excessively high crosslink density, which results in poor flexibility. The cured product obtained from the curable resin composition of the present invention has a lower crosslink density than the cured product obtained from conventional UV-curable adhesives. Even if the temperature of an assembly containing the cured product changes, such a cured product follows the deformation of the components of the assembly, making it less likely to peel from the adherend.

[0059] The curable resin composition of the present invention is -UV curing treatment by ultraviolet (UV) irradiation, and in some cases -Heat curing treatment A cured product can be obtained by subjecting the composition to the above-mentioned treatment.

[0060] Under UV irradiation for the UV curing treatment, the following reactions (1) and (2) occur: (1) Addition of a thiol group to the double bond in a (meth)acryloyloxy group by radical reaction (2) Radical polymerization of the double bond in the (meth)acryloyloxy group (homopolymerization) The reaction of the epoxy group does not occur under UV irradiation.

[0061] On the other hand, under heating for the optional heat curing treatment, the following reactions (3) and (4) occur: (3) Thermal addition of a thiol group to the double bond in the (meth)acryloyloxy group (4) Ring-opening nucleophilic addition of a thiol group to an epoxy group Radical polymerization (homopolymerization) of the double bond in the (meth)acryloyloxy group does not occur under heat.

[0062] When a polyfunctional (meth)acrylate compound and a polyfunctional thiol compound are subjected to the above-mentioned UV curing treatment in the presence of a photoradical initiator (D) without using the regulator (B), - a reaction between a polyfunctional (meth)acrylate compound and a polyfunctional thiol compound (1), and -Reaction between polyfunctional (meth)acrylate compounds (2) happens. Furthermore, when the product obtained by this UV curing treatment is subjected to a heat curing treatment, -Reaction between polyfunctional (meth)acrylate compounds and polyfunctional thiol compounds (3) happens. In such cases, the cured product after UV curing tends to peel off from the adherend due to expansion and / or contraction of the adherend caused by changes in ambient temperature. This is thought to be due to the poor flexibility of the resulting cured product resulting from an excessively high crosslink density.

[0063] On the other hand, when the curable resin composition of the present invention is subjected to the above-mentioned UV curing treatment, in addition to the above reaction, the following reaction occurs: - (b1) the reaction between a monofunctional (meth)acrylate compound and a polyfunctional thiol compound (1), - a reaction between a polyfunctional (meth)acrylate compound and (b1) a monofunctional (meth)acrylate compound (2), and -(b1) Reaction between monofunctional (meth)acrylate compounds (2) happens. Furthermore, if a heat curing accelerator (especially a basic component) is present in the system or on the surface of the adherend, when the product obtained by this UV curing treatment is subjected to a heat curing treatment, in addition to the above reactions, the following reaction occurs: (b1) a reaction between a monofunctional (meth)acrylate compound and a polyfunctional thiol compound (3), and -(b2) Reaction between epoxy resin and polyfunctional thiol compound (4) happens.

[0064] Among these reactions in the presence of the (B) regulator, the reaction (1) between a (b1) monofunctional (meth)acrylate compound and a polyfunctional thiol compound, the reaction (3) between a (b1) monofunctional (meth)acrylate compound and a polyfunctional thiol compound, and the reaction (2) between a polyfunctional (meth)acrylate compound and a (b1) monofunctional (meth)acrylate compound suppress the crosslink density of the cured product. Reactions (1) and (3) cap the thiol groups contained in the polyfunctional thiol compound, suppressing the formation of new crosslinks. Reaction (2) extends the polymer chain, increasing the spacing between crosslinks. The cured product obtained from the curable resin composition of the present invention is a crosslinked polymer. However, as described above, the use of the (B) regulator prevents the crosslink density from increasing during UV curing and thermal curing. Therefore, this polymer has a lower crosslink density than the cured product obtained from a conventional curable resin composition that does not use the (B) regulator.

[0065] When the curable resin composition of the present invention is subjected to only UV curing treatment, the (b2) epoxy resin remains unreacted in the resulting cured product. The unreacted (b2) epoxy resin improves the flexibility of such a cured product. Therefore, when such a curable resin composition is used, the cured product conforms to deformations of the components of an assembly caused by changes in ambient temperature, preventing peeling of the cured product from the adherend.

[0066] On the other hand, when a heat curing accelerator (particularly a basic component) is present in the system or on the surface of the adherend, the curable resin composition of the present invention undergoes the UV curing treatment and heat curing treatment, and the reaction (4) between the (b2) epoxy resin and the polyfunctional thiol compound causes ring-opening of the epoxy group contained in the (b2) epoxy resin, generating a hydroxyl group. This hydroxyl group can contribute to improving the adhesive strength of the cured product to the adherend and, ultimately, preventing peeling of the cured product from the adherend. Furthermore, when the (b2) epoxy resin is a monofunctional epoxy resin, the thiol groups contained in the polyfunctional thiol compound are capped by reaction (4), suppressing the formation of new crosslinks. As a result, reaction (4) does not increase the crosslink density of the cured product. On the other hand, when the (b2) epoxy resin is a polyfunctional epoxy resin, new crosslinks can theoretically be formed by reaction (4). However, in reality, a polymer is formed by the UV curing treatment, restricting the movement of the (b2) epoxy resin within the system, making it difficult for new crosslinks to be formed.

[0067] If desired, the curable resin composition of the present invention may contain optional components other than the above components (A) to (D), such as those described below, as needed.

[0068] (E) Heat curing accelerator If desired, the curable resin composition of the present invention may further contain a thermal curing accelerator (E). By including a thermal curing accelerator, the curable resin composition of the present invention can be cured in a short time even under low-temperature conditions. The thermal curing accelerator used in the present invention is not particularly limited as long as it is a curing catalyst for epoxy resins, and known thermal curing accelerators can be used. In one embodiment of the present invention, the thermal curing accelerator is a basic substance. The thermal curing accelerator is preferably a latent curing catalyst. A latent curing catalyst is a compound that is inactive at room temperature but is activated by heating to function as a curing catalyst. Examples of such a latent curing catalyst include imidazole compounds that are solid at room temperature; solid-dispersed amine adduct latent curing catalysts such as reaction products of amine compounds and epoxy compounds (amine-epoxy adducts); and reaction products of amine compounds and isocyanate compounds or urea compounds (urea adducts).

[0069] Representative examples of commercially available latent curing catalysts include amine-epoxy adducts (amine adducts), such as "Amicure PN-23" (trade name, manufactured by Ajinomoto Fine-Techno Co., Ltd.), "Amicure PN-40" (trade name, manufactured by Ajinomoto Fine-Techno Co., Ltd.), "Amicure PN-50" (trade name, manufactured by Ajinomoto Fine-Techno Co., Ltd.), "Novacure HX-3742" (trade name, manufactured by Asahi Kasei Corporation), and "Novacure HX-3721" (trade name, manufactured by Asahi Kasei Corporation). Examples of suitable curing accelerators include "Novacure HXA9322HP" (trade name, manufactured by Asahi Kasei Corporation), "Novacure HXA3922HP" (trade name, manufactured by Asahi Kasei Corporation), "Novacure HXA3932HP" (trade name, manufactured by Asahi Kasei Corporation), "Novacure HXA5945HP" (trade name, manufactured by Asahi Kasei Corporation), "Novacure HXA9382HP" (trade name, manufactured by Asahi Kasei Corporation), and "Fujicure FXR1121" (trade name, manufactured by T&K TOKA Corporation). Urea adducts include "Fujicure FXE-1000" (trade name, manufactured by T&K TOKA Corporation) and "Fujicure FXR-1030" (trade name, manufactured by T&K TOKA Corporation), but are not limited thereto. The thermal curing accelerator may be used alone or in combination of two or more types. From the viewpoints of pot life and curability, the heat curing accelerator is preferably a solid dispersion type amine adduct latent curing catalyst. The amount of the heat curing accelerator is preferably 0.1 to 20 mass %, more preferably 0.5 to 15 mass %, and even more preferably 1 to 10 mass %, of the curable resin composition.

[0070] Some thermal curing accelerators are provided in the form of a dispersion in a polyfunctional epoxy resin. When such a thermal curing accelerator is used, it should be noted that the amount of the polyfunctional epoxy resin in which it is dispersed is also included in the amount of the epoxy resin (b2) in the curable resin composition of the present invention.

[0071] Fillers The curable resin composition of the present invention may contain a filler, particularly a silica filler and / or a talc filler, if desired. The filler can be added to improve the thermal cycle resistance of the cured product obtained by curing the curable resin composition of the present invention. The reason why the thermal cycle resistance is improved by adding a filler is that the linear expansion coefficient of the cured product is reduced, i.e., the expansion and contraction of the cured product due to thermal cycling is suppressed. Shrinkage during curing is also suppressed.

[0072] When a filler is used, its average particle size is preferably 0.1 to 10 μm. In this specification, unless otherwise specified, the average particle size refers to the volume-based median diameter (d50) measured by laser diffraction in accordance with ISO-13320 (2009).

[0073] When a filler is used, the content thereof is preferably 1 to 70 mass %, more preferably 5 to 60 mass %, relative to the total mass of the curable resin composition.

[0074] The filler may be used alone or in combination of two or more. Specific examples of fillers other than silica filler and talc filler include, but are not limited to, alumina filler, calcium carbonate filler, polytetrafluoroethylene (PTFE) filler, silicone filler, acrylic filler, styrene filler, etc. In the present invention, the filler may be surface-treated.

[0075] Stabilizers The curable resin composition of the present invention may contain a stabilizer if desired. The stabilizer can be added to the curable resin composition of the present invention to improve its storage stability and extend its pot life. Various stabilizers known as stabilizers for one-component adhesives can be used, but at least one selected from the group consisting of liquid borate ester compounds, aluminum chelates, and organic acids is preferred because of its high effect of improving storage stability.

[0076] 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), which allows the viscosity of the formulation to be kept low. As the aluminum chelate, for example, Aluminum Chelate A (manufactured by Kawaken Fine Chemical Co., Ltd.) can be used. As the organic acid, for example, barbituric acid can be used.

[0077] When the curable resin composition of the present invention contains a stabilizer, the amount of the stabilizer is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and even more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the total amount of components (A) to (D).

[0078] Coupling agents The curable resin composition of the present invention may contain a coupling agent if desired. The addition of a coupling agent, particularly a silane coupling agent, is preferred from the viewpoint of improving adhesive strength. Silane coupling agents are organosilicon compounds having two or more different functional groups in their molecules, including a functional group capable of chemically bonding with inorganic materials and a functional group capable of chemically bonding with organic materials. Generally, the functional group capable of chemically bonding with inorganic materials is a hydrolyzable silyl group, and alkoxy groups, particularly silyl groups containing methoxy and / or ethoxy groups, are used as this functional group. Examples of functional groups capable of chemically bonding with organic materials include vinyl groups, epoxy groups, (meth)acrylic groups, styryl groups, unsubstituted or substituted amino groups, mercapto groups, ureido groups, and isocyanate groups. Various silane coupling agents having the above-mentioned functional groups can be used as coupling agents. Specific examples of silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 8-glycidoxyoctyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, and 3-isocyanatepropyltriethoxysilane. These silane coupling agents may be used alone or in combination of two or more. Note that silane coupling agents (including those used for the surface treatment of the above-mentioned fillers) may have reactive functional groups such as (meth)acryloyl groups, epoxy groups, etc. However, in the present invention, silane coupling agents are not included in components (A) to (D).

[0079] When the curable resin composition of the present invention contains a coupling agent, the amount of the coupling agent is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the total amount of components (A) to (D), from the viewpoint of improving adhesive strength.

[0080] Thixotropic agents The curable resin composition of the present invention may contain a thixotropic agent if desired. The thixotropic agent used in the present invention is not particularly limited, and known thixotropic agents can be used. Examples of thixotropic agents used in the present invention include, but are not limited to, silica. The silica may be natural silica (such as silica stone or quartz) or synthetic silica. The synthetic silica can be synthesized by any method, including a dry method and a wet method. The thixotropic agent may be surface-treated with a surface treatment agent (e.g., polydimethylsiloxane). In the present invention, it is preferable that at least a part of the thixotropic agent is surface-treated. The average particle size of the primary particles of the thixotropic agent is preferably 5 to 50 nm.

[0081] The curable resin composition of the present invention preferably contains 0.1 to 30 mass %, more preferably 1 to 20 mass %, and particularly preferably 1 to 15 mass % of the thixotropic agent relative to the total mass of the curable resin composition.

[0082] Other additives If desired, other additives such as carbon black, titanium black, ion trapping agents, leveling agents, antioxidants, antifoaming agents, viscosity modifiers, flame retardants, colorants, solvents, etc. may be added to the curable resin composition of the present invention within the scope of the present invention. The type and amount of each additive are as per usual.

[0083] The method for producing the curable resin composition of the present invention is not particularly limited. For example, the curable resin composition of the present invention can be obtained by simultaneously or separately introducing components (A) to (D) and, if desired, additives into an appropriate mixer, stirring and mixing while melting by heating if necessary, to form a homogeneous composition. The mixer is not particularly limited, and examples that can be used include a Raikai mixer equipped with a stirrer and a heater, a Henschel mixer, a three-roll mill, a ball mill, a planetary mixer, and a bead mill. These devices may also be used in appropriate combination.

[0084] The curable resin composition thus obtained is, as described above, -UV curing treatment by ultraviolet (UV) irradiation, and in some cases -Heat curing treatment The cured product can be converted into a cured product by subjecting the cured product to

[0085] The UV curing treatment can be carried out by exposing the curable resin composition of the present invention to a sufficient cumulative amount of ultraviolet light at room temperature. The irradiation intensity is 100 to 10,000 mW / cm. 2 It is preferable that the intensity is 1000 to 9000 mW / cm 2 The wavelength of the ultraviolet light is preferably 315 to 450 nm, more preferably 340 to 430 nm, and particularly preferably 350 to 380 nm. The light source of the ultraviolet light is not particularly limited, and a gallium nitride UV-LED or the like can be used. The cumulative light amount of the ultraviolet light received by the curable resin composition of the present invention is preferably 200 mJ / cm. 2 or more, more preferably 500 mJ / cm 2 More preferably, 1000 mJ / cm 2 or more, and particularly preferably 2000 mJ / cm 2That's all. There is no particular limit to the upper limit of the cumulative light amount, and it can be freely set within a range that does not impair the spirit of the present invention. The cumulative light amount of ultraviolet light can be measured using measuring devices commonly used in the relevant field, such as an ultraviolet integrating actinometer and a photoreceiver. For example, the cumulative light amount in the ultraviolet wavelength range (310 to 390 nm) with a center wavelength of 365 nm can be measured using an ultraviolet integrating actinometer (UIT-250, manufactured by Ushio Inc.) and a photoreceiver (UVD-S365, manufactured by Ushio Inc.).

[0086] On the other hand, the heat curing treatment can be optionally carried out by heating the curable resin composition of the present invention after the UV curing treatment under appropriate conditions. This heating is preferably carried out at 60 to 120°C, more preferably at 60 to 100°C, and particularly preferably at 70 to 90°C. This heating is also preferably carried out for 5 to 180 minutes, more preferably at 10 to 120 minutes, and particularly preferably at 20 to 70 minutes.

[0087] When the curable resin composition of the present invention is subjected to the above-described UV curing treatment, it gives a cured product that has a lower crosslink density and is more flexible than conventional cured products. Therefore, when two parts (adherends) are joined using the curable resin composition of the present invention, even if the resulting assembly deforms due to a change in temperature after UV curing, the cured product given by the curable resin composition of the present invention is less likely to peel from the adherend.

[0088] The curable resin composition of the present invention can be used, for example, in semiconductor devices including various electronic components, as an adhesive for bonding components that constitute electronic components, or as a raw material thereof.

[0089] The present invention also provides an adhesive containing the curable resin composition of the present invention. The adhesive of the present invention is suitable for fixing modules, electronic components, etc. The present invention also provides a cured product obtained by curing the curable resin composition or adhesive of the present invention.The present invention also provides a semiconductor device including the cured product of the present invention.The present invention also provides a sensor module including the semiconductor device of the present invention. [Example]

[0090] The present invention will be described below with reference to examples, but is not limited to these. In the following examples, parts and % represent parts by mass and % by mass unless otherwise specified.

[0091] Examples 1 to 36, Comparative Examples 1 to 8 Curable resin compositions were prepared by mixing predetermined amounts of each component using a three-roll mill according to the formulation shown in Table 1. In Table 1, the amount of each component is expressed in parts by mass (unit: g).

[0092] (A) Polyfunctional (meth)acrylate compound In the examples and comparative examples, the compounds used as the polyfunctional (meth)acrylate compounds are as follows. (A-1): Dimethyloltricyclodecane diacrylate (trade name: Light Acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd., (meth)acrylate equivalent: 152) (A-2): 2-(2-acryloyloxy-1,1-dimethylethyl)-5-acryloyloxymethyl-5-ethyl-1,3-dioxane (trade name: KAYARAD R-604, manufactured by Nippon Kayaku Co., Ltd., (meth)acrylate equivalent: 163) (A-3): Polyether-based urethane acrylate (trade name: UN-6200, manufactured by Negami Chemical Industrial Co., Ltd., (meth)acrylate equivalent: 3250) (A-4): Ditrimethylolpropane tetraacrylate (trade name: EBECRYL 140, manufactured by Daicel-Allnex Corporation, (meth)acrylate equivalent: 117) (A-5): A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., (meth)acrylate equivalent: 87) (A-6): Tripropylene glycol diacrylate (trade name: NK Ester APG-200, manufactured by Shin-Nakamura Chemical Co., Ltd., (meth)acrylate equivalent: 150)

[0093] (B) Regulator (b1) Monofunctional (meth)acrylate compound In the examples and comparative examples, the compounds used as the monofunctional (meth)acrylate compounds are as follows. (B-1): Isobornyl acrylate (trade name: Light Acrylate IBXA, manufactured by Kyoeisha Chemical Co., Ltd., (meth)acrylate equivalent: 208) (B-2): Phenoxyethyl acrylate (trade name: Light Acrylate PO-A, manufactured by Kyoeisha Chemical Co., Ltd., (meth)acrylate equivalent: 192) (B-3): 4-tert-butylcyclohexyl acrylate (trade name: TBCHA, manufactured by KJ Chemicals Co., Ltd., (meth)acrylate equivalent: 210) (B-4): Dicyclopentanyl acrylate (trade name: FA513AS, manufactured by Showa Denko Materials Co., Ltd., (meth)acrylate equivalent: 206) (B-5): 3-phenoxybenzyl acrylate (trade name: Light Acrylate POB-A, manufactured by Kyoeisha Chemical Co., Ltd., (meth)acrylate equivalent: 254) (B-6): 2-(o-phenylphenoxy)ethyl (meth)acrylate (trade name: HRD-01, manufactured by Nisshoku Techno Fine Chemical Co., Ltd., (meth)acrylate equivalent: 268) (B-7): Isononyl acrylate (trade name: AIN, manufactured by Nippon Shokubai Co., Ltd., (meth)acrylate equivalent: 198) (B-8): (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate (trade name: MEDOL-10, manufactured by Osaka Organic Chemical Industry Co., Ltd., (meth)acrylate equivalent: 200)

[0094] (b2) Epoxy resins that do not have reactive unsaturated double bonds In the examples and comparative examples, the compounds used as epoxy resins having no reactive unsaturated double bonds are as follows. (B-9): Bisphenol A epoxy resin (trade name: JER834, manufactured by Mitsubishi Chemical Holdings Corporation, epoxy equivalent: 250) (B-10): Tri(epoxypentyl)isocyanurate (trade name: TEPIC-VL, manufactured by Nissan Chemical Industries, Ltd., epoxy equivalent: 135) (B-11): Diglycidyl (dimethylolcyclohexane) (trade name: CDMDG, manufactured by Showa Denko K.K., epoxy equivalent: 136)

[0095] (B') Epoxy resin having a reactive unsaturated double bond In the examples and comparative examples, the compounds used as the epoxy resin having a reactive unsaturated double bond are as follows. (B'-1): Epoxidized 1,2-polybutadiene (trade name: BF1000, manufactured by ADEKA Corporation, epoxy equivalent: 168)

[0096] (C) Polyfunctional thiol compounds In the examples and comparative examples, the compounds used as the polyfunctional thiol compounds are as follows. (C-1): Pentaerythritol tetrakis(3-mercaptopropionate) (trade name: PEMP, manufactured by SC Organic Chemical Co., Ltd., thiol equivalent: 122) (C-2): Pentaerythritol trippropanethiol (trade name: PEPT, manufactured by SC Organic Chemical Co., Ltd., thiol equivalent: 124) (C-3): 1,3,4,6-tetrakis(2-mercaptopropyl)glycoluril (trade name: C3 TS-G, manufactured by Shikoku Chemicals Corporation, thiol equivalent: 114)

[0097] (D) Photoradical initiator In the examples and comparative examples, the compounds used as photoradical initiators are as follows. (D-1): 1-hydroxycyclohexyl phenyl ketone (trade name: OMNIRAD 184, manufactured by IGM Resins BV) (D-2): 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name: OMNIRAD TPO, manufactured by IGM Resins BV)

[0098] (E) Heat curing accelerator The compounds used as heat curing accelerators in the examples and comparative examples are as follows. (E-1): Amine adduct-based latent curing catalyst 1 (trade name: Fujicure FXR1121, manufactured by T&K TOKA Corporation) (E-2): Amine adduct-based latent curing catalyst 2 (product name: Amicure PN-23, manufactured by Ajinomoto Fine-Techno Co., Ltd.)

[0099] (F) Other ingredients (f1) Filler The compounds used as fillers in the examples and comparative examples are as follows: (F-1): Synthetic spherical silica (product name: SE2200SEE, manufactured by Admatechs Co., Ltd.) (F-2): Fine particle talc (product name: 5000PJ, manufactured by Matsumura Sangyo Co., Ltd.) (f2) Thixotropic agent The compounds used as thixotropic agents in the examples and comparative examples are as follows: (F-3): Fumed silica (trade name: CAB-O-SIL (registered trademark) TS720, manufactured by Cabot Corporation) (f3) Stabilizer The compounds used as stabilizers in the examples and comparative examples are as follows: (F-4): Triisopropyl borate (Tokyo Chemical Industry Co., Ltd.) (F-5): N-nitroso-N-phenylhydroxylamine aluminum (Fujifilm Wako Pure Chemical Industries, Ltd.) The symbols in the "equivalent number calculation" in the table represent the following: (A+B) / (C): [(A) total number of (meth)acryloyloxy groups for the multifunctional (meth)acrylate compound+(B) total number of (meth)acryloyloxy groups for the regulator+(B) total number of epoxy groups for the regulator] / [(C) total number of thiol groups for the multifunctional thiol compound] (A) / (C): [(A) total number of (meth)acryloyloxy groups in the multifunctional (meth)acrylate compound] / [(C) total number of thiol groups in the multifunctional thiol compound] (B) / (C): [total number of (meth)acryloyloxy groups for (B) modifier + total number of epoxy groups for (B) modifier] / [total number of thiol groups for (C) polyfunctional thiol compound] (b1) / (C): [(b1) total number of (meth)acryloyloxy groups for monofunctional (meth)acrylate compounds + (b1) total number of epoxy groups for monofunctional (meth)acrylate compounds] / [(C) total number of thiol groups for multifunctional thiol compounds] (b2) / (C): [(b2) Total number of epoxy groups for epoxy resins having no reactive unsaturated double bonds] / [(C) Total number of thiol groups for polyfunctional thiol compounds]

[0100] (Evaluation of curability (UV and heat) of curable resin composition) Two glass plates were each coated with a silicone-based release agent. Two rectangular polyimide spacers, each 0.3 mm high, were placed on the release-agent-coated surface of one of the glass plates, and a curable resin composition was applied between them. The other glass plate was placed on top of this glass plate with the release-agent-coated surface facing downwards, so that the curable resin composition and spacers were sandwiched between the two glass plates. The curable resin composition between the two glass plates was irradiated with an integrated light dose of 2000 mJ / cm using a UV LED irradiation device AC475 manufactured by Excelitas Technologies. 2 The curable resin composition was subjected to a UV curing treatment by UV irradiation (measured using a Ushio Inc. UIT-250 (connected to a UVD-365 photodetector)). The curable resin composition was then subjected to a heat curing treatment by heating at 80°C for 60 minutes in a blower dryer. The UV curability and heat curability of the curable resin composition were evaluated based on whether or not the curable resin composition formed a peelable film while maintaining its shape at the completion of the UV curing treatment and the subsequent heat curing treatment. The symbol "◯" in the table indicates that the curable resin composition formed a peelable film while maintaining its shape at the completion of the UV curing treatment or the subsequent heat curing treatment. The symbol "×" in the table indicates that the curable resin composition did not form a peelable film while maintaining its shape at the completion of the UV curing treatment or the subsequent heat curing treatment.

[0101] (Evaluation of Adhesion Reliability of Curable Resin Composition) Using a desktop liquid application robot JR2400N (manufactured by Sanei Tech Co., Ltd.), 8 mg of the curable resin composition contained in a syringe (equipped with a nozzle having a 200 μm inner diameter needle) was applied to a 2.6 cm × 2 cm × 1.5 mm glass plate in a 1.2 cm × 0.9 cm square (with a 1 mm gap in the center of one long side). Two rectangular polyimide spacers, each 0.15 mm high, were placed on a 2 cm × 7 cm × 2 mm polybutylene terephthalate (PBT) plate. The glass plate coated with the curable resin composition was placed on the PBT plate with the coated side facing down, so that the curable resin composition was positioned between the two spacers, and the curable resin composition and spacers were sandwiched between the glass plate and the PBT plate. The curable resin composition between the PBT plate and the glass plate was applied using an Excelitas Technologies UV LED irradiation device AC475 with an integrated light dose of 2000 mJ / cm. 2 The composition was cured by UV irradiation (measured using a Ushio Inc. UIT-250 (connected to a UVD-365 photodetector)). The spacer was then removed, and the UV-cured curable resin composition was heated in a fan dryer at 80°C for 60 minutes. The cured product obtained between the PBT plate and the glass plate was left at room temperature (20°C) for 2 hours, and the degree of peeling of the cured product from the glass plate and / or PBT plate was evaluated by visual observation. When the cured product prepared above was observed from the glass plate side, the cured product adhered to both the glass plate and the PBT plate was perceived as a transparent area, while the cured product peeled from the glass plate and / or the PBT plate was perceived as a white area. The degree of peeling of the cured product was evaluated based on the approximate ratio (%) of the area of ​​the white area to the total area of ​​the transparent and white areas. A similar test was performed four times for each curable resin composition. The results are shown in Table 1. The symbol "◎" in the table indicates that the above ratio was essentially 0% in all four tests. The symbol "○" in the table indicates that the above ratio was greater than 0% and less than 50% in all four tests. The symbol "△" in the table indicates that, of the four tests, the above ratio was greater than 0% and less than 50% in two or three tests, and greater than 50% in one or two tests. The symbol "×" in the table indicates that, of the four tests, the above ratio was greater than 0% and less than 50% in three or four tests. The symbol "-" in the table indicates that evaluation was not performed because UV curing was insufficient (the curable resin composition did not form a peelable film while maintaining its shape).

[0102] [Table 1-1] [Table 1-2] [Table 1-3] [Table 1-4] [Table 1-5]

[0103] (Discussion of results) As is clear from Table 1, all of the curable resin compositions of Examples 1 to 36, which contain appropriate amounts of (A) a polyfunctional (meth)acrylate compound, (B) a regulator, and (C) a polyfunctional thiol compound, can be cured in a short time by UV irradiation. Furthermore, the resulting cured products are not easily peeled from the adherend even after subsequent heating and cooling. The adhesive reliability of the curable resin composition of Example 36, which uses (A) a polyfunctional (meth)acrylate compound having a poly(alkylene glycol) skeleton, was inferior to that of Examples 1 to 35, but better than that of Comparative Examples 1 to 7. On the other hand, the curable resin compositions of Comparative Examples 1 to 7, in which the content of any one of the (A) polyfunctional (meth)acrylate compound, (B) regulator, and (C) polyfunctional thiol compound was inappropriate, could not be cured by UV irradiation, and therefore the adhesion after UV curing could not be measured (Comparative Examples 3 to 5, 7), or could be cured by UV irradiation, but the resulting cured product peeled off from the adherend when subsequently heated and cooled (Comparative Examples 1, 2, 6). Furthermore, the curable resin composition of Comparative Example 8, which contains (B') an epoxy resin having a reactive unsaturated double bond instead of (B) the regulator, can be cured by UV irradiation, but the resulting cured product peels off from the adherend when it is subsequently heated and then cooled. [Industrial Applicability]

[0104] The curable resin composition of the present invention provides a cured product with a lower crosslink density and greater flexibility than conventional products. The curable resin composition of the present invention is highly resistant to peeling from the adherend even when the ambient temperature changes during the heating and / or cooling process after UV curing, making it extremely useful for bonding components of sensor modules, etc.

[0105] The disclosure of Japanese Patent Application No. 2021-116458 (filing date: July 14, 2021) 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

1. The following (A) to (D): (A) a polyfunctional (meth)acrylate compound; (B) A regulator containing the following (b1) and / or (b2): (b1) Monofunctional (meth)acrylate compound (b2) an epoxy resin having no reactive unsaturated double bonds; (C) a polyfunctional thiol compound; (D) a photoradical initiator; and (E) Heat curing accelerator Including, [the total number of (meth)acryloyloxy groups in the (A) polyfunctional (meth)acrylate compound] / [the total number of thiol groups in the (C) polyfunctional thiol compound] is 0.4 to 0.8, [the total number of (meth)acryloyloxy groups in the (B) regulator + the total number of epoxy groups in the (B) regulator] / [the total number of thiol groups in the (C) polyfunctional thiol compound] is 0.05 to 0.65, where: (1) The (B) regulator contains both (b1) a monofunctional (meth)acrylate compound and (b2) an epoxy resin having no reactive unsaturated double bond, and the ratio of [the total number of (meth)acryloyloxy groups in the (B) regulator] to [the total number of epoxy groups in the (B) regulator] is 1:0.01 to 1:20, or (2) The (B) regulator essentially consists of (b1) a monofunctional (meth)acrylate compound; Curable resin composition.

2. The curable resin composition according to claim 1, wherein [(A) the total number of (meth)acryloyloxy groups in the polyfunctional (meth)acrylate compound] / [(C) the total number of thiol groups in the polyfunctional thiol compound] is 0.5 to 0.

7.

3. 2. The curable resin composition according to claim 1, wherein the (B) regulator comprises both (b1) a monofunctional (meth)acrylate compound and (b2) an epoxy resin having no reactive unsaturated double bond, and the ratio of [total number of (meth)acryloyloxy groups in the (B) regulator]:[total number of epoxy groups in the (B) regulator] is 1:0.01 to 1:

20.

4. The curable resin composition according to claim 1, wherein the polyfunctional thiol compound (C) has three or more thiol groups.

5. The curable resin composition according to claim 1, wherein the polyfunctional thiol compound (C) comprises a trifunctional thiol compound and / or a tetrafunctional thiol compound.

6. The curable resin composition according to claim 1, wherein the polyfunctional (meth)acrylate compound (A) comprises a difunctional (meth)acrylate compound.

7. 2. The curable resin composition according to claim 1, wherein the (B) regulator consists essentially of the (b1) monofunctional (meth)acrylate compound, and the ratio of [total number of (meth)acryloyloxy groups in the (B) regulator + total number of epoxy groups in the (B) regulator] / [total number of thiol groups in the (C) polyfunctional thiol compound] is 0.05 to 0.

5.

8. An adhesive comprising the curable resin composition according to any one of claims 1 to 7.

9. A cured product obtained by curing the curable resin composition according to any one of claims 1 to 7.

10. A semiconductor device comprising the cured product according to claim 9.

11. A sensor module comprising the cured product according to claim 9.

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