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

Abstract

The present invention addresses the problem of providing: a curable resin composition capable of reducing misalignment and separation of a cured product from an adherend; an adhesive or sealing material containing same; a cured product thereof; and a semiconductor device and an electronic component containing said cured product.　Provided are: a curable resin composition which contains (A) a (meth)acrylate compound, (B) a polythiol compound, and (C) a photo-radical polymerization initiator that generates a methyl radical or a phenyl radical as an active species, and in which the content of component (C) is 0.01-10 mass% relative to the total mass of the curable resin composition, the curable resin composition may contain (D) a thermal polymerization initiator, and the content of the thermal polymerization initiator (D) is 0-10 mass% relative to the total mass of the curable resin composition; an adhesive or sealing material containing same; a cured product thereof; and a semiconductor device and an electronic component containing said cured product.

Description

Curable resin compositions, adhesives, sealants, cured products, semiconductor devices and electronic components

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

[0002] Photocurable adhesives are used in many fields (for example, Patent Documents 1 and 2), and are particularly popular in optical sensor module applications. Optical sensor modules are used as camera modules in mobile phones and smartphones. The adhesives used in the manufacture of optical sensor modules are used in processes that align the optical axis, such as bonding the sensor part and the lens part of the optical sensor module, and require high photocurability. UV-curable adhesives using the enthiol reaction are known as adhesives that achieve high photocurability.

[0003] Patent Document 3 discloses a resin composition as a UV-curable adhesive using an en-thiol reaction, characterized by containing (A) an acrylic resin, (B) a thiol compound, (C) a latent curing agent, (D) a radical polymerization inhibitor, and (E) an anionic polymerization inhibitor.

[0004] Japanese Patent Publication No. 2009-51954, International Publication No. 2005 / 052021, Japanese Patent Publication No. 2014-077024

[0005] When a photocurable resin composition is used in processes that align the optical axis, such as bonding the sensor and lens parts of an optical sensor module, extremely high curing accuracy is required to prevent misalignment of the optical axis. However, during subsequent processes after fixing such parts by photocuring the resin composition, the position of the photocured parts may shift or the parts may detach from the substrate. For example, if the part is a component of an optical sensor module, even a slight misalignment can cause the optical axis to shift, which is problematic.

[0006] Therefore, the object of the present invention is to provide a curable resin composition that can reduce displacement and peeling of the cured product from the adherend, an adhesive or encapsulant containing the same, a cured product thereof, a semiconductor device and an electronic component containing the cured product thereof.

[0007] The specific means for solving the above problems are as follows. The embodiments of the present invention include the following curable resin compositions, adhesives or encapsulants, cured products, semiconductor devices or electronic components. [1] A curable resin composition comprising (A) a (meth)acrylate compound, (B) a polythiol compound, and (C) a photoradical polymerization initiator that generates a methyl radical or a phenyl radical as an active species, wherein the content of component (C) is 0.01 to 10% by mass with respect to the total mass of the curable resin composition, and the curable resin composition may also contain (D) a thermal polymerization initiator, wherein the content of (D) the thermal polymerization initiator is 0 to 10% by mass with respect to the total mass of the curable resin composition. [2] The curable resin composition according to [1] above, wherein the first to third shear strength change rates obtained by each of the following formulas (1) to (3) are all 60% or less: First shear strength change rate (%) = {|(X2-X1)| / X1} × 100 ... (1) Second shear strength change rate (%) = {|(X3-X2)| / X2} × 100 ... (2) Third shear strength change rate (%) = {|(X3-X1)| / X1} × 100 ... (3) In the formulas, X1 is the curable resin composition when exposed to UV irradiation at a dose of 100 mJ / cm² ２ X2 is the shear strength when cured, where X2 is the curable resin composition when exposed to UV irradiation at a dose of 200 mJ / cm². ２ X3 is the shear strength when cured, where X3 is the curable resin composition when exposed to UV irradiation at a dose of 500 mJ / cm². ２ This is the shear strength when cured. [3] The curable resin composition described in [2] above, wherein the fourth to sixth shear strength change rates obtained by each of the following formulas (4) to (6) are all 30% or less: Fourth shear strength change rate (%) = {|(Y2-Y1)| / Y1} × 100 ... (4) Fifth shear strength change rate (%) = {|(Y3-Y2)| / Y2} × 100 ... (5) Sixth shear strength change rate (%) = {|(Y3-Y1)| / Y1} × 100 ... (6) In the formulas, Y1 is the curable resin composition when irradiated with UV light at a dose of 100 mJ / cm². ２Y2 is the shear strength after curing at 80°C for 60 minutes, where Y2 is the shear strength after curing the curable resin composition with a UV irradiation dose of 200 mJ / cm². ２ Y3 is the shear strength after curing at 80°C for 60 minutes, where Y3 is the shear strength after curing the curable resin composition with a UV irradiation dose of 500 mJ / cm². ２ The shear strength is obtained when cured at 80°C for 60 minutes. [4] A curable resin composition according to any one of the above [1] to [3], wherein the ratio of the number of thiol group equivalents of component (B) to the number of (meth)acryloyl group equivalents of component (A) ([number of thiol group equivalents of component (B)] / [number of (meth)acryloyl group equivalents of component (A)]) is 0.5 to 1.8. [5] A curable resin composition according to any one of the above [1] to [4], wherein the viscosity at 25°C is 0.5 to 80 Pa·s and the thixotropic index (TI) value at 25°C is 1.5 to 8.0. [6] A curable resin composition according to any one of the above [1] to [5], substantially free of solvents. [7] An adhesive or sealant comprising the curable resin composition according to any one of the above [1] to [6]. [8] The adhesive or sealant described in [7] above, used for fixing, bonding, or protecting components constituting a light sensor module. [9] A curable resin composition described in any one of [1] to [6] above, or a cured product obtained by curing the adhesive or sealant described in [7] or [8] above.

[10] A semiconductor device or electronic component containing the cured product described in [9] above.

[11] The semiconductor device or electronic component described in

[10] above, which is a light sensor module.

[0008] According to aspects of the present invention, it is possible to provide a curable resin composition that can reduce displacement and peeling of the cured product from the adherend, an adhesive or encapsulant containing the same, a cured product thereof, a semiconductor device, and an electronic component containing the cured product.

[0009] This is a schematic diagram of a jig for measuring the photocuring depth of a resin composition, viewed from the side. This is a schematic diagram of a jig for measuring the photocuring depth of a resin composition, viewed from above.

[0010] In this specification, following convention in the field of synthetic resins, the term "resin," which usually refers to a polymer (especially a synthetic polymer), may be used to describe components constituting a curable resin composition before curing, even if the component is not a polymer, for example, a prepolymer compound before curing. In this specification, "(meth)acryloyl group" refers to both a methacryloyl group and an acryloyl group. Also, "(meth)acrylate compound" refers to both an acrylate compound and a methacrylate compound. Furthermore, in this specification, "curable resin composition" may be simply referred to as "resin composition."

[0011] [Curable Resin Composition] A curable resin composition according to one aspect of the present invention is a curable resin composition comprising (A) a (meth)acrylate compound, (B) a polythiol compound, and (C) a photoradical polymerization initiator that generates a methyl radical or a phenyl radical as an active species, wherein the content of component (C) is 0.01 to 10% by mass with respect to the total mass of the curable resin composition, and the curable resin composition may also contain (D) a thermal polymerization initiator, wherein the content of (D) the thermal polymerization initiator is 0 to 10% by mass with respect to the total mass of the curable resin composition. According to this aspect, a curable resin composition can be provided that can reduce displacement and peeling of the cured product from the adherend.

[0012] (A) (meth)acrylate compound The curable resin composition of this embodiment contains (A) a (meth)acrylate compound (hereinafter also referred to as "component (A)"). The (A) (meth)acrylate compound can impart transparency and appropriate hardness to the cured resin composition. The (A) (meth)acrylate compound is not particularly limited as long as it has one or more (meth)acryloyl groups, and examples include monofunctional (meth)acrylate compounds having one (meth)acryloyl group and polyfunctional (meth)acrylate compounds having two or more (meth)acryloyl groups. Considering the need to ensure heat resistance, polyfunctional (meth)acrylate compounds having two or more (meth)acryloyl groups are preferred, compounds having two to six (meth)acryloyl groups are more preferred, and compounds having two (meth)acryloyl groups are even more preferred. Furthermore, in addition to polyfunctional (meth)acrylate compounds, monofunctional (meth)acrylate compounds can also be used to adjust viscosity and cured product properties (such as adhesive strength and flexibility).

[0013] Examples of monofunctional (meth)acrylate compounds include: n-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, and phenoxypolyethylene Esters of monohydric alcohols and (meth)acrylic acid, such as 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, 3-phenoxybenzyl (meth)acrylate, etc.; 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-naphthalene methyl (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, noni Phenoxypolyethylene 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 include, but are not limited to, 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. These may be used individually or in combination of two or more.

[0014] Examples of polyfunctional (meth)acrylate compounds include di(meth)acrylate of tris(2-hydroxyethyl) isocyanurate, tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, or their oligomers; pentaerythritol tri(meth)acrylate, or its oligomers; poly(meth)acrylate of dipentaerythritol; tris(acryloxyethyl) isocyanurate; caprolactone-modified tris((meth)acryloxyethyl) isocyanurate; alkyl-modified poly(meth)acrylate of dipentaerythritol; poly(meth)acrylate of caprolactone-modified dipentaerythritol; ethoxylated bisphenol A di(meth)acrylate; dihydrocyclopentadiethyl(meth)acrylate. Examples include, but are not limited to, polyester (meth)acrylate, dimethylol-tricyclodecanedi(meth)acrylate, tricyclodecanedimethanol diacrylate, ditrimethylolpropane poly(meth)acrylate, polycarbonate-based urethane acrylate oligomers, and other polyurethanes having two or more (meth)acryloyl groups in one molecule; polyesters 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 Japanese Patent Publication No. 2024-009452).

[0015] The (meth)acrylate compound may be any one of the (meth)acrylate compounds described above, or two or more may be used in combination.

[0016] Examples of commercially available (meth)acrylate compounds include, but are not limited to, polyester acrylate (product name: EBECRYL810) manufactured by Daicel Ornex Co., Ltd., ditrimethylolpropanetetraacrylate (product name: EBECRYL140) manufactured by Daicel Ornex Co., Ltd., polyester acrylate (product name: M7100) manufactured by Toagosei Co., Ltd., dimethylol-tricyclodecanediaacrylate (product name: Light Acrylate DCP-A) manufactured by Kyoeisha Chemical Co., Ltd., and neopentyl glycol-modified trimethylolpropanediaacrylate (product name: Kayarad R-604) manufactured by Nippon Kayaku Co., Ltd.

[0017] Component (A) preferably has a viscosity of 0.01 to 80 Pa·s, from the viewpoint of preparing the resin composition and its dispensability. In this specification, viscosity refers to the value measured at a measurement temperature of 25°C using an appropriate viscometer according to the viscosity range.

[0018] From the viewpoint of the adhesive strength of the resin composition, the content of component (A) is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, relative to the total mass of the resin composition. Furthermore, the content of component (A) is preferably, for example, 70% by mass or less, more preferably 65% ​​by mass or less, and even more preferably 60% by mass or less, relative to the total mass of the resin composition. Furthermore, the content of component (A) is preferably, for example, 10 to 70% by mass, more preferably 15 to 70% by mass, even more preferably 15 to 65% by mass, and particularly preferably 20 to 60% by mass, relative to the total mass of the resin composition.

[0019] (B) Polythiol Compound The curable resin composition of this embodiment contains (B) a polythiol compound (hereinafter also referred to as "component (B)"). The (B) polythiol compound imparts high photocurability to the resin composition. Component (B) is not particularly limited as long as it has two or more thiol groups. In one embodiment, the polythiol compound includes a combination of a bifunctional thiol compound having two thiol groups and a trifunctional or higher thiol compound having three or more thiol groups.

[0020] Examples of polythiol compounds include pentaerythritol tetrapropanthol 3-{3-(3-mercaptopropoxy)-2,2-bis-[(3-mercaptopropoxy)methyl]propoxy}propan-1-ol, 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluryl, 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluryl, 1,3,4,6-tetrakis(mercaptomethyl)glycoluryl, 1,3,4,6-tetrakis(mercaptomethyl)-3a-methylglycoluryl, and 1,3,4,6-tetrakis(2-mercaptomethyl) Captoethyl)-3a-methylglycoluryl, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a-methylglycoluryl, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-dimethylglycoluryl, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a-dimethylglycoluryl, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-dimethylglycoluryl, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-diphenylglycoluryl, 1, 3,4,6-Tetrakis(2-mercaptoethyl)-3a,6a-diphenylglycoluryl, 1,3,4,6-Tetrakis(3-mercaptopropyl)-3a,6a-diphenylglycoluryl, Tris(2-mercaptoethyl) isocyanurate, Tris(3-mercaptopropyl) isocyanurate, 1,3,5-Tris[3-(2-mercaptoethylsulfanyl)propyl] isocyanurate, 1,3,5-Tris[2-(3-mercaptopropoxy)ethyl] isocyanurate, Pentaerythritol tripropanthol, 3 -[2,3-bis(3-sulfanylpropoxy)propoxy]propane-1-thiol, 1,2,3-tris(3-mercaptopropyloxy)propane, 3-[2,2-bis[(3-mercaptopropoxy)methyl]butoxy]-1-propanthol, pentaerythritol tetrapropanthol, 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-Tritianonane, 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)-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-2,6,8,1 2-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-Hexatiahexadecane, 8-[bis(mercaptomethylthio)methyl]-3,4,12,13-Tetrakis(mercaptomethylthio)-1,15-dimercapto-2,5,7,9,11,14-Hexatiapentadecane, 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] [O]-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-dithiethanyl)]methyl-7,9-bis(mercaptomethylthio)-1,11-dimercapto-2,4,6,10-tetrathia Aundecane, 9-[2-(1,3-dithiethanyl)]methyl-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3-[2-(1,3-dithiethanyl)]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-dithia [Nylthio]-1,3-Dithiane, 4-[3,4,8,9-Tetrakis(mercaptomethylthio)-11-Mercapto-2,5,7,10-Tetrathiaundecyl]-5-Mercaptomethylthio-1,3-Dithiolane, 4,5-Bis[3,4-Bis(mercaptomethylthio)-6-Mercapto-2,5-Dithiahexylthio]-1,3-Dithiolane, 4-[3,4-Bis(mercaptomethylthio)-6-Mercapto-2,5-Dithiahexylthio]-5-Mercaptomethylthio-1,3-Dithiolane, 4-[3-Bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]-5-mercaptomethylthio-1,3-dithiolane, 2-{bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]methyl}-1,3-dithiethane, 2-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]mercaptomethylthiomethyl-1,3-dithiethane, 2-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecylthio]mercaptomethylthiomethyl-1,3-dithiethane, 2-[3(mercaptomethylthio)methyl-5, Various bifunctional thiol compounds disclosed in WO2019 / 082962, such as 6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]mercaptomethylthiomethyl-1,3-dithiethane, 4-{1-[2-(1,3-dithiethanyl)]-3-mercapto-2-thiapropylthio}-5-[1,2-bis(mercaptomethylthio)-4-mercapto-3-thiabutylthio]-1,3-dithiolane, 2,2'-[cyclohexylidenebis(thio-2,1-ethanediylthio)]bis[ethanethiol], 4,4'-[(1,3-phenylene)bis(oxy)]bis[1-butanethiol], and dimers, trimers, and tetramers of the thiol compounds; Trimethylolpropane Tris(3-mercaptopropionate), Tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, Pentaerythritol Tetrakis(3-mercaptopropionate), Tetraethylene glycol Bis(3-mercaptopropionate), Dipentaerythritol Hexakis(3-mercaptopropionate), Butanediol bisthioglycolate, Hexanediol bisthioglycolate, Trimethylolpropane tristhioglycolate, Pentaerythritol Tetrakisthioglycolate, Pentaerythritol Tetrakis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, or 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H) - Trion, etc., are examples, but the system is not limited to these. These may be used individually or in combination of two or more types.

[0021] Examples of commercially available products of component (B) include 1,3,4,6-tetrakis(2-mercaptoethyl) glycoluryl (product name: TS-G, manufactured by Shikoku Chemicals Co., Ltd.), 1,3,4,6-tetrakis(3-mercaptopropyl) glycoluryl (product name: C3 TS-G, manufactured by Shikoku Chemicals Co., Ltd.), pentaerythritol tetrapropanthol 3-{3-(3-mercaptopropoxy)-2,2-bis-[(3-mercaptopropoxy)methyl]propoxy}-propan-1-ol (product name: Multiol) Y-4 (manufactured by Sakai Chemical Industry Co., Ltd.), pentaerythritol tripropanethol (product name: PEPT, manufactured by SC Organic Chemicals), trimethylolpropane tris(3-mercaptopropionate) (product name: TMMP, manufactured by SC Organic Chemicals Co., Ltd.), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate (product name: TEMPIC, manufactured by SC Organic Chemicals Co., Ltd.), pentaerythritol tetrakis(3-mercaptopropionate) (product name: PEMP, manufactured by SC Organic Chemicals Co., Ltd.), tetraethylene glycol bis(3-mercaptopropionate) Examples include, but are not limited to, ) (product name: EGMP-4, manufactured by SC Organic Chemicals Co., Ltd.), dipentaerythritol hexakis(3-mercaptopropionate) (product name: DPMP, manufactured by SC Organic Chemicals Co., Ltd.), pentaerythritol tetrakis(3-mercaptobutyrate) (product name: Karenz MT® PE1, manufactured by Showa Denko K.K.), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (product name: Karenz MT® NR1, manufactured by Showa Denko K.K.), etc.

[0022] In this embodiment, the content of the (B) polythiol compound in the resin composition is preferably, for example, 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, and particularly preferably 20% by mass or more, based on the total mass of the resin composition. Furthermore, the content of the (B) polythiol compound in the resin composition is preferably, for example, 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less, based on the total mass of the resin composition. Furthermore, the content of the (B) polythiol compound in the resin composition is preferably, for example, 1 to 70% by mass, more preferably 5 to 60% by mass, even more preferably 10 to 50% by mass, and particularly preferably 20 to 50% by mass, based on the total mass of the resin composition.

[0023] In the curable resin composition of this embodiment, the ratio of the number of thiol group equivalents of component (B) to the number of (meth)acryloyl group equivalents of component (A) ([number of thiol group equivalents of component (B)] / [number of (meth)acryloyl group equivalents of component (A)]) is preferably 0.5 to 1.8, more preferably 0.6 to 1.6, and even more preferably 0.7 to 1.4. In this specification, functional group equivalents such as thiol equivalents and (meth)acryloyl equivalents represent the molecular weight of the compound per functional group, and functional group equivalent numbers such as the number of thiol group equivalents and (meth)acryloyl equivalents represent the number of functional groups (equivalents) per mass (amount charged) of compound. Theoretically, the thiol group equivalent of the (B) polythiol compound is the molecular weight of the (B) polythiol compound divided by the number of thiol groups in one molecule. The actual thiol group 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 Japanese Patent Application Publication No. 2012-153794. The number of thiol group equivalents of component (B) is the number of thiol groups (equivalents) per mass (amount charged) of component (B), and is the quotient obtained by dividing the mass (g) of the polythiol compound (B) by the thiol equivalent of that polythiol compound (if multiple polythiol compounds are included, it is the sum of such quotients for each polythiol compound). The (meth)acryloyl group equivalent of (A) (meth)acrylate compound is theoretically equal to the number obtained by dividing the molecular weight of the (meth)acrylate compound by the number of acryloyl groups (or methacryloyl groups) in one molecule. The actual (meth)acryloyl group equivalent can be measured, for example, by NMR. The equivalent number of (meth)acryloyl groups in component (A) is the number of (meth)acryloyl groups (equivalent number) per unit mass (amount charged) of component (A), and is the quotient obtained by dividing the mass (g) of the (meth)acrylate compound by the (meth)acryloyl equivalent of that (meth)acrylate compound (if multiple (meth)acrylate compounds are included, it is the sum of such quotients for each (meth)acrylate compound).Setting the ratio of [Number of thiol group equivalents of component (B)] / [Number of (meth)acryloyl group equivalents of component (A)] to the range of 0.5 to 1.8 allows for sufficient reaction between acryloyl groups and thiol groups, thereby enabling the formation of molecular crosslinks and facilitating the development of high adhesive strength.

[0024] The curable resin composition of this embodiment may contain polymerizable compounds other than (A) (meth)acrylate compounds and (B) polythiol compounds, but the total mass of (A) (meth)acrylate compounds and (B) polythiol compounds is preferably 60 to 100% by mass, more preferably 70 to 100% by mass, and even more preferably 80 to 100% by mass, relative to the total mass of all polymerizable compounds in the curable resin composition. Examples of other polymerizable compounds include epoxy compounds.

[0025] (C) Photoradical polymerization initiator that generates a methyl radical or a phenyl radical as an active species The resin composition of this embodiment includes (C) a photoradical polymerization initiator that generates a methyl radical or a phenyl radical as an active species (hereinafter also referred to as "component (C)"). When a curable resin composition is used in a process of aligning the optical axis, such as bonding the sensor part and the lens part of a sensor module, very high curing accuracy is required to prevent optical axis misalignment. However, in a subsequent process after fixing such parts by photocuring the curable resin composition, the position of the parts fixed by photocuring may shift, or the parts may peel off from the adherend. Because the shape of such optical sensor module parts is complex, when UV light is irradiated onto the parts, the amount of light irradiation varies depending on the location of the part, such as places where UV light is directly irradiated, places where UV light does not reach due to the shadow of the part, and places where reflected light from a certain surface of the part reaches and the amount of light irradiation is low, resulting in variations in curing strength. Thus, it has been found that variations in curing strength due to photocuring can cause the position of parts fixed by photocuring to shift or the parts to peel off from the adherend due to impact or vibration during subsequent processes. Furthermore, if there are areas that remain uncured because UV irradiation light does not reach them, the entire resin composition may be fully cured by subsequent thermal curing. However, it has been found that variations in curing strength due to photocuring can cause areas with weak curing strength to soften during thermal curing, potentially leading to displacement of the cured product. In addition, it has been found that variations in curing strength due to photocuring are not completely eliminated even after thermal curing following UV irradiation, making areas with weak adhesive strength more prone to peeling. In the curable resin composition of this embodiment, by using (C) a photoradical polymerization initiator that generates methyl radicals or phenyl radicals as active species, and (D) not including a thermal polymerization initiator, or including it in an amount less than a certain amount, excellent curing depth and adhesive strength can be obtained even when the amount of UV irradiation is low, and displacement and peeling of the cured product from the adherend can be reduced. The mechanism is not limited to this, but the following are possible.Methyl radicals and phenyl radicals have high polymerization initiation activity, and their small molecular weight gives them high mobility. Combined with the chain transfer function of polythiol compounds, this synergistic effect allows for a large curing depth to be achieved in areas that are not easily exposed to UV light, i.e., areas with low UV light irradiation, similar to areas that are directly exposed to UV light, i.e., areas with high UV light irradiation. Furthermore, conventional photocurable resin compositions sometimes contain a large amount of thermal polymerization initiator to account for areas that remain uncured due to lack of UV irradiation light, allowing for subsequent thermal curing. However, it has been confirmed that thermal polymerization initiators partially absorb UV light, inhibiting photocuring. In the curable resin composition of this embodiment, thermal polymerization initiators are either not included or are present in small amounts, thus reducing the inhibition of photocuring by thermal polymerization initiators.

[0026] (C) Examples of photoradical polymerization initiators that generate methyl radicals or phenyl radicals as active species include, but are not limited to, benzyl ketal-based photoradical polymerization initiators and oxime ester-based photoradical polymerization initiators. Examples of benzyl ketal-based photoradical polymerization initiators include, but are not limited to, 2,2-dimethoxy-1,2-diphenylethane-1-one (commercially available as Omnirad 651 from IGM Resins B.V.). For example, 2,2-dimethoxy-1,2-diphenylethane-1-one generates methyl radicals in the following scheme. Examples of oxime ester-based photoinitiators for radical polymerization include 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-carbazole-3-yl]-, 1-(O-acetyloxime) (trade name: Irgacure OXE-02, manufactured by BASF), methanone, ethanone, 1-[9-ethyl-6-(1,3-dioxolan,4-(2-methoxyphenoxy)-9H-carbazole-3-yl]-, 1-(O-acetyloxime) (trade name: ADEKA OPT-N-1919, manufactured by ADEKA), etc., but are not limited thereto. For example, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyloxime) generates methyl radicals according to the following scheme. These may be used alone or in combination of two or more.

[0027] In one embodiment, component (C) is a benzyl ketal-based photoinitiator for radical polymerization. In one embodiment, component (C) is an oxime ester-based photoinitiator for radical polymerization. In one embodiment, component (C) is a combination of a benzyl ketal-based photoinitiator for radical polymerization and an oxime ester-based photoinitiator for radical polymerization. The gas by-produced during radical generation by the oxime ester-based photoinitiator for photopolymerization is mainly CO ２ and since there is no adhesion or contamination to peripheral components, it is less likely to lead to corrosion of semiconductor devices and electronic components and peripheral contamination. Furthermore, the photosensitive sites generated by the decomposition of the oxime ester-based photoinitiator for photopolymerization have a relatively large molecular weight and may be incorporated into the cured matrix of the cured product, so it is difficult to be released as VOC.

[0028] From the viewpoint of radical transfer rate, component (C) is preferably a photoinitiator for radical polymerization that generates methyl radicals as active species.

[0029] From the perspective of the curing depth of the resin composition, the content of component (C) is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and even more preferably 0.05% by mass or more with respect to the total mass of the resin composition. Also, the content of component (C) is preferably, for example, 10% by mass or less, more preferably 7% by mass or less, and even more preferably 5% by mass or less with respect to the total mass of the resin composition. Further, the content of component (C) is, for example, 0.01 to 10% by mass with respect to the total mass of the resin composition, preferably 0.01 to 7% by mass, more preferably 0.03 to 5% by mass, and even more preferably 0.05% by mass to 5% by mass.

[0030] From the perspective of the curing depth of the resin composition, the amount of component (C) relative to component (A) is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.15% by mass or more. Also, the amount of component (C) relative to component (A) is preferably, for example, 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less. Further, the amount of component (C) relative to component (A) is, for example, 0.05 to 20% by mass, preferably 0.1 to 15% by mass, and more preferably 0.15 to 10% by mass.

[0031] From the perspective of the curing depth of the resin composition, the amount of component (C) relative to component (B) is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.15% by mass or more. Also, the amount of component (C) relative to component (B) is preferably, for example, 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less. Further, the amount of component (C) relative to component (B) is, for example, 0.05 to 25% by mass, preferably 0.1 to 20% by mass, and more preferably 0.15 to 15% by mass.

[0032] The amount of component (C) relative to the total amount of component (A) and component (B) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, from the viewpoint of the curing depth of the resin composition. Furthermore, the amount of component (C) relative to the total amount of component (A) and component (B) is preferably, for example, 15% by mass or less, more preferably 10% by mass or less, and even more preferably 7% by mass or less. Furthermore, the amount of component (C) relative to the total amount of component (A) and component (B) is, for example, 0.01 to 15% by mass, preferably 0.05 to 10% by mass, and more preferably 0.1 to 7% by mass.

[0033] (D) Thermal polymerization initiator The curable resin composition of this embodiment may contain (D) a thermal polymerization initiator (hereinafter also referred to as "component (D)"), and the content of (D) a thermal polymerization initiator is 0 to 10% by mass with respect to the total mass of the curable resin composition. (D) A thermal polymerization initiator is a compound that generates active species such as radicals, anions, or cations when heated, and depending on the type of active species, examples include thermal radical polymerization initiators, thermal anionic polymerization initiators, and thermal cationic polymerization initiators. The resin composition of this embodiment can obtain sufficient curing depth and adhesive strength by photocuring alone, so thermal curing after photocuring is not necessarily required. In this embodiment, the thermal polymerization initiator is preferably a thermal radical polymerization initiator or a thermal anionic polymerization initiator, and a combination of a thermal radical polymerization initiator and a thermal anionic polymerization initiator may be used.

[0034] Examples of thermal radical polymerization initiators include methyl ethyl ketone peroxide, methylcyclohexanone peroxide, methyl acetacetate peroxide, acetylacetone peroxide, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, and 2,2-bis(4,4-di-t- (Tyl peroxycyclohexyl)propane, 1,1-bis(t-butylperoxy)cyclododecane, n-butyl 4,4-bis(t-butylperoxy)valerate, 2,2-bis(t-butylperoxy)butane, 1,1-bis(t-butylperoxy)-2-methylcyclohexane, t-butyl hydroperoxide, p-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, t-hexyl hydroperoxide, dicumyl peroxide, 2,5-dimethyl- 2,5-bis(t-butylperoxy)hexane, α,α'-bis(t-butylperoxy)diisopropylbenzene, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyn-3, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, cinnamate peroxide, m-toluyl peroxide, benzoyl peroxide, diisopropyl Peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di(3-methyl-3-methoxybutyl)peroxydicarbonate, di(4-t-butylcyclohexyl)peroxydicarbonate, α,α'-bis(neodecanoylperoxy)diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3,-Tetramethylbutyl peroxyneodecanoate, 1-cyclohexyl-1-methylethyl peroxyneodecanoate, t-hexyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-hexyl peroxypivalate, t-butyl peroxypivalate, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 1-cyclohexyl-1-methylethyl peroxy-2-ethylhexanoate, t-hexyl peroxy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyisobutyrate, t-butyl peroxy Examples include, but are not limited to, ray acid, t-butyl peroxylaurate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butyl peroxyacetate, t-hexyl peroxybenzoate, t-butyl peroxy-m-toluylbenzoate, t-butyl peroxybenzoate, bis(t-butylperoxy)isophthalate, t-butyl peroxyallyl monocarbonate, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, etc. These may be used individually or in combination of two or more.

[0035] Examples of thermal anionic polymerization initiators include amines such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, triethylamine, triethylenediamine, 2-(dimethylaminomethyl)phenol, 1,8-diazabicyclo[5,4,0]undecene-7, tris(dimethylaminomethyl)phenol, and benzyldimethylamine, as well as phosphines such as triphenylphosphine, tributylphosphine, and trioctylphosphine.

[0036] Examples of thermal anionic polymerization initiators include, in addition to the above examples, "thermal latent curing catalysts," which are basic catalysts that are inert at room temperature and become activated by heating to function as polymerization catalysts. Examples of thermal latent curing catalysts include amine compounds that are solid at room temperature; amine adduct-type thermal latent curing catalysts such as reaction products of amine compounds and epoxy compounds (amine-epoxy adduct systems) and reaction products of amine compounds and isocyanate compounds or urea compounds (urea-type adduct systems); solid-disperse thermal latent curing catalysts such as microcapsule-type thermal latent curing catalysts and inclusion-type thermal latent curing catalysts. Amine compounds include aliphatic amines, aromatic amines, and heterocyclic amines.

[0037] Examples of amine compounds that are solid at room temperature include dicyandiamide, 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-methyl-1-imidazolyl-(1))-ethyl-S-triazine, and 2,4-diamino-6-(2′-methylimidazolyl-(1)′)-ethyl-S- Examples include, but are not limited to, triazine 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)-azivoyldiamide.

[0038] The amine compound used as one of the raw materials for the production of amine adduct-type thermal latent curing catalysts is one that has one or more active hydrogen atoms in its molecule that can undergo addition reactions with epoxy groups or isocyanate groups, and has at least one functional group selected from primary amino groups, secondary amino groups, and tertiary amino groups in its molecule. Examples of such amine compounds include, but are not limited to, the above-mentioned amine compounds that are solid at room temperature, as well as aliphatic amines such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4'-diamino-dicyclohexylmethane; aromatic amine compounds such as 4,4'-diaminodiphenylmethane and 2-methylaniline; heterocyclic amine compounds containing nitrogen atoms such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, and piperazine.

[0039] Furthermore, among these, compounds having a tertiary amino group in the molecule and imidazole derivatives are particularly useful as raw materials for providing thermal 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- 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-methylimidazole, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, N-β-hydroxyethylmorpholine, 2-dimethylaminoethanethiol, 2-mercaptopyridine, benzimidazole, 2 Examples include, but are not limited to, alcohols, phenols, thiols, carboxylic acids, and hydrazides having a tertiary amino group or imidazole skeleton in the molecule, such as mercaptobenzimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N,N-dimethylaminobenzoic acid, N,N-dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid, N,N-dimethylglycine hydrazide, N,N-dimethylpropionic acid hydrazide, nicotinic acid hydrazide, and isonicotinic acid hydrazide.

[0040] Examples of epoxy compounds used as raw materials for the production of amine-epoxy adduct-type thermal latent curing catalysts include, but are not limited to, polyglycidyl ethers obtained by reacting polyhydric phenols such as bisphenol A, bisphenol F, catechol, and resorcinol, or polyhydric alcohols such as glycerin and polyethylene glycol with epichlorohydrin; glycidyl ether esters obtained by reacting hydroxycarboxylic acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid with epichlorohydrin; polyglycidyl esters obtained by reacting polycarboxylic acids such as phthalic acid and terephthalic acid with epichlorohydrin; glycidylamine compounds obtained by reacting epichlorohydrin with 4,4'-diaminodiphenylmethane and m-aminophenol; and polyfunctional epoxy compounds such as epoxidized phenol novolac resins, epoxidized cresol novolac resins, and epoxidized polyolefins, as well as monofunctional epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, various phenylphenol glycidyl ethers, and glycidyl methacrylate.

[0041] Examples of isocyanate compounds used as raw materials for the production of amine-urea type adduct-type thermal latent curing catalysts include monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate; polyfunctional isocyanate compounds such as hexamethylene diisocyanate, toluene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate; and compounds containing terminal isocyanate groups obtained by the reaction of these polyfunctional isocyanate compounds with active hydrogen compounds. Examples of such terminal isocyanate group-containing compounds include, but are not limited to, addition compounds having terminal isocyanate groups obtained by the reaction of toluene diisocyanate and trimethylolpropane, and addition compounds having terminal isocyanate groups obtained by the reaction of toluene diisocyanate and pentaerythritol.

[0042] Examples of urea compounds used as raw materials for the production of amine-urea type adduct-based thermal latent curing catalysts include, but are not limited to, urea and thiourea.

[0043] Amine adduct-based thermal latent curing catalysts are, for example, combinations of (a) an amine compound and an epoxy compound, (b) these two components and an active hydrogen compound, or (c) an amine compound and an isocyanate compound and / or urea compound (two or three components). These can be easily prepared by taking and mixing each component, reacting them at a temperature from room temperature to 200°C, then cooling and solidifying them before pulverizing, or by reacting them in a solvent such as methyl ethyl ketone, dioxane, or tetrahydrofuran, removing the solvent, and then pulverizing the solid.

[0044] A microencapsulated thermal latent curing catalyst is a curing catalyst having a structure in which an amine compound, or an amine adduct compound obtained by the reaction of an amine compound with an epoxy compound, isocyanate compound, or urea compound, serves as the core, and is coated with a shell made of a synthetic resin or inorganic oxide. Examples of amine compounds include the aforementioned amine compounds. The amine compound is preferably an imidazole derivative because it exhibits suitable latent properties. 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 serve as 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 serve as the shell include silica, alumina, titania, and magnesia.

[0045] 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" (Ajinomoto Fine Techno Co., Ltd.), "Amicure PN-40" (Ajinomoto Fine Techno Co., Ltd.), "Amicure PN-50" (Ajinomoto Fine Techno Co., Ltd.), "Hardener X-3661S" (ACR Co., Ltd.), "Hardener X-3670S" (ACR Co., Ltd.), "NovaCure HX-3742" (Asahi Kasei Corporation), "NovaCure Examples include, but are not limited to, "HX-3721" (Asahi Kasei Corporation product name), "NovaCure HXA9322HP" (Asahi Kasei Corporation product name), "NovaCure HXA3922HP" (Asahi Kasei Corporation product name), "NovaCure HXA3932HP" (Asahi Kasei Corporation product name), "NovaCure HXA5945HP" (Asahi Kasei Corporation product name), "NovaCure HXA5911HP" (Asahi Kasei Corporation product name), and "NovaCure HXA9382HP" (Asahi Kasei Corporation product name). Examples of the amine-urea type adduct curing catalysts include, but are not limited to, "Fujicure FXE-1000" (T&K TOKA Corporation), "Fujicure FXR1020" (T&K TOKA Corporation), "Fujicure FXR-1030" (T&K TOKA Corporation), "Fujicure FXR1121" (T&K TOKA Corporation), "Fujicure FXR1081" (T&K TOKA Corporation), "Fujicure 1061" (T&K TOKA Corporation), and "Fujicure 1171" (T&K TOKA Corporation).

[0046] A capillary-type thermal latent curing catalyst is a curing catalyst having a structure in which guest molecules, such as amine compounds, are trapped at the molecular level within the crystalline space formed by the host molecule. An example of a commercially available capillary-type thermal latent curing catalyst is "NISSOCURE TIC-188" (product name of Nippon Soda Co., Ltd.).

[0047] As a thermal latent curing catalyst used as a thermal anionic polymerization initiator, one type may be used, or two or more types may be used in combination.

[0048] Examples of thermal cationic polymerization initiators include aromatic iodonium salts such as (4-methylphenyl)[4-(2-methylpropyl)phenyl]iodonium cation, (4-methylphenyl)(4-isopropylphenyl)iodonium cation, (4-methylphenyl)(4-isobutyl)iodonium cation, bis(4-tert-butyl)iodonium cation, bis(4-dodecylphenyl)iodonium cation, and (2,4,6-trimethylphenyl)[4-(1-methylethyl ether)phenyl]iodonium cation, as well as aromatic sulfonium salts such as diphenyl[4-(phenylthio)phenyl]sulfonium cation, triphenylsulfonium cation, and alkyltriphenylsulfonium cation.

[0049] In one embodiment, the resin composition comprises a thermal radical polymerization initiator or a thermal anionic polymerization initiator. In another embodiment, the resin composition comprises a thermal radical polymerization initiator and a thermal anionic polymerization initiator.

[0050] (D) The content of the thermal polymerization initiator is preferably 0 to 10% by mass, more preferably 0 to 8% by mass, more preferably 0 to 5% by mass, and even more preferably 0% or less than 5% by mass, based on the total mass of the resin composition, from the viewpoint of reducing inhibition of photocuring. If the resin composition contains (D) the thermal polymerization initiator, the content of (D) the thermal polymerization initiator is preferably 0.5 to 10% by mass, more preferably 0.5 to 8% by mass, even more preferably 0.5 to 5% by mass, and particularly preferably 0.5% by mass or more and less than 5% by mass.

[0051] (E) Radical polymerization inhibitor The resin composition of this embodiment may contain (E) a radical polymerization inhibitor (hereinafter also referred to as "component (E)") to the extent that it does not impair the effects of the present invention. (E) The radical polymerization inhibitor is added to improve the stability of the resin composition during storage and to suppress the occurrence of unintended radical polymerization reactions. (Meth)acrylate compounds may generate radicals on their own with a low probability, and unintended radical polymerization reactions may occur starting from these radicals. By adding a radical polymerization inhibitor, the occurrence of such unintended radical polymerization reactions can be suppressed.

[0052] Known radical polymerization inhibitors can be used, for example, at least one selected from N-nitroso-N-phenylhydroxylamine aluminum, triphenylphosphine, p-methoxyphenol, and hydroquinone. Alternatively, known radical polymerization inhibitors disclosed in Japanese Patent Publication No. 2010-117545, Japanese Patent Publication No. 2008-184514, etc., can also be used.

[0053] (E) From the viewpoint of pot life, the content of the radical polymerization inhibitor is preferably 0.0001 to 5% by mass, and more preferably 0.001 to 3% by mass, based on the total mass of the resin composition.

[0054] The resin composition of this embodiment may, if desired, further contain other additives, such as photopolymerization initiators other than component (C), fillers, thixotropes, stabilizers, coupling agents, carbon black, titanium black, ion trapping agents, leveling agents, antioxidants, defoaming agents, viscosity modifiers, flame retardants, colorants, dehydrating agents, etc., to the extent that it does not impair the spirit of this embodiment.

[0055] - Photoradical polymerization initiators other than component (C) The curable resin composition of this embodiment may contain photoradical polymerization initiators other than component (C), but the content of photoradical polymerization initiators other than component (C) is preferably less than 6% by mass, more preferably 5% by mass or less, and even more preferably 3% by mass or less, based on the total mass of the photocurable resin composition. If a large amount of photoradical polymerization initiators other than component (C) is included in addition to component (C), surface curability may increase, but a good curing depth may not be obtained. For this reason, it is preferable that the photocurable resin composition of this embodiment does not contain photoradical polymerization initiators other than component (C), or if it does contain them, it is preferably in small amounts.

[0056] Examples of photoradical polymerization initiators other than component (C) include, but are not limited to, alkylphenone compounds, acylphosphine oxide compounds, and compounds having a photosensitive site and a peroxide structure.

[0057] Examples of alkylphenone compounds include 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-hydroxycyclohexylphenyl-ketone (commercially available as Omnirad 184 from IGM Resins B.V.); 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)-butan-1-one (commercially available as Omnirad 379EG from IGM Resins B.V.); and 2-benzyl-2-(dimethylamino)-4'-morpholinbutyrophenone (commercially available as Omnirad from IGM Resins B.V.) 369) are examples, but are not limited to these.

[0058] Examples of acylphosphine oxide compounds include, but are not limited to, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (commercially available as Omnirad TPO H from IGM Resins B.V.) and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (commercially available as Omnirad 819 from IGM Resins B.V.).

[0059] Examples of compounds having a photosensitive site and a peroxide structure, or commercially available products thereof, include, but are not limited to, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone (BTTB), Perdual TA, and Perdual TX (all manufactured by NOF Corporation).

[0060] Other photoradical polymerization initiators besides component (C) include, in addition to the above-mentioned photoradical polymerization initiators, for example, 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, and benzyl Examples include, but are not limited to, dimethyl ketal, benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylic benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate, benzyl, and camphorquinone.

[0061] Furthermore, since the resin composition of this embodiment mainly contains (A) (meth)acrylate compounds and (B) thiol compounds as polymerizable compounds, and from the viewpoint of photocuring rate, it is preferable that the photocuring is performed by a radical polymerization reaction system. For this reason, it is preferable that the resin composition of this embodiment substantially does not contain photoacid generators or photobase generators, for example, that the content of photoacid generators or photobase generators is 1% by mass or less relative to the total mass of the resin composition.

[0062] Fillers are broadly classified into inorganic fillers and organic fillers.

[0063] Inorganic fillers consist of granular bodies formed from inorganic materials and are not particularly limited as long as they have the effect of lowering the coefficient of thermal expansion when added. 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. One or more inorganic fillers may be used, or two or more may be used in combination. As an inorganic filler, silica filler is preferred because it allows for a high filling amount. Amorphous silica is preferred. The surface of the inorganic filler may be surface-treated with a coupling agent such as a silane coupling agent.

[0064] Examples of organic fillers include polytetrafluoroethylene (PTFE) fillers, silicone fillers, acrylic fillers, fillers with a urethane skeleton, fillers with a butadiene skeleton, and styrene fillers. Organic fillers may be surface-treated.

[0065] The shape of the filler is not particularly limited and may be spherical, flake-shaped, needle-shaped, irregular, or any other shape.

[0066] The average particle size of the filler is preferably 6.0 μm or less, more preferably 5.0 μm or less, and even more preferably 4.0 μm or less. In this specification, unless otherwise specified, the average particle size refers to the volume-based median diameter (d) measured by laser diffraction in accordance with ISO-13320 (2009). ５０This refers to the filler. By keeping the average particle size of the filler below the upper limit, the settling of the filler can be suppressed, and the formation of coarse particles can be suppressed, thereby reducing wear on the jet dispenser nozzle and preventing the curable resin composition discharged from the jet dispenser nozzle from scattering outside the desired area. The lower limit of the average particle size of the filler is not particularly limited, but from the viewpoint of the viscosity of the curable resin composition, it is preferably 0.005 μm or more, and more preferably 0.1 μm or more. Fillers with different average particle sizes may be used in combination.

[0067] • Swixer Examples of swixers include silica such as colloidal silica, hydrophobic silica, fine silica, and nanosilica, as well as bentonite, acetylene black, and Ketjenblack. Nanosilica is preferred from the viewpoint of maintaining its shape after coating. Furthermore, from the viewpoint of preventing the resin composition from getting stuck during bonding and improving moisture resistance and adhesion, nanosilica with an average particle size of 10 to 750 nm is more preferred, and nanosilica with an average particle size of 20 to 600 nm is even more preferred. Commercially available products include, but are not limited to, hydrophobic fumed silica manufactured by CABOT (product name: CAB-O-SIL® TS720, average particle size: 12 nm), hydrophobic fumed silica manufactured by Nippon Aerosil (product name: R805, average particle size: 20 nm), and amorphous silica manufactured by Nippon Shokubai (product name: Seahostar KE-P10, average particle size: 100 nm). Here, the average particle size of the nanosilica particles is measured using a dynamic light scattering nanotrac particle size analyzer. The thixotrope may be used alone or in combination of two or more types.

[0068] • Stabilizers Various known acidic compounds can be used as stabilizers. Preferably, the acidic compound is at least one selected from the group consisting of boric acid ester compounds, phosphoric acid compounds, alkyl phosphoric acid ester compounds, sulfonic acid compounds, aluminum chelates, condensates of aluminum chelates and silanol compounds, and organic acids.

[0069] Examples of borate ester compounds include 2,2'-oxybis(5,5'-dimethyl-1,3,2-oxaborinane), trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, trimethoxyboroxine, 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, tripenzyl borate, triphenyl borate, tri-o-tolyl borate, tri-m-tolyl borate, triethanolamine borate, and the like. Among borate ester compounds, those that are liquid at room temperature (25°C) are preferred because they can keep the viscosity of the formulation low. Examples of alkyl phosphate ester compounds include trimethyl phosphate and tributyl phosphate. Examples of sulfonic acid compounds include p-toluenesulfonic acid. As an aluminum chelate, for example, aluminum chelate A (manufactured by Kawaken Fine Chemicals Co., Ltd.) can be used. As a condensate of aluminum chelate and silanol compound, for example, a condensate of aluminum chelate and triphenylsilanol can be used. As an organic acid, for example, barbituric acid can be used.

[0070] The resin composition of this embodiment preferably contains substantially no solvent, for example, 1% by mass or less of the total mass of the resin composition, from the viewpoint of preventing a reduction in curing strength due to photocuring. This also allows for a reduction in the amount of volatile organic compounds (VOCs). Examples of solvents include 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 oil, terpineol, isobornyl acetate, etc.), halogenated solvents (dichloromethane, chloroform, etc.), and other organic solvents common in the field of curable compositions.

[0071] The resin composition of this embodiment preferably contains substantially no sensitizer, for example, 1% by mass or less of the sensitizer content relative to the total mass of the resin composition, from the viewpoint of stability against ambient light and preventing only the surface layer from hardening due to light. Suitable sensitizers include unsaturated ketones represented by chalcone derivatives, dibenzalacetone, etc., 1,2-diketone derivatives represented by benzyl and camphorquinone, etc., benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiaidine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, and tetrapyradinoporphyrazine derivatives. Examples include phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxaliloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrillium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospilopyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler ketone derivatives, α-acyloxyesters, acylphosphine oxides, methylphenylglyoxylates, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone, and the like.

[0072] In the curable resin composition of this aspect, it is preferable that the first to third shear strength change rates obtained by the following formulas (1) to (3) are all 60% or less. First shear strength change rate (%) = {{|(X2 - X1)| / X1}} × 100... (1) Second shear strength change rate (%) = {{|(X3 - X2)| / X2}} × 100... (2) Third shear strength change rate (%) = {{|(X3 - X1)| / X1}} × 100... (3) In the formula, X1 is the shear strength when the curable resin composition is cured at a UV irradiation amount of 100 mJ / cm ２ and X2 is the shear strength when the curable resin composition is cured at a UV irradiation amount of 200 mJ / cm ２ and X3 is the shear strength when the curable resin composition is cured at a UV irradiation amount of 500 mJ / cm ２ By satisfying this change rate, a curable resin composition capable of reducing the displacement and peeling of the cured product from the adherend is provided. The inventors of the present invention, as one of the solutions for reducing the displacement and peeling of the cured product from the adherend, reduce the change rate of the adhesion strength of the cured product to the adherend under each light irradiation amount under the condition that the light irradiation amount varies during photocuring. found that.

[0073] In the curable resin composition of this aspect, it is preferable that the fourth to sixth shear strength change rates obtained by the following formulas (4) to (6) are all 30% or less. Fourth shear strength change rate (%) = {{|(Y2 - Y1)| / Y1}} × 100... (4) Fifth shear strength change rate (%) = {{|(Y3 - Y2)| / Y2}} × 100... (5) Sixth shear strength change rate (%) = {{|(Y3 - Y1)| / Y1}} × 100... (6) In the formula, Y1 is the shear strength when the curable resin composition is cured at a UV irradiation amount of 100 mJ / cm ２ and then cured at 80°C for 60 minutes, and Y2 is the shear strength when the curable resin composition is cured at a UV irradiation amount of 200 mJ / cm ２ and then cured at 80°C for 60 minutes, and Y3 is the shear strength when the curable resin composition is cured at a UV irradiation amount of 500 mJ / cm ２This is the shear strength after curing and then curing at 80°C for 60 minutes.

[0074] In this specification, shear strength can be calculated, for example, by printing a resin composition onto a specific substrate with a diameter of φ2.0 mm and a thickness of 0.12 mm using a stencil printing method, placing a 3.0 mm × 1.5 mm, 0.5 mm thick alumina chip on the printed resin composition, curing under certain curing conditions, and then puncturing the alumina chip from the side with a bond tester, and taking the value when the alumina chip peels off.

[0075] The viscosity of the resin composition in this embodiment at 25°C is preferably 0.5 to 80 Pa·s. The viscosity can be adjusted as appropriate depending on the application and application location of the resin composition. In one embodiment, the viscosity of the resin composition at 25°C may be 30 to 65 Pa·s. In one embodiment, the viscosity of the resin composition at 25°C may be 1.0 to 15 Pa·s. In this specification, unless otherwise specified, viscosity is expressed as a value measured in accordance with Japanese Industrial Standard JIS K6833. Specifically, it can be determined by measuring at 25°C and a rotation speed of 50 rpm using an HBDV or RV type viscometer depending on the viscosity range. There are no particular restrictions on the equipment, rotor, or measurement range used.

[0076] The thixotropic index (TI) value of the resin composition in this embodiment at 25°C is preferably 1.5 to 8.0. The thixotropic index value can be adjusted as appropriate depending on the application and application location of the resin composition. In one embodiment, the thixotropic index (TI) value of the resin composition at 25°C may be 3.0 to 7.0. In another embodiment, the thixotropic index (TI) value of the resin composition at 25°C may be 2.0 to 5.0. In this specification, the thixotropic index (TI) value can be determined by measuring the viscosity at 5 rpm and 50 rpm at 25°C using an HBDV or RV viscometer, depending on the viscosity range, and using the following formula: [TI value] = [Viscosity at 5 rpm] / [Viscosity at 50 rpm]

[0077] In one embodiment, the viscosity of the resin composition at 25°C is 0.5 to 80 Pa·s, and the thixotropic index (TI) value of the resin composition at 25°C is 1.5 to 8.0. In another embodiment, the viscosity of the resin composition at 25°C is 30 to 65 Pa·s, and the thixotropic index (TI) value of the resin composition at 25°C is 3.0 to 7.0. In yet another embodiment, the viscosity of the resin composition at 25°C is 1.0 to 15 Pa·s, and the thixotropic index (TI) value of the resin composition at 25°C is 2.0 to 5.0.

[0078] The resin composition can be obtained, for example, by stirring, melting, mixing, and / or dispersing components (A) to (C), component (D) if necessary, and other additives, either simultaneously or separately, while applying heat treatment as needed. The apparatus for these mixing, stirring, and dispersion processes is not particularly limited. Apparatus such as a Leikai mill, Henschel mixer, three-roll mill, ball mill, planetary mixer, and bead mill, all equipped with stirring and heating devices, can be used. These apparatuses may also be used in appropriate combinations.

[0079] 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 contained in two or more containers, depending on its intended use. In the case of a two-component (or multi-component) resin composition, components (A) to (C) and other optional components as needed can be selected in the same way as for a one-component composition. Also, in the case of a two-component (or multi-component) resin composition, components (A) to (C) and other optional components as needed can be divided into two or multiple liquids in any way without particular restriction. When divided into two or multiple liquids in any way, one or more components selected from components (A) to (C) and other optional components as needed may be contained in each liquid, components (A) to (C) may be contained in one liquid, or there may be a liquid consisting only of components (A) to (C) and / or other optional components as needed. For example, when dividing into liquid A and liquid B, the division may be as follows: liquid A: component (A), liquid B: component (B) and component (C); liquid A: component (A) and component (C), liquid B: component (B); liquid A: component (A) and component (D), liquid B: component (B) and component (C); or liquid A: component (A), liquid B: component (B), component (C), and component (D). If components (A) to (C) are contained in liquid A and the other components are contained in liquid B, liquid A alone, or liquids A and B together, can be considered as the resin composition of this embodiment. On the other hand, if components (A) to (C) are each contained in separate liquids, the respective liquids together can be considered as the resin composition of this embodiment. Examples of cases in which components (A) to (C) are contained in separate liquids include, for example, a resin composition in which components (A) to (C) are divided into two or more containers, specifically a kit composed of multiple liquids containing any of components (A) to (C).

[0080] The resin composition obtained in this way has photocurability and thermocurability.

[0081] When a resin composition is photocured, the light used for irradiation is, for example, ultraviolet (UV) light. In this specification, ultraviolet light refers to light rays with a wavelength in the range of 200 nm to 410 nm. The resin composition of this embodiment can be cured by irradiation at any of the wavelengths of 365 nm, 385 nm, or 405 nm. The irradiation dose of the light is 50 mJ / cm². ２ ~2000mJ / cm ２ It is preferable that this is the case. The resin composition of this embodiment contains a photoradical polymerization initiator that generates a methyl radical or a phenyl radical as an active species, thereby enabling a large curing depth even with a small amount of light irradiation.

[0082] When the resin composition is heat-cured, it can be cured by, for example, a heat treatment at 60 to 200°C for 0.1 to 300 minutes. Under conditions of 100°C, curing is preferably within 5 hours, more preferably within 3 hours, and even more preferably within 1 hour. When the resin composition of this embodiment is used in the manufacture of semiconductor devices or electronic components that include parts that degrade under high-temperature conditions, it is preferable to heat-cur the composition at a temperature of 50 to 90°C for 30 to 120 minutes. For example, when the resin composition is used in an optical sensor module, the curing temperature is preferably 50 to 90°C, and more preferably 70 to 90°C.

[0083] The resin composition of this embodiment can be used, for example, as an adhesive or sealant for fixing, joining, or protecting semiconductor devices or electronic components or the components that make them up, or as a raw material thereof.

[0084] [Adhesive or Sealant] An adhesive or sealant according to one aspect of the present invention comprises the resin composition of the above aspect. This adhesive or sealant enables good fixation, bonding, or protection of 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 constituting semiconductor devices or electronic components. Examples of semiconductor devices include, but are not limited to, HDDs, semiconductor elements, optical sensor modules such as image sensor modules and TOF sensor modules, other semiconductor modules, and integrated circuits.

[0085] 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 contained in two or more containers, depending on its application. When used as a two-component (or multi-component) adhesive or sealant, components (A) to (C) and other optional components as needed can be selected in the same way as for the one-component type, and the curing method is also the same as for the one-component type. Furthermore, when used as a two-component (or multi-component) adhesive or sealant, components (A) to (C) and other optional components as needed can be divided into two or multiple liquids in any way without particular restriction. When divided into two or multiple liquids in any way, one or more components selected from components (A) to (C) and other optional components as needed may be contained in each liquid, components (A) to (C) may be contained in one liquid, or there may be a liquid consisting only of components (A) to (C) and / or other optional components as needed. For example, when dividing into liquid A and liquid B, the division may be as follows: liquid A: component (A), liquid B: component (B) and component (C); liquid A: component (A) and component (C), liquid B: component (B); liquid A: component (A) and component (D), liquid B: component (B) and component (C); or liquid A: component (A), liquid B: component (B), component (C), and component (D). If components (A) to (C) are contained in liquid A and the other components are contained in liquid B, liquid A alone, or liquids A and B together, can be considered as the adhesive or sealant of this embodiment. On the other hand, if components (A) to (C) are each contained in separate liquids, the respective liquids together can be considered as the adhesive or sealant of this embodiment. Examples of cases where components (A) to (C) are each contained in separate liquids include, for example, an adhesive or sealant in which components (A) to (C) are divided into two or more containers, specifically a kit composed of multiple liquids containing any of components (A) to (C).

[0086] [Cured product of resin composition, adhesive or sealant] A cured product according to one aspect of the present invention is a cured product obtained by curing the resin composition, adhesive or sealant according to the above aspect.

[0087] [Semiconductor devices, electronic components] A semiconductor device or electronic component according to one aspect of the present invention includes a cured product according to the above aspect. Here, "semiconductor device" refers to all devices that can function by utilizing semiconductor properties, and includes 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.

[0088] 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 % refer to parts by mass and mass%, respectively, unless otherwise specified.

[0089] [Examples 1-14, Comparative Examples 1-2] Resin compositions were prepared by mixing predetermined amounts of each component using a three-roll mill according to the formulations shown in Table 1. In Table 1, the amount of each component is expressed in parts by mass. The components used in the examples and comparative examples are as follows.

[0090] • (A) (meth)acrylate compounds (component (A)) (A-1): Dimethylol-tricyclodecane diacrylate (product name: Light Acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd., (meth)acryloyl group equivalent: 152 g / eq) (A-2): Polyester acrylate (product name: M7100, manufactured by Toagosei Co., Ltd., (meth)acryloyl group equivalent: 152 g / eq) (A-3): Tricyclodecane dimethanol dimethacrylate (product name: DCP, manufactured by Shin Nakamura Chemical Industry Co., Ltd., (meth)acryloyl group equivalent: 169 g / eq) • (B) Polythiol compounds (component (B)) (B-1): Pentaerythritol tetrakis (3-mercaptopropionate) (product name: PEMP, manufactured by SC Organic Chemical, thiol group equivalent: 122 g / eq) (B-2): 1,3,4,6-tetrakis(3-mercaptopropyl) glycoluryl (product name: C3 TS-G, manufactured by Shikoku Chemicals, Inc., thiol equivalent: 110 g / eq) ・(C) Photoradical polymerization initiator that generates methyl radicals or phenyl radicals as active species (component (C)) (C-1): 2,2-dimethoxy-1,2-diphenylethane-1-one represented by the following formula (product name: Omnirad 651, manufactured by IGM Resins B.V.) (C-2): Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyloxime) (Product name: Irgacure OXE-02, manufactured by BASF) • (C') Photopolymerization initiator other than component (C) (C'-1): 1-hydroxycyclohexyl-phenyl ketone represented by the following formula (product name: Omnirad 184, manufactured by IGM Resins BV) (C'-2): 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, represented by the following formula (product name: Omnirad 907, manufactured by IGM Resins BV) • (D) Thermal polymerization initiator (D-1): Amine-epoxy adduct type thermal latent curing catalyst (product name: Novacure HXA9322HP, core-shell type, manufactured by Asahi Kasei Corporation) (D-2): Amine adduct type thermal latent curing catalyst (product name: Fujicure FXR-1121, mixture of epoxy compound modified imidazoles and urea-modified amines, solid at room temperature, manufactured by T&K TOKA Corporation) • (E) Radical polymerization inhibitor (component (E)) (E-1) N-nitroso-N-phenylhydroxylamine aluminum (manufactured by Wako Pure Chemical Industries, Ltd., molecular weight: 488.33) • (F) Filler (component (F)) (F-1): Surface-treated silica filler (product name: SE5200SEE, average particle size 2 μm, manufactured by Admatex Co., Ltd.)

[0091] The following measurements were performed on the samples obtained for the examples and comparative examples.

[0092] [Photocuring Depth] The photocuring depth of the resin composition was measured using a jig as shown in Figure 1 (schematic diagram of a side view) and Figure 2 (schematic diagram of a top view). Specifically, two heat-resistant tapes 20 (150 μm thick) were attached to a black resin plate 10a (50 mm wide x 25 mm long x 1.5 mm thick) at a distance of 10 mm apart. The resin composition 30 was applied between the two heat-resistant tapes 20 to the same thickness as the heat-resistant tapes 20. The two heat-resistant tapes 20 and the resin composition 30 were sandwiched between resin plate 10a and another resin plate 10b, and both ends of the resin plates were secured with clips (not shown) to prepare a measurement sample. UV irradiation was performed from the top of the measurement sample prepared in this way. The UV irradiation conditions at this time were a UV wavelength of 365 nm (LED lamp) and a UV irradiation dose of 100 mJ / cm². ２ , 200 mJ / cm ２ and 500 mJ / cm ２ These were the three types. Specifically, the LED square irradiator Omnicure was used as the irradiator. （R） Using the AC475-365 SET 2200N mini, the UV irradiator's intensity was set to 400 W / cm². ２The sample was fixed in place and passed under the irradiation device at speeds adjusted to achieve a predetermined UV irradiation dose. After UV irradiation, one of the resin plates 10b that was holding the sample was peeled off, the uncured portion attached to the cured material was removed, and the length L (mm) of the cured portion was measured using a measuring microscope. The results are shown in Table 1.

[0093] [Photocuring Adhesion Strength (Shear Strength)] A resin composition was stencil-printed onto a glass plate with a diameter of φ2.0 mm and a thickness of 0.12 mm. An alumina chip measuring 3.0 mm × 1.5 mm and 0.5 mm thick was placed on top of the printed resin composition. Test specimens were then prepared by UV curing (n=10). The UV irradiation conditions at this time were a UV wavelength of 365 nm (LED lamp) and a UV irradiation dose of 100 mJ / cm². ２ , 200 mJ / cm ２ and 500 mJ / cm ２ These were the three types. Specifically, the LED square irradiator Omnicure was used as the irradiator. （R） Using the AC475-365 SET 2200N mini, the UV irradiator's intensity was set to 400 W / cm². ２ The test specimens were fixed in place and passed under the irradiation device at speeds adjusted to achieve a predetermined UV irradiation dose. After UV irradiation, the alumina chips on the glass plate were punctured from the side using a Nordson Advanced Technologies Series 4000 universal bond tester, and the shear strength (N) was calculated from the value obtained when the alumina chips peeled off. The results are shown in Table 1.

[0094] [Photo- and Thermo-curing Adhesion Strength (Shear Strength)] Test specimens cured to UV light using the same method as for photo-curing adhesion strength (shear strength) described above were left to stand in a forced-air dryer at 80°C for 60 minutes to further thermo-cur the resin composition. An alumina chip on a glass plate was punctured from the side using a Nordson Advanced Technologies Series 4000 universal bond tester, and the shear strength (N) was calculated from the value obtained when the alumina chip peeled off. The results are shown in Table 1.

[0095] [Calculation of Shear Strength Change Rate] The first to third shear strength change rates were calculated using the following formulas (1) to (3). First shear strength change rate (%) = {|(X2-X1)| / X1} × 100 ... (1) Second shear strength change rate (%) = {|(X3-X2)| / X2} × 100 ... (2) Third shear strength change rate (%) = {|(X3-X1)| / X1} × 100 ... (3) In the formulas, X1 is the curable resin composition when exposed to UV irradiation at a dose of 100 mJ / cm². ２ X2 is the shear strength when cured, where X2 is the curable resin composition when exposed to UV irradiation at a dose of 200 mJ / cm². ２ X3 is the shear strength when cured, where X3 is the curable resin composition when exposed to UV irradiation at a dose of 500 mJ / cm². ２ This is the shear strength when cured. The percentage change in shear strength for the fourth to sixth shear strengths was calculated using the following equations (4) to (6). Percentage change in fourth shear strength (%) = {|(Y2-Y1)| / Y1} × 100 ... (4) Percentage change in fifth shear strength (%) = {|(Y3-Y2)| / Y2} × 100 ... (5) Percentage change in sixth shear strength (%) = {|(Y3-Y1)| / Y1} × 100 ... (6) In the equations, Y1 is the curable resin composition when exposed to UV irradiation at a dose of 100 mJ / cm². ２ Y2 is the shear strength after curing at 80°C for 60 minutes, where Y2 is the shear strength after curing the curable resin composition with a UV irradiation dose of 200 mJ / cm². ２ Y3 is the shear strength after curing at 80°C for 60 minutes, where Y3 is the shear strength after curing the curable resin composition with a UV irradiation dose of 500 mJ / cm². ２ This is the shear strength after curing at 80°C for 60 minutes. The results are shown in Table 1.

[0096] [Viscosity and TI Value Measurement] The viscosity of the resin composition is measured at 25°C and a rotation speed of 50 rpm using an HBDV or RV type viscometer, depending on the viscosity range, in accordance with the Japanese Industrial Standard JIS K6833. The thixotropic index (TI) value of the resin composition at 25°C is calculated by measuring the viscosity at 5 rpm and the viscosity at 50 rpm using an HBDV or RV type viscometer, depending on the viscosity range, and using the following formula: [TI value] = [Viscosity at 5 rpm] / [Viscosity at 50 rpm]

[0097]

[0098] As can be seen from Table 1, the curable resin compositions of Examples 1 to 14 that satisfy the configuration of the present invention obtained excellent curing depth and adhesive strength even when the UV light irradiation dose was low, as well as when the UV light irradiation dose was high, and showed little variation in curing depth and adhesive strength. On the other hand, the curable resin compositions of Comparative Examples 1 and 2, which did not contain the photoradical polymerization initiator of component (C) and contained a photopolymerization initiator other than component (C) (C'), showed large variation in curing depth and adhesive strength when the UV light irradiation dose was low and when the UV light irradiation dose was high.

[0099] The disclosure of Japanese Patent Application No. 2024-196938 (filing date: November 11, 2024) is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted to be incorporated by reference.

[0100] 10a Resin plate 10b Resin plate 20 Heat-resistant tape 30 Resin composition

Claims

1. A curable resin composition comprising (A) a (meth)acrylate compound, (B) a polythiol compound, and (C) a photoradical polymerization initiator that generates a methyl radical or a phenyl radical as an active species, wherein the content of component (C) is 0.01 to 10% by mass with respect to the total mass of the curable resin composition, and the curable resin composition may also contain (D) a thermal polymerization initiator, wherein the content of (D) the thermal polymerization initiator is 0 to 10% by mass with respect to the total mass of the curable resin composition.

2. The curable resin composition according to claim 1, wherein the first to third shear strength change rates obtained by each of the following formulas (1) to (3) are all 60% or less: First shear strength change rate (%) = {|(X2-X1)| / X1} × 100 ... (1) Second shear strength change rate (%) = {|(X3-X2)| / X2} × 100 ... (2) Third shear strength change rate (%) = {|(X3-X1)| / X1} × 100 ... (3) In the formulas, X1 is the curable resin composition when exposed to UV irradiation at a dose of 100 mJ / cm² ２ X2 is the shear strength when cured, where X2 is the curable resin composition when exposed to UV irradiation at a dose of 200 mJ / cm². ２ X3 is the shear strength when cured, where X3 is the curable resin composition when exposed to UV irradiation at a dose of 500 mJ / cm². ２ This is the shear strength when hardened.

3. The curable resin composition according to claim 2, wherein the fourth to sixth shear strength change rates calculated by each of the following formulas (4) to (6) are all 30% or less: Fourth shear strength change rate (%) = {|(Y2-Y1)| / Y1} × 100 ... (4) Fifth shear strength change rate (%) = {|(Y3-Y2)| / Y2} × 100 ... (5) Sixth shear strength change rate (%) = {|(Y3-Y1)| / Y1} × 100 ... (6) In the formulas, Y1 is the curable resin composition when exposed to UV irradiation at a dose of 100 mJ / cm². ２ Y2 is the shear strength after curing at 80°C for 60 minutes, where Y2 is the shear strength after curing the curable resin composition with a UV irradiation dose of 200 mJ / cm². ２ Y3 is the shear strength after curing at 80°C for 60 minutes, where Y3 is the shear strength after curing the curable resin composition with a UV irradiation dose of 500 mJ / cm². ２ This is the shear strength after curing and then curing at 80°C for 60 minutes.

4. The curable resin composition according to any one of claims 1 to 3, wherein the ratio of the number of thiol group equivalents of component (B) to the number of (meth)acryloyl group equivalents of component (A) ([number of thiol group equivalents of component (B)] / [number of (meth)acryloyl group equivalents of component (A)]) is 0.5 to 1.

8.

5. A curable resin composition according to any one of claims 1 to 4, wherein the viscosity at 25°C is 0.5 to 80 Pa·s and the thixotropic index (TI) value at 25°C is 1.5 to 8.

0.

6. A curable resin composition according to any one of claims 1 to 5, which is substantially free of solvents.

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

8. The adhesive or sealant according to claim 7, used for fixing, bonding, or protecting components constituting an optical sensor module.

9. A cured product obtained by curing a curable resin composition according to any one of claims 1 to 6, or an adhesive or sealant according to claim 7 or 8.

10. A semiconductor device or electronic component comprising the cured product described in claim 9.

11. The semiconductor device or electronic component according to claim 10, which is an optical sensor module.

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