Photocurable resin composition, adhesive, sealant, coating agent, cured product, semiconductor device, electronic component, and curing, bonding, sealing, and coating methods using photocurable resin composition

Abstract

The present invention addresses the problem of providing a photocurable resin composition for curing using a photon upconversion mechanism and a method for using such a photocurable resin composition, with which it is possible to achieve a favorable cure degree by prolonging a photon upconversion emission lifetime, while also providing an adhesive, sealant, or coating agent including same, a cured product thereof, a semiconductor device or electronic component including said cured product, and a curing method, bonding method, sealing method, and coating method using the photocurable resin composition.　Provided is a photocurable resin composition comprising (A) a polymerizable compound and (B) triplet-triplet annihilation photon upconversion particles, and satisfying at least one of: feature (a) in which the polymerizable compound (A) includes a maleimide compound; and feature (b) in which the photocurable resin composition includes (C) a photopolymerization initiator. Also provided are: an adhesive, sealant, or coating agent including said photocurable resin composition; a cured product thereof; a semiconductor device or electronic component including the cured product; and a curing method, bonding method, sealing method, and coating method using the photocurable resin composition.

Description

Photocurable resin composition, adhesive, sealing material, coating agent, cured product, semiconductor device, electronic component, and curing, adhesion, sealing and coating methods using the photocurable resin composition

[0001] The present invention relates to a photocurable resin composition, an adhesive, a sealing material or a coating agent containing the same, a cured product thereof, a semiconductor device or electronic component containing the cured product, and a curing method, an adhesion method, a sealing method and a coating method using the photocurable resin composition.

[0002] Adhesives that are temporarily fixed by ultraviolet (UV) irradiation and then fully cured by heat are used in many fields (for example, Patent Documents 1 and 2). If the adhesive contains fillers, these fillers may act as shields to the UV irradiation light, or if the area to which the adhesive is applied has a complex shape, the UV irradiation light may be blocked, resulting in areas within the adhesive that are not reached by the UV irradiation light. For this reason, this type of adhesive is used in applications where there are areas that are not reached by the UV irradiation light and remain uncured, with the aim of fully curing by heat.

[0003] JP 2009-51954 A International Publication No. 2005 / 052021

[0004] On the other hand, from the viewpoint of improving productivity and taking into consideration the application to heat-sensitive members, there is a demand for a photocurable resin composition that can be cured by light irradiation alone.

[0005] The present inventors focused on photon upconversion materials capable of converting long-wavelength light to short-wavelength light. When irradiated with specific light, photon upconversion materials generate high-energy states through processes such as multiphoton excitation and triplet-triplet annihilation, and during the relaxation process, emit light with a shorter wavelength than the incident light. The present inventors confirmed that by incorporating this photon upconversion material into a resin composition and irradiating the resin composition with long-wavelength light, the photon upconversion material performs wavelength conversion within the resin composition, and the photon upconversion emission activates a photopolymerization initiator, promoting polymerization of a polymerizable compound in the resin composition, thereby promoting curing of the resin composition. Long-wavelength light has a longer penetration distance into a target object than high-energy short-wavelength light (e.g., 365 nm UV light). It was confirmed that irradiation with long-wavelength light promotes curing of the resin composition through photon upconversion emission, even in areas where UV irradiation is difficult. Based on these findings, Japanese Patent Application No. 2023-119225 (July 21, 2023) was filed for a photocurable resin composition containing a photon upconversion material and a method of using the same.

[0006] As a result of further investigation, it was found that in the curing process of a photocurable resin composition using the triplet-triplet annihilation photon upconversion mechanism, the triplet-triplet annihilation photon upconversion luminescence intensity attenuates over time. When the triplet-triplet annihilation photon upconversion luminescence intensity attenuates, the degree of curing of the photocurable resin composition may be insufficient.

[0007] Therefore, an object of the present invention is to provide a photocurable resin composition for curing using a triplet-triplet annihilation photon upconversion mechanism and a method for using the same, which can achieve a good degree of curing by extending the triplet-triplet annihilation photon upconversion light emission duration, an adhesive, a sealant, or a coating agent containing the same, a cured product thereof, a semiconductor device or electronic component containing the cured product, and a curing method, bonding method, sealing method, and coating method using the photocurable resin composition.

[0008] The specific means for solving the above problems are as follows. The embodiments of the present invention include the following photocurable resin compositions, adhesives, encapsulants or coatings, cured products, semiconductor devices or electronic components, methods for producing cured products, methods for curing photocurable resin compositions, methods for using photocurable resin compositions, methods for bonding, methods for encapsulating, and methods for coating. [1] A photocurable resin composition comprising (A) a polymerizable compound and (B) triplet-triplet annihilation photon upconversion particles, satisfying at least one of the following features (a) and (b): (a) the polymerizable compound (A) comprises a maleimide compound; (b) the photocurable resin composition comprises (C) a photopolymerization initiator. [2] The photocurable resin composition according to [1], wherein the (B) triplet-triplet annihilation photon upconversion particles are particles in which a triplet-triplet annihilation photon upconversion material is dispersed or encapsulated in an organic polymer matrix. [3] The photocurable resin composition according to [1] or [2], wherein, if the above characteristic (a) is satisfied, the maleimide compound is a maleimide compound having an absorption wavelength of 500 nm or less, and if the above characteristic (b) is satisfied, the (C) photopolymerization initiator is a photopolymerization initiator that is activated by light with a wavelength of 500 nm or less. [4] The photocurable resin composition according to any one of [1] to [3], wherein the (C) photopolymerization initiator is a photoradical polymerization initiator, a photoacid generator, a photobase generator, or any combination thereof. [5] The photocurable resin composition according to any one of [1] to [4], wherein the emission wavelength of the (B) triplet-triplet annihilation photon upconversion particles includes a wavelength of 500 nm or less. [6] The photocurable resin composition according to any one of [1] to [5], wherein the (A) polymerizable compound is a radical polymerizable compound, a cationic polymerizable compound, an anionic polymerizable compound, or any combination thereof. [7] The photocurable resin composition according to any one of [1] to [6], wherein the content of component (B) in the photocurable resin composition is 0.01 to 80 parts by mass per 100 parts by mass of the total amount of the polymerizable compound (A).[8] The photocurable resin composition according to any one of [1] to [7], wherein, when the above characteristic (b) is satisfied, the content of (C) photopolymerization initiator in the photocurable resin composition is 0.01 to 15 parts by mass per 100 parts by mass of the total polymerizable compound (A). [9] The photocurable resin composition according to any one of [1] to [8] for use in curing by irradiation with light with a wavelength of more than 500 nm.

[10] The photocurable resin composition according to any one of [1] to [9], for use as an adhesive, encapsulant, or coating agent for semiconductor devices or electronic components.

[11] An adhesive, encapsulant, or coating agent containing the photocurable resin composition according to any one of [1] to

[10] .

[12] A cured product obtained by curing the photocurable resin composition according to any one of [1] to

[10] , or the adhesive, encapsulant, or coating agent according to

[11] .

[13] A semiconductor device or electronic component containing the cured product according to

[12] .

[14] A method for producing a cured product, comprising irradiating a photocurable resin composition according to any one of [1] to

[10] above, or an adhesive, sealant, or coating agent according to

[11] above, with light having a wavelength greater than 500 nm.

[15] A method for curing a photocurable resin composition, comprising irradiating a photocurable resin composition according to any one of [1] to

[10] above with light having a wavelength greater than 500 nm.

[16] Use of a photocurable resin composition according to any one of [1] to

[10] above for curing by irradiation with light having a wavelength greater than 500 nm.

[17] A method for bonding at least two parts with a photocurable resin composition, comprising the steps of: applying a photocurable resin composition according to any one of [1] to

[10] above to at least one of the at least two parts; and irradiating at least one of the at least two parts, the photocurable resin composition, or both thereof with light having a wavelength greater than 500 nm.

[18] A method for sealing gaps between or within parts with a photocurable resin composition, comprising the steps of: applying or injecting a photocurable resin composition according to any one of items [1] to

[10] into the gap between or within parts; and irradiating the photocurable resin composition with light having a wavelength greater than 500 nm.

[19] A method for coating a surface of an object with a photocurable resin composition, comprising the steps of: applying the photocurable resin composition according to any one of [1] to

[10] to the object; and irradiating the photocurable resin composition with light having a wavelength of more than 500 nm.

[0009] According to aspects of the present invention, in a photocurable resin composition for curing using a triplet-triplet annihilation photon upconversion mechanism and a method for using the same, a good degree of curing can be achieved by extending the triplet-triplet annihilation photon upconversion light emission duration. The present invention also provides a photocurable resin composition, an adhesive, a sealant, or a coating agent containing the same, a cured product thereof, a semiconductor device or electronic component containing the cured product, and a curing method, an adhesion method, a sealing method, and a coating method using the photocurable resin composition.

[0010] This figure shows the change over time in the normalized emission intensity of triplet-triplet annihilation photon upconversion emission for the resin compositions of Example 1 and Reference Example 1.

[0011] As used herein, "ultraviolet light" refers to light with a wavelength of 200 nm to 380 nm, "visible light" refers to light with a wavelength of 380 nm to 700 nm, "near-infrared light" refers to light with a wavelength of 700 nm to 2500 nm, and "(mid) infrared light" refers to light with a wavelength of 2.5 μm to 25 μm. In this specification, following the convention in the field of synthetic resins, the term "resin," which normally refers to a polymer (particularly a synthetic polymer), may be used to refer to the components constituting a curable resin composition before curing, even when the component is not a polymer, for example, a prepolymer compound before curing. As used herein, the term "(meth)acryloyl group" includes both a methacryloyl group and an acryloyl group. Furthermore, the term "(meth)acrylate compound" includes both an acrylate compound and a methacrylate compound. Furthermore, in this specification, a "photocurable resin composition" may be simply referred to as a "resin composition."

[0012] [Photocurable Resin Composition] The photocurable resin composition of one embodiment of the present invention is a photocurable resin composition comprising: (A) a polymerizable compound; and (B) triplet-triplet annihilation photon upconversion particles, and satisfies at least one of the following characteristics (a) and (b): (a) The (A) polymerizable compound comprises a maleimide compound; (b) The photocurable resin composition comprises (C) a photopolymerization initiator. It has been confirmed that the use of triplet-triplet annihilation photon upconversion particles in a photocurable resin composition for curing using the triplet-triplet annihilation photon upconversion mechanism can prolong the triplet-triplet annihilation photon upconversion emission duration. According to this embodiment, a photocurable resin composition that can achieve a good degree of cure is provided. In the triplet-triplet annihilation photon upconversion mechanism, collisions between donor and acceptor molecules that enable energy transfer between the donor and acceptor are important, but as the curing of the resin composition progresses, the molecular motion of the donor and acceptor is restricted, reducing the frequency of molecular collisions, resulting in attenuation of the triplet-triplet annihilation photon upconversion luminescence intensity over time. In curing using the triplet-triplet annihilation photon upconversion mechanism, triplet-triplet annihilation photon upconversion luminescence occurs upon irradiation with long-wavelength light, and the curing of the resin composition progresses. If attenuation of the triplet-triplet annihilation photon upconversion luminescence intensity occurs, the degree of curing of the photocurable resin composition may be insufficient. In the photocurable resin composition of this embodiment, by using triplet-triplet annihilation photon upconversion particles that maintain their particle shape even in the photocurable resin composition, it has been confirmed that energy transfer between the donor and acceptor in the particles is possible without being restricted by the progress of curing of the resin composition, and that the triplet-triplet annihilation photon upconversion light emission duration can be extended.

[0013] (A) Polymerizable Compound The photocurable resin composition of this embodiment contains (A) a polymerizable compound (hereinafter also referred to as "component (A)"). The (A) polymerizable compound imparts curability and adhesiveness to the resin composition. In this embodiment, when the photocurable resin composition satisfies characteristic (a), the (A) polymerizable compound contains a maleimide compound. In this embodiment, the (A) polymerizable compound can be appropriately selected from a radical polymerizable compound, a cationically polymerizable compound, an anionically polymerizable compound, or any combination thereof, depending on whether or not the maleimide compound is contained, or the type of (C) photopolymerization initiator described below.

[0014] Examples of the radical polymerizable compound include, but are not limited to, compounds having an unsaturated double bond such as maleimide compounds, (meth)acrylate compounds, (meth)acrylamide compounds, cyanoacrylate compounds, vinyl ether compounds, styrene compounds, and methylene malonates (2-methylene-1,3-dicarbonyl compounds and derivatives thereof), or mixtures of compounds having an unsaturated double bond and thiol compounds (mixtures capable of ene-thiol reaction).

[0015] Maleimide compounds include monofunctional maleimide compounds having one maleimide group and polyfunctional maleimide compounds having two or more maleimide groups. Maleimide compounds having two maleimide groups are sometimes referred to as bismaleimide compounds. In the feature (a) described below, the maleimide compound is activated by light having a wavelength of 500 nm or less generated by triplet-triplet annihilation photon upconversion particles to generate radicals and promote polymerization of a radically polymerizable compound. That is, the maleimide compound is not only a polymerizable compound but also functions as a photoradical polymerization initiator, promoting polymerization of a radically polymerizable compound containing the maleimide compound itself without the need for a separate photopolymerization initiator (C). From the viewpoint of workability under fluorescent lamps, maleimide compounds having an absorption wavelength of less than 500 nm are preferred, maleimide compounds having an absorption wavelength of 475 nm or less are more preferred, and maleimide compounds having an absorption wavelength of 450 nm or less are even more preferred. By matching the absorption characteristics of maleimide compounds with the wavelength of light generated by triplet-triplet annihilation photon upconversion particles, the efficiency of the polymerization reaction can be increased.

[0016] Examples of bismaleimide compounds include N,N'-(4,4'-diphenylmethane)bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, bis-(3-ethyl-5-methyl-4-maleimidophenyl)methane, m-phenylene bismaleimide (N,N'-1,3-phenylene bismaleimide), 1,6-bismaleimidehexane, 1,2-bismaleimideethane (N,N'-ethyl Examples of the dimaleimide include, but are not limited to, N,N'-(1,2-phenylene)bismaleimide, N,N-1,3-phenylene dimaleimide, N,N'-1,4-phenylene dimaleimide, N,N'-(sulfonyldi-p-phenylene)dimaleimide, N,N'-[3,3'-(1,3-phenylenedioxy)diphenyl]bismaleimide, N,N'-[4,4'-(1,3-phenylenedioxy)diphenyl]bismaleimide, and 4,4'-dimaleimide phenyl ether. These may be used alone or in combination of two or more.

[0017] When a low room temperature modulus is required for the cured resin composition, a bismaleimide having a hydrocarbon group derived from a dimer acid can be used as the bismaleimide compound. Such bismaleimides are described, for example, in JP 2015-193725 A. Commercially available bismaleimides having a hydrocarbon group derived from a dimer acid include, but are not limited to, products under the trade names "BMI-689," "BMI-1500," and "BMI-1700," which are liquid at 25°C, and "BMI-3000," which is solid at 25°C (all manufactured by Designer Molecules Inc.). These compounds may be used alone or in combination of two or more.

[0018] Examples of monofunctional maleimide compounds include, but are not limited to, monofunctional aliphatic maleimide compounds such as N-n-butylmaleimide, N-hexylmaleimide, 2-maleimidoethyl-ethyl carbonate, 2-maleimidoethyl-propyl carbonate, and N-ethyl-(2-maleimidoethyl)carbamate; alicyclic monofunctional maleimide compounds such as N-cyclohexylmaleimide; N-arylmaleimides such as N-phenylmaleimide; and N-aralkylmaleimides such as N-benzylmaleimide. The aliphatic maleimides and alicyclic maleimides may have a substituent, and examples of the substituent include a phenyl group, a benzyl group, and a hydroxy group. The N-arylmaleimides and N-aralkylmaleimides may have a substituent, and examples of the substituent include, but are not limited to, an alkyl group, a nitro group, a hydroxy group, an alkoxy group, a carboxyl group, and a halogeno group. Commercially available single-tube maleimide products include, for example, Imilex. （Ｒ） -C, Imilex （Ｒ） -P (both manufactured by Nippon Shokubai Co., Ltd.) and O-CPMI (manufactured by Daiwa Kasei Kogyo Co., Ltd.), but are not limited to these. These may be used alone or in combination of two or more.

[0019] In this specification, a (meth)acrylate compound is a compound having at least one (meth)acryloyl group in its molecule, and includes monofunctional (meth)acrylate compounds having one (meth)acryloyl group and polyfunctional (meth)acrylate compounds having two or more (meth)acryloyl groups. Examples of monofunctional (meth)acrylate compounds include: - Ethyl (meth)acrylate, trifluoroethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, isobornyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, butoxydiethylene glycol (meth) Esters of monohydric alcohols and (meth)acrylic acid, such as acrylates, 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 trimethylolpropaneformal acrylate, 1-naphthalenemethyl (meth)acrylate,1-Ethylcyclohexyl (meth)acrylate, 1-methylcyclohexyl (meth)acrylate, 1-ethylcyclopentyl (meth)acrylate, 1-methylcyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, tetrahydrodicyclopentadienyl (meth)acrylate, 2-(o-phenylphenoxy)ethyl (meth)acrylate, isobol Nylcyclohexyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, 1-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, 2-methyl-2-adamantanyl (meth)acrylate, 2-ethyl-2-adamantanyl (meth)acrylate, 2-isopropyladamantan-2-yl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, (adamantan-1-yloxy)methyl (meth)acrylate, 2- Isopropyl-2-adamantyl (meth)acrylate, 1-methyl-1-ethyl-1-adamantylmethanol (meth)acrylate, 1,1-diethyl-1-adamantylmethanol (meth)acrylate, 2-cyclohexylpropan-2-yl (meth)acrylate, 1-isopropylcyclohexyl (meth)acrylate, 1-methylcyclohexyl (meth)acrylate, 1-ethylcyclopentyl (meth)acrylate, 1-methylcyclohexyl (meth)acrylate, tetrahydropyranyl (meth)acrylate, tetrahydro-2- Examples of the ester include mono(meth)acrylates of polyhydric alcohols or esters of monohydric alcohols and (meth)acrylic acid, such as furanyl(meth)acrylate, 2-oxotetrahydrofuran-3-yl(meth)acrylate, (5-oxotetrahydrofuran-2-yl)methyl(meth)acrylate, (2-oxo-1,3-dioxolan-4-yl)methyl(meth)acrylate, N-acryloyloxyethylhexahydrophthalimide, α-acryloyl-ω-methoxypoly(oxyethylene), and 1-ethoxyethyl(meth)acrylate.These are not the only examples. They may be used individually or in combination of two or more. 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; etoxy Examples of (meth)acrylates include, but are not limited to, bisphenol A cide di(meth)acrylate; dihydrocyclopentadiethyl(meth)acrylate; as well as polyester(meth)acrylate, methylol-tricyclodecane di(meth)acrylate, ditrimethylolpropane poly(meth)acrylate; polyurethane having two or more (meth)acryloyl groups in one molecule; polyester having two or more (meth)acryloyl groups in one molecule; phenoxyethyl(meth)acrylate; isobornyl(meth)acrylate; phenoxydiethylene glycol(meth)acrylate; 4-tert-butylcyclohexyl(meth)acrylate; epoxy resin half(meth)acrylate; and others. The (meth)acrylate compound may be any one of the above-mentioned (meth)acrylate compounds, or two or more may be used in combination. Examples of commercially available (meth)acrylate compounds include 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., and dimethylol-tricyclodecanediaacrylate (product name: Light Acrylate DCP-A) manufactured by Kyoeisha Chemical Co., Ltd.Examples include, but are not limited to, neopentyl glycol modified trimethylolpropane diacrylate (product name: Kayarad R-604) manufactured by Nippon Kayaku Co., Ltd.

[0020] The (meth)acrylamide compound has an acrylamide group (H ２ C=CHCONH-) or methacrylamide group (H ２ C=C(CH ３ The compound has at least one (meth)acrylamide group (CONH-). Examples of (meth)acrylamide compounds include, but are not limited to, N,N'-methylenebis(meth)acrylamide, N,N'-ethylenebis(meth)acrylamide, and 1,2-di(meth)acrylamide ethylene glycol.

[0021] The cyanoacrylate compound is H ２Known groups represented by the formula C═C(CN)—COOR can be used. In this formula, R is an ester residue such as an alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, or aryl group. The number of carbon atoms in the ester residue is not particularly limited, but typically, those having 1 to 8 carbon atoms can be used. Ester residues consisting of substituted hydrocarbon groups such as alkoxyalkyl groups and trialkylsilylalkyl groups can also be used. Examples of cyanoacrylate compounds include alkyl and cycloalkyl cyanoacrylates such as methyl cyanoacrylate, ethyl cyanoacrylate, propyl cyanoacrylate, butyl cyanoacrylate, and cyclohexyl cyanoacrylate; alkenyl and cycloalkenyl cyanoacrylates such as allyl cyanoacrylate, methallyl cyanoacrylate, and cyclohexenyl cyanoacrylate; alkynyl cyanoacrylates such as propanegyl cyanoacrylate; aryl cyanoacrylates such as phenyl cyanoacrylate and toluyl cyanoacrylate; methoxyethyl cyanoacrylate, ethoxyethyl cyanoacrylate, and furfuryl cyanoacrylate containing heteroatoms; trimethylsilylmethyl cyanoacrylate, trimethylsilylethyl cyanoacrylate, trimethylsilylpropyl cyanoacrylate, and dimethylvinylsilylmethyl cyanoacrylate containing silicon; but are not limited thereto.These compounds may be used alone or in combination of two or more.

[0022] The vinyl ether compound has a vinyl ether group (H ２ C═CH—O—). Examples of vinyl ether compounds include, but are not limited to, ethyl vinyl ether, triethylene glycol divinyl ether, trimethylolpropane trivinyl ether, hydroxybutyl vinyl ether, dodecyl vinyl ether, cyclohexyl vinyl ether, 1,4-butanediol divinyl ether, nonanediol divinyl ether, cyclohexanediol divinyl ether, and cyclohexanedimethanol divinyl ether. These compounds may be used alone or in combination of two or more.

[0023] Styrene compounds contain a styrene group (H ２ C=CH-C ６ H ５ -). Examples of the styrene compound include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-t-butylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, N,N-diethyl-4-aminoethylstyrene, and 4-methoxystyrene, but are not limited to these. These may be used alone or in combination of two or more.

[0024] Methylene malonates are malonates having at least one methylene group in the molecule, including monofunctional methylene malonates having one methylene group and polyfunctional methylene malonates having two or more methylene groups. The methylene malonates preferably have a molecular weight of 220 or more. There are no particular limitations on the type of methylene malonate that can be used, and various disclosed methylene malonates can be used, including compounds described in WO 2018 / 212330 A1 and the like. Methylene malonates may be used alone or in combination of two or more.

[0025] In a mixture of a compound having an unsaturated double bond and a thiol compound, the thiol compound is a compound containing at least one thiol group, and this thiol group can undergo a radical addition reaction (en-thiol reaction) with the unsaturated double bond of the compound having the unsaturated double bond. Thiol compounds are broadly classified into thiol compounds that have a hydrolyzable substructure such as an ester bond in the molecule (i.e., hydrolyzable) and thiol compounds that do not have such a substructure (i.e., non-hydrolyzable). Examples of hydrolyzable thiol compounds include trimethylolpropane tris(3-mercaptopropionate) (manufactured by SC Organic Chemicals Co., Ltd.: TMMP), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate (manufactured by SC Organic Chemicals Co., Ltd.: TEMPIC), pentaerythritol tetrakis(3-mercaptopropionate) (manufactured by SC Organic Chemicals Co., Ltd.: PEMP), and tetraethylene glycol bis(3-mercaptopropionate) (manufactured by SC Organic Chemicals Co., Ltd.: EGMP- 4) Examples include, but are not limited to, dipentaerythritol hexakis(3-mercaptopropionate) (manufactured by SC Organic Chemicals Co., Ltd.: DPMP), pentaerythritol tetrakis(3-mercaptobutyrate) (manufactured by Resonaq Corporation: Karenz MT® PE1), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by Resonaq Corporation: Karenz MT® NR1). These may be used individually or in combination of two or more. Examples of non-hydrolyzable polyfunctional thiol compounds include 1,3,4,6-tetrakis(2-mercaptoethyl) glycoluryl (manufactured by Shikoku Chemicals, Inc.: TS-G), (1,3,4,6-tetrakis(3-mercaptopropyl) glycoluryl (manufactured by Shikoku Chemicals, Inc.: C3 TS-G), 1,3,4,6-tetrakis(mercaptomethyl) glycoluryl, 1,3,4,6-tetrakis(mercaptomethyl)-3a-methyl glycoluryl, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a-methyl glycoluryl, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a-methyl glycoluryl, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-dimethylglycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a-dimethylglycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-dimethylglycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-diphenylglycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a-diphenylglycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a, 6a-Diphenylglycoluril, 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 trippropanethiol (manufactured by SC Organic Chemical Co., Ltd.: PEPT), 3-[2,3-bis(3-sulfanylpropoxy)propoxy]propane-1-thiol, 1,2,3-tris(3-mercaptopropyl)isocyanurate, 1,3,5-tris[3-(2-mercaptoethylsulfanyl)propyl]isocyanurate, 1,3,5-tris[2-(3-mercaptopropoxy)ethyl]isocyanurate, pentaerythritol trippropanethiol (manufactured by SC Organic Chemical Co., Ltd.: PEPT), 3-[2,3-bis(3-sulfanylpropoxy)propoxy]propane-1-thiol, (mercaptopropyl)propane, 3-[2,2-bis[(3-mercaptopropoxy)methyl]butoxy]-1-propanethiol, pentaerythritol tetrapropanethiol, 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3-mercaptopropylthio)propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl 1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 1,1,5,5-tetrakis(mercaptomethylthio)-3-thiapentane, 1,1,6,6-tetrakis(mercaptomethylthio)-3,4-dithiahexane, 2,2-bis(mercaptomethylthio)ethanethiol, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptane, 3,6-bis(mercaptomethylthio)-1,9-dimercapto-2,5,8-trithianonane, 3-mercaptomethylthio-1,6-dimercapto-2,5-dithiahexane, 1,1,9,9-tetrakis(mercaptomethylthio)-5-(3,3-bis(mercaptomethylthio)-1-thiapropyl)3,7-dithianonane, tris (2,2-bis(mercaptomethylthio)ethyl)methane, tris(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane, tetrakis(2,2-bis(mercaptomethylthio)ethyl)methane, tetrakis(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane, 3,5,9,11-tetrakis(mercaptomethylthio)-1,13-dimercapto-2,6,8,12-tetrathiatridecane, 3,5,9,11,15,17-hexakis(mercaptomethylthio)-1,19-dimercapto-2,6,8,12,1 4,18-Hexathianonadecane, 9-(2,2-bis(mercaptomethylthio)ethyl)-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3,4,8,9-tetrakis(mercaptomethylthio)-1,11-dimercapto-2,5,7,10-tetrathiaundecane, 3,4,8,9,13,14-hexakis(mercaptomethylthio)-1,16-dimercapto-2,5,7,10,12,15-hexathiahexadecane, 8-[bis(mercaptomethylthio)ethyl]-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane 4-[3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiaheptylthio]-6-mercaptomethylthio-1,3-dithiane, 1,1-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio]-1,3-dithiane, 1,1-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio]-1,3-dithiane,3-bis(mercaptomethylthio)propane, 1-[4-(6-mercaptomethylthio)-1,3-dithianylthio]-3-[2,2-bis(mercaptomethylthio)ethyl]-7,9-bis(mercaptomethylthio)-2,4,6,10-tetrathiaundecane, 3-[2-(1,3-dithietanyl)]methyl-7,9-bis(mercaptomethylthio)-1,11-dimercapto-2,4,6,10-tetrathiaundecane, 9-[2-(1,3-dithietanyl)]methyl-3,5,13,15-tetrakis(mercaptomethylthio)-1,17 -dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3-[2-(1,3-dithietanyl)]methyl-7,9,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,4,6,10,12,16-hexathiaheptadecane, 4,6-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio]-6-[4-(6-mercaptomethylthio)-1,3-dithianylthio]-1,3-dithiane, 4-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7, 10-tetrathiaundecyl]-5-mercaptomethylthio-1,3-dithiolane, 4,5-bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]-1,3-dithiolane, 4-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]-5-mercaptomethylthio-1,3-dithiolane, 4-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]-5-mercaptomethylthio-1, 3-Dithiolane, 2-{bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]methyl}-1,3-dithietane, 2-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]mercaptomethylthiomethyl-1,3-dithietane, 2-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecylthio]mercaptomethylthiomethyl-1,3-dithietane, 2-[3-bis(mercaptomethylthio)methyl-5,Examples of bifunctional thiol compounds disclosed in WO 2019 / 082962 include 6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]mercaptomethylthiomethyl-1,3-dithietane, 4-{1-[2-(1,3-dithietanyl)]-3-mercapto-2-thiapropylthio}-5-[1,2-bis(mercaptomethylthio)-4-mercapto-3-thiabutylthio]-1,3-dithiolane, 2,2'-[cyclohexylidenebis(thio-2,1-ethanediylthio)]bis[ethanethiol], and 4,4'-[(1,3-phenylene)bis(oxy)]bis[1-butanethiol], as well as dimers, trimers, and tetramers of the above thiol compounds, but are not limited to these. These may be used alone or in combination of two or more.

[0026] The radical polymerizable compounds may be used alone or in combination of two or more.

[0027] The cationically polymerizable compound is a compound having one or more cationically polymerizable groups in the molecule. Examples of the cationically polymerizable compound include, but are not limited to, compounds having an epoxy group, compounds having an oxetanyl group, compounds having a vinyl ether group, compounds having other cationically polymerizable groups, and compounds having any combination of these cationically polymerizable groups.

[0028] In this specification, a compound having an epoxy group refers to a compound having at least one epoxy group in the molecule, and is also referred to as an epoxy compound. Examples include monofunctional epoxy compounds having one epoxy group and polyfunctional epoxy compounds having two or more epoxy groups. In one embodiment, the epoxy compound preferably contains at least a polyfunctional epoxy compound, and may contain a combination of a polyfunctional epoxy compound and a monofunctional epoxy compound. Epoxy compounds can be broadly classified into epoxy compounds having an aromatic ring skeleton, aliphatic epoxy compounds, and alicyclic epoxy compounds depending on the type of skeleton.

[0029] In this specification, a compound having an oxetanyl group is a compound having at least one oxetane ring (e.g., a 3-oxetanyl group) in the molecule, and is also referred to as an oxetane compound. In one embodiment, the oxetane compound preferably has 1 to 6 oxetanyl groups in the molecule, and more preferably has 1 to 2 oxetanyl groups in the molecule.

[0030] In this specification, a compound having a vinyl ether group is a compound having at least one vinyl ether group in the molecule.

[0031] Specific examples of the cationic polymerizable compound include glycidyl ethers of tetra(hydrophenyl)alkanes, glycidyl ethers of tetrahydroxybenzophenone, epoxidized polyvinylphenol, p-tert-butylphenyl glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, 1,2-epoxytetradecane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-eth ... 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), propanediol Pan-2,2-diyl-bis(3,4-epoxycyclohexane), 2,2-bis(3,4-epoxycyclohexyl)propane, dicyclopentadiene diepoxide, ethylene bis(3,4-epoxycyclohexanecarboxylate), limonene dioxide (1,2:8,9-diepoxylimonene), (3,3',4,4'-diepoxy)bicyclohexyl, dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, 1,2-epoxy-4-vinylcyclohexane, α-pinene oxide, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, epoxidized polybutadiene, compounds in which some or all of the double bonds of styrene-butadiene copolymers have been epoxidized, bis[1-ethyl(3-oxetanyl)]methyl ether (also known as (3-ethyl-3{[(3-ethyloxetan-3-yl)methoxy]methyl) oxetane), xylylene bisoxetane, 4,4'-bis[3-ethyl-(3-oxetanyl)methoxymethyl]biphenyl, 1,4-bis(3-ethyl-3-oxetanylmethoxy)methylbenzene, (bis[(3-ethyl-3-oxetanyl)methyl]isophthalate), 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyloxetane, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-[(2-ethylhexyloxy)methyl]oxetane, 3-ethyl-3- Examples of the vinyl ether include, but are not limited to, (4-hydroxybutyl)oxymethyloxetane, 3-ethyl-3-phenoxymethyloxetane, oxetanylsilsesquioxetane, 3-ethyl-3{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane, phenol novolac oxetane, 1,4-butanediol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, normal propyl vinyl ether, isopropyl vinyl ether, normal butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, 2-(2-vinyloxyethoxy)ethyl acrylate, 2-(2-vinyloxyethoxy)ethyl methacrylate, 1,4-cyclohexanedimethanol monovinyl ether, and 1,4-cyclohexanedimethanol divinyl ether.

[0032] Commercially available cationically polymerizable compounds include EPICLON (registered trademark) 850, 850-S, EXA-850CRP, and EXA-8067 manufactured by DIC Corporation; AER9000 manufactured by Asahi Kasei Corporation; EP-4000S, EP-4003S, and EP-4010S manufactured by ADEKA Corporation; EPICLON (registered trademark) 830-S, EXA-830LVP, and EXA-835LV manufactured by DIC Corporation; and EPICLON (registered trademark) HP-40 manufactured by DIC Corporation. 32D, HP-720H; EPICLON (registered trademark) N-740, N-770 manufactured by DIC Corporation; EPICLON (registered trademark) N-660, N-670, N-655-EXP-S manufactured by DIC Corporation; ADEKA GLYCIROL (registered trademark) ED-509E, ED-509S manufactured by ADEKA Corporation; OPP-G manufactured by Sanko Co., Ltd.; Epolite 100MF manufactured by Kyoeisha Chemical Co., Ltd.; AER-9000 manufactured by Asahi Kasei Corporation; jER manufactured by Mitsubishi Chemical Corporation YX7400N; jER YX8000 manufactured by Mitsubishi Chemical Corporation; CELLOXIDE (registered trademark) 2021P manufactured by Daicel Corporation; CELLOXIDE (registered trademark) 8010 manufactured by Daicel Corporation; EHPE3150 manufactured by Daicel Corporation; EPOLEAD PB manufactured by Daicel Corporation; EPOFRIEND manufactured by Daicel Corporation; HiREM-1 and HiREM-2 manufactured by Shikoku Chemicals Corporation; OXT-191 manufactured by Toagosei Co., Ltd.; OXT-221 manufactured by Toagosei Co., Ltd.; PHOX manufactured by Toagosei Co., Ltd., and the like, but are not limited to these.

[0033] The cationically polymerizable compounds may be used alone or in combination of two or more.

[0034] Examples of anionically polymerizable compounds include the compounds having an epoxy group listed as examples of the cationic polymerizable compounds, and their curing agents, such as thiol-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, and amine-based curing agents. Furthermore, methylene malonates listed as examples of the radically polymerizable compounds are also listed as anionically polymerizable compounds. Furthermore, (meth)acrylate compounds listed as examples of the radically polymerizable compounds are also listed as anionically polymerizable compounds when used in combination with a thiol compound. These compounds may be used alone or in combination of two or more.

[0035] The polymerizable compound (A) may be any one of a radically polymerizable compound, a cationically polymerizable compound, and an anionically polymerizable compound, or any combination thereof.

[0036] In some embodiments, the content of the polymerizable compound (A) in the photocurable resin composition is preferably 1 to 99 parts by mass, more preferably 5 to 99 parts by mass, and even more preferably 7 to 99 parts by mass, per 100 parts by mass of the total amount of the photocurable resin composition. The photocurable resin composition of this embodiment can be cured by photocuring alone, even in the presence of a large amount of a shielding material such as a filler. In another embodiment, the content of the polymerizable compound (A) in the photocurable resin composition is preferably 1 to 99 parts by mass, more preferably 5 to 99 parts by mass, and even more preferably 10 to 99 parts by mass, per 100 parts by mass of the total amount of the photocurable resin composition. The content of the polymerizable compound (A) in the photocurable resin composition is preferably 1 to 99 parts by mass, more preferably 5 to 99 parts by mass, and even more preferably 10 to 99 parts by mass, per 100 parts by mass of the total amount of all organic substances contained in the photocurable resin composition. The amount of component (A) is preferably 1 to 99.9 parts by mass, more preferably 5 to 99.5 parts by mass, and even more preferably 10 to 99 parts by mass, relative to 100 parts by mass of the total of components (A), (B), and (C).

[0037] (B) Triplet-triplet annihilation photon upconversion particles The photocurable resin composition of this embodiment includes (B) triplet-triplet annihilation photon upconversion particles (hereinafter also referred to as "component (B)"). In this specification, "triplet-triplet annihilation photon upconversion particles" means a triplet-triplet annihilation photon upconversion material that maintains its particle form in the photocurable resin composition.

[0038] Photon upconversion (UC) is a technology that converts low-energy (long-wavelength) light into high-energy (short-wavelength) light. Mechanisms of photon upconversion include triplet-triplet annihilation (TTA), multiphoton excitation of rare-earth element-containing materials, and two-photon absorption. In triplet-triplet annihilation type photon upconversion materials, a combination of a donor and an acceptor is used. In this specification, the combination of a donor and an acceptor may also be referred to as a "triplet-triplet annihilation photon upconversion material." An acceptor (acceptor compound) is a compound (luminescent material) that, after receiving triplet energy transfer from a donor, enters an excited triplet state, and then generates photon upconversion emission when the excited acceptors undergo triplet-triplet annihilation. A donor (donor compound) is a compound that absorbs incident light, becomes an excited triplet state through intersystem crossing from an excited singlet state, and causes triplet-triplet energy transfer to the acceptor. In photocurable resin compositions and methods of use for curing using a photon upconversion mechanism, it has been confirmed that when the donor and acceptor are mixed with a polymerizable compound, they dissolve, and in the dissolved composition, light with a wavelength of 500 nm or less is generated by passing through a triplet-triplet annihilation photon upconversion mechanism, activating the photopolymerization initiator and / or maleimide compound, thereby curing the resin composition. Further investigations have shown that while collisions between donor and acceptor molecules, which enable energy transfer between the donor and acceptor, are important in the triplet-triplet annihilation photon upconversion mechanism, as the curing of the resin composition progresses, the molecular motion of the donor and acceptor is restricted, the frequency of molecular collisions decreases, and the photon upconversion emission intensity decreases over time.In the photocurable resin composition of this embodiment, it was confirmed that by using triplet-triplet annihilation photon upconversion particles that maintain their particle shape even within the photocurable resin composition, energy transfer between donors and acceptors becomes possible within the particles without being limited by the curing progress of the resin composition, thereby extending the duration of photon upconversion emission.

[0039] In this embodiment, the triplet-triplet annihilation photon upconversion particles may be any triplet-triplet annihilation photon upconversion particles that can maintain their particle shape in a photocurable resin composition. An example of such triplet-triplet annihilation photon upconversion particles is a particle in which a triplet-triplet annihilation photon upconversion material is dispersed or encapsulated in an organic polymer matrix.

[0040] The organic polymer matrix is ​​preferably highly transparent. Examples of such organic polymers include (meth)acrylic (e.g., poly(meth)acrylic acid ester), (meth)acrylic-styrene, (meth)acrylic-urethane, polystyrene, polyester, polyurethane, melamine, epoxy, nylon, polyamide, polyimide, silicone, benzoguanamine-formaldehyde, polycarbonate, polyethylene, polypropylene, and polybutadiene, and these may be copolymerized or composited. The organic polymer matrix is ​​not limited to these, and multiple organic polymers may be used. The organic polymer matrix may also be an organic polymer matrix having a crosslinked structure. The organic polymer matrix has the function of retaining the triplet-triplet annihilation photon upconversion material before and after curing using the triplet-triplet annihilation photon upconversion mechanism. In an embodiment, the organic polymer matrix is ​​preferably insoluble in the polymerizable compound (A). In an embodiment, the organic polymer matrix is ​​preferably hydrolysis-resistant. In certain embodiments, the organic polymer matrix preferably has low oxygen permeability. Furthermore, from the viewpoint of retaining the triplet-triplet annihilation photon upconversion material, the organic polymer matrix may be bonded to a portion of the triplet-triplet annihilation photon upconversion material. For example, examples of an acceptor bonded to an organic polymer matrix are known, such as those described in JP 2021-080335 A. In certain embodiments, the thermal decomposition temperature of the organic polymer matrix is ​​preferably 200°C or higher, more preferably 250°C or higher, and even more preferably 300°C or higher. The higher the thermal decomposition temperature of the organic polymer matrix, the more heat-resistant the cured product of the photocurable resin composition obtained. The organic polymer of the organic polymer matrix can be produced by polymerizing monomer materials using an appropriate method, including conventionally known methods. Commercially available polymer beads containing these components can also be used as the organic polymer matrix.

[0041] The surfaces of the triplet-triplet annihilation photon upconversion particles may be coated with an inorganic material or an organic material, and are preferably coated with an inorganic material. The triplet-triplet annihilation photon upconversion mechanism is susceptible to oxygen inhibition, and a coating layer made of an inorganic material can serve as a protective layer against oxygen. In addition, this coating layer can prevent the triplet-triplet annihilation photon upconversion material from being eluted from the particles. Examples of inorganic materials for coating include silica (SiO ２ ), alumina (Al ２ O ３ The thickness of the coating layer is preferably 1 to 100 nm, more preferably 1 to 50 nm, and even more preferably 1 to 20 nm.

[0042] The average particle size of the triplet-triplet annihilation photon upconversion particles may be, for example, 10 nm to 30 μm, preferably 50 nm to 20 μm, and more preferably 80 nm to 10 μm. In this specification, the average particle size of the triplet-triplet annihilation photon upconversion particles is the number-average diameter measured by dynamic light scattering (DLS).

[0043] From the viewpoint of dispersibility, the triplet-triplet annihilation photon up-conversion particles may be surface-treated with a coupling agent such as a silane coupling agent.

[0044] In one embodiment, the (B) triplet-triplet annihilation photon upconversion particles are particles having an average particle size of 10 nm to 30 μm, in which a triplet-triplet annihilation photon upconversion material is dispersed or encapsulated in an organic polymer matrix. In one embodiment, the (B) triplet-triplet annihilation photon upconversion particles are core-shell type triplet-triplet annihilation photon upconversion particles, in which a triplet-triplet annihilation photon upconversion material is dispersed or encapsulated in an organic polymer matrix, in which the surfaces of particles having an average particle size of 10 nm to 30 μm are coated with a silica material.

[0045] Examples of methods for producing triplet-triplet annihilation photon upconversion particles include a method of dispersing or encapsulating a triplet-triplet annihilation photon upconversion material in an organic polymer matrix. Examples of the dispersion or encapsulation method include (1) a method of dispersing a solution in which a triplet-triplet annihilation photon upconversion material and an organic polymer are dissolved in a solvent, in a liquid in which the organic polymer is insoluble, thereby precipitating particles of an organic polymer matrix in which the triplet-triplet annihilation photon upconversion material is dispersed or encapsulated, and (2) a method of mixing a solution in which a triplet-triplet annihilation photon upconversion material is dissolved in an organic solvent with an organic polymer matrix, thereby impregnating the organic polymer matrix with the triplet-triplet annihilation photon upconversion material due to the swelling effect of the organic solvent, thereby dispersing or encapsulating the photon upconversion material in the organic polymer matrix. In the method (1), the solvent used for the solution of the triplet-triplet annihilation photon upconversion material and the organic polymer is not particularly limited as long as it can dissolve the triplet-triplet annihilation photon upconversion material and the organic polymer. Among these, a solvent that is compatible with a liquid in which the organic polymer serving as a dispersion medium is insoluble is preferred. This allows the solvent to dissolve into the dispersion medium when the particles are precipitated in the dispersion medium. Furthermore, in the method (1), the "liquid in which the organic polymer is insoluble" refers to a liquid in which the solubility of the organic polymer is 0.5 g / L or less at room temperature. In the method (2), the organic solvent used for the solution of the triplet-triplet annihilation photon upconversion material is not particularly limited as long as it can dissolve the triplet-triplet annihilation photon upconversion material. Furthermore, in the method (2), the organic polymer matrix is ​​preferably an organic polymer matrix having a crosslinked structure that is insoluble or poorly soluble in the organic solvent used to dissolve the triplet-triplet annihilation photon upconversion material. After dispersion or encapsulation, the particles are coated with an inorganic material such as silica, if necessary. As a method for coating with silica, known methods such as the Stober method can be used.

[0046] Triplet-triplet annihilation photon upconversion materials utilize a combination of donor and acceptor. Examples of triplet-triplet annihilation photon upconversion materials include those described in Japanese Patent Publication No. 2021-080335 and Japanese Patent Publication No. 2020-056030.

[0047] <Acceptor> An acceptor (acceptor compound) is any compound (luminescent material) that, after receiving triplet energy transfer from a donor, becomes an excited singlet state via triplet-triplet annihilation and is capable of photon upconversion luminescence. It is not particularly limited. Examples of acceptors include, but are not limited to, compounds containing naphthalene, anthracene, tetracene, pyrene, perylene, biphenyl, terphenyl, perylenediimide, naphthalenediimide, and BODIPY (boron dipyromethene; 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) structures. Specific examples of acceptors include, but are not limited to, 9,10-diphenylanthracene (DPA), tetra-tert-butylperylene, anthracene (An), 2,5-diphenyloxazole (PPO), rubrene, 2-chloro-bis-phenylethynylanthracene (2CBPEA), 9,10-bis(phenylethynyl)anthracene (BPEA), 9,10-bis(phenylethynyl)naphthacene (BPEN), perylene, coumarin 343 (C343), 9,10-dimethylanthracene (DMA), pyrene, tert-butylpyrene, and boron dipyromethene (BODIPY) derivatives BD-1 and BD-2 having an iodophenyl group, as well as halogenated derivatives of these compounds. Other specific examples of the acceptor include the acceptors described in JP-A-2021-080335 and JP-A-2020-056030.

[0048] <Donor> The donor (donor compound) is not particularly limited as long as it absorbs incident light, undergoes intersystem crossing from an excited singlet state to an excited triplet state, and causes triplet-triplet energy transfer to an acceptor. Examples of donors include, but are not limited to, metal atoms such as Pt, Pd, Zn, Ru, Re, Ir, Os, Cu, Ni, Co, Cd, Au, Ag, Sn, Sb, Pb, P, and As, and compounds containing organic moieties such as a porphyrin structure, a phthalocyanine structure, a fullerene structure, and a 2-phenylpyridinato structure. Specific examples of donors include palladium octabutoxyphthalocyanine (PdOBuPc), platinum tetraphenyltetranaphthoporphyrin (PtTPTNP), palladium(II)-meso-tetraphenyl-tetrabenzoporphyrin (PdTPTBP), [Ru(dmb) ３ ] ２＋ (dmb is 4,4'-dimethyl-2,2'-bipyridine), palladium(II) tertraanthraporphyrin (PdTAP), platinum(II) tetraphenyltetrabenzoporphyrin (PtTPBP), palladium meso-tetraphenyltetrabenzoporphyrin (PdPh4TBP), palladium octaethylporphyrin (PdOEP), 11,15,18,22,25 octabutoxyphthalocyanine (PdPc(OBu) ８ ), octaethylporphyrin (OEP), platinum octaethylporphyrin (PtOEP), zinc(II) octaethylporphyrin (ZnOEP), zinc(II) meso-tetraphenylporphine (ZnTPP), palladium(II) tetraphenyltetrabenzoporphyrin (PdTPBP), palladium(II) meso-tetraphenyl-octamethoxide tetranaphtholporphyrin (PdPh ４ OMe ８ TNP), 2-methoxythioxanthone (2MeOTX), and Ir(ppy) ３ Examples of donors include, but are not limited to, those described in Japanese Patent Publication No. 2021-080335 and Japanese Patent Publication No. 2020-056030.

[0049] By appropriately selecting the combination of donor and acceptor, the wavelengths of incident light and emitted light can be controlled. The combination of donor and acceptor may be one pair or two or more pairs. For example, in certain embodiments, selecting multiple combinations of donor and acceptor enables energy transfer from one photon upconversion material to another photon upconversion material in the resin composition. This stepwise energy transfer allows the emission wavelength of the photon upconversion material to be adjusted from the desired incident light to ultimately include wavelengths of 500 nm or less, thereby allowing the resin composition to be photocured using the desired incident light. The molar ratio of donor to acceptor can be, for example, donor:acceptor = 1:1 to 1:100,000. By appropriately selecting the combination and molar ratio of donor and acceptor, the emission wavelength of (B) triplet-triplet annihilation photon upconversion particles that emit light upon irradiation with light with a wavelength of more than 500 nm can be adjusted to include wavelengths of 500 nm or less.

[0050] The wavelength range of the excitation light that causes such triplet-triplet annihilation photon upconversion particles (B) to emit upconversion light is preferably a wavelength of more than 500 nm, for example, a wavelength in the range of more than 500 nm to 2000 nm. The wavelength of the upconversion light emitted by component (B) preferably includes a wavelength of 500 nm or less, more preferably a wavelength of 450 nm or less, even more preferably a wavelength of 430 nm or less, and particularly preferably a wavelength of 400 nm or less. In an embodiment, the emission wavelength of component (B) includes the wavelength of ultraviolet light (200 nm to 380 nm).

[0051] The donor may use one type or two or more types in combination. The acceptor may use one type or two or more types in combination.

[0052] The content of the triplet-triplet annihilation photon upconversion material in the triplet-triplet annihilation photon upconversion particles can be, for example, 1 to 99% by mass, preferably 1 to 90% by mass, and more preferably 5 to 80% by mass, based on the total mass of the particles. The content of the triplet-triplet annihilation photon upconversion material in the triplet-triplet annihilation photon upconversion particles can be measured by methods such as differential thermal-thermogravimetric analysis, GC-MS, LC-MS, fluorescence emission measurement, absorbance measurement, and ICP (inductively coupled plasma) analysis.

[0053] In this embodiment, the content of component (B) in the photocurable resin composition may be, for example, 0.01 to 80 parts by mass, preferably 0.05 to 50 parts by mass, more preferably 0.1 to 30 parts by mass, and even more preferably 0.5 to 30 parts by mass, based on 100 parts by mass of the total amount of polymerizable compound (A), from the viewpoint of the curability of the photocurable resin composition.

[0054] The photocurable resin composition of this embodiment satisfies at least one of the following features (a) and (b): (a) The polymerizable compound (A) comprises a maleimide compound; (b) The photocurable resin composition comprises (C) a photopolymerization initiator. The maleimide compound and (C) the photopolymerization initiator are activated by light with a wavelength of 500 nm or less generated by (B) triplet-triplet annihilation photon upconversion particles, generating active species such as radicals, cations, and anions, which promote the polymerization of the polymerizable compound. This provides a photocurable resin composition that can be cured by light irradiation alone.

[0055] In feature (a) described above, the maleimide compound is activated by light with a wavelength of 500 nm or less, particularly 450 nm or less, generated by (B) triplet-triplet annihilation photon upconversion particles, generating radicals and promoting the polymerization of the radical polymerizable compound. That is, the maleimide compound is a polymerizable compound and can also function as a photo-radical polymerization initiator, and promotes the polymerization of the radical polymerizable compound containing the maleimide compound itself, even without containing (C) a separate photopolymerization initiator. When feature (a) described above is satisfied, the maleimide compound is preferably a maleimide compound with an absorption wavelength of 500 nm or less, more preferably a maleimide compound with an absorption wavelength of 475 nm or less, and even more preferably a maleimide compound with an absorption wavelength of 450 nm or less. When feature (a) described above is satisfied, the polymerizable compound (A) may include radical polymerizable compounds other than the maleimide compound. Also, when feature (a) described above is satisfied, the photocurable resin composition may contain (C) a photopolymerization initiator (feature (b) described above). When the above characteristic (a) is satisfied, the amount of maleimide compound in the photocurable resin composition is preferably 0.1 to 100 parts by mass, and more preferably 0.2 to 100 parts by mass, based on 100 parts by mass of the total radical polymerizable compounds (i.e., the sum of the maleimide compound and other radical polymerizable compounds), from the viewpoint of photoirradiation reactivity.

[0056] (C) Photopolymerization Initiator The photocurable resin composition of this embodiment, which satisfies the characteristic (b), contains (C) a photopolymerization initiator (hereinafter also referred to as "component (C)"). A photopolymerization initiator is a reactant that absorbs light to generate active species such as radicals, cations, and anions, thereby promoting polymerization of a polymerizable compound. In this embodiment, the (C) photopolymerization initiator is preferably a photopolymerization initiator that is activated (i.e., generates active species) by light with a wavelength of 500 nm or less, and is activated by light with a wavelength of 500 nm or less that has been wavelength-converted by (B) triplet-triplet annihilation photon upconversion particles. The (C) photopolymerization initiator is more preferably activated by light with a wavelength of 450 nm or less, even more preferably by light with a wavelength of 440 nm or less, and particularly preferably by light with a wavelength of 430 nm or less. The efficiency of the polymerization reaction can be increased by matching the absorption characteristics of the (C) photopolymerization initiator with the emission wavelength of the (B) triplet-triplet annihilation photon upconversion particles. The (C) photopolymerization initiator can be appropriately selected from a photoradical polymerization initiator, a photoacid generator, a photobase generator, or any combination thereof. From the viewpoint of photoirradiation reactivity, the content of the (C) photopolymerization initiator in the photocurable resin composition is preferably 0.01 to 15 parts by mass, more preferably 0.01 to 10 parts by mass, even more preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the total of the (A) polymerizable compounds.

[0057] The photoradical polymerization initiator absorbs light to generate radicals as active species, thereby promoting the polymerization of the radical polymerizable compound. Examples of the photoradical polymerization initiator include, but are not limited to, alkylphenone compounds, acylphosphine oxide compounds, oxime ester compounds, and compounds having a photosensitive moiety and a peroxide structure.

[0058] Examples of alkylphenone compounds include benzyl dimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethan-1-one (commercially available as Omnirad 651 from IGM Resins B.V.); α-aminoalkylphenones such as 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one (commercially available as Omnirad 907 from IGM Resins B.V.); α-hydroxyalkylphenones such as 1-hydroxy-cyclohexyl-phenyl-ketone (commercially available as Omnirad 184 from IGM Resins B.V.); 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one (commercially available as Omnirad 184 from IGM Resins B.V.); 379EG), 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone (commercially available as Omnirad 369 manufactured by IGM Resins BV), etc., but are not limited to these. These may be used alone or in combination of two or more.

[0059] Examples of the acylphosphine oxide compound include, but are not limited to, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (commercially available as Omnirad TPO H manufactured by IGM Resins B.V.) and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (commercially available as Omnirad 819 manufactured by IGM Resins B.V.). These compounds may be used alone or in combination of two or more.

[0060] Examples of the oxime ester compound include, but are not limited to, 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)] (trade name: Irgacure OXE-01, manufactured by BASF), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (trade name: Irgacure OXE-02, manufactured by BASF), methanone, ethanone, 1-[9-ethyl-6-(1,3-dioxolane, 4-(2-methoxyphenoxy)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (trade name: ADEKA OPT-N-1919, manufactured by ADEKA Corporation).

[0061] Examples of compounds having a photosensitive moiety and a peroxide structure or commercially available products thereof include 3,3′,4,4′-tetrakis(tert-butylperoxycarbonyl)benzophenone (BTTB), Perdual TA, and Perdual TX (all manufactured by NOF Corporation), but are not limited to these.

[0062] In addition to the photoradical polymerization initiators mentioned above, other examples of photoradical polymerization initiators include 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, and benzyldimethyl Examples include, but are not limited to, ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 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. These may be used individually or in combination of two or more.

[0063] The photoradical polymerization initiators may be used alone or in combination of two or more.

[0064] From the viewpoint of photoirradiation reactivity, the content of the photoradical polymerization initiator in the photocurable resin composition is preferably 0.1 to 10 parts by mass, and more preferably 0.2 to 8 parts by mass, relative to 100 parts by mass of the total of the radical polymerizable compounds.

[0065] The photoacid generator absorbs light to generate an acid as an active species, which promotes the polymerization of the cationic polymerizable compound. ４ － SbF６ -, AsF ６ － , B(C ６ F ５ ) ４ － , Ga(C ６ F ５ ) ４ － , C(CF ３ SO ２ ) ３ － , [P(R １ ) ａ F ６－ａ ] － , [C(R １ SO ２ ) ３ ] － , or [N(R １ SO ２ ) ２ ] － (In the formula, R １ are each independently an alkyl group in which at least a portion of the hydrogen atoms is substituted with a fluorine atom, a is an integer of 0 to 5, and when a is an integer of 2 or more, a plurality of R １ may be the same or different.) or the like as a counter anion, and a sulfonium cation, an iodonium cation, an ammonium cation, a phosphonium cation, or the like as a cation moiety.

[0066] Examples of iodonium cations include iodonium ions such as diphenyliodonium, di-p-tolyliodonium, bis(4-dodecylphenyl)iodonium, bis(4-methoxyphenyl)iodonium, (4-octyloxyphenyl)phenyliodonium, bis(4-decyloxy)phenyliodonium, 4-(2-hydroxytetradecyloxy)phenylphenyliodonium, 4-isopropylphenyl(p-tolyl)iodonium, and 4-isobutylphenyl(p-tolyl)iodonium.

[0067] Examples of sulfonium ions include triphenylsulfonium, tri-p-tolylsulfonium, tri-o-tolylsulfonium, tris(4-methoxyphenyl)sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium, tris(4-fluorophenyl)sulfonium, tri-1-naphthylsulfonium, tri-2-naphthylsulfonium, tris(4-hydroxyphenyl)sulfonium, 4-(phenylthio)phenyldiphenylsulfonium, 4-(p-tolylthio)phenyldi-p-tolylsulfonium, 4-(4-methoxyphenylthio)phenylbis(4-methoxyphenyl)sulfonium, and 4-(phenylthio)phenylbis(4-fluorophenyl (L) sulfonium, 4-(phenylthio)phenylbis(4-methoxyphenyl)sulfonium, 4-(phenylthio)phenyldi-p-tolylsulfonium, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium, [4-(2-thioxanthonylthio)phenyl]diphenylsulfonium, bis[4-(diphenylsulfonio)phenyl]sulfide, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonio}phenyl]sulfide, bis{4-[bis(4-fluorophenyl)sulfonio]phenyl}sulfide, bis{4-[bis(4-methylphenyl)sulfonio]phenyl}sulfide, bis{4-[bis(4-methoxyphenyl)sulfonio] Phenyl sulfide, 4-(4-benzoyl-2-chlorophenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoyl-2-chlorophenylthio)phenyldiphenylsulfonium, 4-(4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-Dihydroanthracen-2-yldiphenylsulfonium, 2-[(di-p-tolyl)sulfonio]thioxanthone, 2-[(diphenyl)sulfonio]thioxanthone, 4-(9-oxo-9H-thioxanthen-2-yl)thiophenyl-9-oxo-9H-thioxanthen-2-ylphenylsulfonium, 4-[4-(4-t-butylbenzoyl)phenylthio]phenyldi-p-tolylsulfonium, 4-[4-(4-t-butylbenzoyl)phenylthio]phenyl triarylsulfoniums such as 4-[4-(benzoylphenylthio)]phenyldi-p-tolylsulfonium, 4-[4-(benzoylphenylthio)]phenyldiphenylsulfonium, 5-(4-methoxyphenyl)thiaanthrenenium, 5-phenylthiaanthrenenium, 5-tolylthiaanthrenenium, 5-(4-ethoxyphenyl)thiaanthrenenium, and 5-(2,4,6-trimethylphenyl)thiaanthrenenium.

[0068] Examples of ammonium cations include pyrrolidiniums such as N,N-dimethylpyrrolidinium, N-ethyl-N-methylpyrrolidinium, and N,N-diethylpyrrolidinium; imidazoliniums such as N,N'-dimethylimidazolinium, N,N'-diethylimidazolinium, N-ethyl-N'-methylimidazolinium, 1,3,4-trimethylimidazolinium, and 1,2,3,4-tetramethylimidazolinium; tetrahydropyrimidiniums such as N,N'-dimethyltetrahydropyrimidinium; and morpholiniums such as N,N'-dimethylmorpholinium. pyridinium such as N-methylpyridinium, N-benzylpyridinium, and N-phenacylpyridinium; imidazolium such as N,N'-dimethylimidazolium; quinolium such as N-methylquinolium, N-benzylquinolium, and N-phenacylquinolium; isoquinolium such as N-methylisoquinolium; thiazonium such as benzylbenzothiazonium and phenacylbenzothiazonium; and acridium such as benzylacridium and phenacylacridium.

[0069] Examples of the phosphonium cation include tetraarylphosphoniums such as tetraphenylphosphonium, tetra-p-tolylphosphonium, tetrakis(2-methoxyphenyl)phosphonium, tetrakis(3-methoxyphenyl)phosphonium, and tetrakis(4-methoxyphenyl)phosphonium; triarylphosphoniums such as triphenylbenzylphosphonium, triphenylphenacylphosphonium, triphenylmethylphosphonium, and triphenylbutylphosphonium; and tetraalkylphosphoniums such as triethylbenzylphosphonium, tributylbenzylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, tetrahexylphosphonium, triethylphenacylphosphonium, and tributylphenacylphosphonium.

[0070] Specific examples of the iodonium salt-based photoacid generator include arsenate-based iodonium salt photoacid generators such as diphenyliodonium hexafluoroarsenate, di(4-chlorophenyl)iodonium hexafluoroarsenate, di(4-bromophenyl)iodonium hexafluoroarsenate, and phenyl(4-methoxyphenyl)iodonium hexafluoroarsenate; 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexafluorophosphate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium tri(pentafluoroethyl)trifluorophosphate (e.g., IK-1 manufactured by San-Apro Co., Ltd.), 4-methylphenyl-4-(2-methylpropyl)phenyliodonium hexafluorophosphate (e.g., IRGACURE (registered trademark) 250 manufactured by BASF), and bis(C １０～１４photoacid generators which are phosphate-based iodonium salts such as 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexafluorophosphate (for example, WPI-113 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.); photoacid generators which are antimonate-based iodonium salts such as 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexafluoroantimonate (for example, WPI-116 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.); iodonium salt-based photoacid generators such as IK-1FG (manufactured by San-Apro Co., Ltd.); 4-methylphenyl-4-(1-methylethyl)phenyliodonium tetrakis(pentafluorophenyl)borate, 4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate (for example, BLUESIL (registered trademark) PI manufactured by ELKEM SILICONES, Inc.); Examples of suitable photoacid generators include, but are not limited to, borate-based iodonium salts such as 2074 and the like.

[0071] Specific examples of sulfonium salt-based photoacid generators include, but are not limited to, borate-based sulfonium salt photoacid generators (for example, San-Apro Ltd. product names: CPI-110B, CPI-310B, CPI-410B, etc., and IGM Resins B.V. product name: Omnirad 290, etc.), phosphate-based sulfonium salt photoacid generators (San-Apro Ltd. product names: CPI-210S, VC-1S, CPI-410S, etc.), and other sulfonium salt-based photoacid generators (San-Apro Ltd. product names: CPI-310FG, VC-1FG, etc.).

[0072] The photoacid generators may be used alone or in combination of two or more.

[0073] The amount of photoacid generator in the photocurable resin composition is preferably 0.5 to 15 parts by mass, and more preferably 1 to 10 parts by mass, based on 100 parts by mass of the total amount of cationic polymerizable compounds.

[0074] The photobase generator absorbs light to generate a base as an active species, thereby promoting the polymerization of the anionically polymerizable compound. Examples of the photobase generator include, but are not limited to, various compounds that generate a base such as an amine, amidine, guanidine, phosphazene, or carbene.Specific examples of photobase generators include, for example, 2-benzyl-2-(dimethylamino)-1-[4-(morpholino)phenyl]-1-butanone, 2-(dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one, 2-nitrobenzyl 4-hydroxypiperidine-1-carboxylate, 4,5-dimethoxy-2-nitrobenzyl 2,6-dimethylpiperidine-1-carboxylate, 1-(9,10-dioxo-9,10-dihydroanthracene-2-yl)ethylcyclohexylcarbamate, 1-(9,10-dioxo-9,10-dihydroanthracene-2-yl)ethyl 1H-imidazole-1-carboxylate, 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine-1- Ium 2-(3-benzoylphenyl)propanoate, diaminomethaneiminium 2-(3-benzoylphenyl)propanoate, (Z)-N-(((bis(dimethylamino)methylene)amino)(isopropylamino)methylene)propane-2-aminium 2-(3-benzoylphenyl)propanoate, 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidium n-butyltriphenylborate, (Z)-{[bis(dimethylamino)methylidene]amino}-N-cyclohexyl(cyclohexylamino)methaniminium tetrakis(3-fluorophenyl)borate, 1,2-diisopropyl-3-[bis(dimethylamino)methylene]guanidium 2-(3-benzoylphenyl)propionate, 9-antrylmethyl Examples include, but are not limited to, N,N-diethylcarbamate, (E)-1-piperidino-3-(2-hydroxyphenyl)-2-propen-1-one, 2-nitrophenylmethyl 4-methacryloyloxypiperidine-1-carboxylate, tetramethylguanidium tetrakis(3-fluorophenyl)borate, tetramethylguanidium tetrakis(4-fluorophenyl)borate, salts containing protonated DBU and tetrakis(3-fluorophenyl)borate anion, and salts containing benzylated DBU and tetrakis(3-fluorophenyl)borate anion. These may be used individually or in combination of two or more.

[0075] The photobase generators may be used alone or in combination of two or more.

[0076] The amount of photobase generator in the photocurable resin composition is preferably 0.5 to 15 parts by mass, and more preferably 1 to 10 parts by mass, based on 100 parts by mass of the total amount of anionic polymerizable compounds.

[0077] The photopolymerization initiator may be one of the following: a photoradical polymerization initiator, a photoacid generator, or a photobase generator, or any combination of these may be used.

[0078] The photocurable resin composition of this embodiment may, if desired, contain components (A) and (B) or any other components other than components (A) to (C), such as those described below.

[0079] Multiphoton Excitation Type Photon Up-Conversion Material The photocurable resin composition of this embodiment may contain a multiphoton excitation type photon up-conversion material, provided that the object of this embodiment is not impaired. The multiphoton excitation type photon up-conversion material is a material that emits up-conversion light by multiphoton excitation. The wavelength of the up-conversion light emitted by the multiphoton excitation type photon up-conversion material preferably includes a wavelength of 500 nm or less, more preferably a wavelength of 450 nm or less, even more preferably a wavelength of 430 nm or less, and particularly preferably a wavelength of 400 nm or less. In an embodiment, the emission wavelength of the multiphoton excitation type photon up-conversion material includes the wavelength of ultraviolet light (200 nm to 380 nm). The multiphoton excitation type photon up-conversion material may have an emission peak in the red or green region in addition to the UV-A, violet, or blue region. In this specification, the red region refers to the wavelength range of light from 600 to 800 nm, the green region refers to the wavelength range of light from 500 to 600 nm, and the blue region refers to the wavelength range of light from 400 to 500 nm.

[0080] In multi-photon excitation type photon up-conversion materials, an optically inactive host material is doped with a rare earth element, thereby exhibiting up-conversion luminescence characteristics. In multi-photon excitation type photon up-conversion materials, up-conversion luminescence of any wavelength can be obtained by appropriately selecting the type and amount of rare earth element contained (doping amount).

[0081] The rare earth element is not particularly limited as long as it is a rare earth element capable of upconversion emission, but typically includes rare earth elements that become trivalent ions. Among them, it is preferable to use a combination of at least two or more rare earth elements selected from the group consisting of erbium (Er), holmium (Ho), praseodymium (Pr), thulium (Tm), neodymium (Nd), gadolinium (Gd), europium (Eu), ytterbium (Yb), samarium (Sm), and cerium (Ce). In addition, examples of the combination of rare earth elements include a combination of ytterbium (Yb), erbium (Er) and thulium (Tm), a combination of praseodymium (Pr), erbium (Er) and thulium (Tm), and a combination of erbium (Er) and thulium (Tm), among which, a combination of ytterbium (Yb), erbium (Er) and thulium (Tm), and a combination of ytterbium (Yb) and thulium (Tm) are preferred. In particular, examples of the combination of rare earth elements having a strong upconversion emission at blue light wavelengths include Yb ３＋ / Tm ３＋ Examples include:

[0082] The wavelength range of the excitation light that causes such a multi-photon excitation type photon upconversion material to emit upconversion light is preferably a wavelength of more than 500 nm, for example, a wavelength in the range of more than 500 nm and not more than 2000 nm.

[0083] The base material (matrix) is a material that supports rare earth elements, and is not particularly limited as long as it supports the rare earth elements in a state capable of upconversion luminescence. It may be an organic material that reacts with the rare earth elements to form complexes, dendrimers, etc., or it may be an inorganic material. An inorganic material is preferred because it is easy to incorporate the rare earth elements in a state capable of luminescence.

[0084] As such inorganic base materials, materials that are transparent to excitation light are preferred from the viewpoint of luminescence efficiency, and specifically, halides such as fluorides and chlorides, oxides, sulfides, and acid sulfides are preferably used. An example of a halide is barium chloride (BaCl). ２ ), lead chloride (PbCl ２ ), lead fluoride (PbF ２ ), cadmium fluoride (CdF ２ ), lanthanum fluoride (LaF ３ ), yttrium fluoride (YF ３ Examples of oxides include, but are not limited to, yttrium oxide (Y ２ O ３ ), cerium oxide (CeO ２ ), aluminum oxide (Al ２ O ３ ), silicon dioxide (SiO ２ ), tantalum oxide (Ta ２ O ５ Examples include, but are not limited to, those listed above. Furthermore, a coating material may be formed around a multiphoton-excited type photon upconversion material that uses a halide as the base material. The oxides listed above can be used as this coating material.

[0085] Multiphoton-excited photon upconversion materials can be manufactured by known methods, such as gas evaporation including high-frequency plasma methods, sputtering, glass crystallization, chemical deposition, reverse micelle methods, sol-gel methods and similar methods, precipitation methods including hydrothermal synthesis and coprecipitation, or spray methods. For example, a method for manufacturing multiphoton-excited photon upconversion materials can be found in the method described in Japanese Patent Application Publication No. 2006-117864. Commercially available multiphoton-excited photon upconversion materials may also be used.

[0086] When a multiphoton-excited type photon upconversion material is included, the amount of the multiphoton-excited type photon upconversion material in the photocurable resin composition is, from the viewpoint of photoconversion efficiency and degree of photocuring, for example, 0.1 to 60 parts by mass, preferably 0.1 to 50 parts by mass, preferably 0.1 to 40 parts by mass, and more preferably 1 to 30 parts by mass, per 100 parts by mass of the total amount of the photocurable resin composition.

[0087] For example, in one embodiment, by using (B) triplet-triplet annihilation photon upconversion particles in combination with a multiphoton-excited type photon upconversion material, energy transfer becomes possible in the photocurable resin composition from (B) triplet-triplet annihilation photon upconversion particles to the multiphoton-excited type photon upconversion material, or from the multiphoton-excited type photon upconversion material to (B) triplet-triplet annihilation photon upconversion particles. Through such stepwise energy transfer, the emission wavelength of the photon upconversion material can be adjusted so that it ultimately includes wavelengths of 500 nm or less from the desired incident light, thereby enabling photocuring of the resin composition using the desired incident light.

[0088] Filler: The photocurable resin composition of this embodiment may contain a filler to the extent that the object of this embodiment is not impaired. By containing a filler in the resin composition, the linear expansion coefficient of the cured product obtained by curing the resin composition can be reduced, and thermal cycle resistance can be improved. Furthermore, if the filler has a low elastic modulus, stress generated in the cured product can be alleviated, and long-term reliability can be improved. Fillers are broadly classified into inorganic fillers and organic fillers.

[0089] The inorganic filler is not particularly limited as long as it is made of granular material formed from an inorganic material and has the effect of lowering the linear expansion coefficient when added. Examples of inorganic materials that can be used include silica, talc, alumina, aluminum nitride, calcium carbonate, aluminum silicate, magnesium silicate, magnesium carbonate, barium sulfate, barium carbonate, lime sulfate, aluminum hydroxide, calcium silicate, potassium titanate, titanium oxide, zinc oxide, silicon carbide, silicon nitride, and boron nitride. Any one of the inorganic fillers may be used alone, or two or more may be used in combination. As the inorganic filler, silica filler is preferably used because it can increase the loading amount. As the silica, amorphous silica is preferred.

[0090] The inorganic filler may be surface-treated with a coupling agent such as a silane coupling agent, thereby allowing the thixotropic index (TI) of the resin composition to fall within an appropriate range.

[0091] The organic filler is not particularly limited, but examples thereof include organic fine particles of acrylic resin, polyolefin, polybutadiene rubber, polyvinyl alcohol, polyester, polyurethane, melamine, nylon, polyvinyl butyral, polyarylate, polymethyl methacrylate, polyethylene, polypropylene, polycarbonate, acrylic rubber, polystyrene, NBR, SBR, polytetrafluoroethylene, benzoguanamine-formaldehyde, silicone rubber, silicone-modified resin, phenol resin, and copolymers containing these as components. The organic filler may also be surface-treated.

[0092] The shape of the filler is not particularly limited, and may be any of spherical, flaky, needle-like, irregular, etc.

[0093] The average particle size of the filler is preferably 0.01 to 15 μm, more preferably 0.01 to 10 μm. From the viewpoint of the transmittance of long-wavelength light irradiated to the resin composition, the maximum particle size of the filler is preferably 50 μm or less, more preferably 30 μm or less.

[0094] In this specification, the average particle size of the filler is the particle size at 50% of the cumulative value in the particle size distribution on a volume basis measured by a laser diffraction / scattering method, and the maximum particle size is the maximum particle size in the particle size distribution on a volume basis measured by a laser diffraction / scattering method.

[0095] When a filler is contained, the content of the filler is preferably 0.5 to 80% by mass, more preferably 1 to 70% by mass, based on the total mass of the photocurable resin composition.

[0096] The photocurable resin composition of this embodiment may contain a thixotropic agent to the extent that the effects of this embodiment are not impaired. Examples of thixotropic agents include silica such as colloidal silica, hydrophobic silica, fine silica, and nanosilica, as well as bentonite, acetylene black, and ketjen black. Nanosilica is preferred from the viewpoint of shape retention after application. Furthermore, from the viewpoints of preventing the resin composition from biting during bonding and moisture-resistant adhesion, the thixotropic agent is more preferably nanosilica having an average particle size of 10 to 750 nm, and even more preferably nanosilica having an average particle size of 20 to 600 nm. Commercially available products include hydrophobic fumed silica manufactured by CABOT Corporation (product name: CAB-O-SIL (registered trademark) 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: Seahoster KE-P10, average particle size 100 nm), but are not limited to these. Here, the average particle size of the nanosilica particles is measured using a dynamic light scattering Nanotrac particle size analyzer. The thixotropic agent may be used alone or in combination of two or more types.

[0097] When a thixotropic agent is contained, the content of the thixotropic agent is preferably 0.01 to 30 mass %, more preferably 0.05 to 25 mass %, and even more preferably 0.1 to 20 mass %, relative to the total mass of the photocurable resin composition.

[0098] Light-blocking agent: The photocurable resin composition of this embodiment may contain a light-blocking agent to the extent that the effect of this embodiment is not impaired. Light-blocking properties may be required depending on the application of the cured product of the photocurable resin composition. In such cases, the photocurable resin composition of this embodiment may contain a light-blocking agent. Long-wavelength light can be transmitted through a light-blocking agent that blocks ultraviolet light. The photocurable resin composition of this embodiment can be cured by irradiating it with long-wavelength light without or with minimal influence from the light-blocking agent. Examples of light-blocking agents include, but are not limited to, carbon black and titanium black. These light-blocking agents can also be used as light-to-heat conversion materials that convert long-wavelength light into heat.

[0099] Other Additives If desired, the photocurable resin composition of this embodiment may further contain other additives, such as a photosensitizer, a conductive filler, a stabilizer, a radical polymerization inhibitor, an anionic polymerization inhibitor, a coupling agent, an ion trapping agent, a leveling agent, an antioxidant, an antifoaming agent, a viscosity modifier, a flame retardant, a colorant, a plasticizer, a solvent, a thermal radical polymerization initiator, a thermal acid generator, a thermal base generator, etc. The type and amount of each additive are as usual.

[0100] The viscosity of the photocurable resin composition of this embodiment is preferably 0.1 to 100 Pa·s. The viscosity can be adjusted appropriately depending on the application and application location of the resin composition. The photocurable resin composition of this embodiment is excellent for application to areas with complex shapes that are difficult to irradiate with UV light, or for application to narrow areas. In this specification, viscosity is expressed as a value measured in accordance with Japanese Industrial Standard JIS K6833, unless otherwise specified. Specifically, it can be determined by measuring using an E-type viscometer at a rotation speed of 10 rpm. There are no particular limitations on the equipment, rotor, or measurement range used.

[0101] The photocurable resin composition of this embodiment can be a one-component resin composition contained in a single container, or a two-component (or multi-component) resin composition divided into two or more containers, depending on the intended use. When using a two-component (or multi-component) resin composition, the two components (or multiple components) are mixed to form a photocurable resin composition for use. When using a two-component (or multi-component) resin composition, the components (A) and (B) or the components (A) to (C), and other optional components as needed, can be selected in the same manner as for a one-component resin composition. Furthermore, when using a two-component (or multi-component) resin composition, the components (A) and (B) or the components (A) to (C), and other optional components as needed, can be divided into two or multiple components in any manner without particular limitation. When the composition is separated into two or more liquids by any separation method, each liquid may contain one or more components selected from the group consisting of component (A) and component (B) or component (A) to component (C) and other optional components as required; one liquid may contain component (A) and component (B) or component (A) to component (C) and other optional components as required; or there may be a liquid consisting only of component (A) and component (B) or component (A) to component (C) and / or other optional components as required. For example, when the solution is separated into Solution A and Solution B, the separation may be as follows: Solution A: component (A) (including a maleimide compound), Solution B: component (B), Solution A: component (A), Solution B: component (B) and component (C), Solution A: component (A) and component (B), Solution B: component (C), Solution A: component (A) and component (C), Solution B: component (B), Solution A: component (A) and component (B), Solution B: component (A) and component (C). When Solution A contains components (A) and (B) or components (A) to (C), Solution B may contain one or more components selected from components (A) and (B) or components (A) to (C). In addition, components other than components (A) and (B) or components (A) to (C) may be contained in both or either Solution A and Solution B in the above combinations.When components (A) and (B) or components (A) to (C) are contained in liquid A and other components are contained in liquid B, liquid A alone or a combination of liquid A and liquid B can be considered the resin composition of this embodiment. On the other hand, when components (A) and (B) or components (A) to (C) are each contained in separate liquids, the respective liquids can be considered the resin composition of this embodiment. Examples of when components (A) and (B) or components (A) to (C) are each contained in separate liquids include resin compositions in which components (A) and (B) or components (A) to (C) are separated into two or more containers, specifically kits composed of multiple liquids containing either components (A) and (B) or components (A) to (C).

[0102] The method for producing the photocurable resin composition of this embodiment is not particularly limited. For example, the resin composition of this embodiment can be obtained by simultaneously or separately introducing component (A) and component (B) or components (A) to (C), and other optional components as necessary, into an appropriate mixer and mixing them by stirring to form a uniform composition. The mixer is not particularly limited, but examples of the mixer that can be used include a Raikai mixer, a Henschel mixer, a three-roll mill, a ball mill, a planetary mixer, and a bead mill equipped with a stirring device and a heating device. These devices may also be used in appropriate combination.

[0103] The photocurable resin composition obtained in this manner is cured by irradiation with long-wavelength light (e.g., longer than 500 nm), and does not require main curing by heat. Conventionally, high-energy short-wavelength light (e.g., UV light of 365 nm) is generally used to photocure conventionally used UV-curable adhesives. Therefore, when the adhesive contains a filler or the like, the penetration distance of light into the UV-curable adhesive is short when irradiated with short-wavelength light, and there is a problem that curing does not proceed in areas where the light does not reach due to a shielding object or the like. Regarding the latter in particular, for example, when the shielding object is a silicon substrate and the relationship between the wavelength of irradiated light and the penetration distance of light on the silicon substrate is examined, ultraviolet light of 380 nm or less penetrates the silicon substrate by several to several tens of nanometers, while visible light of 380 to 700 nm penetrates by several hundred nanometers to several microns, and infrared light of 700 nm or more penetrates by several tens of microns to the order of millimeters (see, for example, Optical Properties of Silicon, [online], PVEducation,<https: / / www.pveducation.org / pvcdrom / materials / optical-properties-of-silicon> (See reference 2003). The penetration distance of light when irradiating a resin composition with ultraviolet light is deeper than that of a silicon substrate, but increasing the irradiation wavelength can be said to be useful as a method for increasing the degree of cure of the resin composition. The photocurable resin composition of this embodiment can be cured by light irradiation alone, but may be subjected to a heat treatment before and / or after light irradiation.

[0104] The photocurable resin composition of this embodiment can be used, for example, as an adhesive, sealant, or coating agent for fixing, joining, or protecting semiconductor devices or electronic components, or components constituting these, or as a raw material thereof. In one embodiment, the photocurable resin composition of this embodiment can be used for curing by irradiation with light having a wavelength of more than 500 nm. In one embodiment, the photocurable resin composition of this embodiment can be used as an adhesive, sealant, or coating agent for semiconductor devices or electronic components.

[0105] [Bonding Method] Another aspect of the present invention is a method for bonding at least two parts with a photocurable resin composition, the bonding method comprising the steps of: applying the photocurable resin composition of the above aspect to at least one of the at least two parts; and irradiating at least one of the at least two parts, the photocurable resin composition, or both thereof with light having a wavelength greater than 500 nm.

[0106] As a first step, the photocurable resin composition according to the above embodiment is applied to at least one of at least two parts. The parts are preferably components constituting a semiconductor device or electronic component, such as semiconductor elements or substrates, but are not limited thereto. The material of the parts may be any of the following: engineering plastics (e.g., LCP (liquid crystal polymer), polyamide, polycarbonate, etc.), ceramics, or metals (e.g., copper, nickel). The method of applying the resin composition is not particularly limited, and for example, it can be applied to a desired part of a part such as a substrate by a known printing method, dispensing method, or coating method. Examples of printing methods include, but are not limited to, inkjet printing, screen printing, lithographic printing, cardboard printing, metal printing, offset printing, gravure printing, flexographic printing, etc. Examples of dispensing methods include, but are not limited to, methods using jet dispensers, air dispensers, etc. Examples of coating methods include, but are not limited thereto.

[0107] Next, one part is attached to the part coated with the photocurable resin composition via the photocurable resin composition, or the part coated with the photocurable resin composition is attached to the other part via the photocurable resin composition. Any known method of attachment may be used. If necessary, the parts can be pressed together under load after attachment.

[0108] Next, at least one of the at least two components, the photocurable resin composition, or both of them is irradiated with light having a wavelength of more than 500 nm, for example, light having a wavelength in the range of more than 500 nm and not more than 2000 nm. As a result, the triplet-triplet annihilation photon upconversion particles within the resin composition undergo wavelength conversion, generating light having a wavelength of 500 nm or less, preferably light having a wavelength of 450 nm or less, more preferably light having a wavelength of 430 nm or less, and particularly preferably light having a wavelength of 400 nm or less, which activates the photopolymerization initiator and cures the polymerizable compound, thereby bonding the at least two components together. The wavelength of the irradiated light may be, for example, 532 nm, 980 nm, 1064 nm, or 1550 nm, but is not limited to these wavelengths. The light source may be an LED, laser, LD module, or other coherent light source. The cumulative dose of the irradiated light is 1 mJ / cm. ２ ~2000 J / cm ２ The irradiation intensity can be 1 mW / cm ２ ~1000 W / cm ２ The cumulative irradiation amount and irradiation intensity of the irradiated light can be adjusted appropriately depending on the desired degree of cure. In this embodiment, either spot irradiation, in which light is irradiated to a local area, or area irradiation, in which light is irradiated to a wide area, can be performed. Since the resin composition used in this embodiment can be cured even in the shadow area of ​​the part, in the bonding method of this embodiment, the resin composition can be irradiated with light not only directly but also through the part.

[0109] [Sealing Method] Another aspect of the present invention is a method for sealing gaps between or within components with a photocurable resin composition, the sealing method comprising the steps of applying or injecting the photocurable resin composition of the above-described embodiment into the gaps between or within the components, and irradiating the photocurable resin composition with light having a wavelength of more than 500 nm. The components and the light irradiation are the same as those in the above-described bonding method. Examples of application or injection methods include, but are not limited to, the application method in the above-described bonding method and a potting method. The resin composition used in this embodiment achieves a high cure depth due to the extended triplet-triplet annihilation photon upconversion light emission duration. Therefore, the sealing method of this embodiment can cure the resin composition present deep in gaps that are difficult for ultraviolet light to reach, thereby achieving suitable sealing.

[0110] [Coating Method] Another aspect of the present invention is a method for coating the surface of an object with a photocurable resin composition, the method comprising: applying the photocurable resin composition of the above aspect to the object; and irradiating the photocurable resin composition with light having a wavelength of more than 500 nm. The object may be a semiconductor device or electronic component, or a component constituting the same. Examples of semiconductor devices or electronic components include, but are not limited to, HDDs, semiconductor elements, sensor modules such as image sensor modules, other semiconductor modules, and integrated circuits. Components constituting the semiconductor device or electronic component include, but are not limited to, semiconductor elements, substrates, etc. The material of the component may be any of engineering plastics (e.g., LCP (liquid crystal polymer), polyamide, polycarbonate, etc.), ceramics, or metals (e.g., copper, nickel), etc. The application method is the same as that in the bonding method. The light irradiation method is the same as that in the bonding method.

[0111] [Adhesive, Sealant, or Coating Agent] Another embodiment of the present invention is an adhesive, sealant, or coating agent that includes the photocurable resin composition of the above embodiment. This adhesive, sealant, or coating agent provides excellent fixation, bonding, or protection for engineering plastics (e.g., LCP (liquid crystal polymer), polyamide, polycarbonate, etc.), ceramics, and metals (e.g., copper, nickel, etc.), and can be used to fix, bond, or protect semiconductor devices or electronic components, or the components that make them up. Examples of semiconductor devices or electronic components include, but are not limited to, HDDs, semiconductor elements, sensor modules such as image sensor modules, other semiconductor modules, and integrated circuits. The adhesive, sealant, or coating agent of this embodiment can be completely cured by irradiation with long-wavelength light (e.g., longer than 500 nm), which allows for high productivity and makes it suitable for use, for example, in the manufacture of semiconductor devices and electronic components.

[0112] [Cured product of a photocurable resin composition or adhesive, sealant or coating agent] Another embodiment of the present invention is a cured product obtained by curing the photocurable resin composition or adhesive, sealant or coating agent of the above embodiment.

[0113] [Semiconductor Device, Electronic Component] A semiconductor device or electronic component according to another embodiment of the present invention includes the cured product of the above-described embodiment, and therefore has high reliability. Here, the term "semiconductor device" refers to any device that can function by utilizing semiconductor properties, including electronic components, semiconductor circuits, modules incorporating these, electronic devices, etc. Examples of semiconductor devices or electronic components include, but are not limited to, HDDs, semiconductor elements, sensor modules such as image sensor modules, other semiconductor modules, and integrated circuits.

[0114] [Curing Method, Method for Producing Cured Product] Another aspect of the present invention is a method for producing a cured product, comprising irradiating the photocurable resin composition of the above-described aspect, or the adhesive, sealant, or coating agent of the above-described aspect, with light having a wavelength of greater than 500 nm. Yet another aspect of the present invention is a method for curing a photocurable resin composition, comprising irradiating the photocurable resin composition of the above-described aspect with light having a wavelength of greater than 500 nm. By irradiating the resin composition with light having a wavelength of greater than 500 nm, for example, light having a wavelength in the range of greater than 500 nm and less than or equal to 2000 nm, triplet-triplet annihilation photon upconversion particles perform wavelength conversion within the resin composition, generating light having a wavelength of 500 nm or less, preferably light having a wavelength of 450 nm or less, more preferably light having a wavelength of 430 nm or less, and particularly preferably light having a wavelength of 400 nm or less, which activates the photopolymerization initiator and cures the polymerizable compound. The details of the irradiation with light having a wavelength of greater than 500 nm in these methods are the same as those in the above-described bonding method, sealing method, and coating method. In this embodiment, either spot irradiation, in which light is irradiated onto a local region, or area irradiation, in which light is irradiated onto a wide region, can be performed.

[0115] The present invention will be described in more detail below with reference to examples and reference 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.

[0116] [Production of Photocurable Resin Compositions] Resin compositions of Examples 1 to 3 and Reference Example 1 were prepared by mixing predetermined amounts of each component according to the formulations shown in Tables 1 and 2. In Tables 1 and 2, the amount of each component is expressed in parts by mass. The components used in the Examples and Reference Example are as follows:

[0117] (A) Polymerizable Compound (A-1): Dimethylol-tricyclodecane diacrylate (product name: Light Acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd.) (A-2): Bismaleimide having a hydrocarbon group derived from dimer acid (product name: BMI-689, manufactured by Designer Molecules Inc.) (B) Triplet-Triplet Annihilation Photon Up-Conversion Particle (B-1): Triplet-Triplet Annihilation Photon Up-Conversion Particle 1 0.18 mL of styrene (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.2 mL of divinylbenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a MilliQ solution (9 mL) containing 5 mg of potassium peroxodisulfate (manufactured by Sigma-Aldrich Japan), and the mixture was heated at 80°C to prepare cross-linked polystyrene (average particle size: 118 nm) by emulsion polymerization. Next, a solution of 0.46 mg of platinum(II) octaethylporphyrin (PtOEP) (Sigma-Aldrich Japan) as the donor and 5.3 mg of diphenylanthracene (DPA) (Tokyo Chemical Industry Co., Ltd.) as the acceptor in dichloromethane (0.4 mL) was impregnated into a MiliiQ dispersion (10 mL) containing 100 mg of cross-linked polystyrene particles, thereby dispersing the triplet-triplet annihilation photon upconversion material into the cross-linked polystyrene particles by the swelling effect, yielding nanoparticles. Next, ethanol (6 mL) and 6 mL of 28% aqueous ammonia (Fujifilm Wako Pure Chemical Industries) were added to the nanoparticles (95 mg), and the mixture was heated at 40°C for 6 hours. Subsequently, an ethanol solution (6 mL) containing 47.5 mg of tetraethoxysilane (TEOS, manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, and the mixture was heated at 40°C for 12 hours to coat the nanoparticle surface with silica by the Stober method, yielding (B-1) triplet-triplet annihilation photon upconversion particles 1. The mass ratio of the donor and acceptor PtOEP:DPA was 1:11 (molar ratio 1:25). The content of DPA in the crosslinked polystyrene particles was estimated by differential thermal thermogravimetry (Rigaku TG-DTA8122) and was found to be 9.2 parts by mass per 100 parts by mass of the crosslinked polystyrene particles. This component (B-1) maintained its particle shape even when mixed with (A) the polymerizable compound.(B-2): Triplet-triplet annihilation photon upconversion particle 2 A solution of 0.5 mg of platinum(II) octaethylporphyrin (PtOEP) (Sigma-Aldrich Japan) as a donor and 12 mg of diphenylanthracene (DPA) (Tokyo Chemical Industry Co., Ltd.) as an acceptor in chloroform (500 mL) was added to 100 mg of cross-linked polystyrene particles (product name: Chemisnow). ＴＭ The triplet-triplet annihilation photon up-conversion material was mixed with polystyrene particles (SX-130H, manufactured by Soken Chemical & Engineering Co., Ltd., average particle size: 1.3 μm) and gently stirred at room temperature for 2 hours to disperse the triplet-triplet annihilation photon up-conversion material into the cross-linked polystyrene particles by the swelling effect. （Ｒ） The mixture was centrifuged at 10,000 rpm for 30 seconds using a 1.2 ml personal centrifuge (Merck Millipore Corporation) to separate the liquid component from the polystyrene particles, and the liquid component was removed as much as possible. 1.5 ml of ethanol was added to the remaining polystyrene particles, which were then stirred for about 1 minute. （Ｒ）The mixture was centrifuged at 10,000 rpm for 30 seconds using a 1.2 personal centrifuge, and the supernatant was discarded and washed, taking care not to entrain the settled polystyrene particles. This washing procedure was repeated five times, and it was confirmed that the supernatant became clear. The particles were then dried by heating in a dryer at 80°C for 2 hours to obtain (B-2) triplet-triplet annihilation photon upconversion particles 2. The DPA and PtOEP contents in the crosslinked polystyrene particles were quantified by absorptiometry from the dispersion solution and the residue after centrifugation. The DPA and PtOEP contents in the crosslinked polystyrene particles were also measured by GC-MS. This component (B-2) maintained its particle form even when mixed with (A) the polymerizable compound. Platinum(II) octaethylporphyrin (PtOEP) (Sigma-Aldrich Japan) was used as the donor for (B') triplet-triplet annihilation photon upconversion material that is not in particle form. Diphenylanthracene (DPA) (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the acceptor. The mass ratio of the donor and acceptor PtOEP:DPA was set to 1:11 (molar ratio 1:25), and (B') a non-particulate triplet-triplet annihilation photon upconversion material was obtained. This component (B') was dissolved by mixing with (A) the polymerizable compound. (C) Photopolymerization initiator (C-1): 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one (product name: Omnirad 379EG, manufactured by IGM Resins B.V.).

[0118] In the examples and reference examples, the properties of the resin compositions were measured as follows.

[0119] [Measurement of Light-Emitting Properties of Resin Compositions] The resin compositions of Example 1 and Reference Example 1 were irradiated with visible light at a wavelength of 532 nm, and the change in photon upconversion luminescence over time was evaluated. The upconversion luminescence spectra were measured using an MCPD-9800 (manufactured by Otsuka Electronics Co., Ltd.) as a detector, using an externally attached semiconductor laser (532 nm) with adjustable laser intensity as excitation light. FIG. 1 shows the change in normalized luminescence intensity of photon upconversion luminescence over time for the resin compositions of Example 1 and Reference Example 1. As shown in FIG. 1, the resin composition of Reference Example 1, which contained the triplet-triplet annihilation photon upconversion material (B') not in particulate form, exhibited attenuation of photon upconversion luminescence intensity over time. On the other hand, the resin composition of Example 1, which contained triplet-triplet annihilation photon upconversion particles 1 (B-1), exhibited suppressed attenuation of photon upconversion luminescence intensity over time, and exhibited a longer luminescence duration compared to the resin composition of Reference Example 1.

[0120] [Evaluation of Curability of Resin Composition] In a dark place at a temperature of 22°C ± 5°C and a humidity of 50% ± 10%, a drop (approximately 0.02 g) of the photocurable resin composition was placed on a glass slide, which was then inserted with another glass slide to prepare a test piece, and the test piece was then irradiated with visible light. The visible light irradiation conditions were as follows: visible light with a wavelength of 532 nm and an irradiation intensity of 10 mW / cm, using a semiconductor-excited solid-state laser (Class 3R green laser pointer LP-GL1016BK, manufactured by Sanwa Supply Co., Ltd.) at a position 4 cm above the light source from the top surface of the glass slide. ２ The cumulative light intensity is 5000 to 10000 mJ / cm ２ The material was continuously irradiated until curing occurred. In this test, one slide glass was peeled off the test specimen, and the photocurability was evaluated in three stages: cured (○), partially uncured (△), and uncured (×) by visual inspection and palpation with a bamboo skewer. The results are shown in Tables 1 and 2.

[0121]

[0122]

Claims

1. A photocurable resin composition comprising (A) a polymerizable compound and (B) triplet-triplet annihilation photon upconversion particles, which satisfies at least one of the following characteristics (a) and (b): (a) (A) the polymerizable compound comprises a maleimide compound; (b) the photocurable resin composition comprises (C) a photopolymerization initiator.

2. The photocurable resin composition according to claim 1, wherein the triplet-triplet annihilation photon upconversion particles (B) are particles in which a triplet-triplet annihilation photon upconversion material is dispersed or encapsulated in an organic polymer matrix.

3. The photocurable resin composition according to claim 1 or 2, wherein, when characteristic (a) is satisfied, the maleimide compound is a maleimide compound having an absorption wavelength of 500 nm or less, and when characteristic (b) is satisfied, the (C) photopolymerization initiator is a photopolymerization initiator that is activated by light having a wavelength of 500 nm or less.

4. The photocurable resin composition according to any one of claims 1 to 3, wherein the (C) photopolymerization initiator is a photoradical polymerization initiator, a photoacid generator, a photobase generator, or any combination thereof.

5. The photocurable resin composition according to any one of claims 1 to 4, wherein the emission wavelength of the triplet-triplet annihilation photon upconversion particles (B) includes a wavelength of 500 nm or less.

6. The photocurable resin composition according to any one of claims 1 to 5, wherein the polymerizable compound (A) is a radical polymerizable compound, a cation polymerizable compound, an anion polymerizable compound, or any combination thereof.

7. The photocurable resin composition according to any one of claims 1 to 6, wherein the content of component (B) in the photocurable resin composition is 0.01 to 80 parts by mass per 100 parts by mass of the total amount of the polymerizable compound (A).

8. The photocurable resin composition according to any one of claims 1 to 7, wherein, when characteristic (b) is satisfied, the content of the photopolymerization initiator (C) in the photocurable resin composition is 0.01 to 15 parts by mass per 100 parts by mass of the total of the polymerizable compounds (A).

9. The photocurable resin composition according to any one of claims 1 to 8, which is used for curing by irradiation with light having a wavelength of more than 500 nm.

10. The photocurable resin composition according to any one of claims 1 to 9, which is used as an adhesive, sealant or coating agent for semiconductor devices or electronic parts.

11. An adhesive, sealant or coating agent comprising the photocurable resin composition according to any one of claims 1 to 10.

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

13. A semiconductor device or electronic component comprising the cured product according to claim 12.

14. A method for producing a cured product, comprising irradiating the photocurable resin composition according to any one of claims 1 to 10, or the adhesive, sealant, or coating agent according to claim 11, with light having a wavelength of more than 500 nm.

15. A method for curing a photocurable resin composition, comprising irradiating the photocurable resin composition according to any one of claims 1 to 10 with light having a wavelength of more than 500 nm.

16. Use of the photocurable resin composition according to any one of claims 1 to 10 for curing by irradiation with light having a wavelength of more than 500 nm.

17. A method for bonding at least two components with a photocurable resin composition, comprising the steps of: applying the photocurable resin composition according to any one of claims 1 to 10 to at least one of the at least two components; and irradiating at least one of the at least two components, the photocurable resin composition, or both of them with light having a wavelength of more than 500 nm.

18. A method for sealing gaps between or within components with a photocurable resin composition, comprising the steps of applying or injecting the photocurable resin composition according to any one of claims 1 to 10 into the gaps between or within the components, and irradiating the photocurable resin composition with light having a wavelength of more than 500 nm.

19. A method for coating the surface of an object with a photocurable resin composition, comprising the steps of: applying the photocurable resin composition according to any one of claims 1 to 10 to the object; and irradiating the photocurable resin composition with light having a wavelength of more than 500 nm.

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