Photocurable resin composition, adhesive, sealing material, 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 that does not require full curing by heat; an adhesive, a sealing material, or a coating agent containing the photocurable resin composition; a cured product thereof; a semiconductor device or an electronic component containing the cured product; and a curing method, an adhesion method, a sealing method, and a coating method using a photocurable resin composition.　Provided are: a photocurable resin composition containing (A) a polymerizable compound, (B) a photopolymerization initiator, and (C) a photon upconversion material; an adhesive, a sealing material, or a coating agent containing the photocurable resin composition; a cured product thereof; a semiconductor device or an electronic component containing the cured product; and a curing method, an adhesion method, a sealing method, and a coating method using a 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 (e.g., Patent Documents 1 and 2). If the adhesive contains a filler or the like, the filler or the like may act as a shield against UV irradiation light, or if the area where the adhesive is applied has a complex shape, the UV irradiation light may be blocked, resulting in areas in the adhesive that are not reached by UV irradiation light. In such cases, those areas remain uncured, making it difficult to achieve the desired degree of cure. For this reason, this type of adhesive is used in applications where there are areas that are not reached by 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 case where the adhesive is applied to heat-sensitive members, there is a demand for an adhesive that can be completely cured by light irradiation alone, without requiring main curing by heat.

[0005] Therefore, an object of the present invention is to provide a photocurable resin composition that does not require main curing by heat, 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 that use the photocurable resin composition.

[0006] Specific means for solving the above problems are as follows. Aspects of the present invention include the following curable resin composition, adhesive, encapsulant or coating agent, cured product, semiconductor device or electronic component, method for producing a cured product, method for curing a photocurable resin composition, use of a photocurable resin composition, bonding method, encapsulating method, and coating method. (1) A photocurable resin composition comprising (A) a polymerizable compound, (B) a photopolymerization initiator, and (C) a photon upconversion material. (2) The photocurable resin composition according to (1), wherein the (B) photopolymerization initiator is a photopolymerization initiator activated by light having a wavelength of 500 nm or less. (3) The photocurable resin composition according to (1) or (2), wherein the (B) photopolymerization initiator is a photoradical polymerization initiator, a photoacid generator, a photobase generator, or any combination thereof. (4) The photocurable resin composition according to any one of (1) to (3), wherein the (C) photon upconversion material has an emission wavelength of 500 nm or less. (5) The photocurable resin composition according to any one of (1) to (4), wherein the polymerizable compound (A) is a radically polymerizable compound, a cationically polymerizable compound, an anionically polymerizable compound, or any combination thereof. (6) The photocurable resin composition according to any one of (1) to (5), for use in curing by irradiation with light having a wavelength of more than 500 nm. (7) The photocurable resin composition according to any one of (1) to (6), for use in an adhesive, encapsulant, or coating agent for semiconductor devices or electronic components. (8) An adhesive, encapsulant, or coating agent comprising the photocurable resin composition according to any one of (1) to (7). (9) A cured product obtained by curing the photocurable resin composition according to any one of (1) to (7), or the adhesive, encapsulant, or coating agent according to (8). (10) A semiconductor device or electronic component comprising the cured product according to (9). (11) A method for producing a cured product, comprising irradiating the photocurable resin composition according to any one of (1) to (7) above, or the adhesive, sealant, or coating agent according to (8) above, with light having a wavelength of more than 500 nm. (12) A method for curing a photocurable resin composition, comprising irradiating the photocurable resin composition according to any one of (1) to (7) above with light having a wavelength of more than 500 nm.(13) Use of the photocurable resin composition according to any one of (1) to (7) above for curing by irradiation with light having a wavelength of longer than 500 nm. (14) 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 (1) to (7) above 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 longer than 500 nm. (15) A method for sealing a gap 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 (1) to (7) above into the gap between or within the components, and irradiating the photocurable resin composition with light having a wavelength of longer than 500 nm. (16) A method for coating a surface of an object with a photocurable resin composition, comprising: a step of applying the photocurable resin composition according to any one of (1) to (7) to the object; and a step of irradiating the photocurable resin composition with light having a wavelength of more than 500 nm.

[0007] According to aspects of the present invention, there are provided a photocurable resin composition that does not require main curing by heat, 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 that use the photocurable resin composition.

[0008] 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 780 nm, "near-infrared light" refers to light with a wavelength of 780 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."

[0009] [Photocurable Resin Composition] The photocurable resin composition according to one embodiment of the present invention includes: (A) a polymerizable compound; (B) a photopolymerization initiator; and (C) a photon upconversion material. According to this embodiment, it is possible to provide a photocurable resin composition that does not require main curing by heat.

[0010] The present inventors focused on photon upconversion materials that can convert long-wavelength light to short-wavelength light. When irradiated with specific light, photon upconversion materials generate high-energy states through multiphoton excitation, triplet-triplet annihilation, or other processes, and emit light with a shorter wavelength than the incident light during the relaxation process. The present inventors hypothesized that by incorporating this photon upconversion material into a resin composition and irradiating the resin composition with long-wavelength light, the photon upconversion material would perform wavelength conversion within the resin composition, generating short-wavelength light and activating a photopolymerization initiator. The present inventors confirmed that photon upconversion light emission promotes curing of the resin composition. The present inventors also confirmed that photon upconversion light emission promotes curing of the resin composition even in the presence of an object blocking UV irradiation light, eliminating the need for thermal main curing.

[0011] (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, the (A) polymerizable compound can be appropriately selected from a radical polymerizable compound, a cation polymerizable compound, an anion polymerizable compound, or any combination thereof, depending on the type of (B) photopolymerization initiator described below.

[0012] Examples of the radical polymerizable compound include, but are not limited to, compounds having an unsaturated double bond such as (meth)acrylate compounds, (meth)acrylamide compounds, cyanoacrylate compounds, maleimide 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).

[0013] In this specification, the (meth)acrylate compound refers to a compound having at least one (meth)acryloyl group in the molecule, and includes a monofunctional (meth)acrylate compound having one (meth)acryloyl group and a polyfunctional (meth)acrylate compound having two or more (meth)acryloyl groups. Examples of the monofunctional (meth)acrylate compound 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 acrylate, methoxydipropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, 2-ethylhexyldiethylene glycol (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, and 3-phenoxybenzyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, octyl acrylate, nonyl acrylate, isononyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, cyclic trimethylolpropane formal acrylate, and 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, isobornyl Cyclohexyl (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-isopropyladamantan-2-yl (meth)acrylate, 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-furan Examples of the acrylic acid ester include mono(meth)acrylates of polyhydric alcohols or esters of monohydric alcohols and (meth)acrylic acid, such as 5-oxotetrahydrofuranyl(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.The polyfunctional (meth)acrylate compound is not limited to these. These may be used alone or in combination of two or more. Examples of the polyfunctional (meth)acrylate compound include diacrylate and / or dimethacrylate of tris(2-hydroxyethyl)isocyanurate; tris(2-hydroxyethyl)isocyanurate triacrylate and / or trimethacrylate; trimethylolpropane triacrylate and / or trimethacrylate, or an oligomer thereof; pentaerythritol triacrylate and / or trimethacrylate, or an oligomer thereof; polyacrylate and / or polymethacrylate of dipentaerythritol; tris(acryloxyethyl)isocyanurate; caprolactone-modified tris(acryloxyethyl)isocyanurate; caprolactone-modified tris(methacryloxyethyl)isocyanurate; polyacrylate and / or polymethacrylate of alkyl-modified dipentaerythritol; caprolactone-modified dipentaerythritol Examples of the (meth)acrylate compound include, but are not limited to, polyacrylates and / or polymethacrylates of teflon, ethoxylated bisphenol A diacrylate and / or ethoxylated bisphenol A dimethacrylate, dihydrocyclopentadiethyl acrylate and / or dihydrocyclopentadiethyl methacrylate, polyester acrylate and / or polyester methacrylate, dimethylol-tricyclodecane diacrylate, poly(meth)acrylates of ditrimethylolpropane, polyurethanes having two or more (meth)acryloyl groups per molecule, polyesters having two or more (meth)acryloyl groups per molecule, phenoxyethyl acrylate, isobornyl acrylate, phenoxydiethylene glycol (meth)acrylate, 4-tert-butylcyclohexyl acrylate, and epoxy resin half acrylate. The (meth)acrylate compound may be any one of the above-mentioned (meth)acrylate compounds, or two or more of them may be used in combination. Commercially available (meth)acrylate compounds include, for example, polyester acrylate (product name: EBECRYL810) manufactured by Daicel-Allnex Corporation, ditrimethylolpropane tetraacrylate (product name: EBECRYL140) manufactured by Daicel-Allnex Corporation,Examples of such an acrylate include, but are not limited to, polyester acrylate (product name: M7100) manufactured by Toagosei Co., Ltd., dimethylol-tricyclodecane diacrylate (product name: Light Acrylate DCP-A) manufactured by Kyoeisha Chemical Co., Ltd., and neopentyl glycol-modified trimethylolpropane diacrylate (product name: Kayarad R-604) manufactured by Nippon Kayaku Co., Ltd.

[0014] The (meth)acrylamide compound has an acrylamide group (H ２ C=CHCONH-) or methacrylamide group ((H ２ C=C(CH ３ )CONH-) Examples of the (meth)acrylamide compound include, but are not limited to, N,N'-methylenebis(meth)acrylamide, N,N'-ethylenebis(meth)acrylamide, 1,2-di(meth)acrylamide ethylene glycol, and the like.

[0015] 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.

[0016] In this specification, a maleimide compound is a compound having at least one maleimide group. Maleimide compounds include monofunctional maleimide compounds having one maleimide group and polyfunctional maleimide compounds having two or more maleimide groups, and maleimide compounds having two maleimide groups in particular are sometimes called bismaleimide compounds. Examples of bismaleimide compounds include N,N'-(4,4'-diphenylmethane)bismaleimide and 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-bismaleimidohexane, 1,2-bismaleimidoethane (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 compound having a hydrocarbon group derived from a dimer acid can be used. Such bismaleimide compounds are described, for example, in JP 2015-193725 A. Commercially available bismaleimide compounds 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. These compounds may be used alone or in combination of two or more. Commercially available monofunctional maleimides 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.

[0019] The vinyl ether compound has a vinyl ether group (H ２C═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.

[0020] 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.

[0021] 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.

[0022] The thiol compound in the mixture of the compound having an unsaturated double bond and the thiol compound is a compound containing at least one thiol group, and the thiol group can undergo a radical addition reaction (ene-thiol reaction) with the unsaturated double bond of the compound having an unsaturated double bond. Thiol compounds are broadly classified into thiol compounds having a hydrolyzable partial structure such as an ester bond in the molecule (i.e., hydrolyzable) and thiol compounds not having such a partial structure (i.e., non-hydrolyzable). Examples of hydrolyzable thiol compounds include trimethylolpropane tris(3-mercaptopropionate) (manufactured by SC Organic Chemical Industry Co., Ltd.: TMMP), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate (manufactured by SC Organic Chemical Industry Co., Ltd.: TEMPIC), pentaerythritol tetrakis(3-mercaptopropionate) (manufactured by SC Organic Chemical Industry Co., Ltd.: PEMP), and tetraethylene glycol bis(3-mercaptopropionate) (manufactured by SC Organic Chemical Industry Co., Ltd.: EGMP- 4), dipentaerythritol hexakis(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: DPMP), pentaerythritol tetrakis(3-mercaptobutyrate) (manufactured by Resonac Co., Ltd.: Karenz MT (registered trademark) PE1), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by Resonac Co., Ltd.: Karenz MT (registered trademark) NR1), and the like can be mentioned, but are not limited to these. These may be used alone or in combination of two or more. Examples of non-hydrolyzable polyfunctional thiol compounds include 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril (manufactured by Shikoku Chemical Industry Co., Ltd.: TS-G), 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril (manufactured by Shikoku Chemical Industry Co., Ltd.: C3 TS-G), 1,3,4,6-tetrakis(mercaptomethyl)glycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a-methylglycoluril, and 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(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 Chemicals Co., Ltd.: PEPT), 3-[2,3-bis(3-sulfanylpropoxy)propoxy]propane-1-thiol, 1,2,3-tris(3-mercaptopropoxy)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-1,11-dimercapto-3,6,9-trithiaundecane undecane, 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-2,6,8,12,14,18-hexathianonadecane, 9-(2,2-bis(mercaptomethylthio)ethyl)methane 3,4,8,9-tetrakis(mercaptomethylthio)-1,11-dimercapto-2,5,7,10-tetrathiaundecane, 3,4,8,9,13,14-hexakis(mercaptomethylthio)-1,16-dimercapto-2,5,7,10,12,15-hexathiahexadecane, 8-[bis(mercaptomethylthio)methyl]-3,4,12,13-tetrakis(mercaptomethylthio)ethyl 1,15-dimercapto-2,5,7,9,11,14-hexathiapentadecane, 4,6-bis[3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiaheptylthio]-1,3-dithiane, 4-[3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiaheptylthio]-6-mercaptomethylthio-1,3-dithiane, 1,1-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio]-1,3-bis(mercaptomethylthio)propane, 1-[4-(6-mercaptomethylthio)-1,3-dithianylthio]-3-[2,2-bis(mercaptomethylthio)ethyl]-7,9-bis(mercaptomethylthio)-2,4,6,10-tetrathiaundecane, 3-[2-(1,3-dithietanyl)]methyl-7,9-bis(mercaptomethylthio)-1,11-dimercapto-2,4,6,10-tetrathiaundecane, 9-[2-(1,3-dithietanyl)]methyl-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3-[2-(1,3-dithietanyl)]methyl-7,9-bis(mercaptomethylthio)-2,4,6,10-tetrathiaundecane thietanyl)]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]- thio]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-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]mercaptomethylthiomethyl-1,Examples of bifunctional thiol compounds disclosed in WO 2019 / 082962 include 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.

[0023] The cationically polymerizable compound is a compound having one or more cationically polymerizable groups in the molecule. Examples of the cationically polymerizable group include, but are not limited to, an epoxy group, an oxetanyl group, a vinyl ether group, etc. Examples of the cationically polymerizable compound include, but are not limited to, an epoxy compound, an oxetane compound, a polystyrene-based compound, a vinyl ether compound, etc.

[0024] The epoxy compound includes a monofunctional epoxy compound having one epoxy group and a polyfunctional epoxy compound having two or more epoxy groups. The polyfunctional epoxy compound is roughly classified into an aromatic polyfunctional epoxy compound and a polyfunctional epoxy compound having no aromatic ring.

[0025] Epoxy resins having an aromatic ring skeleton include polyfunctional epoxy resins, specifically bisphenol A epoxy resins (EPICLON (registered trademark) 850, 850-S, EXA-850CRP, EXA-8067, etc., manufactured by DIC Corporation), special epoxy resins containing compounds in which a polyalkylene oxide structure is added to an epoxy resin and bisphenol A skeleton (AER9000 manufactured by Asahi Kasei Corporation, EP-4000S, EP-4003S, EP-4010S, manufactured by ADEKA Corporation), and bisphenol F epoxy resins (EP-4000S, EP-4003S, EP-4010S, manufactured by DIC Corporation). Examples of the polyfunctional epoxy resin include EPICRON (registered trademark) 830-S and EXA-830LVP manufactured by DIC Corporation), bisphenol AD ​​type epoxy resin, bisphenol S type epoxy resin, naphthalene type epoxy resin (EPICLON (registered trademark), HP-4032D, HP-720H manufactured by DIC Corporation, etc.), phenol novolac type epoxy resin (EPICLON (registered trademark), N-740, N-770 manufactured by DIC Corporation, etc.), cresol novolac type epoxy resin (EPICLON (registered trademark), N-660, N-670, N-655-EXP-S manufactured by DIC Corporation, etc.). Specific examples of the polyfunctional epoxy compound contained in the polyfunctional epoxy resin include glycidyl ether of tetra(hydrophenyl)alkane, glycidyl ether of tetrahydroxybenzophenone, and epoxidized polyvinylphenol. Specific examples of compounds contained in monofunctional epoxy resins include p-tert-butylphenyl glycidyl ether (ADEKA GLYCIROL (registered trademark), ED-509E, ED-509S, etc., manufactured by ADEKA CORPORATION).

[0026] The epoxy resin having an alicyclic skeleton may be any epoxy resin having an alicyclic skeleton in one molecule, and may include a cycloalkylene oxide compound in which an epoxy group is formed by two carbon atoms and one oxygen atom forming an alicyclic structure. The epoxy resin having an alicyclic skeleton may also include an epoxy compound having an alicyclic skeleton. Examples of the epoxy compound having an alicyclic skeleton include cyclohexane-based, cyclohexyl methyl ester-based, cyclohexyl methyl ether-based, spiro-based, and tricyclodecane-based epoxy compounds. Specific examples of epoxy resins having an alicyclic skeleton include 3',4'-epoxycyclomethyl 3,4-epoxycyclohexane carboxylate (Celloxide (registered trademark) 2021P manufactured by Daicel Corporation, etc.), (3,3',4,4'-diepoxy)bicyclohexyl (Celloxide (registered trademark) 8010 manufactured by Daicel Corporation, etc.), 1,2:8,9-diepoxylimonene, 1,2-epoxy-4-vinylcyclohexane, and 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (EHPE3150 manufactured by Daicel Corporation, etc.).

[0027] Examples of aliphatic epoxy resins include polyglycidyl ethers of polyhydric alcohols or their alkylene oxide adducts. Specific examples of aliphatic epoxy compounds contained in aliphatic epoxy resins include 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 (such as Epolite 100MF manufactured by Kyoeisha Chemical Co., Ltd.), and polyethylene glycol diglycidyl ether. Examples of aliphatic cyclic epoxy resins include hydrogenated bisphenol A diglycidyl ether (such as jER YX8000 manufactured by Mitsubishi Chemical Corporation).

[0028] The epoxy group equivalent of the epoxy compound is preferably 90 g / eq to 1000 g / eq. The epoxy group equivalent of the epoxy compound may be 800 g / eq or less, 600 g / eq or less, 500 g / eq or less, 400 g / eq or less, 120 g / eq or more, 130 g / eq or more, 150 g / eq or more, 180 g / eq or more, or 200 g / eq or more.

[0029] Specific examples of the oxetane compound include 3-ethyl-3-hydroxymethyloxetane (oxetane alcohol) (OXT-101 manufactured by Toagosei Co., Ltd., etc.), 2-ethylhexyloxetane (OXT-212 manufactured by Toagosei Co., Ltd., etc.), xylylene bisoxetane (OXT-121 manufactured by Toagosei Co., Ltd., etc.), 3-ethyl-3{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane (OXT-221 manufactured by Toagosei Co., Ltd., etc.), oxetanyl silsesquioxetane (OXT-191 manufactured by Toagosei Co., Ltd., etc.), phenol novolac oxetane (PHOX manufactured by Toagosei Co., Ltd., etc.), and 3-ethyl-3-phenoxymethyloxetane (OXT-211 manufactured by Toagosei Co., Ltd., etc.). The oxetane group equivalent of the oxetane compound is preferably 90 g / eq to 500 g / eq, and may be 100 g / eq to 300 g / eq.

[0030] Examples of vinyl ether compounds include, but are not limited to, ethyl vinyl ether, triethylene glycol divinyl ether, trimethylolpropane trivinyl ether, hydroxybutyl vinyl ether, vinyl ether of 1,4-cyclohexanedimethanol, dodecyl vinyl ether, cyclohexyl vinyl ether, etc. These may be used alone or in combination of two or more.

[0031] Examples of anionically polymerizable compounds include the epoxy compounds listed above as examples of 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. Methylene malonates listed above as examples of radically polymerizable compounds are also listed as anionically polymerizable compounds. Furthermore, (meth)acrylate compounds listed above as examples of radically polymerizable compounds are also listed as anionically polymerizable compounds when used in combination with thiol compounds. These compounds may be used alone or in combination of two or more.

[0032] 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.

[0033] The content of the polymerizable compound (A) in the resin composition may be 1 to 99 parts by mass, based on 100 parts by mass of the total resin composition. In some embodiments, the content is preferably 5 to 50 parts by mass, and more preferably 7 to 30 parts by mass, based on 100 parts by mass of the total resin composition. The 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 resin composition is preferably 30 to 99 parts by mass, more preferably 50 to 99 parts by mass, and even more preferably 60 to 99 parts by mass, based on 100 parts by mass of the total resin composition. The content of the polymerizable compound (A) in the resin composition is preferably 75 to 99 parts by mass, more preferably 80 to 99.5 parts by mass, and even more preferably 85 to 98 parts by mass, based on 100 parts by mass of all organic materials (excluding low-stress-imparting materials such as organic fillers and elastomers) contained in the resin composition. The amount of component (A) is preferably 75 to 99.9 parts by mass, more preferably 80 to 99.5 parts by mass, and even more preferably 85 to 99 parts by mass, relative to 100 parts by mass of the total of components (A), (B), and (C).

[0034] (B) Photopolymerization Initiator The resin composition of this embodiment contains (B) a photopolymerization initiator (hereinafter also referred to as "component (B)"). 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 (B) 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 a (C) photon upconversion material, as described below. The (B) 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. Matching the absorption characteristics of the photopolymerization initiator with the wavelength of light generated by the photon upconversion material can increase the efficiency of the polymerization reaction. The (B) photopolymerization initiator can be appropriately selected from a photoradical polymerization initiator, a photoacid generator, a photobase generator, or any combination thereof.

[0035] 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.

[0036] 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.

[0037] 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.

[0038] Examples of oxime ester compounds include, but are not limited to, 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)] (trade name: Irgacure OXE-01, manufactured by BASF), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (trade name: Irgacure OXE-02, manufactured by BASF), methanone, ethanone, 1-[9-ethyl-6-(1,3-dioxolane, 4-(2-methoxyphenoxy)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (trade name: ADEKA OPT-N-1919, manufactured by ADEKA Corporation). These compounds may be used alone or in combination of two or more.

[0039] 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.

[0040] In addition to the above-mentioned photoradical polymerization initiators, examples of the photoradical polymerization initiator include 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, and benzyl dimethyl Examples of the benzoxanthone include, but are not limited to, ketals, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenyl glyoxylate, benzyl, camphorquinone, etc. These may be used alone or in combination of two or more.

[0041] The photoradical polymerization initiators may be used alone or in combination of two or more.

[0042] From the viewpoint of photoirradiation reactivity, the content of the photoradical polymerization initiator in the 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.

[0043] 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.

[0044] 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.

[0045] 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, 4-(phenylthio)phenylbis(4-fluorophenyl)sulfonium, phenyl)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-dihydroanthracen-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p-tolylsulfonium,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.

[0046] 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.

[0047] 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.

[0048] 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.); photoacid generators which are iodonium salts such as IK-1FG (manufactured by San-Apro Co., Ltd.); photoacid generators which are borate-based iodonium salts such as 4-methylphenyl-4-(1-methylethyl)phenyliodonium tetrakis(pentafluorophenyl)borate and 4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate (for example, BLUESIL (registered trademark) PI 2074 manufactured by ELKEM SILICONES, etc.) These include, but are not limited to:

[0049] 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.).

[0050] The photoacid generators may be used alone or in combination of two or more.

[0051] The content of the photoacid generator in the resin composition is preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass, per 100 parts by mass of the total of the cationically polymerizable compounds.

[0052] 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 the photobase generator include 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-dihydroanthracen-2-yl)ethyl cyclohexylcarbamate, 1-(9,10-dioxo-9,10-dihydroanthracen-2-yl)ethyl 1H-imidazole-1-carboxylate, 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine-1- ammonium 2-(3-benzoylphenyl)propanoate, diaminomethaniminium 2-(3-benzoylphenyl)propanoate, (Z)-N-(((bis(dimethylamino)methylene)amino)(isopropylamino)methylene)propan-2-aminium 2-(3-benzoylphenyl)propanoate, 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidinium n-butyltriphenylborate, (Z)-{[bis(dimethylamino)methylidene]amino}-N-cyclohexyl(cyclohexylamino)methaniminium tetrakis(3-fluorophenyl)borate, 1,2-diisopropyl-3-[bis(dimethylamino)methylene]guanidinium 2-(3-benzoylphenyl)propionate, 9-anthrylmethyl Examples of the diastereoisopropyl methyl ester 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 anions, and salts containing benzylated DBU and tetrakis(3-fluorophenyl)borate anions. These may be used alone or in combination of two or more.

[0053] The photobase generators may be used alone or in combination of two or more.

[0054] The content of the photobase generator in the resin composition is preferably 0.5 to 15 parts by mass, and more preferably 1 to 10 parts by mass, per 100 parts by mass of the total of the anionically polymerizable compounds.

[0055] The photopolymerization initiator may be any one of a photoradical polymerization initiator, a photoacid generator, and a photobase generator, or any combination thereof.

[0056] (C) Photon Up-Conversion Material The resin composition of this embodiment contains (C) a photon up-conversion material (hereinafter also referred to as "component (C)"). When irradiated with specific light, the photon up-conversion material generates a high-energy state through multiphoton excitation, triplet-triplet annihilation, or the like, and emits light with a shorter wavelength than the incident light during the relaxation process. By incorporating this photon up-conversion material into a resin composition and irradiating the resin composition with long-wavelength light, the photon up-conversion material performs wavelength conversion within the resin composition. This allows the photon up-conversion material to generate light with a wavelength of 500 nm or less, activate the photopolymerization initiator, and cure the resin composition. In this embodiment, the emission wavelength of the photon up-conversion material (C) 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 some embodiments, the emission wavelength of component (C) includes ultraviolet light wavelengths (200 nm to 380 nm).

[0057] Photon upconversion (UC) is a technology for converting low-energy (long-wavelength) light into high-energy (short-wavelength) light. Photon upconversion mechanisms include triplet-triplet annihilation (TTA), multi-photon excitation of rare-earth element-containing materials, and two-photon absorption. In this embodiment, a photon upconversion material based on any of the photon upconversion mechanisms can be used, but the (C) photon upconversion material is preferably a (C1) triplet-triplet annihilation type photon upconversion material, a (C2) multi-photon excitation type photon upconversion material, or a combination thereof.

[0058] (C1) Triplet-triplet annihilation type photon upconversion material In one embodiment, the photon upconversion material is a triplet-triplet annihilation type photon upconversion material (hereinafter also referred to as "component (C1)"). Triplet-triplet annihilation type photon upconversion material uses a combination of a donor and an acceptor. As triplet-triplet annihilation type photon upconversion materials, for example, those described in JP 2021-080335 A and JP 2020-056030 A can be used.

[0059] <Acceptor> The acceptor (acceptor compound) is not particularly limited as long as it is a compound (light emitter) that can be excited into a singlet state after receiving triplet energy transfer from a donor and generate photon upconversion luminescence. Examples of acceptors include, but are not limited to, compounds having a naphthalene structure, an anthracene structure, a tetracene structure, a pyrene structure, a perylene structure, a biphenyl structure, a terphenyl structure, a perylene diimide structure, a naphthalene diimide structure, or a BODIPY (boron dipyrromethene; 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) structure. 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 dipyrromethene (BODIPY) derivatives BD-1 and BD-2 having an iodophenyl group, and 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.

[0060] <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 (ppy = 2-phenylpyridine) are included, but are not limited to these. Other specific examples of the donor include donors described in JP-A-2021-080335 and JP-A-2020-056030.

[0061] 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 the triplet-triplet annihilation type photon upconversion material (C1) that emits light upon irradiation with light with a wavelength of more than 500 nm can be adjusted to include wavelengths of 500 nm or less.

[0062] The wavelength range of the excitation light that causes upconversion emission from such a triplet-triplet annihilation type photon upconversion material (C1) 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 emission from component (C1) 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 (C1) includes the wavelength of ultraviolet light (200 nm to 380 nm).

[0063] Any one of the donors may be used alone or in combination of two or more thereof. Any one of the acceptors may be used alone or in combination of two or more thereof.

[0064] In this embodiment, from the viewpoint of the curability of the resin composition, the content of component (C1) in the resin composition is preferably 0.001 to 10 parts by mass, more preferably 0.005 to 10 parts by mass, and even more preferably 0.01 to 10 parts by mass, per 100 parts by mass of the total amount of the resin composition. Furthermore, the amount of component (C1) is preferably 0.001 to 20 parts by mass, more preferably 0.005 to 15 parts by mass, and even more preferably 0.01 to 10 parts by mass, per 100 parts by mass of the total of components (A), (B), and (C). In one embodiment, the amount of component (C1) is 0.001 to 1 part by mass, per 100 parts by mass of the total of components (A), (B), and (C). In one embodiment, the amount of component (C1) is preferably 1 mmol / L to 6 mol / L, more preferably 2 mmol / L to 5 mol / L, even more preferably 6 mmol / L to 4 mol / L, particularly preferably 10 mmol / L to 3 mol / L, and most preferably 50 mmol / L to 2 mol / L.

[0065] (C2) Multiphoton Excitation Type Photon Up-Conversion Material In one embodiment, the photon up-conversion material is a multiphoton excitation type photon up-conversion material (hereinafter also referred to as "component (C2)"). A 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 component (C2) 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 one embodiment, the emission wavelength of component (C2) includes an ultraviolet light wavelength (200 nm to 380 nm). Component (C2) may have an emission peak in the red or green region in addition to the UV-A, purple, or blue region. In this specification, the red region refers to a light wavelength region of 600 to 800 nm, the green region refers to a light wavelength region of 500 to 600 nm, and the blue region refers to a light wavelength region of 400 to 500 nm. In this embodiment, the component (C2) preferably has an emission intensity in the wavelength region of 500 nm or less.

[0066] In component (C2), an optically inactive host material is doped with a rare earth element, thereby exhibiting upconversion luminescence characteristics. By appropriately selecting the type and amount of rare earth element contained in component (C2), upconversion luminescence of any wavelength can be obtained.

[0067] 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:

[0068] The wavelength range of the excitation light that causes upconversion emission of such component (C2) 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.

[0069] The host material (host material) is not particularly limited as long as it supports a rare earth element and supports the rare earth element in a state capable of upconversion emission, and may be an organic substance that reacts with the rare earth element to form a complex, dendrimer, etc., or an inorganic substance. Inorganic substances are preferred because it is easy to incorporate the rare earth element in a state capable of emitting light.

[0070] As such an inorganic base material, a material that is transparent to the excitation light is preferred from the viewpoint of luminous efficiency, and specifically, among them, halides such as fluorides and chlorides, oxides, sulfides, oxysulfides, etc. are preferably used. Examples of such halides include 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 ) and the like, but are not limited to these. A coating material may be formed around the component (C2) whose base material is a halide. The oxides listed above can be used as this coating material.

[0071] Also, the core (NaYREF ４ ) / Shell (NaYF ４ ) (RE=rare earth element) can also be used.

[0072] Component (C2) can be produced by known methods, such as gas evaporation methods including high-frequency plasma methods, sputtering methods, glass crystallization methods, chemical precipitation methods, reverse micelle methods, sol-gel methods and similar methods, precipitation methods including hydrothermal synthesis and coprecipitation methods, spray methods, etc. For the production method of component (C2), reference can be made to the method described in JP-A-2006-117864, for example.

[0073] Component (C2) may be a commercially available product, for example, a core-shell upconversion phosphor nanoparticle with an excitation wavelength of 975 nm and an emission wavelength of 365 nm is commercially available from Hefei Fluonano Biotech Co., Ltd. under the product code 201-30-365.

[0074] Component (C2) may be used alone or in combination of two or more. For example, in one embodiment, the use of two or more components (C2) in combination 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 so that it ultimately includes a wavelength of 500 nm or less, thereby allowing the resin composition to be photocured using the desired incident light.

[0075] The content of component (C2) in the resin composition is, from the viewpoint of light conversion efficiency and photocuring degree, 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, relative to 100 parts by mass of the total amount of the resin composition.

[0076] In this embodiment, either the triplet-triplet annihilation type photon upconversion material (C1) or the multiphoton excitation type upconversion material (C2) may be used alone, or any combination thereof may be used. For example, in certain embodiments, the use of a combination of component (C1) and component (C2) enables energy transfer from component (C1) to component (C2) or from component (C2) to component (C1) in the resin composition. This stepwise energy transfer allows the emission wavelength of the photon upconversion material from the desired incident light to be adjusted to ultimately include wavelengths of 500 nm or less, thereby allowing the resin composition to be photocured using the desired incident light.

[0077] If desired, the resin composition of this embodiment may contain optional components other than the components (A) to (C), such as those described below, as needed.

[0078] Filler The 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.

[0079] 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.

[0080] 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.

[0081] Examples of the organic filler include polytetrafluoroethylene (PTFE) filler, silicone filler, acrylic filler, styrene filler, etc. The organic filler may be surface-treated.

[0082] The shape of the filler is not particularly limited, and may be any of spherical, flaky, needle-like, irregular, etc.

[0083] 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.

[0084] In this specification, the average particle size is the particle size at an integrated value of 50% 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.

[0085] When a filler is contained, the content of the filler is preferably 0.5 to 80 mass %, more preferably 1 to 70 mass %, based on the total mass of the resin composition.

[0086] Thixotropic Agent The 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, nanosilica having an average particle size of 10 to 750 nm is more preferred, and nanosilica having an average particle size of 20 to 600 nm is even more preferred. 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.

[0087] 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 resin composition.

[0088] Light-blocking agent The 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 resin composition. In such cases, the 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 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.

[0089] Other Additives If desired, the 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, etc. The type and amount of each additive are as usual, provided that the purpose of the present embodiment is not impaired.

[0090] The viscosity of the 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 resin composition of this embodiment is excellent for application to areas with complex shapes where UV light irradiation is difficult, 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.

[0091] 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) 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 mixture is separated into two or more liquids by any method, each liquid may contain one or more components selected from components (A) to (C) and other optional components as needed. Alternatively, components (A) to (C) and other optional components as needed may be contained in a single liquid. Alternatively, there may be a liquid consisting solely of components (A) to (C) and / or other optional components as needed. For example, when the mixture is separated into liquids A and B, the separation may be as follows: liquid A: component (A), liquid B: component (B) and component (C), liquid A: component (A) and component (B), liquid B: component (C), or liquid A: component (A) and component (C), and liquid B: component (B). When components (A) to (C) are contained in liquid A, liquid B may contain one or more components selected from components (A) to (C). Additionally, components other than components (A) to (C) may be contained in either or both of liquids A and B in the above combinations. When the components (A) to (C) are contained in Liquid A and the 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 the components (A) to (C) are contained in separate liquids, the respective liquids can be considered together to be the resin composition of this embodiment.Examples of the case where the components (A) to (C) are contained in separate liquids include a resin composition in which the components (A) to (C) are separated into two or more containers, specifically a kit composed of multiple liquids containing any of the components (A) to (C).

[0092] The method for producing the resin composition of this embodiment is not particularly limited. For example, the resin composition of this embodiment can be obtained by simultaneously or separately introducing components (A) to (C), and 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 a Raikai mixer, Henschel mixer, three-roll mill, ball mill, planetary mixer, bead mill, or the like equipped with a stirring device and a heating device can be used. Furthermore, these devices may be used in appropriate combination.

[0093] The 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 for photocuring of 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, whereas visible light of 380 to 780 nm penetrates by several hundred nanometers to several microns, and infrared light of 780 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.) Although the penetration distance of ultraviolet light when irradiating a resin composition is deeper than that of a silicon substrate, increasing the irradiation wavelength can be said to be useful as a method for increasing the degree of cure of the resin composition.

[0094] The 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.

[0095] [Bonding Method] Another aspect of the present invention is a method for bonding at least two components with a photocurable resin composition, the bonding method including the steps of: applying the photocurable resin composition of the present embodiment 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.

[0096] In the first step, the photocurable resin composition of the above embodiment is applied to at least one of at least two components. The components are preferably components constituting a semiconductor device or electronic component, such as, but not limited to, a semiconductor element or a substrate. 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 method for applying the resin composition is not particularly limited, and it can be applied to a desired portion of a component, such as a substrate, by a known printing method, dispensing method, or coating method. Printing methods include, but are not limited to, inkjet printing, screen printing, lithographic printing, carton printing, metal printing, offset printing, gravure printing, flexographic printing, etc. Dispensing methods include, but are not limited to, methods using a jet dispenser, an air dispenser, etc. Coating methods include, but are not limited to, dip coating, spray coating, bar coater coating, gravure coating, reverse gravure coating, spin coater coating, etc.

[0097] Next, another 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 may be used for the attachment. If necessary, after attachment, the parts may be pressed together while applying a load.

[0098] 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. This causes the photon upconversion material within the resin composition to 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, but is not limited to, 532 nm, 980 nm, 1064 nm, or 1550 nm. 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.

[0099] [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 aspect 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 the application method in the above-described bonding method and potting, but are not limited to these. The resin composition used in this embodiment achieves a high cure depth, so 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.

[0100] [Coating Method] Another aspect of the present invention is a method for coating the surface of an object with a curable composition, the method comprising: applying the photocurable resin composition of the above-described embodiment 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.

[0101] [Adhesive, Sealant, or Coating Agent] Another embodiment of the present invention is an adhesive, sealant, or coating agent that includes the 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.

[0102] [Cured Product of Resin Composition, Adhesive, Sealant, or Coating Agent] A cured product according to another embodiment of the present invention is a cured product obtained by curing the resin composition, adhesive, sealant, or coating agent according to the above-described embodiment.

[0103] [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.

[0104] [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 more 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 more than 500 nm. By irradiating the resin composition with light having a wavelength of more than 500 nm, for example, light having a wavelength of more than 500 nm but not more than 2000 nm, the photon upconversion material within the resin composition undergoes 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. The details of the irradiation with light having a wavelength of more than 500 nm in these methods are the same as those in the bonding method, sealing method, and coating method. In this aspect, either spot irradiation, in which light is irradiated to a localized area, or area irradiation, in which light is irradiated to a wide area, can be performed.

[0105] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following examples, parts and % represent parts by mass and % by mass unless otherwise specified.

[0106] [Experimental Example 1] Resin compositions of Examples 1 to 18 and Comparative Examples 1 to 6 were prepared by mixing predetermined amounts of each component according to the formulations shown in Table 1. A triplet-triplet annihilation photon upconversion material (C1) was mixed with a polymerizable compound and a photopolymerization initiator to obtain a resin composition. When a multiphoton excitation upconversion material (C2) was included, a predetermined amount of component (C2) was mixed with the resin composition. In Table 1, the amount of each component is expressed in mass %. The components used in the examples and comparative examples are as follows:

[0107] (A) Polymerizable Compound (A-1): Dimethylol-tricyclodecane diacrylate (product name: Light Acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd.) (A-2): Bisphenol A type / bisphenol F type mixed epoxy resin (product name: EPICLON 835LV, manufactured by DIC Corporation) (A-3): Alicyclic epoxy resin (product name: CELLOXIDE 2021P, manufactured by Daicel Corporation) (A-4): Hydroxylated BisA type epoxy resin (product name: YX8000, manufactured by Mitsubishi Chemical Corporation) (B) Photopolymerization Initiator (B-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.) (B-2): 1-hydroxycyclohexyl phenyl ketone (product name: Omnirad 184, manufactured by IGM Resins B.V.) (B-3): 2,4,6-trimethylbenzoyldiphenylphosphine oxide (product name: Omnirad TPO, manufactured by IGM Resins B.V.) (B-4): Iodonium salt-based photocationic initiator (product name: BLUESIL (registered trademark) PI 2074, manufactured by ELKEM SILICONES) (B-5): Sulfonium, tris[4-[(4-acetylphenyl)thio]phenyl]-, tetrakis(2,3,4,5,6-pentafluorophenyl)borate (product name: Omnirad 290, manufactured by IGM Resins B.V.) (C) Photon upconversion material (C1) Triplet-triplet annihilation photon up-conversion material (C1-1D): Platinum(II) octaethylporphyrin (PtOEP) (manufactured by Sigma-Aldrich Japan) as a donor (C1-1A): Diphenylanthracene (DPA) (manufactured by Tokyo Chemical Industry Co., Ltd.) as an acceptor. The mass ratio of the donor and acceptor PtOEP:DPA was 1:8 (molar ratio 1:17), and the photon up-conversion material (C1-1) was obtained. (C2) Multiphoton excitation photon up-conversion material (C2-1): CeO ２ / 3.0Er ３＋ , 0.6Yb ３＋ (The synthesis method is shown below)　　 CeO ２ (Fujifilm Wako Pure Chemical Industries, special grade reagent) ３＋ , Yb ３＋ are doped with Er at 3.0 mol % and 0.6 mol %, respectively. ２ O ３ (Fujifilm Wako Pure Chemical Industries, 99.0% or more), Yb ２ O ３ (Fujifilm Wako Pure Chemical Industries, 98.0% or more) was weighed and crushed and mixed in a mortar. This powder was pre-calcined at 1200°C (heating rate: 600°C / hour, firing time: 2 hours), crushed again in a mortar, and then fired at 1500°C (heating rate: 600°C / hour, firing time: 4 hours) to obtain CeO ２ / 3.0Er ３＋ , 0.6Yb ３＋ It was confirmed by XRD that there was no unreacted material. (C2-2): Y ２ O ３ / 2.0Er ３＋ , 2.0Yb ３＋ (The synthesis method is shown below) 　　 Y ２ O ３ (Fujifilm Wako Pure Chemical Industries, special grade reagent) ３＋ , Yb ３＋ and Er so that ２ O ３ (Fujifilm Wako Pure Chemical Industries, 99.0% or more), Yb ２ O ３ (Fujifilm Wako Pure Chemical Industries, 98.0% or more) was weighed and crushed and mixed in a mortar. This powder was pre-calcined at 1400°C (heating rate: 600°C / hour, firing time: 2 hours), crushed again in a mortar, and then fired at 1600°C (heating rate: 600°C / hour, firing time: 4 hours) to obtain Y. ２ O ３ / 2.0Er ３＋ , 2.0Yb ３＋The absence of unreacted materials was confirmed by XRD. (D) Filler (D-1): High-purity synthetic spherical silica (product name: SE-2300, manufactured by Admatechs Co., Ltd., volume average particle size: 0.6 μm) (E) Thixotropic agent (E-1): Hydrophobic fumed silica (product name: CAB-O-SIL (registered trademark) TS720, manufactured by CABOT Corporation, average particle size: 12 nm) (F) Light-shielding agent (F-1): Carbon black (product name: Special Black 4, manufactured by Orion Engineered Carbons Co., Ltd.) (F-2): Titanium black (product name: Titanium Black 13M, manufactured by Mitsubishi Materials Corporation)

[0108] In the examples and comparative examples, the properties of the resin compositions were measured as follows.

[0109] [Evaluation of curability of resin composition] A drop (about 0.02 g) of the photocurable resin composition was placed on a glass slide in a dark place at a temperature of 22°C ± 5°C and a humidity of 50% ± 10%, and the glass slide was inserted to prepare a test piece. The test piece was then irradiated with ultraviolet light, visible light, and infrared light. The ultraviolet light irradiation conditions were as follows: a single-wavelength UV LED light source (OmniCure (registered trademark) AC475, manufactured by Excelitas Technologies) was used, and the ultraviolet light was irradiated at a position 4 cm above the light source, with a wavelength of 365 nm and an irradiation intensity of 500 mW / cm. ２ The cumulative light intensity is 2000 mJ / cm ２ The visible light irradiation conditions were as follows: visible light with a wavelength of 532 nm and an irradiation intensity of 1 mW / cm, using a semiconductor pumped 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 slide glass. ２ The cumulative light intensity is 720 mJ / cm ２ The infrared light irradiation experiment was carried out using an infrared semiconductor laser (Labo Laser System, manufactured by CiviLaser) at a position 4 cm above the light source from the top surface of the slide glass, with infrared light of wavelength 980 nm and irradiation intensity of 200 mW / cm. ２The cumulative light intensity is 720 kJ / cm ２ Irradiation was continued until the photocurability reached a certain level. In this test, one of the slide glasses was peeled off from the test piece, and the photocurability was evaluated based on appearance and palpation with a toothpick using a three-point scale: cured (◯), partially uncured (△), and uncured (×). The results are shown in Tables 1-1, 1-2, and 1-3.

[0110]

[0111]

[0112]

[0113] Comparative Examples 1, 5, and 6 were resin compositions consisting of a polymerizable compound (A) and a photopolymerization initiator (B) that did not contain an upconversion material (C1). These compositions did not cure with visible light irradiation but cured only with ultraviolet light irradiation. Comparative Examples 2 and 3 were resin compositions containing only donor or acceptor molecules of a triplet-triplet annihilation photon upconversion material (C1). As with Comparative Example 1, these compositions did not cure with visible light irradiation but cured only with ultraviolet light irradiation. Comparative Example 4 was a resin composition consisting of a polymerizable compound (A) and an upconversion material (C1) that did not contain a photopolymerization initiator (B). These compositions did not cure with ultraviolet or visible light irradiation. On the other hand, as shown in Example 1, a resin composition consisting of a polymerizable compound (A), a photopolymerization initiator (B), and an upconversion material (C1) containing both donor and acceptor molecules cured not only with ultraviolet light but also with visible light irradiation. As shown in Examples 2, 3, 10, 13, and 14, resin compositions containing a filler (D), a thixotropic agent (E), a light-blocking agent (F), or a combination thereof were cured by both ultraviolet and visible light irradiation. Examples 12 and 13, in which the type of photopolymerization initiator (B) was changed, also cured by ultraviolet and visible light irradiation. Examples 17 and 18, in which the type of photopolymerization initiator (B) was changed, also cured by ultraviolet and visible light irradiation. Examples 15 and 16 are resin compositions containing a polymerizable compound (A), a photopolymerization initiator (B), a triplet-triplet annihilation photon upconversion material (C1), and a multiphoton excitation upconversion material (C2), and were cured by infrared light irradiation in addition to ultraviolet and visible light irradiation.

[0114] [Experimental Example 2] In the evaluation of the curability of the resin composition of Example 7, the two glass slides were replaced with various substrate materials shown in Table 2, and ultraviolet light and visible light were irradiated. The results are shown in Table 2. The resin composition cured on a 1.0 mm thick Pyrex glass substrate when irradiated with ultraviolet light and visible light. On an FR4 substrate, the resin composition cured up to a thickness of 2.0 mm with ultraviolet light irradiation, but not at thicknesses greater than that. On the other hand, visible light irradiation completely cured the FR4 substrate up to a thickness of 5.0 mm. Furthermore, a 0.125 mm thick polyimide film did not cure with ultraviolet light irradiation, but cured with visible light irradiation.

[0115]

[0116] The disclosure of Japanese Patent Application No. 2023-119225 (filing date: July 21, 2023) is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards mentioned herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A photocurable resin composition comprising: (A) a polymerizable compound; (B) a photopolymerization initiator; and (C) a photon upconversion material.

2. The photocurable resin composition according to claim 1, wherein the photopolymerization initiator (B) is a photopolymerization initiator that is activated by light having a wavelength of 500 nm or less.

3. The photocurable resin composition according to claim 1 or 2, wherein the (B) photopolymerization initiator is a photoradical polymerization initiator, a photoacid generator, a photobase generator, or any combination thereof.

4. A photocurable resin composition according to any one of claims 1 to 3, wherein the emission wavelength of the photon upconversion material (C) includes a wavelength of 500 nm or less.

5. A photocurable resin composition according to any one of claims 1 to 4, wherein the polymerizable compound (A) is a radical polymerizable compound, a cationically polymerizable compound, an anionically polymerizable compound, or any combination thereof.

6. The photocurable resin composition according to any one of claims 1 to 5, for use in curing by irradiation with light having a wavelength of more than 500 nm.

7. The photocurable resin composition according to any one of claims 1 to 6, which is used as an adhesive, sealant or coating agent for semiconductor devices or electronic parts.

8. An adhesive, sealant or coating agent comprising the photocurable resin composition according to any one of claims 1 to 7.

9. A cured product obtained by curing the photocurable resin composition according to any one of claims 1 to 7, or the adhesive, sealant or coating agent according to claim 8.

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

11. A method for producing a cured product, comprising irradiating the photocurable resin composition according to any one of claims 1 to 7, or the adhesive, sealant or coating agent according to claim 8, with light having a wavelength of more than 500 nm.

12. A method for curing a photocurable resin composition, comprising irradiating the photocurable resin composition according to any one of claims 1 to 7 with light having a wavelength of more than 500 nm.

13. Use of the photocurable resin composition according to any one of claims 1 to 7 for curing by irradiation with light having a wavelength of more than 500 nm.

14. A method for bonding at least two parts with a photocurable resin composition, comprising the steps of: applying the photocurable resin composition according to any one of claims 1 to 7 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, with light having a wavelength of more than 500 nm.

15. 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 7 into the gaps between or within the components; and irradiating the photocurable resin composition with light having a wavelength of more than 500 nm.

16. A method for coating a surface of an object with a photocurable resin composition, comprising: a step of applying the photocurable resin composition according to any one of claims 1 to 7 to the object; and a step of irradiating the photocurable resin composition with light having a wavelength of more than 500 nm.

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