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

Abstract

The present invention addresses the problem of providing: a photocurable resin composition that is cured only by light irradiation and does not require full curing by heat; an adhesive, a sealant 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, a bonding method, a sealing method, and a coating method using the photocurable resin composition.　Provided are: a photocurable resin composition containing (A) a maleimide compound, and (B) a photon upconversion material; an adhesive, a sealant, 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, a bonding method, a sealing method, and a coating method using the photocurable resin composition.

Description

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

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

[0002] Adhesives that are temporarily fixed by ultraviolet (UV) irradiation and then fully cured by heat are used in many fields (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 composition is applied to heat-sensitive members, there is a demand for a photocurable resin composition 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 can be cured by light irradiation alone and does not require main curing by heat, an adhesive, a sealant or a coating agent containing the same, a cured product thereof, a semiconductor device or electronic component containing the cured product, and a curing method, an adhesion method, a sealing method and a coating method 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 photocurable 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 maleimide compound and (B) a photon upconversion material. [2] The photocurable resin composition according to [1] above, which is substantially free of a photoradical polymerization initiator. [3] The photocurable resin composition according to [1] or [2] above, in which the emission wavelength of the photon upconversion material (B) includes a wavelength of 500 nm or less. [4] The photocurable resin composition according to any one of [1] to [3] above, further comprising (C) a radical polymerizable compound other than the maleimide compound (A). [5] The photocurable resin composition according to any one of [1] to [4] above, which is used for curing by irradiation with light with a wavelength of more than 500 nm. [6] The photocurable resin composition according to any one of [1] to [5] above, which is used as an adhesive, encapsulant, or coating agent for semiconductor devices or electronic components. [7] An adhesive, encapsulant, or coating agent comprising the photocurable resin composition according to any one of [1] to [6] above. [8] A cured product obtained by curing the photocurable resin composition according to any one of [1] to [6] above, or the adhesive, encapsulant, or coating agent according to [7] above. [9] A semiconductor device or electronic component comprising the cured product according to [8] above.

[10] A method for producing a cured product, which comprises irradiating the photocurable resin composition according to any one of [1] to [6] above, or the adhesive, encapsulant, or coating agent according to [7] above, with light having a wavelength of more than 500 nm.

[11] A method for curing a photocurable resin composition, which comprises irradiating the photocurable resin composition according to any one of [1] to [6] above with light having a wavelength of more than 500 nm.

[12] Use of the photocurable resin composition according to any one of [1] to [6] above for curing by irradiation with light having a wavelength of more than 500 nm.

[13] A method for bonding at least two components with a photocurable resin composition, comprising the steps of: applying the photocurable resin composition described in any one of [1] to [6] 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, with light having a wavelength of more than 500 nm.

[14] A method for sealing a gap between or within a component with a photocurable resin composition, comprising the steps of applying or injecting the photocurable resin composition described in any one of [1] to [6] to the gap between or within the component, and irradiating the photocurable resin composition with light having a wavelength of more than 500 nm.

[15] A method for coating the surface of an object with a photocurable resin composition, comprising the steps of applying the photocurable resin composition described in any one of [1] to [6] to the object; and 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 can be cured by light irradiation alone and 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 is a photocurable resin composition comprising (A) a maleimide compound and (B) a photon upconversion material. According to this embodiment, a photocurable resin composition is provided that can be cured by light irradiation alone and does not require main curing by heat.

[0010] The present inventors focused on photon upconversion materials capable of converting long-wavelength light into short-wavelength light. When irradiated with specific light, photon upconversion materials generate high-energy states through processes such as multiphoton excitation and triplet-triplet annihilation, and during the relaxation process, emit light with a shorter wavelength than the incident light. The present inventors 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. After extensive investigation, they confirmed that photon upconversion emission actually activates the photopolymerization initiator, causing polymerization of a polymerizable compound in the resin composition, thereby promoting curing of the resin composition. Long-wavelength light has a longer penetration distance into a target object than high-energy short-wavelength light (e.g., 365 nm UV light). The present inventors have confirmed that irradiation with long-wavelength light causes photon upconversion emission, which allows curing of a resin composition to proceed even in places where UV irradiation is difficult to reach, and that curing is completed by light irradiation alone, eliminating the need for main curing by heat. Based on this finding, the present applicant filed Japanese Patent Application No. 2023-119225 (July 21, 2023) regarding a photocurable resin composition containing a photon upconversion material. After further investigation, the present inventors have found that when the polymerizable compound in the resin composition is a maleimide compound, the maleimide compound itself, activated by photon upconversion emission, generates radicals and promotes polymerization of a radically polymerizable compound. In other words, the maleimide compound is not only a polymerizable compound but can also function as a photoradical initiator, promoting polymerization of a radically polymerizable compound containing the maleimide compound itself, even without the need for a separate photoradical initiator.

[0011] (A) Maleimide Compound The photocurable resin composition of this embodiment contains (A) a maleimide compound (hereinafter also referred to as "component (A)"). In this specification, a maleimide compound is a compound having at least one maleimide group. In this embodiment, the maleimide compound activated by photon upconversion light emission generates radicals and functions as a photoradical initiator, while also polymerizing itself as a polymerizable compound, thereby imparting curability and adhesiveness to the resin composition. From the viewpoint of workability under fluorescent lamps, the maleimide compound is preferably a maleimide compound having an absorption wavelength of 500 nm or less, more preferably a maleimide compound having an absorption wavelength of 475 nm or less, and even more preferably a maleimide compound having an absorption wavelength of 450 nm or less. The efficiency of the polymerization reaction can be increased by matching the absorption characteristics of the maleimide compound with the emission wavelength of the (B) photon upconversion material. 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.

[0012] Examples of bismaleimide compounds include N,N'-(4,4'-diphenylmethane)bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, bis-(3-ethyl-5-methyl-4-maleimidophenyl)methane, m-phenylene bismaleimide (N,N'-1,3-phenylene bismaleimide), 1,6-bismaleimidehexane, 1,2-bismaleimideethane (N,N'-ethyl Examples of the dimaleimide include, but are not limited to, N,N'-(1,2-phenylene)bismaleimide, N,N-1,3-phenylene dimaleimide, N,N'-1,4-phenylene dimaleimide, N,N'-(sulfonyldi-p-phenylene)dimaleimide, N,N'-[3,3'-(1,3-phenylenedioxy)diphenyl]bismaleimide, N,N'-[4,4'-(1,3-phenylenedioxy)diphenyl]bismaleimide, and 4,4'-dimaleimide phenyl ether. These may be used alone or in combination of two or more.

[0013] When a low room temperature modulus is required for the cured resin composition, a bismaleimide having a hydrocarbon group derived from a dimer acid can be used as the bismaleimide compound. Such bismaleimides are described, for example, in JP 2015-193725 A. Commercially available bismaleimides having a hydrocarbon group derived from a dimer acid include, but are not limited to, products under the trade names "BMI-689," "BMI-1500," and "BMI-1700," which are liquid at 25°C, and "BMI-3000," which is solid at 25°C (all manufactured by Designer Molecules Inc.). These compounds may be used alone or in combination of two or more.

[0014] Examples of monofunctional maleimide compounds include, but are not limited to, monofunctional aliphatic maleimide compounds such as N-n-butylmaleimide, N-hexylmaleimide, 2-maleimidoethyl-ethyl carbonate, 2-maleimidoethyl-propyl carbonate, and N-ethyl-(2-maleimidoethyl)carbamate; alicyclic monofunctional maleimide compounds such as N-cyclohexylmaleimide; N-arylmaleimides such as N-phenylmaleimide; and N-aralkylmaleimides such as N-benzylmaleimide. The aliphatic maleimides and alicyclic maleimides may have a substituent, and examples of the substituent include a phenyl group, a benzyl group, and a hydroxy group. The N-arylmaleimides and N-aralkylmaleimides may have a substituent, and examples of the substituent include, but are not limited to, an alkyl group, a nitro group, a hydroxy group, an alkoxy group, a carboxyl group, and a halogeno group. Commercially available 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. These may be used alone or in combination of two or more.

[0015] From the viewpoint of reactivity, the maleimide group equivalent of the maleimide compound is preferably 2000 g / eq or less, more preferably 1800 g / eq or less, and even more preferably 1600 g / eq or less. From the viewpoint of suppressing volatilization, the maleimide group equivalent of the maleimide compound is preferably 100 g / eq or more, more preferably 120 g / eq or more, and even more preferably 150 g / eq or more.

[0016] From the viewpoint of polymerization rate, the maleimide compound is preferably in a liquid state at room temperature, or, if it is solid at room temperature, is preferably used by dissolving it in a liquid radically polymerizable compound or the like.

[0017] From the viewpoint of photoirradiation reactivity, the content of the maleimide compound (A) in the photocurable resin composition is preferably 0.1 to 100 parts by mass, more preferably 1 to 100 parts by mass, and even more preferably 10 to 100 parts by mass, relative to 100 parts by mass of all radically polymerizable compounds (i.e., the total of the maleimide compound and the radically polymerizable compounds other than the maleimide compound).

[0018] In the photocurable resin composition of this embodiment, the maleimide compound can function as a photoradical initiator, so the photocurable resin composition of this embodiment may be substantially free of other photoradical polymerization initiators. In this specification, the phrase "the photocurable resin composition is substantially free of other photoradical polymerization initiators" means that the content of other photoradical polymerization initiators is less than 0.1 parts by mass per 100 parts by mass of all radical polymerizable compounds (i.e., the total of the maleimide compound and radical polymerizable compounds other than the maleimide compound). Examples of other photoradical polymerization initiators include alkylphenone compounds, acylphosphine oxide compounds, oxime ester compounds, and compounds having a photosensitive moiety and a peroxide structure.

[0019] Examples of alkylphenone compounds include benzyl dimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethan-1-one (commercially available as Omnirad 651 from IGM Resins B.V.); α-aminoalkylphenones such as 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one (commercially available as Omnirad 907 from IGM Resins B.V.); α-hydroxyalkylphenones such as 1-hydroxy-cyclohexyl-phenyl-ketone (commercially available as Omnirad 184 from IGM Resins B.V.); 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one (commercially available as Omnirad 184 from IGM Resins B.V.); 379EG), 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone (commercially available as Omnirad 369, manufactured by IGM Resins BV), and the like.

[0020] Examples of the acylphosphine oxide compound include, but are not limited to, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (commercially available as Omnirad TPO H manufactured by IGM Resins B.V.), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (commercially available as Omnirad 819 manufactured by IGM Resins B.V.), and the like.

[0021] Examples of the oxime ester compound include, but are not limited to, 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)] (trade name: Irgacure OXE-01, manufactured by BASF), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (trade name: Irgacure OXE-02, manufactured by BASF), methanone, ethanone, 1-[9-ethyl-6-(1,3-dioxolane, 4-(2-methoxyphenoxy)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (trade name: ADEKA OPT-N-1919, manufactured by ADEKA Corporation).

[0022] 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.

[0023] 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, benzil, camphorquinone, and the like.

[0024] (B) Photon Up-Conversion Material The photocurable resin composition of this embodiment contains (B) a photon up-conversion material (hereinafter also referred to as "component (B)"). 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 maleimide compound, and cure the resin composition. In this embodiment, the emission wavelength of the (B) photon up-conversion material preferably includes a wavelength of 500 nm or less, more preferably a wavelength of 450 nm or less, even more preferably a wavelength of 430 nm or less, and particularly preferably a wavelength of 400 nm or less. In some embodiments, the emission wavelength of component (B) includes ultraviolet light wavelengths (200 nm to 380 nm).

[0025] Photon upconversion (PUC) 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 (B) photon upconversion material is preferably a (B1) triplet-triplet annihilation type photon upconversion material, a (B2) multi-photon excitation type photon upconversion material, or a combination thereof.

[0026] (B1) 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 (B1)"). 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.

[0027] <Acceptor> The acceptor (acceptor compound) is not particularly limited as long as it is a compound (light emitter) that undergoes triplet energy transfer from a donor, becomes an excited singlet state through triplet-triplet annihilation, and is capable of generating 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.

[0028] <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.

[0029] 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 (B1) that emits light upon irradiation with light having a wavelength exceeding 500 nm can be adjusted to include wavelengths of 500 nm or less.

[0030] The wavelength range of the excitation light that causes upconversion emission from such a triplet-triplet annihilation type photon upconversion material (B1) 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 (B1) 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 (B1) includes the wavelength of ultraviolet light (200 nm to 380 nm).

[0031] 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.

[0032] In this embodiment, from the viewpoint of the curability of the photocurable resin composition, the content of component (B1) in the photocurable 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, relative to 100 parts by mass of the total amount of the photocurable resin composition. Furthermore, the content of component (B1) 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, relative to 100 parts by mass of the total amount of component (A), component (B), and component (C) described below. In one embodiment, the amount of component (B1) is 0.001 to 1 part by mass, relative to 100 parts by mass of the total amount of component (A), component (B), and component (C) described below. In one embodiment, the amount of component (B1) is preferably 0.001 mmol / L to 1 mmol / L, more preferably 0.001 mmol / L to 0.9 mmol / L, even more preferably 0.001 mmol / L to 0.8 mmol / L, particularly preferably 0.001 mmol / L to 0.7 mmol / L, and most preferably 0.001 mmol / L to 0.5 mmol / L.

[0033] In this embodiment, the content of the donor in the photocurable resin composition is preferably 0.0001 to 10 parts by mass, and more preferably 0.005 to 5 parts by mass, relative to 100 parts by mass of the total amount of the photocurable resin composition. In this embodiment, the content of the acceptor in the photocurable resin composition is preferably 0.001 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the total amount of the photocurable resin composition.

[0034] (B2) Multiphoton Excitation Type Photon Up-Conversion Material In certain embodiments, the photon up-conversion material is a multiphoton excitation type photon up-conversion material (hereinafter also referred to as "component (B2)"). 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 (B2) 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 certain embodiments, the emission wavelength of component (B2) includes an ultraviolet light wavelength (200 nm to 380 nm). Component (B2) 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 (B2) preferably has an emission intensity in the wavelength region of 500 nm or less.

[0035] In component (B2), 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 (B2) (doping amount), upconversion luminescence of any wavelength can be obtained.

[0036] 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:

[0037] The wavelength range of the excitation light that causes upconversion emission of such component (B2) 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.

[0038] 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.

[0039] 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 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 (B2) whose base material is a halide. As this coating material, the oxides listed above can be used.

[0040] Also, the core (NaYREF ４ ) / Shell (NaYF ４ ) (RE=rare earth element) can also be used.

[0041] Component (B2) 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 (B2), reference can be made to the method described in JP-A-2006-117864, for example.

[0042] Component (B2) 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.

[0043] Component (B2) may be used alone or in combination of two or more. For example, in one embodiment, the use of two or more components (B2) 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.

[0044] From the viewpoints of light conversion efficiency and photocurability, the content of component (B2) in the photocurable resin composition is preferably 0.1 to 60 parts by mass, and more preferably 1 to 60 parts by mass, relative to 100 parts by mass of the total amount of the photocurable resin composition.

[0045] In this embodiment, either the triplet-triplet annihilation type photon upconversion material (B1) or the multiphoton excitation type upconversion material (B2) may be used alone, or any combination thereof may be used. For example, in certain embodiments, the use of a combination of component (B1) and component (B2) enables energy transfer from component (B1) to component (B2) or from component (B2) to component (B1) 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.

[0046] (C) Radical Polymerizable Compound Other Than Maleimide Compound The photocurable resin composition of this embodiment may further contain (C) a radical polymerizable compound other than the (A) maleimide compound (hereinafter also referred to as "(C) other radical polymerizable compound" or "component (C)"). Radicals are generated from the maleimide compound activated by photon upconversion light emission, and polymerization of the maleimide compound itself and the radical polymerizable compound other than the maleimide compound proceeds. Examples of radical polymerizable compounds other than maleimide compounds include, but are not limited to, compounds having an unsaturated double bond such as (meth)acrylate compounds, (meth)acrylamide compounds, cyanoacrylate compounds, vinyl ether compounds, styrene compounds, and methylene malonates (2-methylene-1,3-dicarbonyl compounds and derivatives thereof), or mixtures of compounds having an unsaturated double bond and thiol compounds (mixtures capable of ene-thiol reaction).

[0047] 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, isobol Nylcyclohexyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, 1-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, 2-methyl-2-adamantanyl (meth)acrylate, 2-ethyl-2-adamantanyl (meth)acrylate, 2-isopropyladamantan-2-yl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, (adamantan-1-yloxy)methyl (meth)acrylate, 2- Isopropyl-2-adamantyl (meth)acrylate, 1-methyl-1-ethyl-1-adamantylmethanol (meth)acrylate, 1,1-diethyl-1-adamantylmethanol (meth)acrylate, 2-cyclohexylpropan-2-yl (meth)acrylate, 1-isopropylcyclohexyl (meth)acrylate, 1-methylcyclohexyl (meth)acrylate, 1-ethylcyclopentyl (meth)acrylate, 1-methylcyclohexyl (meth)acrylate, tetrahydropyranyl (meth)acrylate, tetrahydro-2- Examples of the ester include mono(meth)acrylates of polyhydric alcohols or esters of monohydric alcohols and (meth)acrylic acid, such as furanyl(meth)acrylate, 2-oxotetrahydrofuran-3-yl(meth)acrylate, (5-oxotetrahydrofuran-2-yl)methyl(meth)acrylate, (2-oxo-1,3-dioxolan-4-yl)methyl(meth)acrylate, N-acryloyloxyethylhexahydrophthalimide, α-acryloyl-ω-methoxypoly(oxyethylene), and 1-ethoxyethyl(meth)acrylate.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 di(meth)acrylate of tris(2-hydroxyethyl)isocyanurate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, or an oligomer thereof; pentaerythritol tri(meth)acrylate, or an oligomer thereof; poly(meth)acrylate of dipentaerythritol; tris(acryloxyethyl)isocyanurate; caprolactone-modified tris((meth)acryloxyethyl)isocyanurate; poly(meth)acrylate of alkyl-modified dipentaerythritol; poly(meth)acrylate of caprolactone-modified dipentaerythritol; ethoxylated bisphenol A di(meth)acrylate; Examples of the (meth)acrylate include, but are not limited to, dihydrocyclopentadiethyl (meth)acrylate, polyester (meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, ditrimethylolpropane poly(meth)acrylate, polyurethane having two or more (meth)acryloyl groups in one molecule, polyester having two or more (meth)acryloyl groups in one molecule, phenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, epoxy resin half (meth)acrylate, and (meth)acrylate having an allyloxymethyl group (see JP 2024-009452 A). The (meth)acrylate compound may be any one of the above-mentioned (meth)acrylate compounds, or two or more 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, polyester acrylate (product name: M7100) manufactured by Toagosei Co., Ltd., and dimethylol-tricyclodecane diacrylate (product name: Light Acrylate DCP-A) manufactured by Kyoeisha Chemical Co., Ltd.Examples include, but are not limited to, neopentyl glycol modified trimethylolpropane diacrylate (product name: Kayarad R-604) manufactured by Nippon Kayaku Co., Ltd.

[0048] 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.

[0049] 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.

[0050] The vinyl ether compound has a vinyl ether group (H ２ C═CH—O—). Examples of vinyl ether compounds include, but are not limited to, ethyl vinyl ether, triethylene glycol divinyl ether, trimethylolpropane trivinyl ether, hydroxybutyl vinyl ether, dodecyl vinyl ether, cyclohexyl vinyl ether, 1,4-butanediol divinyl ether, nonanediol divinyl ether, cyclohexanediol divinyl ether, and cyclohexanedimethanol divinyl ether. These compounds may be used alone or in combination of two or more.

[0051] 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.

[0052] 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.

[0053] The thiol compound in the mixture of a compound having an unsaturated double bond and a 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. Examples of thiol compounds include monofunctional thiol compounds having one thiol group and polyfunctional thiol compounds having two or more thiol groups. In one embodiment, the thiol compound contains at least a polyfunctional thiol compound. In one embodiment, the thiol compound contains a combination of a bifunctional thiol compound and a trifunctional or higher functional thiol compound. In one embodiment, the thiol compound contains a combination of a monofunctional thiol compound and a polyfunctional thiol compound. Thiol compounds can also be divided 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 Co., Ltd.: TMMP), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate (manufactured by SC Organic Chemical Co., Ltd.: TEMPIC), pentaerythritol tetrakis(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: PEMP), and tetraethylene glycol bis(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: 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 (Shikoku Chemical Industry Co., Ltd.: C3 TS-G), 1,3,4,6-tetrakis(mercaptomethyl)glycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-dimethylglycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a-di Methyl glycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-dimethyl glycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-diphenyl glycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a-diphenyl glycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-diphenyl glycoluril, tris(3-mercaptopropyl) isocyanurate, 1,3,5-tris[3-(2-mercaptopropyl)methyl]-3a,6a-diphenyl glycoluril, 1,3,5-tris[2-(3-mercaptoethylsulfanyl)propyl]isocyanurate, 1,3,5-tris[2-(3-mercaptopropoxy)ethyl]isocyanurate, pentaerythritol trippropanethiol (manufactured by SC Organic Chemical Co., Ltd.: PEPT), 3-[2,3-bis(3-sulfanylpropoxy)propoxy]propane-1-thiol, 1,2,3-tris(3-mercaptopropoxy)propane, 3-[2,2-bis[(3-mercaptopropoxy)methyl]butoxy]-1-propanethiol, pentaerythritol tetrapropane thiol, 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3-mercaptopropylthio)propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 1,1,5,5-tetrakis(mercaptomethylthio)-3-thiapentane, 1,1,6,6-tetrakis(mercaptomethylthio)-3,4-dithiahexane, 2,2-bis(mercaptomethylthio)ethanethiol, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptane, 3,6-bis(mercaptomethylthio)-1,9-dimercapto-2,5,8-trithianonane, 3-mercaptomethylthio-1,6-dimercapto-2,5-dithiahexane, 1,1,9,9-tetrakis(mercaptomethylthio)-5-(3,3-bis(mercaptomethylthio)-1-thiapropyl)3,7-dithianonane, tris(2,2-bis(mercaptomethylthio)ethyl)methane, tris(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane , tetrakis(2,2-bis(mercaptomethylthio)ethyl)methane, tetrakis(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane, 3,5,9,11-tetrakis(mercaptomethylthio)-1,13-dimercapto-2,6,8,12-tetrathiatridecane, 3,5,9,11,15,17-hexakis(mercaptomethylthio)-1,19-dimercapto-2,6,8,12,14,18-hexathianonadecane, 9-(2,2-bis(mercaptomethylthio)ethyl)-3,5,13,15-tetrakis(mercapto 3,4,8,9-tetrakis(mercaptomethylthio)-1,11-dimercapto-2,5,7,10-tetrathiaundecane, 3,4,8,9,13,14-hexakis(mercaptomethylthio)-1,16-dimercapto-2,5,7,10,12,15-hexathiahexadecane, 8-[bis(mercaptomethylthio)methyl]-3,4,12,13-tetrakis(mercaptomethylthio)-1,15-dimercapto-2,5,7,9,11,14-Hexathiapentadecane, 4,6-bis[3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiaheptylthio]-1,3-dithiane, 4-[3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiaheptylthio]-6-mercaptomethylthio-1,3-dithiane, 1,1-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio]-1,3-bis(mercaptomethylthio)propane, 1-[4-(6-mercaptomethylthio)-1,3-dithianylthio]-3-[2,2-bis(mercaptomethylthio) methylthio)ethyl]-7,9-bis(mercaptomethylthio)-2,4,6,10-tetrathiaundecane, 3-[2-(1,3-dithietanyl)]methyl-7,9-bis(mercaptomethylthio)-1,11-dimercapto-2,4,6,10-tetrathiaundecane, 9-[2-(1,3-dithietanyl)]methyl-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3-[2-(1,3-dithietanyl)]methyl-7,9,13,15-tetrakis bis(mercaptomethylthio)-1,17-dimercapto-2,4,6,10,12,16-hexathiaheptadecane, 4,6-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio]-6-[4-(6-mercaptomethylthio)-1,3-dithianylthio]-1,3-dithiane, 4-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecyl]-5-mercaptomethylthio-1,3-dithiolane, 4,5-bis[3,4-bis(mercaptomethylthio)-6-mercapto- 2,5-dithiahexylthio]-1,3-dithiolane, 4-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]-5-mercaptomethylthio-1,3-dithiolane, 4-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]-5-mercaptomethylthio-1,3-dithiolane, 2-{bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]methyl}-1,3-dithietane, 2-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]mercaptomethylthiomethyl-1,3-dithietane, 2-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecylthio]mercaptomethylthiomethyl-1,3-dithietane, 2-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]mercaptomethylthiomethyl-1,3-dithietane, 4-{1-[2-(1,3 -dithietanyl)]-3-mercapto-2-thiapropylthio}-5-[1,2-bis(mercaptomethylthio)-4-mercapto-3-thiabutylthio]-1,3-dithiolane, 2,2'-[cyclohexylidenebis(thio-2,1-ethanediylthio)]bis[ethanethiol], 4,4'-[(1,3-phenylene)bis(oxy)]bis[1-butanethiol], and the various bifunctional thiol compounds disclosed in WO 2019 / 082962, as well as dimers, trimers, and tetramers of the above thiol compounds, can be mentioned, but are not limited to these. These may be used alone or in combination of two or more.

[0054] The content of the (C) other radical polymerizable compound in the photocurable resin composition may be, for example, 0 to 99 parts by mass, or 0 to 90 parts by mass, relative to 100 parts by mass of all radical polymerizable compounds (i.e., the total of the maleimide compound and the radical polymerizable compounds other than the maleimide compound).

[0055] The total content of the (A) maleimide compound and the (C) other radical polymerizable compound in the photocurable resin composition may be 1 to 99.9 parts by mass, relative to 100 parts by mass of the total amount of the photocurable resin composition. The photocurable resin composition of this embodiment can be cured by photocuring alone, even in the presence of a large amount of a shielding material such as a filler. In one embodiment, the total content of the (A) maleimide compound and the (C) other radical polymerizable compound in the photocurable resin composition is preferably 5 to 50 parts by mass, more preferably 7 to 30 parts by mass, relative to 100 parts by mass of the total amount of the photocurable resin composition. In another embodiment, the total content of the (A) maleimide compound and the (C) other radical polymerizable compound in the photocurable resin composition is preferably 30 to 99.9 parts by mass, more preferably 50 to 99.5 parts by mass, and even more preferably 60 to 99.5 parts by mass, relative to 100 parts by mass of the total amount of the photocurable resin composition. The total content of the (A) maleimide compound and the (C) other radical polymerizable compound in the resin composition is preferably 30 to 99 parts by mass, more preferably 40 to 99 parts by mass, and even more preferably 50 to 98 parts by mass, per 100 parts by mass of the total amount of all organic substances contained in the resin composition (excluding low-stress-imparting materials such as organic fillers and elastomers). The total content of the (A) maleimide compound and the (C) other radical polymerizable compound is preferably 30 to 99.9 parts by mass, more preferably 40 to 99.5 parts by mass, and even more preferably 50 to 99 parts by mass, per 100 parts by mass of the total of components (A), (B), and (C).

[0056] The photocurable resin composition of this embodiment may contain optional components other than the components (A) to (C) as desired, such as those described below.

[0057] Filler: The photocurable resin composition of this embodiment may contain a filler to the extent that the object of this embodiment is not impaired. By including a filler in the photocurable resin composition, the linear expansion coefficient of the cured product obtained by curing the photocurable resin composition can be reduced, improving thermal cycle resistance. Furthermore, a filler with a low elastic modulus can alleviate stress generated in the cured product, improving long-term reliability. Fillers are broadly classified into inorganic fillers and organic fillers.

[0058] 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. One type of inorganic filler may be used, or two or more types may be used in combination. In one embodiment, the inorganic filler may be a silica filler, as this allows for a high loading amount. The silica may be, for example, amorphous silica.

[0059] 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.

[0060] The organic filler is not particularly limited, but examples thereof include organic fine particles of acrylic resin, polyolefin, polybutadiene rubber, polyvinyl alcohol, polyester, polyurethane, melamine, nylon, polyvinyl butyral, polyarylate, polymethyl methacrylate, polyethylene, polypropylene, polycarbonate, acrylic rubber, polystyrene, NBR, SBR, polytetrafluoroethylene, benzoguanamine-formaldehyde, silicone rubber, silicone-modified resin, phenol resin, and copolymers containing these as components. The organic filler may also be surface-treated.

[0061] The shape of the filler is not particularly limited, and may be any of spherical, flaky, needle-like, irregular, etc.

[0062] 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 photocurable resin composition, the maximum particle size of the filler is preferably 50 μm or less, more preferably 30 μm or less.

[0063] 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.

[0064] When a filler is contained, the content of the filler is preferably 0.5 to 80% by mass, more preferably 1 to 70% by mass, based on the total mass of the photocurable resin composition.

[0065] The photocurable resin composition of this embodiment may contain a thixotropic agent to the extent that the effects of this embodiment are not impaired. Examples of thixotropic agents include silica such as colloidal silica, hydrophobic silica, fine silica, and nanosilica, as well as bentonite, acetylene black, and ketjen black. Nanosilica is preferred from the viewpoint of shape retention after application. Furthermore, from the viewpoints of preventing the resin composition from biting during bonding and moisture-resistant adhesion, the thixotropic agent is more preferably nanosilica having an average particle size of 10 to 750 nm, and even more preferably nanosilica having an average particle size of 20 to 600 nm. Commercially available products include hydrophobic fumed silica manufactured by CABOT Corporation (product name: CAB-O-SIL (registered trademark) TS720, average particle size: 12 nm), hydrophobic fumed silica manufactured by Nippon Aerosil (product name: R805, average particle size: 20 nm), and amorphous silica manufactured by Nippon Shokubai (product name: Seahoster KE-P10, average particle size 100 nm), but are not limited to these. Here, the average particle size of the nanosilica particles is measured using a dynamic light scattering Nanotrac particle size analyzer. The thixotropic agent may be used alone or in combination of two or more types.

[0066] When a thixotropic agent is contained, the content of the thixotropic agent is preferably 0.01 to 30 mass %, more preferably 0.05 to 25 mass %, and even more preferably 0.1 to 20 mass %, relative to the total mass of the photocurable resin composition.

[0067] Light-blocking agent: The photocurable resin composition of this embodiment may contain a light-blocking agent to the extent that the effect of this embodiment is not impaired. Light-blocking properties may be required depending on the application of the cured resin composition. In such cases, the photocurable resin composition of this embodiment may contain a light-blocking agent. Long-wavelength light can be transmitted through a light-blocking agent that blocks ultraviolet light. The photocurable resin composition of this embodiment can be cured by irradiating it with long-wavelength light without or with minimal influence from the light-blocking agent. Examples of light-blocking agents include, but are not limited to, carbon black and titanium black. These light-blocking agents can also be used as light-to-heat conversion materials that convert long-wavelength light into heat.

[0068] Other Additives: If desired, the photocurable resin composition of this embodiment may further contain other additives, such as photosensitizers, conductive fillers, stabilizers, radical polymerization inhibitors, anionic polymerization inhibitors, coupling agents, ion trapping agents, leveling agents, antioxidants, antifoaming agents, viscosity modifiers, flame retardants, colorants, plasticizers, and solvents, within the scope of this embodiment. The type and amount of each additive are conventional. From the viewpoints of reducing the curing strength and adhesion upon photocuring and preventing outgassing and bleeding, the resin composition of this embodiment is substantially free of liquid components such as water, solvents, and ionic liquids (excluding liquid components (A) to (C)). For example, the content of liquid components is preferably 3% by mass or less, and more preferably 1% by mass or less, relative to the total mass of the resin composition. Examples of the solvent include organic solvents commonly used in the field of curable compositions, such as hydrocarbons (benzene, toluene, xylene, cyclohexane, etc.), aprotic polar solvents (N,N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, etc.), nitriles (acetonitrile, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (ethyl acetate, butyl acetate, etc.), ethers (cyclopentyl methyl ether, diethyl ether, tetrahydrofuran, dimethoxyethane, etc.), alcohols (methanol, ethanol, propanol, butanol, etc.), terpenes (turpentine, terpineol, isobornyl acetate, etc.), and halogenated solvents (dichloromethane, chloroform, etc.).

[0069] The viscosity of the photocurable resin composition of this embodiment is preferably 0.1 to 100 Pa·s. The viscosity can be adjusted appropriately depending on the application and application location of the resin composition. The photocurable resin composition of this embodiment is excellent for application to areas with complex shapes that are difficult to irradiate with UV light, or for application to narrow areas. In this specification, viscosity is expressed as a value measured in accordance with Japanese Industrial Standard JIS K6833, unless otherwise specified. Specifically, it can be determined by measuring using an E-type viscometer at a rotation speed of 10 rpm. There are no particular limitations on the equipment, rotor, or measurement range used.

[0070] The photocurable resin composition of this embodiment can be a one-component resin composition contained in a single container, or a two-component (or multi-component) resin composition divided into two or more containers, depending on the intended use. When using a two-component (or multi-component) resin composition, the two components (or multiple components) are mixed to form a photocurable resin composition for use. When using a two-component (or multi-component) resin composition, the components (A) and (B) or 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 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 separation method, each liquid may contain one or more components selected from the group consisting of component (A) and component (B) or components (A) to (C) and other optional components as needed, or a single liquid may contain component (A) and component (B) or components (A) to (C) and other optional components as needed, or a liquid may consist solely of component (A) and component (B) or 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), or liquid A: component (A), liquid B: component (B) and component (C), or liquid A: component (A and component (B), liquid B: component (C), or liquid A: component (A) and component (C), liquid B: component (B). When component (A) and component (B) or component (A) to component (C) are contained in liquid A, liquid B may contain one or more selected from component (A) and component (B) or component (A) to component (C). In addition, components other than component (A) and component (B) or component (A) to component (C) may be contained in both or either liquid A and liquid B in the above combination. When component (A) and component (B) or component (A) to component (C) are contained in liquid A and other components are contained in liquid B, only liquid A or a combination of liquid A and liquid B can be considered to be the resin composition of this embodiment.On the other hand, when the components (A) and (B) or the components (A) to (C) are contained in separate liquids, the liquids can be collectively regarded as the resin composition of this embodiment. Examples of the case where the components (A) and (B) or the components (A) to (C) are contained in separate liquids include a resin composition in which the components (A) and (B) or the components (A) to (C) are separated into two or more containers, specifically a kit composed of multiple liquids containing either the components (A) and (B) or the components (A) to (C).

[0071] The method for producing the photocurable resin composition of this embodiment is not particularly limited. For example, the resin composition of this embodiment can be obtained by simultaneously or separately introducing component (A), component (B), and, if necessary, component (C) and other optional components into an appropriate mixer and mixing them by stirring to form a uniform composition. The mixer is not particularly limited, but examples of the mixer that can be used include a Raikai mixer, a Henschel mixer, a three-roll mill, a ball mill, a planetary mixer, and a bead mill equipped with a stirring device and a heating device. These devices may also be used in appropriate combination.

[0072] The photocurable resin composition obtained in this manner is cured by irradiation with long-wavelength light (e.g., longer than 500 nm), and curing is completed by light irradiation alone; no thermal curing is required. Conventionally, high-energy short-wavelength light (e.g., 365 nm UV light) is generally used to photocure UV-curable adhesives. Therefore, if the adhesive contains a filler or the like, the penetration distance of light into the UV-curable adhesive when irradiated with short-wavelength light is short, and curing does not proceed in areas where the light cannot reach due to a shielding object or the like. Regarding the latter issue in particular, for example, when the shielding object is a silicon substrate and the relationship between the wavelength of irradiated light and the penetration distance of light on the silicon substrate is examined, ultraviolet light of 380 nm or less penetrates the silicon substrate by several to several tens of nanometers, while visible light of 380 to 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.

[0073] The photocurable resin composition of this embodiment can be used, for example, as an adhesive, sealant, or coating agent for fixing, joining, or protecting semiconductor devices or electronic components, or components constituting these, or as a raw material thereof. In one embodiment, the photocurable resin composition of this embodiment can be used for curing by irradiation with light having a wavelength of more than 500 nm. In one embodiment, the photocurable resin composition of this embodiment can be used as an adhesive, sealant, or coating agent for semiconductor devices or electronic components.

[0074] [Bonding Method] Another aspect of the present invention is a method for bonding at least two components with a curable resin composition, the bonding method including the steps of applying the photocurable resin composition of the above aspect 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.

[0075] 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 general-purpose plastics (e.g., PE, PS, PP, etc.), engineering plastics (e.g., LCP (liquid crystal polymer), polyamide, polycarbonate, etc.), ceramics, or metals (e.g., copper, nickel). The method for applying the resin composition is not particularly limited, and the resin composition 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. Examples of coating methods include, but are not limited to, dip coating, spray coating, bar coater coating, gravure coating, reverse gravure coating, and spin coater coating.

[0076] 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.

[0077] 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 generate light having a wavelength of 450 nm or less, preferably light having a wavelength of 430 nm or less, and more preferably light having a wavelength of 400 nm or less, thereby activating the maleimide compound and curing the radical polymerizable compound containing the maleimide 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, 650 nm, 940 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 photocurable resin composition used in this embodiment can be cured even in the shadow area of ​​a component, in the bonding method of this embodiment, the photocurable resin composition can be irradiated with light not only directly but also through a component.

[0078] [Sealing Method] Another aspect of the present invention is a method for sealing gaps between or within components with a curable resin composition, the sealing method comprising the steps of applying or injecting the photocurable resin composition of the above-described embodiment into the gap 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 photocurable 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.

[0079] [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, optical sensor modules such as image sensor modules and time-of-flight (TOF) 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 general-purpose plastics (e.g., PE, PS, PP, etc.), engineering plastics (e.g., LCP (liquid crystal polymer), polyamide, polycarbonate, etc.), ceramics, or metals (e.g., copper, nickel). 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.

[0080] [Adhesive, Sealant, or Coating Agent] Another embodiment of the present invention is an adhesive, sealant, or coating agent that includes the photocurable resin composition of the above embodiment. This adhesive, sealant, or coating agent provides excellent fixation, bonding, or protection for general-purpose plastics (e.g., PE, PS, PP, etc.), engineering plastics (e.g., LCP (liquid crystal polymer), polyamide, polycarbonate, etc.), ceramics, and metals (e.g., copper, nickel, etc.), and can be used to fix, bond, or protect semiconductor devices or electronic components, or components that constitute these. Examples of semiconductor devices or electronic components include, but are not limited to, HDDs, semiconductor elements, optical sensor modules such as image sensor modules and time-of-flight (TOF) 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.

[0081] [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 photocurable resin composition, adhesive, sealant, or coating agent according to the above-described embodiment.

[0082] [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 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, optical sensor modules such as image sensor modules and time-of-flight (TOF) sensor modules, other semiconductor modules, and integrated circuits.

[0083] [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 aspect, or the adhesive, sealant, or coating agent of the above 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 aspect with light having a wavelength of more than 500 nm. Yet another aspect of the present invention is use of the photocurable resin composition of the above aspect for curing by irradiation with light having a wavelength of more than 500 nm. By irradiating the photocurable resin composition 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, the photon upconversion material within the photocurable resin composition generates 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, thereby activating the maleimide compound and curing the radical polymerizable compound containing the maleimide compound. The details of the light irradiation with wavelengths of more than 500 nm in these methods are the same as those in the bonding method, sealing method, and coating method. 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.

[0084] 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.

[0085] [Experimental Example 1] Resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 were prepared by mixing predetermined amounts of each component according to the formulations shown in Table 1. A triplet-triplet annihilation photon upconversion material (B1) was mixed with (A) a maleimide compound and an optional (C) radically polymerizable compound other than a maleimide compound to obtain a 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:

[0086] (A) Maleimide Compounds (A-1): Bismaleimide 1 having a hydrocarbon group derived from a dimer acid (product name: BMI-689, manufactured by Designer Molecules Inc.) (A-2): Bismaleimide 2 having a hydrocarbon group derived from a dimer acid (product name: BMI-1500, manufactured by Designer Molecules Inc.) (A-3): N-phenylmaleimide (product name: Imilex （Ｒ） -P, Nippon Shokubai Co., Ltd.) (B) Photon up-conversion material (B1) Triplet-triplet annihilation photon up-conversion material (B1-1D): Platinum(II) octaethylporphyrin (PtOEP) as a donor (manufactured by Sigma-Aldrich Japan K.K.) (B1-1A): Diphenylanthracene (DPA) as an acceptor (manufactured by Tokyo Chemical Industry Co., Ltd.) The mass ratio of the donor and acceptor PtOEP:DPA was 1:24 (molar ratio 1:50), and the photon up-conversion material (B1-1) was obtained. (B1-2D): Zinc(II) octaethylporphyrin (ZnOEP) as a donor (manufactured by Sigma-Aldrich Japan) (B1-2A): Diphenylanthracene (DPA) as an acceptor (manufactured by Tokyo Chemical Industry Co., Ltd.) The mass ratio of the donor and acceptor ZnOEP:DPA was 1:24 (molar ratio 1:50), to obtain the photon upconversion material (B1-2). - (C) Radical polymerizable compounds other than maleimide compounds (C-1): Dimethylol-tricyclodecane diacrylate (product name: Light Acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd.) (C-2): n-Octyl acrylate (product name: NOAA, Osaka Organic Chemical Industry Ltd.)

[0087] In the examples and comparative examples, the properties of the resin compositions were measured as follows.

[0088] [Evaluation of curability of resin composition] In a dark place at a temperature of 22°C ± 5°C and a humidity of 50% ± 10%, one drop (approximately 0.02 g) of the photocurable resin composition was dropped onto a glass slide, and the glass slide was inserted into the glass slide to prepare a test piece, which was then irradiated with visible light. The visible light irradiation conditions for Examples 1 to 6 and Comparative Examples 1 to 3 were as follows: a semiconductor-pumped solid-state laser (Class 3R green laser pointer LP-GL1016BK, manufactured by Sanwa Supply Co., Ltd.) was used, and the wavelength of visible light was 532 nm, and the irradiation intensity was 10 mW / cm, at a position 4 cm above the light source from the top surface of the glass slide. ２ The cumulative light intensity is 10 J / cm ２ For Example 7, an LED lamp (straight tube lamp system yellow light LDL40TY / 17 / 21-Y2, Toshiba Lighting & Technology Corporation) was used to irradiate the slide glass with visible light containing 570 nm wavelength at a position 4 cm above the light source, with an irradiation intensity of 3 mW / cm. ２ The total light intensity is 300 J / cm ２ In this test, one of the slide glasses was peeled off from the test piece, and the photocuring property was checked by appearance and palpation with a toothpick. ２ The results were evaluated on a three-point scale, with ⊚ indicating that the composition had cured at or below this temperature, ◯ indicating that the composition had cured at or above this temperature, and × indicating that the composition did not cure. The results are shown in Table 1.

[0089]

[0090] As shown in Examples 1 to 7, resin compositions containing (A) a maleimide compound, (B) a photon upconversion material, and any (C) radically polymerizable compound other than a maleimide compound were cured by visible light irradiation. Comparative Example 1 was a resin composition containing (A) a maleimide compound but not (B) a photon upconversion material, and did not cure by visible light irradiation. Comparative Examples 2 and 3 were resin compositions containing (A) a maleimide compound and only either the donor or acceptor of (B1) a triplet-triplet annihilation photon upconversion material, and like Comparative Example 1, did not cure by visible light irradiation.

[0091] The disclosure of Japanese Patent Application No. 2024-116918 (filing date: July 22, 2024) is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards mentioned herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A photocurable resin composition comprising: (A) a maleimide compound; and (B) a photon upconversion material.

2. The photocurable resin composition according to claim 1, which is substantially free of a photoradical polymerization initiator.

3. The photocurable resin composition according to claim 1 or 2, wherein the emission wavelength of the photon upconversion material (B) includes wavelengths of 500 nm or less.

4. A photocurable resin composition according to any one of claims 1 to 3, further comprising (C) a radically polymerizable compound other than the maleimide compound (A).

5. A photocurable resin composition according to any one of claims 1 to 4, for use in curing by irradiation with light having a wavelength of more than 500 nm.

6. The photocurable resin composition according to any one of claims 1 to 5, which is used as an adhesive, sealant or coating agent for semiconductor devices or electronic parts.

7. An adhesive, sealant or coating agent comprising the photocurable resin composition according to any one of claims 1 to 6.

8. A cured product obtained by curing the photocurable resin composition according to any one of claims 1 to 6, or the adhesive, sealant or coating agent according to claim 7.

9. A semiconductor device or electronic part comprising the cured product according to claim 8.

10. A method for producing a cured product, comprising irradiating the photocurable resin composition according to any one of claims 1 to 6, or the adhesive, sealant, or coating agent according to claim 7, with light having a wavelength of more than 500 nm.

11. A method for curing a photocurable resin composition, comprising irradiating the photocurable resin composition according to any one of claims 1 to 6 with light having a wavelength of more than 500 nm.

12. Use of the photocurable resin composition according to any one of claims 1 to 6 for curing by irradiation with light having a wavelength of more than 500 nm.

13. A method for bonding at least two components with a photocurable resin composition, comprising the steps of: applying the photocurable resin composition according to any one of claims 1 to 6 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.

14. 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 6 into the gaps between or within the components, and irradiating the photocurable resin composition with light having a wavelength of more than 500 nm.

15. A method for coating the surface of an object with a photocurable resin composition, comprising the steps of: applying the photocurable resin composition according to any one of claims 1 to 6 to the object; and irradiating the photocurable resin composition with light having a wavelength of more than 500 nm.

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