WO2026023321A1 - Photocurable resin composition, adhesive, sealant, coating agent, cured product, semiconductor device, electronic component, and curing, bonding, sealing, and coating methods using photocurable resin composition - Google Patents

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

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

Adhesives that are temporarily fixed by ultraviolet (UV) irradiation and then fully hardened by heat are used in many fields (for example, Patent Documents 1 and 2). If the adhesive contains a filler, the filler may act as a blocker of UV light, or if the area where the adhesive is applied has a complex shape, the UV light may be blocked, resulting in areas of the adhesive that the UV light does not reach. In such cases, those areas remain unhardened, making it difficult to achieve the desired degree of hardening. For this reason, this type of adhesive is used in applications where there are areas that are not hardened by UV light, with the aim of fully hardening them with heat.

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

On the other hand, from the perspective of improving productivity and considering applications to heat-sensitive components, there is a demand for photocurable resin compositions that can be cured completely by light irradiation alone, without requiring thermal curing.

The present invention therefore aims to provide a photocurable resin composition that cures completely by irradiation with light alone and does not require thermal curing; an adhesive, sealant, or coating agent containing the same; a cured product thereof; a semiconductor device or electronic component containing the cured product; and a curing method, bonding method, sealing method, and coating method that use the photocurable resin composition.

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 the cured product, method for curing the photocurable resin composition, use of the photocurable resin composition, adhesion method, encapsulation 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], which is substantially free of a photoradical polymerization initiator.
[3] The photocurable resin composition according to [1] or [2], wherein 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], further comprising (C) a radical polymerizable compound other than the (A) maleimide compound.
[5] The photocurable resin composition according to any one of [1] to [4] above, 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 [1] to [5], which is used as an adhesive, a sealant, or a coating agent for semiconductor devices or electronic components.
[7] An adhesive, a sealant, or a 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, sealant, 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, comprising irradiating the photocurable resin composition according to any one of [1] to [6] above, or the adhesive, sealant, 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, comprising 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 parts with a photocurable resin composition, comprising:
The method includes applying the photocurable resin composition according to 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 of them with light having a wavelength of more than 500 nm.
Adhesion method.
[14] A method for sealing gaps between or within components with a photocurable resin composition, comprising:
applying or injecting the photocurable resin composition according to any one of [1] to [6] into the gap between or within the components; and irradiating the photocurable resin composition with light having a wavelength of more than 500 nm.
Sealing method.
[15] A method for coating a surface of an object with a photocurable resin composition, comprising:
A coating method comprising the steps of: applying the photocurable resin composition according to 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.

According to aspects of the present invention, there are provided a photocurable resin composition that cures completely by irradiation with light alone and does not require thermal curing; an adhesive, sealant, or coating agent containing the same; a cured product thereof; a semiconductor device or electronic component containing the cured product; and a curing method, bonding method, sealing method, and coating method that use the photocurable resin composition.

In this specification, "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, a name including the term "resin," which normally refers to a polymer (particularly a synthetic polymer), may be used for a component constituting a curable resin composition before curing, even if the component is not a polymer, for example, a prepolymer compound before curing.
In this specification, the term "(meth)acryloyl group" includes both methacryloyl groups and acryloyl groups, and the term "(meth)acrylate compound" includes both acrylate compounds and methacrylate compounds.
In addition, in this specification, the "photocurable resin composition" may be simply referred to as the "resin composition."

[Photocurable resin composition]
The photocurable resin composition according to one embodiment of the present invention comprises:
The present invention provides a photocurable resin composition comprising (A) a maleimide compound and (B) a photon upconversion material. According to this aspect, the photocurable resin composition is cured by light irradiation alone, and does not require main curing by heat.

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.
As a result of 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 light emission generates radicals and promotes polymerization of the radically polymerizable compound. That is, the maleimide compound is not only a polymerizable compound but also can function as a photoradical initiator, and promotes polymerization of a radically polymerizable compound containing the maleimide compound itself without the need for a separate photoradical initiator.

(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, the 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.

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-bismaleimide Examples of suitable dimaleimide compounds include, but are not limited to, hexane, 1,2-bismaleimide, 1,2-bismaleimide (N,N'-ethylenedimaleimide), N,N'-(1,2-phenylene)bismaleimide, N,N-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, 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'-dimaleimidephenyl ether. These compounds may be used alone or in combination of two or more.

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 named "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 may be used alone or in combination of two or more types.

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, but are not limited to, Imilex® ^- C and ^Imilex® -P (both manufactured by Nippon Shokubai Co., Ltd.) and O-CPMI (manufactured by Daiwa Chemical Industry Co., Ltd.), which may be used alone or in combination of two or more.

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. Furthermore, 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.

From the viewpoint of polymerization rate, it is preferable that the maleimide compound be liquid at room temperature, or if it is solid at room temperature, it be dissolved in a liquid radically polymerizable compound or the like before use.

From the viewpoint of photoirradiation reactivity, the content of the (A) maleimide compound 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, per 100 parts by mass of all radically polymerizable compounds (i.e., the sum of the maleimide compound and radically polymerizable compounds other than the maleimide compound).

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 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 sum 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.

Examples of alkylphenone compounds include benzyl dimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethan-1-one (commercially available as Omnirad 651, manufactured by IGM Resins B.V.); α-aminoalkylphenones such as 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one (commercially available as Omnirad 907, manufactured by IGM Resins B.V.); 1-hydroxy-cyclohexyl-phenyl-ketone (commercially available as IGM Resins B.V.); Examples of suitable hydroxyalkylphenones include, but are not limited to, α-hydroxyalkylphenones such as Omnirad 184 (manufactured by IGM Resins B.V.); 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one (commercially available as Omnirad 379EG, manufactured by IGM Resins B.V.), and 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone (commercially available as Omnirad 369, manufactured by IGM Resins B.V.).

Examples of acylphosphine oxide compounds 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.).

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).

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

In addition to the above-mentioned photoradical polymerization initiators, examples of photoradical polymerization initiators include 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, and benzyl dimethyl Examples of suitable benzoxanthones include, but are not limited to, benzoylketal, 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, and camphorquinone.

(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).

Photon upconversion (PUC) is a technology that converts low-energy (long-wavelength) light into high-energy (short-wavelength) light. Mechanisms of photon upconversion include triplet-triplet annihilation (TTA), 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 of these.

(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.

<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 can 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.

<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 the 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), but are not limited thereto. Other specific examples of donors include donors described in, for example, JP 2021-080335 A and JP 2020-056030 A.

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 one embodiment, selecting multiple combinations of donor and acceptor enables energy transfer from one photon upconversion material to another photon upconversion material within 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 (B1) triplet-triplet annihilation type photon upconversion material that emits light upon irradiation with light with a wavelength exceeding 500 nm can be adjusted to include wavelengths of 500 nm or less.

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 greater than 500 nm, for example, a wavelength in the range of greater than 500 nm and less than or equal to 2000 nm. The wavelength of the upconversion emission from component (B1) preferably includes wavelengths of 500 nm or less, more preferably wavelengths of 450 nm or less, even more preferably wavelengths of 430 nm or less, and particularly preferably wavelengths of 400 nm or less. In one embodiment, the emission wavelength of component (B1) includes the wavelength of ultraviolet light (200 nm to 380 nm).

Any one of the donors may be used, or two or more may be used in combination. Any one of the acceptors may be used, or two or more may be used in combination.

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, per 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, per 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, per 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.

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, per 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, per 100 parts by mass of the total amount of the photocurable resin composition.

(B2) 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 (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 one embodiment, 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.

In component (B2), a rare earth element is doped into an optically inactive host material, resulting in upconversion luminescence characteristics. By appropriately selecting the type and amount (doping amount) of rare earth element contained in component (B2), upconversion luminescence of any wavelength can be obtained.

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).
Furthermore, 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 the combinations of ytterbium (Yb), erbium (Er), and thulium (Tm), and ytterbium (Yb) and thulium (Tm) are preferred.
In particular, a rare earth element combination that has strong upconversion emission at blue light wavelengths is, for example, Yb ³⁺ /Tm ³⁺ .

The wavelength range of the excitation light that causes component (B2) to emit upconversion light is preferably greater than 500 nm, for example, greater than 500 nm but not greater than 2000 nm.

The host material (base 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 luminescence. It 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, as this makes it easier to incorporate the rare earth element in a luminescent state.

As such an inorganic base material, a material that is transparent to excitation light is preferred from the viewpoint of luminous efficiency, and specifically, halides such as fluorides and chlorides, oxides, sulfides, oxysulfides, etc. are preferably used. Examples of halides include, but are not limited to, barium chloride (BaCl ₂ ), lead chloride (PbCl ₂ ), lead fluoride (PbF ₂ ), cadmium fluoride (CdF ₂ ), lanthanum fluoride (LaF ₃ ), yttrium fluoride (YF ₃ ), etc. 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 ), etc. Note that a coating material may be formed around the component (B2) that uses a halide as a base material. The coating material may be any of the oxides listed above.

It is also possible to use a core-shell type upconversion material composed of a core (NaYREF ₄ )/shell (NaYF ₄ ) (RE=rare earth element).

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, or spray methods. For the production method of component (B2), see, for example, the method described in JP 2006-117864 A.

Component (B2) may be a commercially available product. For example, Hefei Fluonano Biotech Co., Ltd. offers core-shell upconversion phosphor nanoparticles with an excitation wavelength of 975 nm and an emission wavelength of 365 nm under the product code 201-30-365.

Component (B2) may be used alone or in combination of two or more types. For example, in one embodiment, the use of two or more types of component (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 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.

From the viewpoint of light conversion efficiency and degree of photocuring, 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, per 100 parts by mass of the total amount of the photocurable resin composition.

In this embodiment, either (B1) the triplet-triplet annihilation type photon upconversion material or (B2) the multiphoton excitation type upconversion material may be used alone, or any combination of these may be used. For example, in one embodiment, by using a combination of component (B1) and component (B2), energy transfer from component (B1) to component (B2) or from component (B2) to component (B1) is possible within 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.

(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).

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 Esters of monohydric alcohols and (meth)acrylic acid such as 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)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, etc. Acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, octyl acrylate, nonyl acrylate, isononyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, cyclic trimethylolpropane formal acrylate, 1-naphthalenemethyl (meth)acrylate, 1-ethylcyclohexyl (meth)acrylate, 1-methylcyclohexyl (meth)acrylate, 1-ethylcyclopentyl (meth)acrylate, 1-methylcyclopentyl (meth)acrylate , dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, tetrahydrodicyclopentadienyl (meth)acrylate, 2-(o-phenylphenoxy)ethyl (meth)acrylate, isobornylcyclohexyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, 1-adamantyl (Meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, 2-methyl-2-adamantanyl (meth)acrylate, 2-ethyl-2-adamantanyl (meth)acrylate, 2-isopropyladamantan-2-yl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, (adamantan-1-yloxy)methyl (meth)acrylate, 2-isopropyl-2-adamantyl (meth)acrylate, 1-methyl-1-ethyl-1-adamantylmethanol (Meth)acrylate, 1,1-diethyl-1-adamantylmethanol (meth)acrylate, 2-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-furanyl (meth)acrylate, 2-oxotetrahydrofuran-3 Examples of suitable acrylates include, but are not limited to, mono(meth)acrylates of polyhydric alcohols or esters of monohydric alcohols and (meth)acrylic acid, such as (5-oxotetrahydrofuran-2-yl)methyl(meth)acrylate, (2-oxo-1,3-dioxolan-4-yl)methyl(meth)acrylate, N-acryloyloxyethylhexahydrophthalimide, α-acryloyl-ω-methoxypoly(oxyethylene), and 1-ethoxyethyl(meth)acrylate. These acrylates may be used alone or in combination of two or more.
Examples of polyfunctional (meth)acrylate compounds include di(meth)acrylate of tris(2-hydroxyethyl)isocyanurate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, or 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 acrylate include, but are not limited to, dihydrocyclopentadiethyl (meth)acrylate, polyester (meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, poly(meth)acrylate of ditrimethylolpropane, 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).
As the (meth)acrylate compound, any one of the above-mentioned (meth)acrylate compounds may be used alone, or two or more of them may be used in combination.
Examples of commercially available (meth)acrylate compounds include, but are not limited to, 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., 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.

The (meth)acrylamide compound is a compound having at least one 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, and 1,2-di(meth)acrylamide ethylene glycol.

The cyanoacrylate compound can be a known compound represented by the formula H ₂ C═C(CN)—COOR. 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, one 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, but are not limited to, 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 propangyl cyanoacrylate; aryl cyanoacrylates such as phenyl cyanoacrylate and toluyl cyanoacrylate; heteroatom-containing methoxyethyl cyanoacrylate, ethoxyethyl cyanoacrylate, and furfuryl cyanoacrylate; silicon-containing trimethylsilylmethyl cyanoacrylate, trimethylsilylethyl cyanoacrylate, trimethylsilylpropyl cyanoacrylate, and dimethylvinylsilylmethyl cyanoacrylate.
These may be used alone or in combination of two or more.

A vinyl ether compound is a compound having at least one 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.

A styrene compound is a compound having at least one styrene group (H ₂ C═CH—C ₆ H ₅ —). Examples of styrene compounds 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 compounds may be used alone or in combination of two or more.

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. Methylene malonates preferably have a molecular weight of 220 or greater. There are no particular restrictions on the types of methylene malonates that can be used, and in addition to compounds described in WO 2018/212330 A1 and the like, various disclosed methylene malonates can be used. Methylene malonates may be used alone or in combination of two or more types.

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 (manufactured by Shikoku Chemical Industry Co., Ltd.: C3 TS-G), 1,3,4,6-tetrakis(mercaptomethyl)glycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-dimethylglycoluril, and 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-dimethylglycoluril. (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, 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)propane 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(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathiaheptane Tadecane, 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-hexathiapentane Benzene, 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-di thianylthio]-3-[2,2-bis(mercaptomethylthio)ethyl]-7,9-bis(mercaptomethylthio)-2,4,6,10-tetrathiaundecane, 3-[2-(1,3-dithietanyl)]methyl-7,9-bis(mercaptomethylthio)-1,11-dimercapto-2,4,6,10-tetrathiaundecane, 9-[2-(1,3-dithietanyl)]methyl-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10 ,12,16-hexathiaheptadecane, 3-[2-(1,3-dithietanyl)]methyl-7,9,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,4,6,10,12,16-hexathiaheptadecane, 4,6-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio]-6-[4-(6-mercaptomethylthio)-1,3-dithianylthio]-1,3-dithiane, 4-[3,4,8,9-tetrakis(mercaptomethylthio)- 11-mercapto-2,5,7,10-tetrathiaundecyl]-5-mercaptomethylthio-1,3-dithiolane, 4,5-bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]-1,3-dithiolane, 4-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]-5-mercaptomethylthio-1,3-dithiolane, 4-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)methyl 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-methyl 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-thiapropylthio]mercaptomethylthiomethyl-1,3-dithietane, Examples of the bifunctional thiol compounds disclosed in WO 2019/082962 include, but are not limited to, various bifunctional thiol compounds such as 2,2'-[cyclohexylidenebis(thio-2,1-ethanediylthio)]bis[ethanethiol], 4,4'-[(1,3-phenylene)bis(oxy)]bis[1-butanethiol], and dimers, trimers, and tetramers of the above thiol compounds. These may be used alone or in combination of two or more.

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

The total content of the (A) maleimide compound and (C) other radical polymerizable compound in the photocurable resin composition may be 1 to 99.9 parts by mass per 100 parts by mass of the total 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 (C) other radical polymerizable compound in the photocurable resin composition is preferably 5 to 50 parts by mass, and more preferably 7 to 30 parts by mass, per 100 parts by mass of the total photocurable resin composition. In another embodiment, the total content of the (A) maleimide compound and (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, per 100 parts by mass of the total photocurable resin composition. The total content of the (A) maleimide compound and (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 all organic materials 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 (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).

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

Filler The photocurable resin composition of this embodiment may contain a filler to the extent that the object of this embodiment is not impaired. By containing a filler in the photocurable resin composition, the linear expansion coefficient of the cured product obtained by curing the photocurable 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.

The inorganic filler is not particularly limited as long as it is made of granular 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 these inorganic fillers may be used alone, or two or more 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.

The inorganic filler may be surface-treated with a coupling agent such as a silane coupling agent. This allows the thixotropic index (TI) of the resin composition to fall within an appropriate range.

The organic filler is not particularly limited, but examples 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, phenolic resin, and copolymers containing these as components. The organic filler may also be surface-treated.

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

The average particle size of the filler is preferably 0.01 to 15 μm, and more preferably 0.01 to 10 μm. From the perspective of transparency of the long-wavelength light irradiated onto the photocurable resin composition, the maximum particle size of the filler is preferably 50 μm or less, and more preferably 30 μm or less.

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

If a filler is contained, the filler content is preferably 0.5 to 80 mass %, and more preferably 1 to 70 mass %, relative to the total mass of the photocurable resin composition.

Thixotropic Agent The photocurable resin composition of this embodiment may contain a thixotropic agent within a range that does not impair the effects of this embodiment.
Examples of thixotropic agents include colloidal silica, hydrophobic silica, fine silica, nanosilica, and other silica, bentonite, acetylene black, and ketjen black. Nanosilica is preferred from the viewpoint of shape retention after application. Furthermore, from the viewpoint 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). Here, the average particle size of the nanosilica particles is measured using a dynamic light scattering Nanotrac particle size analyzer. The thixotropic agents may be used alone or in combination of two or more.

If 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.

Light-Shielding Agent The photocurable resin composition of this embodiment may contain a light-shielding agent within a range that does not impair the effects of this embodiment.
Depending on the application of the cured product of the resin composition, light-blocking properties may be required. In such cases, the photocurable resin composition of this embodiment may contain a light-blocking agent. Long-wavelength light can be transmitted through the light-blocking agent that blocks ultraviolet light. The photocurable resin composition of this embodiment may be cured by irradiating it with long-wavelength light without or with minimal influence of the light-blocking agent. Examples of light-blocking agents include, but are not limited to, carbon black and titanium black. These light-blocking agents may also be used as light-to-heat conversion materials that convert long-wavelength light into heat.

Other Additives If desired, the photocurable resin composition of this embodiment may further contain other additives, such as a photosensitizer, a conductive filler, a stabilizer, a radical polymerization inhibitor, an anionic polymerization inhibitor, a coupling agent, an ion trapping agent, a leveling agent, an antioxidant, an antifoaming agent, a viscosity modifier, a flame retardant, a colorant, a plasticizer, a solvent, etc. The type and amount of each additive are as usual, provided that the purpose of the present embodiment is not impaired.
From the viewpoint of preventing a reduction in curing strength and adhesion due to photocuring and preventing outgassing and bleeding, the resin composition of this embodiment is substantially free of liquid components such as water, solvents, ionic liquids, etc. (excluding liquid components (A) to (C)). For example, the content of liquid components relative to the total mass of the resin composition is preferably 3 mass% or less, and more preferably 1 mass% or less. 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.).

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 intended use and location of the resin composition. The photocurable resin composition of this embodiment is excellent for application to areas with complex shapes where UV light irradiation is difficult, and for application to narrow areas. Unless otherwise specified, viscosity in this specification is expressed as a value measured in accordance with Japanese Industrial Standard JIS K6833. Specifically, it can be determined by measuring using an E-type viscometer at a rotation speed of 10 rpm. There are no particular restrictions on the equipment, rotor, or measurement range used.

Depending on the intended use, 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. When using a two-component (or multi-component) resin composition, the two components (or multiple components) are mixed to form the photocurable resin composition in 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 way 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 restriction. 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 components 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, liquid A alone, or liquid A and liquid B together, can be considered the resin composition of this embodiment. On the other hand, when component (A) and component (B) or component (A) to component (C) are each contained in separate liquids, the respective liquids together can be considered the resin composition of this embodiment. Examples of cases in which components (A) and (B) or components (A) to (C) are contained in separate liquids include a resin composition in which components (A) and (B) or components (A) to (C) are separated into two or more containers, specifically a kit composed of multiple liquids containing either components (A) and (B) or components (A) to (C).

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, stirring and mixing them to form a uniform composition. This mixer is not particularly limited, but examples that can be used include a Raikai mixer, Henschel mixer, three-roll mill, ball mill, planetary mixer, and bead mill equipped with a stirring device and a heating device. These devices may also be used in appropriate combinations.

The photocurable resin composition thus obtained is cured by irradiation with light of a long wavelength (for example, longer than 500 nm), and the curing is completed by light irradiation alone, and main curing by heat is not required.
Conventionally, high-energy, short-wavelength light (e.g., 365 nm UV light) is typically used to photocure UV-curable adhesives. Therefore, when the adhesive contains fillers or other materials, the short-wavelength light only penetrates the UV-curable adhesive to a limited extent, and curing does not proceed in areas blocked by obstructions. Regarding the latter issue in particular, for example, when the obstruction 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 to a depth of several to several tens of nanometers, while visible light of 380 to 780 nm penetrates to a depth of several hundred nanometers to several microns, and infrared light of 780 nm or more penetrates to a depth of several tens of microns to millimeters (see, for example, Optical Properties of Silicon, [online], PVEducation, <https://www.pveducation.org/pvcdrom/materials/optical-properties-of-silicon>). Although the penetration distance of light when irradiating a resin composition with ultraviolet light is deeper than that of a silicon substrate, it can be said that increasing the irradiation wavelength is useful as a method for increasing the degree of cure of the resin composition.

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 the components that make up these, or as a raw material for these. 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.

[Adhesion method]
Another aspect of the present invention is a method for bonding at least two components with a curable resin composition, the method comprising the steps of:
The method includes 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.

In the first step, the photocurable resin composition of the above embodiment is applied to at least one of at least two components.
The component is preferably a component constituting a semiconductor device or electronic component, such as, but not limited to, a semiconductor element, a substrate, 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, metals (e.g., copper, nickel), etc.
The method for applying the resin composition is not particularly limited, and for example, 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, and flexographic printing. Dispensing methods include, but are not limited to, methods using a jet dispenser or an air dispenser. Coating methods include, but are not limited to, dip coating, spray coating, bar coater coating, gravure coating, reverse gravure coating, and spin coater coating.

Next, another part is attached to the part to which the photocurable resin composition has been applied, via this photocurable resin composition, or the part to which the photocurable resin composition has been applied is attached to another part via this photocurable resin composition. Any known attachment method may be used. If necessary, after attachment, the parts can be pressed together while applying pressure.

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 may be 1 mJ/cm ² to 2000 J/cm ^2. The irradiation intensity may be 1 mW/cm ² to 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 the component, in the bonding method of this embodiment, the photocurable resin composition can be irradiated with light not only directly but also through the component.

[Sealing method]
Furthermore, another aspect of the present invention is a method for sealing a gap between or within components with a curable resin composition, the sealing method comprising:
The method includes the steps of applying or injecting the photocurable resin composition of the above aspect into 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 were the same as those in the above-mentioned bonding method.
Examples of the application or injection method include the application method in the bonding method and a potting method, but are not limited to these.
The photocurable resin composition used in this embodiment can achieve a high cure depth, and therefore, in the sealing method of this embodiment, it is possible to cure the resin composition present deep in gaps that are difficult for ultraviolet light to reach, thereby enabling suitable sealing.

[Coating method]
Furthermore, another aspect of the present invention is a method for coating a surface of an object with a curable composition, the method comprising:
The method includes the steps of: applying the photocurable resin composition of the above aspect to the object; and irradiating the photocurable resin composition with light having a wavelength of more than 500 nm.
The target 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 TOF sensor modules, other semiconductor modules, and integrated circuits. Examples of components constituting the semiconductor device or electronic component include, but are not limited to, semiconductor elements and substrates. 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, metals (e.g., copper, nickel), etc.
The application method is the same as that in the above-mentioned adhesion method.
The light irradiation method is the same as that in the above-mentioned adhesion method.

[Adhesives, sealants or coatings]
Another embodiment of the present invention relates to an adhesive, sealant, or coating agent that includes the photocurable resin composition of the above embodiment. This adhesive, sealant, or coating agent enables good fixation, bonding, or protection of general-purpose plastics (e.g., PE, PS, PP, etc.), engineering plastics (e.g., LCP (liquid crystal polymer), polyamide, polycarbonate, etc.), ceramics, and metals (e.g., copper, nickel, etc.), and can be used to fix, bond, or protect 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 sensor modules, other semiconductor modules, and integrated circuits.
The adhesive, sealant, or coating agent of this embodiment can be completely cured by irradiation with light of a long wavelength (e.g., longer than 500 nm), and therefore has high productivity and is suitable for use, for example, in the manufacture of semiconductor devices and electronic components.

[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 embodiment.

[Semiconductor devices, electronic components]
Another aspect of the present invention is a semiconductor device or electronic component that includes the cured product of the above aspect, 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.

[Curing method and manufacturing method of 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 of more than 500 nm but 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 irradiation with light having a wavelength of more than 500 nm in these methods are the same as those in the above-mentioned adhesion method, sealing method, and coating method. In this embodiment, either spot irradiation, in which light is irradiated onto a local region, or area irradiation, in which light is irradiated onto a wide region, can be performed.

The present invention will be explained 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 percentages indicate parts by mass and percentages by mass unless otherwise specified.

[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. The 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:

(A) Maleimide Compound (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® -P, Nippon Shokubai Co., Ltd.)
(B) Photon up-conversion material (B1) Triplet-triplet annihilation photon up-conversion material (B1-1D): Platinum(II) octaethylporphyrin (PtOEP) (Sigma-Aldrich Japan) as a donor
(B1-1A): Diphenylanthracene (DPA) (Tokyo Chemical Industry Co., Ltd.) as an acceptor
The mass ratio of the donor and acceptor PtOEP:DPA was set to 1:24 (molar ratio 1:50), to obtain a photon up-conversion material (B1-1).
(B1-2D): Zinc(II) octaethylporphyrin (ZnOEP) (Sigma-Aldrich Japan) as a donor
(B1-2A): Diphenylanthracene (DPA) (Tokyo Chemical Industry Co., Ltd.) as an acceptor
The mass ratio of the donor and acceptor ZnOEP:DPA was set to 1:24 (molar ratio 1:50), to obtain a photon up-conversion material (B1-2).
(C) Radically polymerizable compound other than maleimide compound (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.)

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

[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 placed on a glass slide, which was then inserted with another 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, at a height of 4 cm from the top surface of the slide glass to the light source, wavelength: 532 nm visible light, irradiation intensity: 10 mW / cm ² , and continuous irradiation was performed until the cumulative light amount reached 10 J / cm ² or more. Also, for Example 7, an LED lamp (straight tube lamp system yellow light LDL40TY / 17 / 21-Y2, Toshiba Lighting & Technology Corporation) was used, at a height of 4 cm from the top surface of the slide glass to the light source, wavelength: Visible light including 570 nm, irradiation intensity: 3 mW / cm ² , and continuous irradiation was performed until the cumulative light amount reached 300 J / cm ² or more.
In this test, one of the glass slides was peeled off from the test piece, and the photocurability was evaluated by appearance and palpation with a toothpick, with a three-level rating: ⊚ if the photocuring was at an integrated light dose of 10 J/ ^cm2 or less, ◯ if the photocuring was at a dose of more than 10 J/cm2, and × if the photocuring was not successful. The results are shown in Table 1.

As shown in Examples 1 to 7, a resin composition containing (A) a maleimide compound, (B) a photon upconversion material, and any (C) radical polymerizable compound other than a maleimide compound was cured by irradiation with visible light.
Comparative Example 1 was a resin composition containing (A) a maleimide compound and not containing (B) a photon upconversion material, and did not cure with 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 with visible light irradiation.

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

Claims (15)

A photocurable resin composition comprising (A) a maleimide compound and (B) a photon upconversion material. The photocurable resin composition according to claim 1, which is substantially free of a photoradical polymerization initiator. 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. The photocurable resin composition according to any one of claims 1 to 3, further comprising (C) a radically polymerizable compound other than the (A) maleimide compound. The 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. 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 components. An adhesive, sealant, or coating agent comprising the photocurable resin composition according to any one of claims 1 to 6. A cured product obtained by curing the photocurable resin composition described in any one of claims 1 to 6, or the adhesive, sealant, or coating agent described in claim 7. A semiconductor device or electronic component comprising the cured product described in claim 8. A method for producing a cured product, comprising irradiating the photocurable resin composition described in any one of claims 1 to 6, or the adhesive, sealant, or coating agent described in claim 7, with light having a wavelength of more than 500 nm. 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. Use of the photocurable resin composition described in any one of claims 1 to 6 for curing by irradiation with light having a wavelength of more than 500 nm. A method for bonding at least two components with a photocurable resin composition, comprising:
A bonding method comprising: a step 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 a step of 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. A method for sealing gaps between or within components with a photocurable resin composition, comprising:
A sealing method comprising the steps of: applying or injecting the photocurable resin composition according to any one of claims 1 to 6 into a gap between or within the components; and irradiating the photocurable resin composition with light having a wavelength of more than 500 nm. A method for coating a surface of an object with a photocurable resin composition, comprising:
A coating method 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.