Curing function expressing paste, adhesive, sealing material, coating agent, cured product, semiconductor device, electronic component, and curing, bonding, sealing, and coating method using curing function expressing paste

Abstract

The present invention addresses the problem of providing: a curing function expressing paste for curing which uses a triplet-triplet annihilation photon upconversion mechanism and a method for using the same, wherein the curing function expressing paste is capable of achieving a good degree of curing by prolonging the triplet-triplet annihilation photon upconversion emission duration; an adhesive, a sealing material, or a coating agent containing the same; 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 curing function expressing paste.　Provided is a curing function expressing paste containing (A) a polymerizable compound, (B) a photopolymerization initiator, (C) a photosensitizer, and (D) a light emitter, wherein the polymerizable compound (A) contains at least a polymerizable compound having a functional group equivalent of 105 or more, the photosensitizer (C) is a compound capable of absorbing light having a wavelength of more than 500 nm and causing triplet-triplet energy transfer to the light emitter (D), and the light emitter (D) can exhibit photon upconversion emission having a wavelength of 500 nm or less. Further provided are: an adhesive, a sealing material, or a coating agent containing the same; 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 curing function expressing paste.

Description

Curable functional paste, adhesive, sealant, coating agent, cured product, semiconductor device, electronic component, and curing, bonding, sealing and coating methods using the curable functional paste.

[0001] The present invention relates to a curable functional paste, an adhesive, a encapsulant or coating agent containing the same, a cured product thereof, a semiconductor device or electronic component containing the cured product thereof, and a curing method, bonding method, encapsulation method and coating method using the curable functional paste.

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

[0003] Japanese Patent Publication No. 2009-51954, International Publication No. 2005 / 052021

[0004] On the other hand, from the perspective of improving productivity and considering applications to heat-sensitive components, there is a demand for adhesives, sealants, and other pastes that exhibit curing properties through light irradiation alone.

[0005] The present inventors focused on using a photon upconversion material that can convert long-wavelength light into short-wavelength light in a curable functional paste. They confirmed that photon upconversion emission occurring in the paste upon irradiation with long-wavelength light activates the photopolymerization initiator, promoting polymerization of polymerizable compounds and allowing the paste to harden even in areas where UV irradiation light is difficult to reach. Based on this finding, the applicant has filed Japanese Patent Application No. 2023-119225 (July 21, 2023) and PCT / JP2024 / 025880 (July 19, 2024) for a photocurable resin composition and adhesive containing a photon upconversion material.

[0006] Further investigation revealed that in the curing process using a triplet-triplet annihilation photon upconversion mechanism in a curable functional paste, the intensity of the triplet-triplet annihilation photon upconversion emission decreases over time. This decrease in the intensity of the triplet-triplet annihilation photon upconversion emission can result in insufficient curing of the curable functional paste, which can be problematic when used as an adhesive or sealant.

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

[0008] The specific means for solving the above problems are as follows. The aspects of the present invention include the following curable functional paste, adhesive, encapsulant or coating agent, cured product, semiconductor device or electronic component, method for manufacturing a cured product, method for curing a curable functional paste, use of a curable functional paste, bonding method, encapsulation method and coating method. (1) A curable functional paste comprising (A) a polymerizable compound, (B) a photopolymerization initiator, (C) a photosensitizer, and (D) a light emitter, wherein the (A) polymerizable compound comprises at least a polymerizable compound with a functional group equivalent of 105 or more, the (C) photosensitizer is a compound that absorbs light with a wavelength greater than 500 nm and can cause triplet-triplet energy transfer to the (D) light emitter, and the (D) light emitter can exhibit photon upconversion emission with a wavelength of 500 nm or less. (2) The curable function-expressing paste according to (1), wherein the polymerizable compound (A) comprises at least one polymerizable compound having at least one aliphatic group selected from the group consisting of a polyalkylene oxide group, an alkyl group having 6 or more carbon atoms, an alkylene group having 6 or more carbon atoms, a group derived from an alicyclic diol, and a group derived from a sugar alcohol. (3) The curable function-expressing paste according to (1) or (2), wherein the polymerizable compound (A) comprises a curing agent selected from the group consisting of a 2-4 functional thiol curing agent, a 2-4 functional phenol curing agent, a 2-4 functional acid anhydride curing agent, and a 2-4 functional amine curing agent. (4) The curable function-expressing paste according to any one of (1) to (3), wherein the photopolymerization initiator (B) can be activated by light with a wavelength of 500 nm or less. (5) The curable function-expressing paste according to any one of (1) to (4), for use in curing by irradiation with light with a wavelength greater than 500 nm. (6) A curable function-granting paste according to any one of (1) to (5) above, used as an adhesive, encapsulant, or coating agent for semiconductor devices or electronic components. (7) An adhesive, encapsulant, or coating agent containing the curable function-granting paste according to any one of (1) to (6) above. (8) A cured product obtained by curing the curable function-granting paste 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 described in (8) above. (10) Use of the curable function-granting paste described in any one of (1) to (6) above for curing by irradiation with light with a wavelength exceeding 500 nm. (11) A method for producing a cured product, comprising irradiating the curable function-granting paste described in any one of (1) to (6) above, or the adhesive, sealant, or coating agent described in (7) above, with light with a wavelength exceeding 500 nm. (12) A method for curing a curable function-granting paste, comprising irradiating the curable function-granting paste described in any one of (1) to (6) above with light with a wavelength exceeding 500 nm. (13) A method for bonding at least two components with a curable functional paste, comprising the steps of: applying the curable functional paste described in any one of (1) to (6) above to at least one of the at least two components; and irradiating at least one of the at least two components, the curable functional paste, or both thereof with light having a wavelength greater than 500 nm. (14) A method for sealing gaps between or within components with a curable functional paste, comprising the steps of: applying or injecting the curable functional paste described in any one of (1) to (6) above into the gaps between or within components; and irradiating the curable functional paste with light having a wavelength greater than 500 nm. (15) A method for coating the surface of an object with a curable functional paste, comprising the steps of: applying the curable functional paste described in any one of (1) to (6) above to the object; and irradiating the curable functional paste with light having a wavelength greater than 500 nm.

[0009] According to aspects of the present invention, a curable function-emphasizing paste for curing using a triplet-triplet annihilation photon upconversion mechanism and a method of using the same are provided, which can achieve a good degree of curing by extending the duration of the triplet-triplet annihilation photon upconversion emission, a curable function-emphasizing paste, an adhesive, a encapsulant or coating agent containing the same, a cured product thereof, a semiconductor device or electronic component containing the cured product thereof, and a curing method, bonding method, encapsulation method and coating method using the curable function-emphasizing paste are provided.

[0010] In this specification, "curable functional paste" refers to a paste-like composition that exhibits some function after a curing reaction. Examples of functions exhibited after a curing reaction include adhesive function, sealing function, coating function, etc. Also in this specification, "curable functional paste" may be simply referred to as "paste." 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 convention in the field of synthetic resins, the term "resin," which usually refers to a polymer (especially a synthetic polymer), may be used for components constituting a curable functional paste before curing, even if the component is not a polymer, for example, if it is a prepolymer compound before curing. Conversely, even if the component is a polymer, the term "compound" may be used, focusing on the functional group. In this specification, "(meth)acryloyl group" includes both methacryloyl and acryloyl groups. Also, "(meth)acrylate compound" includes both acrylate and methacrylate compounds. In this specification, numerical ranges indicated using "~" include the numbers before and after "~" as the minimum and maximum values, respectively. In numerical ranges described stepwise in this specification, the upper or lower limit of one numerical range may be replaced by the upper or lower limit of another stepwise numerical range. Furthermore, in numerical ranges described in this disclosure, the upper or lower limit of that range may be replaced by the values ​​shown in the examples. In this specification, each component may contain multiple types of the corresponding substance. If multiple types of the substance corresponding to each component are present in a composition, the content or amount of each component means the total content or amount of the multiple types of substances present in the composition, unless otherwise specified.

[0011] [Curable Functional Paste] A curable functional paste according to one aspect of the present invention is a curable functional paste comprising (A) a polymerizable compound, (B) a photopolymerization initiator, (C) a photosensitizer, and (D) a light emitter, wherein (A) the polymerizable compound comprises at least a polymerizable compound with a functional group equivalent of 105 or more, (C) the photosensitizer is a compound that absorbs light with a wavelength greater than 500 nm and can cause triplet-triplet energy transfer to (D) the light emitter, and (D) the light emitter can exhibit photon upconversion emission with a wavelength of 500 nm or less. According to this aspect, a curable functional paste that can achieve a good degree of curing can be provided.

[0012] In the triplet-triplet annihilation photon upconversion mechanism, collisions between donor and acceptor molecules are crucial for energy transfer between them. However, as the paste hardens, the molecular motion of the donor and acceptor is restricted, reducing the frequency of molecular collisions, and causing a decrease in the intensity of triplet-triplet annihilation photon upconversion emission over time. In curing using the triplet-triplet annihilation photon upconversion mechanism, irradiation with long-wavelength light generates triplet-triplet annihilation photon upconversion emission, activating the photopolymerization initiator and promoting polymerization of the polymerizable compound, thus hardening the paste. If the intensity of triplet-triplet annihilation photon upconversion emission decreases, the degree of hardening of the paste exhibiting curable function may become insufficient. Further investigation revealed that a curable functional paste that provides a cured product with low crosslinking density and / or uniform and flexible segments allows for energy transfer between donors and acceptors without being limited by the curing progress of the curable functional paste, thereby extending the duration of triplet-triplet annihilation photon upconversion luminescence and increasing the degree of curing, thus completing this embodiment.

[0013] (A) Polymerizable Compound The curable functional paste of this embodiment contains (A) polymerizable compound (hereinafter also referred to as "component (A)"). The polymerizable compound (A) has reactive groups for curing and causes the functional paste to exhibit functions such as adhesive function, sealing function, and coating function. In this embodiment, the polymerizable compound (A) contains at least a polymerizable compound with a functional group equivalent of 105 or more. In this embodiment, the polymerizable compound (A) can be appropriately selected from radical polymerizable compounds, cationic polymerizable compounds, anionic polymerizable compounds, or any combination thereof, depending on the type of photopolymerization initiator (B) described later.

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

[0015] Maleimide compounds include monofunctional maleimide compounds having one maleimide group and polyfunctional maleimide compounds having two or more maleimide groups. Maleimide compounds having two maleimide groups are sometimes called bismaleimide compounds. Maleimide compounds are activated by photon upconversion emission with a wavelength of 500 nm or less, emitted from the (D) emitter described later, generating radicals that promote the polymerization of radical polymerizable compounds, including the maleimide compound itself. Since the maleimide compound itself absorbs the light emitted by the (D) emitter and generates radicals, the curable functional paste of this embodiment containing a maleimide compound does not require the use of the (B) photopolymerization initiator described later, or may only require a small amount. In other words, the maleimide compound also acts as a photopolymerization initiator. In this specification, a curable functional paste containing a maleimide compound and not containing the (B) photopolymerization initiator other than the maleimide compound described later is considered to be an embodiment containing the (A) polymerizable compound and the (B) photopolymerization initiator. From the viewpoint of workability under fluorescent lighting, maleimide compounds with an absorption wavelength of 500 nm or less are preferred, maleimide compounds with an absorption wavelength of 475 nm or less are more preferred, and maleimide compounds with an absorption wavelength of 450 nm or less are even more preferred. By matching the absorption characteristics of the maleimide compound with the emission wavelength of the (D) light emitter, the efficiency of the polymerization reaction can be increased.

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

[0017] Another example of a maleimide compound is a bismaleimide having a hydrocarbon group derived from a dimer acid. Such a bismaleimide is described, for example, in Japanese Patent Publication No. 2015-193725. Commercially available bismaleimides having a hydrocarbon group derived from a dimer acid include, but are not limited to, "BMI-689", "BMI-1500", "BMI-1700", which are liquid at 25°C, or "BMI-3000", which is solid at 25°C (all manufactured by Designer Molecules Inc.). These may be used individually or in combination of two or more.

[0018] Examples of monofunctional maleimide compounds include, but are not limited to, monofunctional aliphatic maleimide compounds such as N-n-butylmaleimide, N-hexylmaleimide, 2-maleimidoethyl-ethyl carbonate, 2-maleimidoethyl-propyl carbonate, and N-ethyl-(2-maleimidoethyl)carbamate; alicyclic monofunctional maleimide compounds such as N-cyclohexylmaleimide; N-arylmaleimides such as N-phenylmaleimide; and N-aralkylmaleimides such as N-benzylmaleimide. The aliphatic and alicyclic maleimides may have substituents, such as phenyl groups, benzyl groups, and hydroxyl groups. The N-arylmaleimides and N-aralkylmaleimides may also have substituents, such as alkyl groups, nitro groups, hydroxyl groups, alkoxy groups, carboxyl groups, and halogen groups. These may be used individually or in combination of two or more. Examples of commercially available monofunctional maleimides include Imilex. （Ｒ） -C, Imilex （Ｒ） Examples include -P (both manufactured by Nippon Shokubai Co., Ltd.) and O-CPMI (manufactured by Yamato Kasei Kogyo Co., Ltd.), but are not limited to these.

[0019] In this specification, a (meth)acrylate compound is a compound having at least one (meth)acryloyl group in its molecule, and includes monofunctional (meth)acrylate compounds having one (meth)acryloyl group and polyfunctional (meth)acrylate compounds having two or more (meth)acryloyl groups. Examples of monofunctional (meth)acrylate compounds include: - Ethyl (meth)acrylate, trifluoroethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, isobornyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, butoxydiethylene glycol ( Esters of monohydric alcohols and (meth)acrylic acid, such as meth)acrylate, methoxydipropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, 2-ethylhexyldiethylene glycol (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, 3-phenoxybenzyl (meth)acrylate, etc.; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate,Cyclic trimethylolpropane formal (meth)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, nonylphenoxypolyethylene glycol (meth)acrylate, tetrahydrodicyclopene Tadienyl (meth)acrylate, 2-(o-phenylphenoxy)ethyl (meth)acrylate, isobornylcyclohexyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, 1-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, 2-methyl-2-adamantanyl (meth)acrylate, 2-ethyl-2-adamantanyl (meth)acrylate, 2-isopropyladamantan-2-yl (meth)acrylate, 3-hydroxy- 1-Adamantyl (meth)acrylate, (adamantan-1-yloxy)methyl (meth)acrylate, 2-isopropyl-2-adamantyl (meth)acrylate, 1-methyl-1-ethyl-1-adamantylmethanol (meth)acrylate, 1,1-diethyl-1-adamantylmethanol (meth)acrylate, 2-cyclohexylpropane-2-yl (meth)acrylate, 1-isopropylcyclohexyl (meth)acrylate, 1-methylcyclohexyl (meth)acrylate, 1-ethylcyclopentyl (meth)acrylate, 1 - Methylcyclohexyl (meth)acrylate, tetrahydropyranyl (meth)acrylate, tetrahydro-2-furanyl (meth)acrylate, 2-oxotetrahydrofuran-3-yl (meth)acrylate, (5-oxotetrahydrofuran-2-yl)methyl (meth)acrylate, (2-oxo-1,3-dioxolan-4-yl)methyl (meth)acrylate, N-acryloyloxyethylhexahydrophthalimide, α-(meth)acryloyl-ω-methoxypoly(oxyethylene), 1-ethoxyethyl (meth)acrylate, etc.Examples of polyfunctional (meth)acrylate compounds include, but are not limited to, mono(meth)acrylates of polyhydric alcohols or esters of monohydric alcohols and (meth)acrylic acid. These may be used individually or in combination of two or more. Examples of polyfunctional (meth)acrylate compounds include di(meth)acrylate of tris(2-hydroxyethyl) isocyanurate, tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, or their oligomers; pentaerythritol tri(meth)acrylate, or its oligomer; poly(meth)acrylate of dipentaerythritol; tris(acryloxyethyl) isocyanurate; caprolactone-modified tris((meth)acryloxyethyl) isocyanurate; alkyl-modified poly(meth)acrylate of dipentaerythritol; poly(meth)acrylate of caprolactone-modified dipentaerythritol Examples of (meth)acrylates include, but are not limited to, (meth)acrylates; bisphenol A di(meth)acrylate; bisphenol F di(meth)acrylate; polyalkylene oxide-modified bisphenol A di(meth)acrylate; polyalkylene oxide-modified bisphenol F di(meth)acrylate; dihydrocyclopentadiethyl (meth)acrylate; as well as 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, etc. Other examples of (meth)acrylate compounds include, but are not limited to, epoxy resin half (meth)acrylate, (meth)acrylate having an allyloxymethyl group (see Japanese Patent Publication No. 2024-009452), etc. The (meth)acrylate compound may be any one of the (meth)acrylate compounds mentioned above, or two or more may be used in combination. Examples of commercially available (meth)acrylate compounds include polyester acrylate (product name: EBECRYL810) manufactured by Daicel Ornex Co., Ltd., and ditrimethylolpropanetetraacrylate (product name: EBECRYL140) manufactured by Daicel Ornex Co., Ltd.Examples include, but are not limited to, polyester acrylate manufactured by Toagosei Co., Ltd. (product name: Aronics M7100), dimethylol-tricyclodecane diacrylate manufactured by Kyoeisha Chemical Co., Ltd. (product name: Light Acrylate DCP-A), and neopentyl glycol-modified trimethylolpropane diacrylate manufactured by Nippon Kayaku Co., Ltd. (product name: Kayarad R-604).

[0020] In this specification, allyl compounds refer to allyl group (-CH ２ -CH=CH ２ This refers to a compound having at least one allyl group. Examples of allyl compounds include monofunctional allyl compounds having one allyl group, and polyfunctional allyl compounds having two or more allyl groups. When a radical polymerizable compound contains an allyl compound, the allyl compound is preferably a polyfunctional allyl compound, or a combination of a polyfunctional allyl compound and a monofunctional allyl compound.

[0021] Examples of allyl compounds include diallyl terephthalate ether, diallyl isophthalate ether, triallyl trimellitate ether, tetraallyl pyromellitate ether, diallyl biphenyl-2,2'-dicarboxylic acid ether, allyl compounds having a bisphenol skeleton (e.g., bisphenol A bisallyl ether, bisphenol C bisallyl ether), allylphenol compounds having a bisphenol skeleton (e.g., 2,2'-diallylbisphenol A, 2,2'-diallylbisphenol C), other allylphenol compounds (e.g., allylphenol compounds described in Japanese Patent Publication No. 2019-052258), and cyanuric acid. Examples include, but are not limited to, allyl compounds having an isocyanuric acid skeleton such as trialyl, allyl cyanurate derivatives, and trialyl isocyanurate; allyl compounds having a glycoluryl skeleton such as 1,3,4,6-tetraallyl glycoluryl; glycerin monoallyl ether, allyl glycidyl ether, allyl hydroxyacetate, allyl hydroxypropanoate, allyl hydroxyhexanoate, allyl 4-hydroxycyclohexylacetate, trimethylolpropanediallyl ether, pentaerythritol trialyl ether, pentaerythritol tetraallyl ether, and (meth)acrylates having an allyloxymethyl group.Examples of commercially available allyl compounds include diallylbisphenol A (e.g., BPA-CA from Konishi Chemical Industry Co., Ltd., DABPA from Yamato Chemical Industry Co., Ltd., DA-BPA from Yokkaichi Synthetic Co., Ltd.), biphenylene resin (SBA series from Gun-ei Chemical Industry Co., Ltd.), allylphenol resin (APG series from Gun-ei Chemical Industry Co., Ltd.), allylphenol resin (LVA series from Gun-ei Chemical Industry Co., Ltd.), propenyl biphenylene resin (BPN series from Gun-ei Chemical Industry Co., Ltd.), and allyl ethers. Examples include, but are not limited to, phenolic resins (FTC-AE series manufactured by Gun-ei Chemical Industry Co., Ltd.), polyfunctional allylphenolic resins (FATC series manufactured by Gun-ei Chemical Industry Co., Ltd.), allyl cyanurate derivatives (e.g., MA-DGIC, DAMGIC, MeDAIC, L-DAIC, DD-1 manufactured by Shikoku Chemicals, Inc.), triallyl isocyanurate (e.g., TAIC manufactured by Shinryo Co., Ltd.), and 1,3,4,6-tetraallyl glycoluryl (TA-G manufactured by Shikoku Chemicals, Inc.). These may be used individually or in combination of two or more.

[0022] (meth)acrylamide compounds contain an acrylamide group (H ２ C=CHCONH-) or methacrylamide group ((H ２ C = C(CH) ３ The compound has at least one (meth)acrylamide group (CONH-). Examples of (meth)acrylamide compounds include, but are not limited to, N,N'-methylenebis(meth)acrylamide, N,N'-ethylenebis(meth)acrylamide, and 1,2-di(meth)acrylamide ethylene glycol.

[0023] Cyanoacrylate compounds are H ２Known compounds represented by C═C(CN)−COOR can be used. In the formula, R is an ester residue such as an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, or an aryl group. Also, the number of carbon atoms in the ester residue is not particularly limited, but those having usually 1 to 8 carbon atoms can be used. Further, ester residues composed of substituted hydrocarbon groups such as alkoxyalkyl groups and trialkylsilylalkyl groups can also be used. Examples of the cyanoacrylate compound include alkyl and cycloalkyl cyanoacrylates such as methyl cyanoacrylate, ethyl cyanoacrylate, propyl cyanoacrylate, butyl cyanoacrylate, cyclohexyl cyanoacrylate, alkenyl and cycloalkenyl cyanoacrylates such as allyl cyanoacrylate, methallyl cyanoacrylate, cyclohexenyl cyanoacrylate, alkynyl cyanoacrylates such as propargyl cyanoacrylate, aryl cyanoacrylates such as phenyl cyanoacrylate, toluyl cyanoacrylate, methoxyethyl cyanoacrylate containing a heteroatom, ethoxyethyl cyanoacrylate, furfuryl cyanoacrylate, trimethylsilylmethyl cyanoacrylate containing silicon, trimethylsilylethyl cyanoacrylate, trimethylsilylpropyl cyanoacrylate, dimethylvinylsilylmethyl cyanoacrylate, etc., but are not limited thereto. These may be used alone or in combination of two or more.

[0024] The vinyl ether compound is a compound having at least one vinyl ether group (H ２ C═CH−O−). Examples of the vinyl ether compound include 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, cyclohexanedimethanol divinyl ether, etc., but are not limited thereto. These may be used alone or in combination of two or more.

[0025] Styrene compounds, styrene group (H ２ C = CH - C ６ H ５ The compound has at least one (-). Examples of styrene compounds include, but are not limited to, 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, 4-methoxystyrene, etc. These may be used alone or in combination of two or more.

[0026] Methylene malonates are malonates having at least one methylene group in their molecule, and include 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 higher. There are no particular restrictions on the types of methylene malonates that can be used; in addition to compounds described in WO2018 / 212330A1, etc., various disclosed methylene malonates can be used. Methylene malonates may be used individually or in combination of two or more types.

[0027] In a mixture of a compound having an unsaturated double bond and a thiol compound, the thiol compound is a compound containing at least one thiol group, and this thiol group can undergo a radical addition reaction (en-thiol reaction) with the unsaturated double bond of the compound having the unsaturated double bond. 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 includes at least a polyfunctional thiol compound. In one embodiment, the thiol compound includes a combination of a difunctional thiol compound and a trifunctional or more functional thiol compound. In one embodiment, the thiol compound includes a combination of a monofunctional thiol compound and a polyfunctional thiol compound. Thiol compounds can also be divided into thiol compounds having hydrolyzable substructures such as ester bonds in the molecule (i.e., hydrolyzable) and thiol compounds not having such substructures (i.e., non-hydrolyzable). Examples of hydrolyzable thiol compounds include trimethylolpropane tris(3-mercaptopropionate) (manufactured by SC Organic Chemicals Co., Ltd.: TMMP), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate (manufactured by SC Organic Chemicals Co., Ltd.: TEMPIC), pentaerythritol tetrakis(3-mercaptopropionate) (manufactured by SC Organic Chemicals Co., Ltd.: PEMP), and tetraethylene glycol bis(3-mercaptopropionate) (manufactured by SC Organic Chemicals Co., Ltd.: EGMP- 4) Examples include, but are not limited to, dipentaerythritol hexakis(3-mercaptopropionate) (manufactured by SC Organic Chemicals Co., Ltd.: DPMP), pentaerythritol tetrakis(3-mercaptobutyrate) (manufactured by Resonaq Corporation: Karenz MT® PE1), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by Resonaq Corporation: Karenz MT® NR1), etc. 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) glycoluryl (manufactured by Shikoku Chemicals Co., Ltd.: TS-G), (1,3,4,6-Tetrakis(3-mercaptopropyl) glycoluryl (manufactured by Shikoku Chemicals, Inc.: C3 TS-G), 1,3,4,6-Tetrakis(mercaptomethyl) glycoluryl, 1,3,4,6-Tetrakis(mercaptomethyl)-3a-methyl glycoluryl, 1,3,4,6-Tetrakis(2-mercaptoethyl)-3a-methyl glycoluryl, 1,3,4,6-Tetrakis(3-mercaptopropyl)-3a-methyl glycoluryl, 1,3,4,6-Tetrakis(mercaptomethyl)-3a,6a-dimethyl glycoluryl, 1,3,4,6-Tetrakis(2-mercaptoethyl)-3a,6a-dimethyl glycoluryl Methyl glycol uryl, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-dimethyl glycol uryl, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-diphenyl glycol uryl, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a-diphenyl glycol uryl, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-diphenyl glycol uryl, tris(3-mercaptopropyl) isocyanurate, 1,3,5-tris[3-(2-methyl Lucaptoethylsulfanyl)propyl]isocyanurate, 1,3,5-Tris[2-(3-mercaptopropoxy)ethyl]isocyanurate, pentaerythritol tripropanthol (manufactured by SC Organic Chemicals Co., Ltd.: PEPT), 3-[2,3-bis(3-sulfanylpropoxy)propoxy]propane-1-thiol, 1,2,3-tris(3-mercaptopropyloxy)propane, 1,3-bis(3-mercaptopropyloxy)-2-propanol or derivative thereof, 3-[2,2-bis[(3-mercaptopropyl [Ropoxy)methyl]butoxy]-1-propanthol, pentaerythritol tetrapropanthol, 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3-mercaptopropylthio)propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-Tritiaundecane, 4,8-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Tritiaundecane, 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(mercaptomethyl Thio)-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-hexatianonadecane, 9-(2 ,2-bis(mercaptomethylthio)ethyl)-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexatiaheptadecane,3,4,8,9-tetrakis(mercaptomethylthio)-1,11-dimercapto-2,5,7,10-tetrathiaundecane,3,4,8,9,13,14-hexakis(mercaptomethylthio)-1,16-dimercapto-2,5,7,10,12,15-hexatiahexadecane,8-[bis(mercaptomethylthio)methyl]-3,4,12,13-Tetrakis(mercaptomethylthio)-1,15-dimercapto-2,5,7,9,11,14-hexatiapentadecane, 4,6-bis[3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiaheptylthio]-1,3-dithiane, 4-[3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiaheptylthio]-6-mercaptomethylthio-1,3-dithiane, 1,1-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio]-1,3-bis(mercaptomethylthio)propane, 1-[4-(6-mercaptomethylthio)-1,3-dithianylthio]-3-[2,2-bis(mercaptomethylthio)ethyl]-7,9-bis(mercaptomethylthio)-2,4,6,10-tetrathiaundecane, 3-[2-(1,3-dithiethanyl)]methyl-7,9-bis(mercaptomethylthio)-1,11-dimercapto-2,4,6,10-tetrathiaundecane, 9-[2-(1,3-dithiethanyl)]methyl-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12, 16-Hexathiaheptadecane, 3-[2-(1,3-dithiethanyl)]methyl-7,9,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,4,6,10,12,16-Hexathiaheptadecane, 4,6-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio]-6-[4-(6-mercaptomethylthio)-1,3-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-dithiethane, 2-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]mercaptomethylthiomethyl-1,3-dithiethane, 2-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecylthio]mercaptomethylthiomethyl-1,3-dithiethane, 2-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl]mercaptomethyl Examples include, but are not limited to, various bifunctional thiol compounds disclosed in WO2019 / 082962, such as ruthiomethyl-1,3-dithiethan, 4-{1-[2-(1,3-dithiethanyl)]-3-mercapto-2-thiapropylthio}-5-[1,2-bis(mercaptomethylthio)-4-mercapto-3-thiabutylthio]-1,3-dithiolane, 2,2'-[cyclohexyllidenebis(thio-2,1-ethanediylthio)]bis[ethanethiol], and 4,4'-[(1,3-phenylene)bis(oxy)]bis[1-butanethiol], as well as dimers, trimers, and tetramers of the thiol compounds. These may be used individually or in combination of two or more.

[0028] Any one radical polymerizable compound may be used, or two or more may be used in combination.

[0029] The glass transition temperature of the radical polymerizable compound is preferably 60°C or lower, for example, 55°C or lower, for example, 50°C or lower, for example, 45°C or lower, for example, 40°C or lower, for example, 35°C or lower, for example, 30°C or lower, for example, 25°C or lower. In this specification, the glass transition temperature of the radical polymerizable compound refers to the glass transition temperature when each radical polymerizable compound is a homopolymer, and refers to a value obtained, for example, by differential scanning calorimetry (DSC).

[0030] Cationic polymerizable compounds are compounds having one or more cationic polymerizable groups in their molecule. Examples of cationic polymerizable compounds include, but are not limited to, compounds having epoxy groups, compounds having oxetanyl groups, compounds having vinyl ether groups, compounds having other cationic polymerizable groups, and compounds having any combination of these cationic polymerizable groups.

[0031] In this specification, a compound having an epoxy group is a compound having at least one epoxy group in its molecule, and is also referred to as an epoxy compound. Examples include monofunctional epoxy compounds having one epoxy group and polyfunctional epoxy compounds having two or more epoxy groups. In one embodiment, the epoxy compound preferably contains at least a polyfunctional epoxy compound, and may contain a combination of a polyfunctional epoxy compound and a monofunctional epoxy compound. Epoxy compounds can be broadly classified into epoxy compounds having an aromatic ring skeleton, aliphatic epoxy compounds, and alicyclic epoxy compounds, depending on the type of skeleton.

[0032] In this specification, a compound having an oxetanyl group is a compound having at least one oxetane ring (e.g., a 3-oxetanyl group) in its molecule, and is also referred to as an oxetane compound. In one embodiment, the oxetane compound preferably has 1 to 6 oxetanyl groups in its molecule, and more preferably has 1 to 2 oxetanyl groups in its molecule.

[0033] In this specification, a compound having a vinyl ether group is a compound having at least one vinyl ether group in its molecule.

[0034] Specific examples of cationic polymerizable compounds include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, novolac type epoxy compounds, glycidyl ethers of tetra(hydrophenyl)alkanes, glycidyl ethers of tetrahydroxybenzophenone, epoxidized polyvinylphenol, p-tert-butylphenyl glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, 1,2-epoxytetradecane, and 3,4-epoxycyclohexylmethyl-3,4 -Epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate , bis(3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexane carboxylate, methylenebis(3,4-epoxycyclohexane), propane-2,2-diyl-bis(3,4-epoxycyclohexane), 2,2-bis(3,4-epoxycyclohexyl)propane, dicyclopentadiene diepoxide, ethylenebis(3,4-epoxycyclohexane carboxylate), limonene dioxide (1,2:8,9-diepoxylimonene), (3,3',4,4'-Diepoxy)bicyclohexyl, dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, 1,2-epoxy-4-vinylcyclohexane, α-pinene oxide, 1,2-epoxy-4-(2-oxyranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, epoxidized polybutadiene, compounds in which some or all of the double bonds of styrene-butadiene copolymers are epoxidized, polyalkylene oxide-modified bisphenol A epoxy, polyalkylene oxide-modified bisphenol F epoxy, lauryl alcohol polyethylene glycol glycidyl ether, diglycidyl ether of alicyclic diols, diglycidyl ether of polyalkylene oxide adducts of alicyclic diols, bis[1-ethyl(3-O Xetanyl) methyl ether (also known as (3-ethyl-3{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane)), xylylene bisoxetane, 4,4'-bis[3-ethyl-(3-oxetanyl)methoxymethyl]biphenyl, 1,4-bis(3-ethyl-3-oxetanylmethoxy)methylbenzene, (bis[(3-ethyl-3-oxetanyl)methyl]isophthalate), 3-ethyl-3-hydroxymethyloxetane, 2-Ethylhexyloxetane, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-[(2-ethylhexyloxy)methyl]oxetane, 3-ethyl-3-(4-hydroxybutyl)oxymethyloxetane, 3-ethyl-3-phenoxymethyloxetane, oxetanylsilsesquioxetane, 3-ethyl-3{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane, phenol novolac oxetane, 1,Examples include, but are not limited to, 4-butanediol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, 2-(2-vinyloxyethoxy)ethyl acrylate, 2-(2-vinyloxyethoxy)ethyl methacrylate, 1,4-cyclohexanedimethanol monovinyl ether, and 1,4-cyclohexanedimethanol divinyl ether.

[0035] Commercially available cationic polymerizable compounds include EPICLON® 850, 850-S, EXA-850CRP, EXA-8067 from DIC Corporation; AER9000 from Asahi Kasei Corporation; EP-4000S, EP-4003S, EP-4005, EP-4010S, EP-4088S, EP-4088L from ADEKA Corporation; Rikaresin BEO-60E from Shin Nippon Rika Co., Ltd.; EX-171 from Nagase ChemteX Corporation; and EPICLON® 830-S, EXA from DIC Corporation. -830LVP, EXA-835LV; EPICLON® HP-4032D, HP-720H manufactured by DIC Corporation; EPICLON® N-740, N-770 manufactured by DIC Corporation; EPICLON® N-660, N-670, N-655-EXP-S manufactured by DIC Corporation; Adekaglycirol® ED-509E, ED-509S manufactured by ADEKA Corporation; OPP-G manufactured by Sanko Co., Ltd.; Epolite 100MF manufactured by Kyoeisha Chemical Co., Ltd.; jER manufactured by Mitsubishi Chemical Corporation Examples include, but are not limited to, YX7400N; jER YX8000 manufactured by Mitsubishi Chemical Corporation; Celoxide® 2021P manufactured by Daicel Corporation; Celoxide® 8010 manufactured by Daicel Corporation; EHPE3150 manufactured by Daicel Corporation; EPOLEAD PB manufactured by Daicel Corporation; EPOFRIEND manufactured by Daicel Corporation; HiREM-1 and HiREM-2 manufactured by Shikoku Chemicals, Inc.; OXT-191 manufactured by Toagosei Co., Ltd.; OXT-221 manufactured by Toagosei Co., Ltd.; and PHOX manufactured by Toagosei Co., Ltd.

[0036] Any one cationic polymerizable compound may be used, or two or more may be used in combination.

[0037] Examples of anionic polymerizable compounds include epoxy group compounds, as shown as examples of cationic polymerizable compounds, and their curing agents, such as thiol-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, and amine-based curing agents. Methylene malonates, as shown as examples of radical polymerizable compounds, can also be cited as anionic polymerizable compounds. Furthermore, (meth)acrylate compounds, as shown as examples of radical polymerizable compounds, can also be cited as anionic polymerizable compounds when used in combination with thiol compounds. These may be used individually or in combination of two or more.

[0038] The thiol compound mentioned above can be used as the thiol-based curing agent.

[0039] Examples of phenolic curing agents include, but are not limited to, monomers, oligomers, and polymers in general that have phenolic hydroxyl groups, such as phenol novolac resins and their alkylated or allylated derivatives, cresol novolac resins, phenol aralkyl (including phenylene and biphenylene skeletons) resins, naphthol aralkyl resins, triphenolmethane resins, and dicyclopentadiene-type phenolic resins.

[0040] Examples of acid anhydride-based curing agents include, but are not limited to, methyltetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride such as methylhexahydrophthalic anhydride and methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhymic anhydride, succinic anhydride substituted with alkenyl groups, methylnadic anhydride, and glutaric anhydride.

[0041] Examples of amine-based curing agents include, but are not limited to, aliphatic polyamines such as triethylenetetraamine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, and 2-methylpentamethylenediamine; alicyclic polyamines such as isophoronediamine, 1,3-bisaminomethylcyclohexane, bis(4-aminocyclohexyl)methane, norbornenediamine, and 1,2-diaminocyclohexane; piperazine-type polyamines such as N-aminoethylpiperazine and 1,4-bis(2-amino-2-methylpropyl)piperazine; and aromatic polyamines such as diethyltoluenediamine, dimethylthiotoluenediamine, 4,4'-diamino-3,3'-diethyldiphenylmethane, bis(methylthio)toluenediamine, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, diethyltoluenediamine, trimethylenebis(4-aminobenzoate), and polytetramethyleneoxide-di-p-aminobenzoate. Other commercially available products include, but are not limited to, Epicure-W, Epicure-Z (product names from Yoka Shell Epoxy Co., Ltd.), jER Cure®-W, jER Cure®-Z (product names from Mitsubishi Chemical Corporation), Kaya Hard A-A, Kaya Hard A-B, Kaya Hard A-S (product names from Nippon Kayaku Co., Ltd.), Totamine HM-205 (product name from Nippon Steel & Sumitomo Metal Chemical Co., Ltd.), Adeka Hardner EH-101 (product name from ADEKA Corporation), Epomic Q-640, Epomic Q-643 (product names from Mitsui Chemicals, Inc.), DETDA80 (product name from Lonza), and Totamine HM-205 (product name from Nippon Steel & Sumitomo Metal Chemical Co., Ltd.).

[0042] (A) The polymerizable compound may be any one of the following: a radical polymerizable compound, a cationic polymerizable compound, or an anionic polymerizable compound, or any combination of these may be used.

[0043] In one embodiment, the polymerizable compound (A) includes a compound having an epoxy group and a curing agent thereof. When the polymerizable compound (A) includes a compound having an epoxy group and a curing agent thereof, the ratio of the number of epoxy group equivalents of the compound having an epoxy group to the number of functional group equivalents of the curing agent ([number of epoxy group equivalents of the compound having an epoxy group] / [number of functional group equivalents of the curing agent]) is preferably 0.1 to 1000, more preferably 0.1 to 100, and even more preferably 0.2 to 10. In one embodiment, the polymerizable compound (A) includes a (meth)acrylate compound and a thiol compound. (A) When the polymerizable compound includes a (meth)acrylate compound and a thiol compound, the ratio of the number of (meth)acryloyl group equivalents of the (meth)acrylate compound to the number of thiol group equivalents of the thiol compound ([number of (meth)acryloyl group equivalents of the (meth)acrylate compound] / [number of thiol group equivalents of the thiol compound]) is preferably 0.1 to 1000, more preferably 0.1 to 100, and even more preferably 0.2 to 10.

[0044] In this embodiment, (A) the polymerizable compound comprises at least one polymerizable compound with a functional group equivalent of 105 or more. The functional group equivalent is preferably 150 or more, more preferably 170 or more, and even more preferably 200 or more. This makes it possible to prolong the duration of triplet-triplet annihilation photon upconversion emission and achieve a good degree of curing. The upper limit of the functional group equivalent of the polymerizable compound with a functional group equivalent of 105 or more is not particularly limited, but may be, for example, 10,000 or less, 8,000 or less, 6,000 or less, 4,000 or less, 3,000 or less, 2,000 or less, or 1,000 or less. (A) The amount of polymerizable compound with a functional group equivalent of 105 or more, relative to 100 parts by mass of the total amount of polymerizable compound, is preferably 5 to 100 parts by mass, more preferably 10 to 100 parts by mass, even more preferably 15 to 100 parts by mass, even more preferably 20 to 100 parts by mass, even more preferably 25 to 100 parts by mass, even more preferably 30 to 100 parts by mass, even more preferably 35 to 100 parts by mass, even more preferably 40 to 100 parts by mass, even more preferably 45 to 100 parts by mass, and even more preferably 50 to 100 parts by mass.

[0045] In this embodiment, (A) the polymerizable compound preferably comprises at least one polymerizable compound having at least one aliphatic group selected from the group consisting of polyalkylene oxide groups, alkyl groups having 6 or more carbon atoms, alkylene groups having 6 or more carbon atoms, groups derived from alicyclic diols, and groups derived from sugar alcohols. This makes it possible to extend the duration of triplet-triplet annihilation photon upconversion luminescence and achieve a better degree of curing. The number of aliphatic groups in the polymerizable compound having at least one aliphatic group selected from the group consisting of polyalkylene oxide groups, alkyl groups having 6 or more carbon atoms, and alkylene groups having 6 or more carbon atoms may be one or two or more. When the number of aliphatic groups is two or more, the types of aliphatic groups are each selected independently. In one embodiment, the polyalkylene oxide group is polyethylene oxide, polypropylene oxide, polybutylene oxide, polytrimethylene oxide, polytetramethylene oxide, or a combination thereof. The average number of repeating alkylene oxides n in the polyalkylene oxide group can be, for example, 1 to 20. The number of carbon atoms in the alkyl group can be 6 to 50. The alkyl group may be linear or branched and may have substituents such as hydroxyl groups, alkoxy groups, or amino groups. The number of carbon atoms in the alkylene group can be 6 to 50. The alkylene group may be linear or branched and may have substituents such as hydroxyl groups, alkoxy groups, or amino groups. A group derived from an alicyclic diol refers to a group present in a compound synthesized using an alicyclic diol as a raw material, and means the part derived from the aliphatic diol. Examples of compounds synthesized using an alicyclic diol as a raw material include mono or diglycidyl ethers of alicyclic diols and mono or di(meth)acrylates of alicyclic diols. A group derived from a sugar alcohol refers to a group present in a compound synthesized using a sugar alcohol as a raw material, and means the part derived from the sugar alcohol. Compounds synthesized from sugar alcohols include, for example, mono, di, or trialcanthiols of pentaerythritol, mono, di, or tri(meth)acrylates of pentaerythritol, and poly(meth)acrylates of dipentaerythritol.(A) If the polymerizable compound includes at least one polymerizable compound having at least one aliphatic group selected from the group consisting of a polyalkylene oxide group, an alkyl group having 6 or more carbon atoms, an alkylene group having 6 or more carbon atoms, a group derived from an alicyclic diol, and a group derived from a sugar alcohol, the polymerizable compound having at least one aliphatic group may also have an aromatic ring. Furthermore, (A) the polymerizable compound may also include a polymerizable compound having an aromatic ring but not having the aforementioned aliphatic group.

[0046] In one embodiment, (A) the polymerizable compound includes a curing agent selected from the group consisting of a 2-4 functional thiol curing agent, a 2-4 functional phenol curing agent, a 2-4 functional acid anhydride curing agent, and a 2-4 functional amine curing agent. By using such a curing agent, the duration of triplet-triplet annihilation photon upconversion luminescence can be prolonged, and a good degree of curing can be achieved. The curing agent may also contain a curing agent with 5 or more functions.

[0047] The content of polymerizable compound (A) in the curable function-expressing paste may be 1 to 99 parts by mass per 100 parts by mass of the total amount of the curable function-expressing paste. In one embodiment, the content of polymerizable compound (A) in the curable function-expressing paste 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 amount of the curable function-expressing paste. The curable function-expressing paste of this embodiment can be cured by photocuring alone, even if there are many shielding materials such as fillers. In another embodiment, the content of polymerizable compound (A) in the curable function-expressing paste is preferably 30 to 99 parts by mass, more preferably 50 to 99 parts by mass, and even more preferably 60 to 99 parts by mass, per 100 parts by mass of the total amount of the curable function-expressing paste. Furthermore, the content of polymerizable compound (A) in the curable function-expressing paste is preferably 75 to 99 parts by mass, more preferably 80 to 99.5 parts by mass, and even more preferably 85 to 98 parts by mass, based on 100 parts by mass of the total amount of organic matter contained in the curable function-expressing paste (excluding low-stress-imparting materials such as organic fillers and elastomers). Furthermore, the amount of component (A) is preferably 75 to 99.9 parts by mass, more preferably 80 to 99.5 parts by mass, and even more preferably 85 to 99 parts by mass, based on 100 parts by mass of the total of components (A), (B), (C), and (D).

[0048] (B) Photopolymerization Initiator The curable function paste of this embodiment contains (B) a photopolymerization initiator (hereinafter also referred to as "component (B)"). A photopolymerization initiator is a reactant that absorbs light to generate active species such as radicals, cations, and anions, thereby promoting the polymerization of polymerizable compounds. In this embodiment, (B) the photopolymerization initiator is preferably a photopolymerization initiator that can be activated by light with a wavelength of 500 nm or less (i.e., can generate active species), and can be activated by photon upconversion emission with a wavelength of 500 nm or less, as shown by (D) the light emitter described later, and can generate active species. (B) the photopolymerization initiator is more preferably activated by light with a wavelength of 450 nm or less, even more preferably activated by light with a wavelength of 440 nm or less, and particularly preferably activated by light with a wavelength of 430 nm or less. By matching the absorption characteristics of (B) the photopolymerization initiator with the wavelength of light produced by (D) the light emitter, the efficiency of the polymerization reaction can be increased. (B) The photopolymerization initiator can be appropriately selected from photoradical polymerization initiators, photoacid generators, photobase generators, or any combination thereof.

[0049] Photoradical polymerization initiators absorb light and generate radicals as active species, thereby promoting the polymerization of radically polymerizable compounds. Examples of photoradical polymerization initiators include, but are not limited to, alkylphenone compounds, acylphosphine oxide compounds, oxime ester compounds, and compounds having a photosensitive site and a peroxide structure.

[0050] Examples of alkylphenone compounds include benzyldimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethane-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-hydroxycyclohexylphenyl-ketone (commercially available as Omnirad 184 from IGM Resins B.V.); and 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)-butan-1-one (commercially available as Omnirad from IGM Resins B.V.) Examples include, but are not limited to, 379EG), 2-benzyl-2-(dimethylamino)-4'-morpholinobtyrophenone (commercially available as Omnirad 369 from IGM Resins B.V.). These may be used individually or in combination of two or more.

[0051] Examples of acylphosphine oxide compounds include, but are not limited to, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (commercially available as Omnirad TPO H from IGM Resins B.V.) and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (commercially available as Omnirad 819 from IGM Resins B.V.). These may be used individually or in combination of two or more.

[0052] Examples of oxime ester compounds include, but are not limited to, 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyl oxime)] (trade name: Irgacure OXE-01, manufactured by BASF), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyloxime) (trade name: Irgacure OXE-02, manufactured by BASF), methanone, ethanone, 1-[9-ethyl-6-(1,3-dioxolane,4-(2-methoxyphenoxy)-9H-carbazole-3-yl]-,1-(O-acetyloxime) (trade name: ADEKA OPT-N-1919, manufactured by ADEKA). These may be used individually or in combination of two or more.

[0053] Examples of compounds having a photosensitive site and a peroxide structure, or commercially available products thereof, include, but are not limited to, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone (BTTB), Perdual TA, and Perdual TX (all manufactured by NOF Corporation).

[0054] In addition to the photoradical polymerization initiators mentioned above, other examples of photoradical polymerization initiators include 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, and benzyldimethyl Examples include, but are not limited to, ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylic benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate, benzyl, and camphorquinone. These may be used individually or in combination of two or more.

[0055] Any one type of photoradical polymerization initiator may be used, or two or more types may be used in combination.

[0056] From the viewpoint of photoirradiation reactivity, the content of the photoradical polymerization initiator in the curable function paste is preferably 0.1 to 10 parts by mass, and more preferably 0.2 to 8 parts by mass, per 100 parts by mass of the polymerizable compound (A).

[0057] A photoacid generator absorbs light and generates acid as an active species, thereby promoting the polymerization of cationic polymerizable compounds. Various compounds described in Japanese Patent Publication No. 2022-080366 can be used as the photoacid generator, and are not particularly limited. A preferred acid generator is BF ４ － SbF ６ -, AsF ６ － , B (C ６ F ５ ) ４ － Ga(C) ６ F ５ ) ４ － , C (CF ３ SO ２ ) ３ － [P(R １ ) ａ F ６－ａ ] － [C(R １ SO ２ ) ３ ] － , or [N(R １ SO ２ ) ２ ] － (In the formula, R １ Each of these is an alkyl group in which at least some of the hydrogen atoms are substituted with fluorine atoms, and a is an integer from 0 to 5. If a is an integer of 2 or more, there are multiple R groups. １ Various onium salts are available, in which the counter anions are iodonium cations, sulfonium cations, ammonium cations, and phosphonium cations, etc., and the cation moiety is iodonium cation, sulfonium cation, ammonium cation, etc., which may be the same or different from each other.

[0058] Examples of iodonium cations include iodonium ions such as diphenyliodonium, di-p-tolyliodonium, bis(4-dodecylphenyl)iodonium, bis(4-methoxyphenyl)iodonium, (4-octyloxyphenyl)phenyliodonium, bis(4-decyloxy)phenyliodonium, 4-(2-hydroxytetradecyloxy)phenylphenyliodonium, 4-isopropylphenyl(p-tolyl)iodonium, and 4-isobutylphenyl(p-tolyl)iodonium.

[0059] Examples of sulfonium ions include triphenylsulfonium, tri-p-tolylsulfonium, tri-o-tolylsulfonium, tris(4-methoxyphenyl)sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium, tris(4-fluorophenyl)sulfonium, tri-1-naphthylsulfonium, tri-2-naphthylsulfonium, tris(4-hydroxyphenyl)sulfonium, 4-(phenylthio)phenyldiphenylsulfonium, 4-(p-tolylthio)phenyldi-p-tolylsulfonium, 4-(4-methoxyphenylthio)phenylbis(4-methoxyphenyl)sulfonium, and 4-(phenylthio)phenylbis(4-fluorophenyl (L) sulfonium, 4-(phenylthio)phenylbis(4-methoxyphenyl)sulfonium, 4-(phenylthio)phenyldi-p-tolylsulfonium, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium, [4-(2-thioxanthonylthio)phenyl]diphenylsulfonium, bis[4-(diphenylsulfonio)phenyl]sulfide, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonio}phenyl]sulfide, bis{4-[bis(4-fluorophenyl)sulfonio]phenyl}sulfide, bis{4-[bis(4-methylphenyl)sulfonio]phenyl}sulfide, bis{4-[bis(4-methoxyphenyl)sulfonio] Phenyl sulfide, 4-(4-benzoyl-2-chlorophenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoyl-2-chlorophenylthio)phenyldiphenylsulfonium, 4-(4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene-2-yldiphenylsulfonium, 2-[(di-p-tolyl)sulfonio]thioxanthone, 2-[(diphenyl)sulfonio]thioxanthone, 4-(9-oxo-9H-thioxanthene-2-yl)thiophenyl-9-oxo-9H-thioxanthene-2-ylphenylsulfonium, 4-[4-(4-t-butylbenzoyl)phenylthio]phenyldi-p-tolylsulfonium, 4-[4-(4-t-butylbenzoyl)phenylthio]phenyl Examples of triarylsulfonium compounds include nyldiphenylsulfonium, 4-[4-(benzoylphenylthio)]phenyldi-p-tolylsulfonium, 4-[4-(benzoylphenylthio)]phenyldiphenylsulfonium, 5-(4-methoxyphenyl)thiaanthurenium, 5-phenylthiaanthurenium, 5-tolylthiaanthurenium, 5-(4-ethoxyphenyl)thiaanthurenium, and 5-(2,4,6-trimethylphenyl)thiaanthurenium.

[0060] Examples of ammonium cations include pyrrolidinium such as N,N-dimethylpyrrolidinium, N-ethyl-N-methylpyrrolidinium, and N,N-diethylpyrrolidinium; imidazolinium such as N,N'-dimethylimidazolinium, N,N'-diethylimidazolinium, N-ethyl-N'-methylimidazolinium, 1,3,4-trimethylimidazolinium, and 1,2,3,4-tetramethylimidazolinium; tetrahydropyrimidinium such as N,N'-dimethyltetrahydropyrimidinium; and mole ammonium cations such as N,N'-dimethylmorpholinium. Examples include piperidinium such as phorinium and N,N'-diethylpiperidinium, pyridinium such as N-methylpyridinium, N-benzylpyridinium and N-phenacylpyridinium, imidazolium such as N,N'-dimethylimidazolium, quinorium such as N-methylquinorium, N-benzylquinorium and N-phenacylquinorium, isoquinorium such as N-methylisoquinorium, thiazonium such as benzylbenzothiazonium and phenacylbenzothiazonium, and acridium such as benzylacridium and phenacylacridium.

[0061] Examples of phosphonium cations include tetraarylphosphoniums such as tetraphenylphosphonium, tetra-p-tolylphosphonium, tetrakis(2-methoxyphenyl)phosphonium, tetrakis(3-methoxyphenyl)phosphonium, and tetrakis(4-methoxyphenyl)phosphonium; triarylphosphoniums such as triphenylbenzylphosphonium, triphenylphenacylphosphonium, triphenylmethylphosphonium, and triphenylbutylphosphonium; and tetraalkylphosphoniums such as triethylbenzylphosphonium, tributylbenzylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, tetrahexylphosphonium, triethylphenacylphosphonium, and tributylphenacylphosphonium.

[0062] Specific examples of iodonium salt-based photoacid generators include photoacid generators that are arsenate-type iodonium salts such as diphenyliodonium hexafluoroarsenate, di(4-chlorophenyl)iodonium hexafluoroarsenate, di(4-bromphenyl)iodonium hexafluoroarsenate, and phenyl(4-methoxyphenyl)iodonium hexafluoroarsenate; 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexafluorophosphate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium tri(pentafluoroethyl)trifluorophosphate (e.g., IK-1 manufactured by Sunapro Co., Ltd.), 4-methylphenyl-4-(2-methylpropyl)phenyliodonium hexafluorophosphate (e.g., IRGACURE® 250 manufactured by BASF), and bis(C) １０～１４Photoacid generators that are phosphate-based iodonium salts such as alkylphenyl)iodonium hexafluorophosphate (e.g., WPI-113 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.); photoacid generators that are antimonate-based iodonium salts such as 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexafluoroantimonate (e.g., WPI-116 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.); photo / thermal acid generators that are gallate-based iodonium salts such as IK-1FG (manufactured by Sunapro Co., Ltd.); 4-methylphenyl-4-(1-methylethyl)phenyliodonium tetrakis(pentafluorophenyl) borate, 4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl) borate (e.g., BLUESIL® PI manufactured by ELKEM SILICONES). Examples include photoacid generators such as borate-based iodonium salts (e.g., 2074), but are not limited to these.

[0063] Specific examples of sulfonium salt-based photoacid generators include, but are not limited to, borate-based sulfonium salt photoacid generators (e.g., products manufactured by Sunapro Co., Ltd.: CPI-110B, CPI-310B, CPI-410B, etc., and Omnirad 290 manufactured by IGM Resins B.V., etc.), phosphate-based sulfonium salt photoacid generators (products manufactured by Sunapro Co., Ltd.: CPI-210S, VC-1S, CPI-410S, etc.), and gallate-based sulfonium salt photoacid generators (products manufactured by Sunapro Co., Ltd.: CPI-310FG, VC-1FG, etc.).

[0064] You may use one type of photoacid generator, or you may use two or more types in combination.

[0065] The content of the photoacid generator in the curable function paste is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and even more preferably 1 to 15 parts by mass, per 100 parts by mass of the polymerizable compound (A).

[0066] Photobase generators absorb light and generate bases as active species, thereby promoting the polymerization of anionic polymerizable compounds. Examples of photobase generators include, but are not limited to, various compounds that generate bases such as amines, amidines, guanidines, phosphazenes, and carbenes.Specific examples of photobase generators include, for example, 2-benzyl-2-(dimethylamino)-1-[4-(morpholino)phenyl]-1-butanone, 2-(dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one, 2-nitrobenzyl 4-hydroxypiperidine-1-carboxylate, 4,5-dimethoxy-2-nitrobenzyl 2,6-dimethylpiperidine-1-carboxylate, 1-(9,10-dioxo-9,10-dihydroanthracene-2-yl)ethylcyclohexylcarbamate, 1-(9,10-dioxo-9,10-dihydroanthracene-2-yl)ethyl 1H-imidazole-1-carboxylate, 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine-1- Ium 2-(3-benzoylphenyl)propanoate, diaminomethaneiminium 2-(3-benzoylphenyl)propanoate, (Z)-N-(((bis(dimethylamino)methylene)amino)(isopropylamino)methylene)propane-2-aminium 2-(3-benzoylphenyl)propanoate, 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidium n-butyltriphenylborate, (Z)-{[bis(dimethylamino)methylidene]amino}-N-cyclohexyl(cyclohexylamino)methaniminium tetrakis(3-fluorophenyl)borate, 1,2-diisopropyl-3-[bis(dimethylamino)methylene]guanidium 2-(3-benzoylphenyl)propionate, 9-antrylmethyl Examples include, but are not limited to, N,N-diethylcarbamate, (E)-1-piperidino-3-(2-hydroxyphenyl)-2-propen-1-one, 2-nitrophenylmethyl 4-methacryloyloxypiperidine-1-carboxylate, tetramethylguanidium tetrakis(3-fluorophenyl)borate, tetramethylguanidium tetrakis(4-fluorophenyl)borate, salts containing protonated DBU and tetrakis(3-fluorophenyl)borate anion, and salts containing benzylated DBU and tetrakis(3-fluorophenyl)borate anion. These may be used individually or in combination of two or more.

[0067] Any one type of photobase generator may be used, or two or more types may be used in combination.

[0068] The content of the photobase generator in the curable function paste is preferably 0.5 to 15 parts by mass, and more preferably 1 to 10 parts by mass, per 100 parts by mass of the polymerizable compound (A).

[0069] The photopolymerization initiator may be one of the following: a photoradical polymerization initiator, a photoacid generator, or a photobase generator, or any combination of these may be used.

[0070] (C) Photosensitizer The curable functional paste of this embodiment contains (C) a photosensitizer (hereinafter also referred to as "component (C)"). In this specification, the photosensitizer corresponds to a donor (donor compound) in a triplet-triplet annihilation type photon upconversion material.

[0071] 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), multiphoton excitation of rare-earth element-containing materials, and two-photon absorption. Photon upconversion materials generate high-energy states through multiphoton excitation, triplet-triplet annihilation, etc., when irradiated with specific light, and emit light with a shorter wavelength than the incident light during the relaxation process. By incorporating this photon upconversion material into a curable functional paste and irradiating the curable functional paste with long-wavelength light, the photon upconversion material performs wavelength conversion within the curable functional paste. As a result, the photon upconversion material generates light with a wavelength of 500 nm or less, activating the photopolymerization initiator and curing the curable functional paste. In this embodiment, a photon upconversion material based on a triplet-triplet annihilation type photon upconversion mechanism is used. In the triplet-triplet annihilation type photon upconversion material, a combination of a donor (photosensitizer) and an acceptor (luminescent material) is used.

[0072] In this embodiment, the photosensitizer is not particularly limited as long as it absorbs light with a wavelength greater than 500 nm as incident light, becomes an excited triplet state through intersystem crossing from an excited singlet state, and causes triplet-triplet energy transfer to the (D) light emitter described later. Examples of photosensitizers include, but are not limited to, compounds containing metal atoms such as Pt, Pd, Zn, Ru, Re, Ir, Os, Cu, Ni, Co, Cd, Au, Ag, Sn, Sb, Pb, P, As, and organic moieties such as porphyrin structures, phthalocyanine structures, fullerene structures, and 2-phenylpyridinate structures. Specific examples of photosensitizers include palladium octab-toxyphthalocyanine (PdOBuPc), platinum tetraphenyltetranaphthoporphyrin (PtTPNP), palladium(II)-meso-tetraphenyl-tetrabenzoporphyrin (PdTPBP), and [Ru(dmb)] ３ ] ２＋ (dmb is 4,4'-dimethyl-2,2'-bipyridine), palladium(II) tertraanthraporphyrin (PdTAP), platinum(II) tetraphenyltetrabenzoporphyrin (PtTPBP), palladium mesotetraphenyltetrabenzoporphyrin (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-tetraphenylporphyrin (ZnTPP), palladium(II) tetraphenyltetrabenzoporphyrin (PdTPBP), palladium(II) meso-tetraphenyl-octamethoxidetetranaphtholporphyrin (PdPh ４ OMe ８ TNP), 2-methoxythioxanthone (2MeOTX), and Ir(ppy) ３(ppy = 2-phenylpyridine) is one example, but is not limited to these. Other specific examples of photosensitizers include, for example, the photosensitizers described in Japanese Patent Publication No. 2021-080335 and Japanese Patent Publication No. 2020-056030. Any one of the photosensitizers may be used, or two or more may be used in combination.

[0073] (D) Luminescent material The curable functional paste of this embodiment includes (D) a luminescent material (hereinafter also referred to as "component (D)"). In this specification, the luminescent material corresponds to an acceptor (acceptor compound) in a triplet-triplet annihilation type photon upconversion material. In this embodiment, the luminescent material is not particularly limited as long as it is a compound that, after receiving triplet energy transfer from the photosensitizer, becomes an excited singlet state via triplet-triplet annihilation and exhibits photon upconversion luminescence. Examples of luminescent materials include, but are not limited to, compounds containing a naphthalene structure, anthracene structure, tetracene structure, pyrene structure, perylene structure, biphenyl structure, terphenyl structure, perylenediimide structure, naphthalenediimide structure, and BODIPY (boron dipyromethene; 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) structure. Specific examples of light-emitting materials include, but are not limited to, 9,10-diphenylanthracene (DPA), tetra-tert-butylperylene, anthracene (An), 2,5-diphenyloxazole (PPO), rubrene, 2-chloro-bis-phenylethynylanthracene (2CBPEA), 9,10-bis(phenylethynyl)anthracene (BPEA), 9,10-bis(phenylethynyl)naphthacene (BPEN), perylene, coumarin 343 (C343), 9,10-dimethylanthracene (DMA), pyrene, tert-butylpyrene, and boron dipyromethene (BODIPY) derivatives BD-1 and BD-2 having an iodophenyl group, as well as halogenated derivatives of these compounds. Other specific examples of light-emitting materials include, for example, the light-emitting materials described in Japanese Patent Publication No. 2021-080335 and Japanese Patent Publication No. 2020-056030. You may use one type of light-emitting material, or you may use two or more types in combination.

[0074] By appropriately selecting a combination of photosensitizer and light emitter, the wavelengths of incident light and emitted light can be controlled. The combination of photosensitizer and light emitter may be one set or two or more sets. For example, in one embodiment, by selecting multiple combinations of photosensitizer and light emitter, energy transfer becomes possible in the curable functional paste from one combination of photosensitizer and light emitter to another. Through such stepwise energy transfer, the emission wavelength of the light emitter can be adjusted so that it ultimately includes wavelengths of 500 nm or less from the desired incident light, thereby enabling photocuring of the curable functional paste using the desired incident light. The molar ratio of photosensitizer to light emitter can be, for example, photosensitizer:light emitter = 1:1 to 1:100,000. By appropriately selecting the combination of photosensitizer and light emitter and the molar ratio, the photon upconversion emission shown from the light emitter can be adjusted to include light of wavelengths of 500 nm or less when irradiated with light with a wavelength greater than 500 nm.

[0075] The wavelength range of the excitation light for the photosensitizer is preferably greater than 500 nm, for example, within the range of greater than 500 nm and less than or equal to 2000 nm. It is also desirable to use light near the wavelength absorbed by the photosensitizer within the wavelength range greater than 500 nm. The wavelength of the photon upconversion emission of the light emitter preferably includes wavelengths of 500 nm or less, more preferably includes wavelengths of 450 nm or less, even more preferably includes wavelengths of 430 nm or less, and particularly preferably includes wavelengths of 400 nm or less. In one embodiment, the emission wavelength of the light emitter includes ultraviolet light wavelengths (200 nm to 380 nm).

[0076] In this embodiment, the total content of (C) photosensitizer and (D) light-emitting agent in the curable functional paste 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, based on 100 parts by mass of the total amount of the curable functional paste. Furthermore, the total content of (C) photosensitizer and (D) light-emitting agent 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, based on 100 parts by mass of the total of components (A), (B), (C), and (D). In one embodiment, the total content of (C) photosensitizer and (D) light emitter is preferably 1 mmol / L to 6 mol / L, more preferably 2 mmol / L to 5 mol / L, even more preferably 6 mmol / L to 4 mol / L, particularly preferably 10 mmol / L to 3 mol / L, and most preferably 50 mmol / L to 2 mol / L.

[0077] The curable function-exhibiting paste of this embodiment may, if desired, contain any components other than components (A) to (D) above, for example, those described below, as needed.

[0078] • Thermal Acid Generator The curable function-expressing paste of this embodiment may contain a thermal acid generator to the extent that it does not impair the purpose of this embodiment. The thermal acid generator is a compound that generates an acid (cation) as an active species by the heat that can be generated by the curing reaction of the curable function-expressing paste, and is activated by the heat that can be generated by the curing reaction of the curable function-expressing paste to promote the polymerization of cationic polymerizable compounds. Examples of thermal acid generators include BF ４ － SbF ６ -, AsF ６ － , B (C ６ F ５ ) ４ － Ga(C) ６ F ５ ) ４ － , C (CF ３ SO ２ )３ － [P(R １ ) ａ F ６－ａ ] － [C(R １ SO ２ ) ３ ] － , or [N(R １ SO ２ ) ２ ] － (In the formula, R １ Each of these is an alkyl group in which at least some of the hydrogen atoms are substituted with fluorine atoms, and a is an integer from 0 to 5. If a is an integer of 2 or more, there are multiple R groups. １ Various onium salts are available, in which the counter anions are iodonium cations, sulfonium cations, ammonium cations, and phosphonium cations, etc., and the cation moiety is iodonium cation, sulfonium cation, ammonium cation, etc., which may be the same or different from each other. Examples of thermal acid generators include dimethylphenyl(4-methoxybenzyl)ammonium tetrakis(pentafluorophenyl) borate, a borate-based quaternary ammonium salt (e.g., product name: CXC-1821, manufactured by King Industries, Inc.), 4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl) borate, a borate-based iodonium salt (e.g., product name: BLUESIL® PI 2074, manufactured by ELKEM SILICONES), 4-methylphenyl-4-(1-methylethyl)phenyliodonium tri(pentafluoroethyl)trifluorophosphate (e.g., product name: IK-1, manufactured by Sunapro Co., Ltd.), and a phosphate-based sulfonium salt thermal cationic polymerization initiator represented by the following formula (e.g., product name: TA-100, manufactured by Sunapro Co., Ltd.). A photo / thermal acid generator which is a gallate-type iodonium salt represented by the following formula (for example, product name: IK-1FG manufactured by Sunapro Co., Ltd., see Japanese Patent Publication No. 2022-080366). A gallate-based sulfonium salt, represented by the following formula, is a thermal cationic polymerization initiator (for example, product name: TA-100FG, manufactured by Sunapro Co., Ltd., see WO2018 / 020974). These are some examples, but are not limited to these.

[0079] - Thermal base generator The curable function-expressing paste of this embodiment may contain a thermal base generator to the extent that it does not impair the purpose of this embodiment. The thermal base generator is a compound that generates a base (anion) as an active species when heated, and can be activated by the heat that can be generated by the curing reaction of the curable function-expressing paste, thereby promoting the polymerization of anionic polymerizable compounds.

[0080] Examples of thermobase generating agents include amines such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, triethylamine, triethylenediamine, 2-(dimethylaminomethyl)phenol, 1,8-diazabicyclo[5,4,0]undecene-7, tris(dimethylaminomethyl)phenol, and benzyldimethylamine, as well as phosphines such as triphenylphosphine, tributylphosphine, and trioctylphosphine.

[0081] Examples of thermal base generators include, in addition to the above examples, "thermal latent curing catalysts," which are basic catalysts that are inert at room temperature and become activated by heat to function as polymerization catalysts. Examples of thermal latent curing catalysts include amine compounds that are solid at room temperature; amine adduct-type thermal latent curing catalysts such as reaction products of amine compounds and epoxy compounds (amine-epoxy adduct systems) and reaction products of amine compounds and isocyanate compounds or urea compounds (urea-type adduct systems); solid-disperse thermal latent curing catalysts such as microcapsule-type thermal latent curing catalysts and inclusion-type thermal latent curing catalysts. Amine compounds include aliphatic amines, aromatic amines, and heterocyclic amines.

[0082] Examples of amine compounds that are solid at room temperature include dicyandiamide, 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-undecylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 2,4-diamino-6-(2-methyl-1-imidazolyl-(1))-ethyl-S-triazine, and 2,4-diamino-6-(2′-methylimidazolyl-(1)′)-ethyl-S- Examples include, but are not limited to, triazine isocyanuric acid adducts, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, N-(2-methylimidazolyl-1-ethyl)-urea, and N,N'-(2-methylimidazolyl-(1)-ethyl)-azivoyldiamide.

[0083] Representative examples of commercially available thermal latent curing catalysts include, but are not limited to, the following: Amine-epoxy adduct curing catalysts include "Amicure PN-23" (Ajinomoto Fine Techno Co., Ltd.), "Amicure PN-40" (Ajinomoto Fine Techno Co., Ltd.), "Amicure PN-50" (Ajinomoto Fine Techno Co., Ltd.), "Hardener X-3661S" (ACR Co., Ltd.), "Hardener X-3670S" (ACR Co., Ltd.), "NovaCure HX-3742" (Asahi Kasei Corporation), "NovaCure Examples include, but are not limited to, "HX-3721" (Asahi Kasei Corporation product name), "NovaCure HXA9322HP" (Asahi Kasei Corporation product name), "NovaCure HXA3922HP" (Asahi Kasei Corporation product name), "NovaCure HXA3932HP" (Asahi Kasei Corporation product name), "NovaCure HXA5945HP" (Asahi Kasei Corporation product name), "NovaCure HXA5911HP" (Asahi Kasei Corporation product name), and "NovaCure HXA9382HP" (Asahi Kasei Corporation product name). All Novacure products are supplied in a state where microcapsule particles are dispersed in epoxy resin. When Novacure is used as a thermal latent curing catalyst, the resin composition will contain epoxy resin. Examples of the aforementioned amine-urea type adduct curing catalysts include, but are not limited to, "Fujicure FXE-1000" (T&K TOKA Corporation product name), "Fujicure FXR1020" (T&K TOKA Corporation product name), "Fujicure FXR-1030" (T&K TOKA Corporation product name), "Fujicure FXR1121" (T&K TOKA Corporation product name), "Fujicure FXR1081" (T&K TOKA Corporation product name), "Fujicure 1061" (T&K TOKA Corporation product name), "Fujicure 1171" (T&K TOKA Corporation product name), and "Fujicure 2015" (T&K TOKA Corporation product name). Other commercially available thermal latent curing catalysts include, but are not limited to, "Fujicure 7550" (product name of T&K TOKA Co., Ltd.).

[0084] A claustrophobic thermal latent curing catalyst is a curing catalyst having a structure in which guest molecules, such as amine compounds, are trapped at the molecular level within the crystalline space formed by the host molecule. An example of a commercially available claustrophobic thermal latent curing catalyst is "NISSOCURE TIC-188" (product name of Nippon Soda Co., Ltd.).

[0085] - Thermal radical polymerization initiator The curable function-expressing paste of this embodiment may contain a thermal radical polymerization initiator to the extent that it does not impair the purpose of this embodiment. A thermal radical polymerization initiator is a compound that generates radicals as active species when heated, and can be activated by the heat that can be generated by the curing reaction of the curable function-expressing paste, thereby promoting the polymerization of radical polymerizable compounds.

[0086] Examples of thermal radical polymerization initiators include methyl ethyl ketone peroxide, methylcyclohexanone peroxide, methyl acetacetate peroxide, acetylacetone peroxide, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, and 2,2-bis(4,4-di-t- (Tyl peroxycyclohexyl)propane, 1,1-bis(t-butylperoxy)cyclododecane, n-butyl 4,4-bis(t-butylperoxy)valerate, 2,2-bis(t-butylperoxy)butane, 1,1-bis(t-butylperoxy)-2-methylcyclohexane, t-butyl hydroperoxide, p-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, t-hexyl hydroperoxide, dicumyl peroxide, 2,5-dimethyl- 2,5-bis(t-butylperoxy)hexane, α,α'-bis(t-butylperoxy)diisopropylbenzene, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyn-3, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, cinnamate peroxide, m-toluyl peroxide, benzoyl peroxide, diisopropyl Peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di(3-methyl-3-methoxybutyl)peroxydicarbonate, di(4-t-butylcyclohexyl)peroxydicarbonate, α,α'-bis(neodecanoylperoxy)diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3,-Tetramethylbutyl peroxyneodecanoate, 1-cyclohexyl-1-methylethyl peroxyneodecanoate, t-hexyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-hexyl peroxypivalate, t-butyl peroxypivalate, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 1-cyclohexyl-1-methylethyl peroxy-2-ethylhexanoate, t-hexyl peroxy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyisobutyrate, t-butyl peroxy Examples include, but are not limited to, ray acid, t-butyl peroxylaurate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butyl peroxyacetate, t-hexyl peroxybenzoate, t-butyl peroxy-m-toluylbenzoate, t-butyl peroxybenzoate, bis(t-butylperoxy)isophthalate, t-butyl peroxyallyl monocarbonate, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, etc. These may be used individually or in combination of two or more.

[0087] - Fillers The curable function-developing paste of this embodiment may contain fillers to the extent that it does not impair the purpose of this embodiment. By including fillers in the curable function-developing paste, the coefficient of linear expansion of the cured product obtained by curing the curable function-developing paste can be lowered, improving thermal cycle resistance. In addition, if a filler with a low modulus of elasticity is used, the stress generated in the cured product can be alleviated, improving long-term reliability. Fillers are broadly classified into inorganic fillers and organic fillers.

[0088] Inorganic fillers consist of granular bodies formed from inorganic materials and are not particularly limited as long as they have the effect of lowering the coefficient of thermal expansion when added. Examples of inorganic materials include silica, talc, alumina, aluminum nitride, calcium carbonate, aluminum silicate, magnesium silicate, magnesium carbonate, barium sulfate, barium carbonate, lime sulfate, aluminum hydroxide, calcium silicate, potassium titanate, titanium oxide, zinc oxide, silicon carbide, silicon nitride, and boron nitride. One or more inorganic fillers may be used. Silica fillers are preferred because they allow for a higher filling capacity. Amorphous silica is preferred.

[0089] Inorganic fillers may be those whose surfaces have been surface-treated with a coupling agent such as a silane coupling agent. This allows the thixotropic index (TI) of the curable functional paste to be within an appropriate range.

[0090] Examples of organic fillers include polytetrafluoroethylene (PTFE) fillers, silicone fillers, acrylic fillers, and styrene fillers. Organic fillers may also be surface-treated.

[0091] The shape of the filler is not particularly limited and may be spherical, flake-shaped, needle-shaped, irregular, or any other shape.

[0092] The average particle size of the filler is preferably 0.01 to 15 μm, and more preferably 0.01 to 10 μm. From the viewpoint of transmittance of long-wavelength light irradiated onto the curable function paste, the maximum particle size of the filler is preferably 50 μm or less, and more preferably 30 μm or less.

[0093] In this specification, the average particle size is the particle size at 50% of the cumulative value in the volume-based particle size distribution, measured by laser diffraction and scattering. The maximum particle size is the largest particle size in the volume-based particle size distribution, measured by laser diffraction and scattering.

[0094] If a filler is included, the filler content is preferably 0.5 to 80% by mass, and more preferably 1 to 70% by mass, relative to the total mass of the curable function paste.

[0095] • Swipaster The curable function-exhibiting paste of this embodiment may contain a swipaster, to the extent that it does not impair the effects of this embodiment. Examples of swipasters include silica such as colloidal silica, hydrophobic silica, fine silica, and nanosilica, as well as bentonite, acetylene black, and Ketjenblack. Nanosilica is preferred from the viewpoint of maintaining its shape after application. Furthermore, from the viewpoint of preventing the curable function-exhibiting paste from getting stuck during bonding and improving moisture resistance and adhesion, nanosilica with an average particle size of 10 to 750 nm is more preferred, and nanosilica with an average particle size of 20 to 600 nm is even more preferred. Commercially available products include, but are not limited to, hydrophobic fumed silica manufactured by CABOT Corporation (product name: CAB-O-SIL® TS720, average particle size: 12 nm), hydrophobic fumed silica manufactured by Nippon Aerosil (product name: R805, average particle size: 12 nm), and amorphous silica manufactured by Nippon Shokubai (product name: Seahostar KE-P10, average particle size: 100 nm). Here, the average particle size of the nanosilica particles is measured using a dynamic light scattering nanotrack particle size analyzer. The thixotrope may be used alone or in combination of two or more types.

[0096] If a quivistatement is included, the quivistatement content is preferably 0.01 to 30% by mass, more preferably 0.05 to 25% by mass, and even more preferably 0.1 to 20% by mass, based on the total mass of the curable function paste.

[0097] • Light-shielding agent The curable functional paste of this embodiment may contain a light-shielding agent to the extent that it does not impair the effects of this embodiment. Depending on the application of the cured product of the curable functional paste, light-shielding may be required. In that case, the curable functional paste of this embodiment may contain a light-shielding agent. Long-wavelength light can pass through light-shielding agents that block ultraviolet light. The curable functional paste of this embodiment can be cured by irradiation with long-wavelength light, with little to no effect from the light-shielding agent. Examples of light-shielding agents include, but are not limited to, carbon black and titanium black. Furthermore, these light-shielding agents can also be used as photothermal conversion materials that convert long-wavelength light into heat.

[0098] - Multiphoton-excited type photon upconversion material The curable functional paste of this embodiment may contain a multiphoton-excited type photon upconversion (PUC) material, to the extent that it does not impair the effects of this embodiment. A multiphoton-excited type photon upconversion material is a material that emits upconversion light by multiphoton excitation. For example, in one embodiment, by using a photosensitizer and a light emitter in combination with a multiphoton-excited type photon upconversion material, energy transfer becomes possible in the curable functional paste from the light emitter to the multiphoton-excited type photon upconversion material, or from the multiphoton-excited type photon upconversion material to the photosensitizer. Through such stepwise energy transfer, the photon upconversion emission wavelength of the light emitter can be adjusted so that it ultimately includes wavelengths of 500 nm or less from the desired incident light, thereby enabling the curable functional paste to be photocured using the desired incident light.

[0099] In multiphoton-excited photon upconversion materials, a rare earth element is doped into an optically inert matrix material, thereby exhibiting upconversion emission characteristics. By appropriately selecting the type and amount (doping amount) of rare earth element contained in the multiphoton-excited photon upconversion material, upconversion emission at any desired wavelength can be obtained.

[0100] The rare earth element is not particularly limited as long as it is a rare earth element capable of up-conversion luminescence, but generally, rare earth elements that form trivalent ions can be mentioned. Among them, it is preferable to use in combination 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).

[0101] The matrix material (base material) is one that supports rare earth elements, and is not particularly limited as long as it supports the rare earth elements in a state capable of up-conversion luminescence. It may be an organic substance that reacts with rare earth elements to form complexes, dendrimers, etc., or an inorganic substance. From the viewpoint of easily containing the rare earth elements in a luminescent state, it is preferably an inorganic substance.

[0102] Such an inorganic base material is preferably a material having transparency to excitation light from the viewpoint of luminous efficiency. Specifically, among others, halides such as fluorides and chlorides, oxides, sulfides, oxysulfides, etc. are preferably used. Examples of such halides include barium chloride (BaCl ２ ), lead chloride (PbCl ２ ), lead fluoride (PbF ２ ), cadmium fluoride (CdF ２ ), lanthanum fluoride (LaF ３ ), yttrium fluoride (YF ３ ), etc., but are not limited thereto. Examples of oxides include 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 ５Examples include, but are not limited to, these. A coating material may be formed around a multi-photon excitation type photon up-conversion material using a halide as a base material. As this coating material, oxides such as those listed above can be used.

[0103] Also, a core-shell type up-conversion material composed of core (NaYREF ４ ) / shell (NaYF ４ )(RE = rare earth element) can also be used.

[0104] The multi-photon excitation type photon up-conversion material can be produced by known methods, for example, gas evaporation methods including high-frequency plasma method, sputtering method, glass crystallization method, chemical precipitation method, reverse micelle method, sol-gel method and similar methods, precipitation methods including hydrothermal synthesis method and coprecipitation method, or spray method, etc. For the production method of the multi-photon excitation type photon up-conversion material, for example, the method described in JP-A-2006-117864 can be referred to. A commercially available product may be used as the multi-photon excitation type photon up-conversion material.

[0105] ・Other additives If desired, the curable functional expression paste of this embodiment may further contain other additives, for example, photosensitizers other than component (C), conductive fillers, stabilizers, radical polymerization inhibitors, anionic polymerization inhibitors, coupling agents, ion trap agents, leveling agents, antioxidants, defoaming agents, viscosity modifiers, flame retardants, colorants, plasticizers, solvents, etc., within a range not impairing the gist of this embodiment. The type and addition amount of each additive are as per conventional methods.

[0106] The curable function paste of this embodiment is preferably substantially free of liquid components such as water, solvents, and ionic liquids (excluding liquid components (A) to (D)) from the viewpoint of preventing reduced curing strength and adhesion due to photocuring, and preventing outgassing and bleeding. 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 curable function paste. Examples of solvents include common organic solvents 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 oil, terpineol, isobornyl acetate, etc.), and halogenated solvents (dichloromethane, chloroform, etc.).

[0107] In this embodiment, it is preferable that the curable functional paste is designed to produce a cured product in which the peak value of the loss coefficient tanδ in dynamic viscoelasticity measurement is 2.5 or less, and the absolute value of the slope of the line passing through two points, the peak value of tanδ and the tanδ value at a temperature of +20°C or -20°C from the peak temperature of tanδ, is greater than 0 and 0.125 or less. A cured product in which the peak value of the loss coefficient tanδ in dynamic viscoelasticity measurement and the slope of the line between the two points are within the above range has a low crosslinking density and / or uniform and flexible segments, allowing energy transfer between the photosensitizer and the light emitter without being limited by the curing progress of the curable functional paste, which can prolong the duration of triplet-triplet annihilation photon upconversion emission from the light emitter and increase the degree of curing. In the dynamic viscoelasticity measurement of the cured product, the peak value of the loss coefficient tanδ and the absolute value of the slope of the line passing through the peak value of tanδ and the tanδ value at a temperature of +20°C or -20°C from the peak temperature of tanδ can be adjusted, for example, by the type and amount of polymerizable compound and / or the type and amount of filler and thixotrope. The peak value of the loss coefficient tanδ in the dynamic viscoelasticity measurement of the cured product is preferably 2.5 or less, for example, it may be 0.01 to 2.5, preferably 0.05 to 2.5, more preferably 0.1 to 2.25, and even more preferably 0.15 to 2.0. By having the peak value of the loss coefficient tanδ within the above numerical range, it becomes easier to obtain a cured product with excellent adhesion, and the duration of triplet-triplet annihilation photon upconversion luminescence from the light emitter can be extended. The absolute value of the slope of the line passing through the peak value of tanδ and the tanδ value at a temperature of +20°C or -20°C from the peak temperature of tanδ is preferably 0.00008 to 0.125, for example, it may be 0.00010 to 0.125, preferably 0.0010 to 0.113, and more preferably 0.0030 to 0.100. By having the absolute value of the slope within the above numerical range, it becomes easier to obtain a cured product with excellent adhesion and crack resistance, and the duration of triplet-triplet annihilation photon upconversion emission from the light-emitting material can be extended. The peak temperature of tanδ of the cured product is preferably in the range of -40°C to 150°C.In one embodiment, the curable functional paste preferably yields a cured product having a storage modulus G' at 22°C ± 5°C, measured in dynamic viscoelasticity tests, of 0.000001 to 10.0 GPa. More preferably, the storage modulus G' of the cured product at 22°C ± 5°C, measured in dynamic viscoelasticity tests, is 0.00001 to 9.0 GPa, even more preferably 0.00001 to 8.0 GPa, and particularly preferably 0.00001 to 7.0 GPa. In one embodiment, the storage modulus G' of the cured product at 22°C ± 5°C, measured in dynamic viscoelasticity tests, is, for example, 0.0000001 to 3.0 GPa and 0.0000001 to 2.0 GPa. The storage modulus of the cured product can be adjusted, for example, by the type and amount of polymerizable compound and / or the type and amount of filler and thixotrope. In one embodiment, it is preferable that the product has no melting point in the temperature range of 25°C to 300°C. In this specification, dynamic viscoelasticity measurements of cured materials can be performed from -60°C using dynamic viscoelasticity measurement (DMA) by tensile method, in accordance with JIS C6481, with a heating rate of 3°C / min, a frequency of 10 Hz. The cured materials to be measured are those cured by irradiation with excitation light.

[0108] Furthermore, controlling the temperature of the curable function-emerging paste to an appropriate temperature can also help to prolong the duration of triplet-triplet annihilation photon upconversion luminescence from the light emitter. For example, the duration of photon upconversion luminescence can be prolonged by heating the curable function-emerging paste while irradiating it with light, by incorporating a light-to-heat conversion material (such as carbon black) into the curable function-emerging paste to raise the paste's temperature, or by utilizing the heat of polymerization.

[0109] The degree of curing of the cured product of the curable functional paste is preferably 50% or more, more preferably 60% or more, even more preferably 65% ​​or more, and particularly preferably 75% or more. When the above degree of curing is met, good adhesion and long-term reliability can be obtained. In this specification, the degree of curing can be determined by total internal reflection (ATR) measurement using an infrared spectrophotometer. More specifically, the measurement method is as follows. The degree of curing can be measured using an infrared spectrophotometer (Perkin Elmer Spectrum 3) equipped with an ATR stage. The ATR spectra of the paste before curing and the surface of the cured product after curing are obtained, respectively. The degree of curing is defined as the percentage change (%) in the ratio of the stretching vibration peak area of ​​the same functional group in the ATR spectrum of the surface of the cured product after curing, relative to the ratio of the stretching vibration peak area of ​​the functional group involved in the polymerization reaction in the ATR spectrum of the paste before curing. For example, if the functional group involved in the polymerization reaction is a (meth)acryloyl group, the C=C / C=O stretching vibration peak area ratio is calculated. If the functional groups involved in the polymerization reaction are a thiol group and a (meth)acryloyl group, the S-H / C=O stretching vibration area ratio is calculated. Furthermore, the area ratios of other functional groups involved in polymerization reactions can also be calculated.

[0110] The viscosity of the curable functional paste according to this embodiment at 22±5°C immediately after preparation is preferably 0.01 to 200 Pa·s. The viscosity can be adjusted as appropriate depending on the application and application location of the curable functional paste. The curable functional paste according to this embodiment is excellent for application to areas with complex shapes where UV light irradiation is difficult, and 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 with an E-type viscometer at a rotation speed of 10 rpm. There are no particular restrictions on the equipment, rotor, or measurement range used.

[0111] The curable functional paste of this embodiment can be a one-component curable functional paste contained in a single container, or a two-component (or multi-component) curable functional paste contained in two or more containers, depending on its application. In the case of a two-component (or multi-component) curable functional paste, the two (or multi-component) components are mixed at the time of use to form the curable functional paste in the intended use form. When a two-component (or multi-component) curable functional paste is used, components (A) to (D) and other optional components as needed can be selected in the same way as in the one-component type. Furthermore, when a two-component (or multi-component) curable functional paste is used, components (A) to (D) and other optional components as needed can be divided into two or multiple components in any way without particular restriction. When dividing into two or more liquids in any way, each liquid may contain one or more components selected from components (A) to (D) and other optional components as needed, or components (A) to (D) and other optional components as needed may be contained in one liquid, or there may be a liquid consisting only of components (A) to (D) and / or other optional components as needed. For example, when dividing into liquid A and liquid B, the division may be: liquid A: component (A) and component (B), liquid B: component (A), component (C) and component (D); liquid A: component (A), component (B) and component (C), liquid B: component (A) and component (D); liquid A: component (A), component (B) and component (D), liquid B: component (A) and component (C); or liquid A: component (A), component (C) and component (D), liquid B: component (B). If components (A) to (D) are contained in liquid A, liquid B may contain one or more components selected from components (A) to (D). In addition, components other than components (A) to (D) may be contained in both or either liquid A and liquid B in the above combination. If components (A) to (D) are contained in liquid A and other components are contained in liquid B, liquid A alone, or liquids A and B together, can be considered as the curable function-exhibiting paste of this embodiment. On the other hand, if components (A) to (D) are each contained in separate liquids, the respective liquids together can be considered as the curable function-exhibiting paste of this embodiment.Examples of cases where components (A) to (D) are each contained in separate liquids include, for example, a curable functional paste in which components (A) to (D) are divided into two or more containers, and more specifically, a kit composed of multiple liquids containing any of components (A) to (D).

[0112] The method for producing the curable functional paste of this embodiment is not particularly limited. For example, the curable functional paste of this embodiment can be obtained by introducing components (A) to (D), and optionally other optional components, simultaneously or separately into a suitable mixer, stirring and mixing them to form a homogeneous composition. The mixer is not particularly limited, but a Leikai mixer, Henschel mixer, three-roll mill, ball mill, planetary mixer, and bead mill, etc., equipped with a stirring device and a heating device, can be used. These devices may also be used in appropriate combinations.

[0113] In this embodiment, it is preferable that the curable functional paste contains an appropriate amount of oxygen. In the field of technology utilizing photon upconversion mechanisms, if the photosensitizer is decomposed, triplet-triplet energy cannot be transferred to the light emitter, and photon upconversion emission from the light emitter is not exhibited. Therefore, the decomposition of the photosensitizer should normally be avoided. On the other hand, if the photosensitizer is decomposed appropriately after or while triplet-triplet energy transfer to the light emitter is occurring, the light emitter receives energy transfer and emits light, and the incident light is no longer absorbed by the decomposed photosensitizer. As a result, the transmittance of incident light to the curable functional paste increases, and the incident light reaches deep into the curable functional paste. As a result, photon upconversion emission is exhibited at both the light-irradiated surface and the deep parts of the curable functional paste, the photopolymerization initiator is activated, polymerization of the polymerizable compound progresses, and a high curing depth is obtained. Methods for incorporating oxygen into the curable functional paste include, for example, handling the curable functional paste in the atmosphere, not subjecting each raw material of the curable functional paste and / or the manufactured curable functional paste to a degassing process and / or a reduced pressure process, or subjecting them to a light degassing process, and not including an oxygen scavenger in the curable functional paste. Examples of degassing processes include bubbling the object with an inert gas such as nitrogen or argon, heating, freeze-degassing, vacuum degassing, or any combination thereof. The oxygen content in the curable functional paste is preferably, for example, 0.1 to 10,000 ppm by mass, more preferably 1 to 1,000 ppm by mass, and even more preferably 5 to 1,000 ppm by mass.

[0114] The curable functional paste obtained in this way is cured by irradiation with long-wavelength light (e.g., over 500 nm), and curing is possible by light irradiation alone. Conventionally, UV-curable adhesives that have been used conventionally are generally cured by high-energy, short-wavelength light (e.g., 365 nm UV light). Therefore, if the adhesive contains fillers, etc., the penetration distance of light into the UV-curable adhesive is short with short-wavelength light irradiation, and curing does not proceed in areas where light cannot reach due to shielding materials, etc. In particular, regarding the latter, if we look at the relationship between the wavelength of the irradiated light and the penetration distance of the light in the silicon substrate, for example, if the shielding material is a silicon substrate, the penetration distance into the silicon substrate for ultraviolet light below 380 nm is several to tens of nm, while for visible light between 380 and 780 nm it is several hundred nm to several microns, and for infrared light above 780 nm it reaches tens of microns to the order of millimeters (for example, Optical Properties of Silicon [online], PVEducation,<https: / / www.pveducation.org / pvcdrom / materials / optical-properties-of-silicon> (See reference). Although the penetration distance of light into the curable functional paste during ultraviolet light irradiation is deeper than that of the silicon substrate, increasing the irradiation wavelength can be said to be a useful method for improving the degree of curing of the curable functional paste.

[0115] Photocuring of the curable functional paste is performed by irradiating the paste with light having a wavelength greater than 500 nm, for example, light in the range of 500 nm to 2000 nm. It is also desirable to use light near the wavelength absorbed by the photosensitizer in the wavelength range greater than 500 nm. This causes wavelength conversion of the light within the curable functional paste via the sensitizer and light emitter, resulting in photon upconversion emission from the light emitter at wavelengths of 500 nm or less, preferably 450 nm or less, more preferably 430 nm or less, and particularly preferably 400 nm or less, activating the photopolymerization initiator and curing the polymerizable compound. The wavelength of the irradiated light may be, for example, 525 nm, 532 nm, 980 nm, 1064 nm, or 1550 nm, but is not limited to these wavelengths. The irradiation intensity of the irradiated light is, for example, 1 mW / cm². ２ ~1000W / cm ２ This is possible. The cumulative irradiation dose of the irradiated light is 1 mJ / cm². ２ ~2000 J / cm ２ This is possible. The light source may be an LED, laser, LD module, or other coherent light source. Light irradiation can be either spot irradiation, which irradiates a local area, or area irradiation, which irradiates a wide area. The light irradiation process may be carried out under atmospheric conditions or under an inert gas atmosphere such as nitrogen. In one embodiment, light with a wavelength of 500 nm or less and light with a wavelength exceeding 500 nm may be irradiated simultaneously or sequentially to the curable function-developing paste. Once the surface of the curable function-developing paste is cured by irradiation with light with a wavelength of 500 nm or less, the light with a wavelength exceeding 500 nm, which is irradiated simultaneously or subsequently, penetrates into the interior (deep part) of the curable function-developing paste without being affected by oxygen in the atmospheric conditions, making it easier to achieve both surface curability and deep curability of the curable function-developing paste. Alternatively, by first irradiating with light with a wavelength exceeding 500 nm, the interior (deep part) of the resin composition is cured, and then by irradiating with light with a wavelength of 500 nm or less, the surface of the photocurable resin composition is cured, making it easier to achieve both surface curing and deep curing properties in the curable function paste.

[0116] The curable functional paste of this embodiment can be used, for example, as an adhesive, encapsulant, or coating agent, or as a raw material, for fixing, joining, or protecting semiconductor devices or electronic components, or the components that constitute them. In one embodiment, the curable functional paste of this embodiment can be cured by irradiation with light with a wavelength of more than 500 nm. In one embodiment, the curable functional paste of this embodiment can be used as an adhesive, encapsulant, or coating agent for semiconductor devices or electronic components.

[0117] [Adhesive, Sealant, or Coating Agent] Another embodiment of the present invention includes a curable functional paste according to 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, polyphthalamide, polybutylene terephthalate, polyimide, etc.), glass, ceramics, metals (e.g., copper, nickel, SUS, etc.), organic substrates (e.g., FR4, etc.), flexible printed circuit boards (FPC), etc., and can be used to fix, bond, or protect semiconductor devices or electronic components or the components that constitute them. Examples of semiconductor devices or electronic components include, but are not limited to, HDDs, semiconductor elements, sensor modules such as image sensor modules, other semiconductor modules, and integrated circuits. The adhesive, sealant, or coating agent according to this embodiment can be cured by irradiation with long-wavelength light (e.g., more than 500 nm), so it has high productivity and is suitable for use, for example, in the manufacture of semiconductor devices and electronic components.

[0118] [Cured product of a curable functional paste or adhesive, sealant or coating agent] Another embodiment of the present invention is a cured product obtained by curing the curable functional paste or adhesive, sealant or coating agent of the above embodiment. The peak value of the loss coefficient tanδ in the dynamic viscoelasticity measurement of the cured product is preferably 2.5 or less, for example, it may be 0.01 to 2.5, preferably 0.05 to 2.5, more preferably 0.1 to 2.25, and even more preferably 0.15 to 2.0. The absolute value of the slope of the line passing through the peak value of tanδ in the dynamic viscoelasticity measurement of the cured product and the tanδ value at a temperature of +20°C or -20°C from the peak temperature of tanδ is preferably greater than 0 and 0.125 or less, for example, it may be 0.0010 to 0.125, preferably 0.0020 to 0.113, and more preferably 0.0045 to 0.100. The peak temperature of tanδ of the cured product is preferably in the range of -40°C to 150°C. In one embodiment, the storage modulus G' of the cured product at 22°C ± 5°C in dynamic viscoelasticity measurement is preferably 0.000001 to 10.0 GPa, more preferably 0.00001 to 9.0 GPa, even more preferably 0.00001 to 8.0 GPa, and particularly preferably 0.00001 to 7.0 GPa. In another embodiment, the storage modulus G' is, for example, 0.0000001 to 3.0 GPa and 0.0000001 to 2.0 GPa. The degree of curing of the cured product is preferably 50% or more, more preferably 60% or more, even more preferably 65% ​​or more, and particularly preferably 75% or more.

[0119] [Semiconductor devices, electronic components] Another embodiment of the present invention includes a cured product of the above embodiment, and therefore these semiconductor devices or electronic components have high reliability. Here, "semiconductor device" refers to all devices that can function by utilizing semiconductor properties, and includes electronic components, semiconductor circuits, modules incorporating these, electronic equipment, etc. Examples of semiconductor devices or electronic components include, but are not limited to, HDDs, semiconductor elements, sensor modules such as image sensor modules, other semiconductor modules, and integrated circuits.

[0120] [Curing Method, Method for Manufacturing a Cured Product] Another aspect of the present invention is a method for manufacturing a cured product, comprising irradiating the curable functional paste of the above aspect, or the adhesive, sealant, or coating agent of the above aspect, with light having a wavelength greater than 500 nm. A further aspect of the present invention is a method for curing a curable functional paste, comprising irradiating the curable functional paste of the above aspect with light having a wavelength greater than 500 nm. By irradiating with light having a wavelength greater than 500 nm, for example, light in the range of wavelengths greater than 500 nm and less than or equal to 2000 nm, the photosensitizer and light emitter perform wavelength conversion of the light inside the curable functional paste, and the light emitter exhibits photon upconversion emission with a wavelength of 500 nm or less, preferably photon upconversion emission with a wavelength of 450 nm or less, more preferably photon upconversion emission with a wavelength of 430 nm or less, and particularly preferably photon upconversion emission with a wavelength of 400 nm or less, thereby activating the photopolymerization initiator and curing the polymerizable compound. The wavelength of the irradiated light in these methods may be, for example, 525 nm, 532 nm, 980 nm, 1064 nm, or 1550 nm, but is not limited to these wavelengths. Furthermore, it is desirable to use light near the wavelength absorbed by the photosensitizer in the wavelength range above 500 nm. The irradiation intensity of the irradiated light is, for example, 1 mW / cm². ２ ~1000W / cm ２ This is possible. The cumulative irradiation dose of the irradiated light is 1 mJ / cm². ２ ~2000 J / cm ２This is possible. The light source may be an LED, laser, LD module, or other coherent light source. Light irradiation can be either spot irradiation, which irradiates a local area, or area irradiation, which irradiates a wide area. The light irradiation process may be carried out under atmospheric conditions or under an inert gas atmosphere such as nitrogen. In one embodiment, light with a wavelength of 500 nm or less and light with a wavelength exceeding 500 nm may be irradiated simultaneously or sequentially to the curable function-developing paste. Once the surface of the curable function-developing paste is cured by irradiation with light with a wavelength of 500 nm or less, the light with a wavelength exceeding 500 nm, which is irradiated simultaneously or subsequently, penetrates into the interior (deep part) of the curable function-developing paste without being affected by oxygen in the atmospheric conditions, making it easier to achieve both surface curability and deep curability of the curable function-developing paste. Alternatively, by first irradiating with light with a wavelength exceeding 500 nm, the interior (deep part) of the resin composition is cured, and then by irradiating with light with a wavelength of 500 nm or less, the surface of the photocurable resin composition is cured, making it easier to achieve both surface curing and deep curing properties in the curable function paste.

[0121] [Bonding Method] Another aspect of the present invention is a method for bonding at least two components with a curable functional paste, the bonding method comprising the steps of: applying the curable functional paste 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 curable functional paste, or both thereof with light having a wavelength greater than 500 nm.

[0122] As a first step, the curable function-emerging paste according to the above embodiment is applied to at least one of at least two parts. The parts are preferably components constituting a semiconductor device or electronic component, such as semiconductor elements or substrates, but are not limited thereto. The material of the parts may be any of the following: general-purpose plastics (e.g., PE, PS, PP, etc.), engineering plastics (e.g., LCP (liquid crystal polymer), polyamide, polycarbonate, polyphthalamide, polybutylene terephthalate, polyimide, etc.), glass, ceramics, metals (e.g., copper, nickel, SUS), organic substrates (e.g., FR4, etc.), flexible printed circuit boards (FPC), etc. The method of applying the curable function-emerging paste is not particularly limited, and can be applied to a desired part of the part, such as a substrate, by known printing, dispensing, or coating methods. Examples of printing methods include, but are not limited to, inkjet printing, screen printing, lithographic printing, cardboard printing, metal printing, offset printing, gravure printing, flexographic printing, etc. Dispensing methods include, but are not limited to, methods using jet dispensers, air dispensers, etc. Coating methods include, but are not limited to, dip coating, spray coating, bar coating, gravure coating, reverse gravure coating, spin coating, etc.

[0123] Next, the component to which the curable function-developing paste has been applied is attached to the other component via the curable function-developing paste, or the component to which the curable function-developing paste has been applied is attached to the other component via the curable function-developing paste. Any known method of attachment may be used. If necessary, the components can be pressed together under load after attachment.

[0124] Next, at least one of the at least two components, the curable functional paste, or both thereof are irradiated with light having a wavelength greater than 500 nm, for example, light in the range of wavelengths between 500 nm and 2000 nm. This causes the photosensitizer and light emitter to undergo wavelength conversion within the curable functional paste, and the light emitter emits photon upconversion emission at wavelengths of 500 nm or less, preferably 450 nm or less, more preferably 430 nm or less, and particularly preferably 400 nm or less, activating the photopolymerization initiator, curing the polymerizable compound, and bonding the at least two components. The wavelength of the irradiated light may be, for example, 525 nm, 532 nm, 980 nm, 1064 nm, or 1550 nm, but is not limited to these wavelengths. Furthermore, it is desirable to use light near the wavelength absorbed by the photosensitizer in the wavelength range greater than 500 nm. The irradiation intensity of the irradiated light is, for example, 1 mW / cm². ２ ~1000W / cm ２ This is possible. The cumulative irradiation dose of the irradiated light is 1 mJ / cm². ２ ~2000 J / cm ２This is possible. The light source may be an LED, laser, LD module, or other coherent light source. Light irradiation can be either spot irradiation, which irradiates a local area, or area irradiation, which irradiates a wide area. The light irradiation process may be carried out under atmospheric conditions or under an inert gas atmosphere such as nitrogen. In one embodiment, light with a wavelength of 500 nm or less and light with a wavelength greater than 500 nm may be irradiated simultaneously or sequentially to the curable function-expressing paste. Once the surface of the curable function-expressing paste is cured by irradiation with light with a wavelength of 500 nm or less, the light with a wavelength greater than 500 nm, which is irradiated simultaneously or subsequently, penetrates into the interior (deep part) of the curable function-expressing paste without being affected by oxygen in the atmospheric conditions, making it easier to achieve both surface curability and deep curability of the curable function-expressing paste. Alternatively, by irradiating with light with a wavelength greater than 500 nm first, the interior (deep part) of the resin composition is cured, and then by irradiating with light with a wavelength of 500 nm or less, the surface of the photocurable resin composition is cured, making it easier to achieve both surface curability and deep curability of the curable function-expressing paste. Since the curable functional paste used in this embodiment can be cured even in the shaded areas of the component, the bonding method in this embodiment allows for light irradiation not only directly onto the curable functional paste but also through the component.

[0125] [Sealing Method] Furthermore, another aspect of the present invention is a method for sealing gaps between or within parts using a curable functional paste, the sealing method comprising the steps of applying or injecting the curable functional paste of the above aspect into the gaps between or within parts, and irradiating the curable functional paste with light having a wavelength greater than 500 nm. The parts and light irradiation are the same as those in the bonding method described above. As for the application or injection method, in addition to the application method in the bonding method described above, a potting method can be mentioned, but is not limited to these. Since the curable functional paste used in this aspect can achieve a high curing depth, the sealing method of this aspect can cure the curable functional paste located deep inside gaps where ultraviolet light is difficult to reach, and can seal them effectively.

[0126] [Coating Method] Furthermore, another aspect of the present invention is a method for coating the surface of an object with a curable functional paste, the method comprising the steps of applying the curable functional paste of the above aspect to the object, and irradiating the curable functional paste with light having a wavelength greater than 500 nm. The object may be a semiconductor device or electronic component, or a component that constitutes them. Examples of semiconductor devices or electronic components include, but are not limited to, HDDs, semiconductor elements, sensor modules such as image sensor modules, other semiconductor modules, and integrated circuits. Examples of components that constitute a semiconductor device or electronic component include, but are not limited to, semiconductor elements and substrates. The material of the component may be any of the following: general-purpose plastics (e.g., PE, PS, PP, etc.), engineering plastics (e.g., LCP (liquid crystal polymer), polyamide, polycarbonate, polyphthalamide, polybutylene terephthalate, polyimide, etc.), glass, ceramics, metals (e.g., copper, nickel, SUS), organic substrates (e.g., FR4, etc.), flexible printed circuit boards (FPC), etc. The application method is the same as that used in the bonding method. The light irradiation method is the same as that used in the bonding method.

[0127] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following examples, parts and % refer to parts by mass and mass%, respectively, unless otherwise specified.

[0128] [Preparation of Curable Functional Paste] Curable functional pastes for Examples 1 to 11 and the Comparative Example were prepared by mixing predetermined amounts of each component according to the formulations shown in Table 1. In Table 1, the amount of each component is expressed in mass %. The components used in the Examples and Comparative Example are as follows:

[0129] • (A) Polymerizable compounds (A-1): Dimethylol-tricyclodecane diacrylate (product name: Light Acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd., (meth)acryloyl equivalent: 152 g / eq) (A-2): Isodecyl acrylate (product name: IDAA, manufactured by Osaka Organic Chemical Industry Co., Ltd., (meth)acryloyl equivalent: 212 g / eq, Tg: -63℃) (A-3) Trimethylolpropane triacrylate (product name: TMPTA, manufactured by Osaka Organic Chemical Industry Co., Ltd., (meth)acryloyl equivalent: 99 g / eq) • (B) Photopolymerization initiator (B-1): 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)-butan-1-one (product name: Omnirad 379EG, IGM Resins) B.V. (Photoradical polymerization initiator) (C) Photosensitizer (C-1): Platinum(II) octaethylporphyrin (PtOEP) (Sigma-Aldrich Japan) (D) Luminescent material (D-1): Diphenylanthracene (DPA) (Tokyo Chemical Industries) The molar ratio of PtOEP:DPA used was 1:50.

[0130] In the examples and comparative examples, the properties of the curable function-exhibiting paste were measured as follows.

[0131] [Evaluation of Adhesion Strength of Curable Functional Paste] 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 curable functional paste was placed on a glass slide, and a test specimen was prepared by sandwiching it with another glass slide. Visible light irradiation was then performed. The visible light irradiation conditions were as follows: an LED light source (4-color LED light, manufactured by Alonefire) was used, with a height of 4 cm from the top surface of the glass slide, and visible light of wavelength: 532 nm, irradiation intensity: 10 mW / cm2, and continuous irradiation until the cumulative light amount reached 36 J / cm2. When peeling the glass slide from one side of the cured material of the test specimen, those that felt resistance were classified as having adhesive strength (indicated as "Yes" in the table), and those that did not feel resistance were classified as having no adhesive strength (indicated as "No" in the table).

[0132] [Measurement of Luminescence Duration of Curable Functional Paste] The curable functional pastes described in Examples 1 to 11 and Comparative Example 1 were prepared under atmospheric pressure and poured into PMMA semi-micro disposable cells (12.5 mm × 12.5 mm × 45 mm, manufactured by BRAND Corporation) at a rate of 1 mL or more. The cell was set in the rectangular cell holder of a fluorescence spectrophotometer RF-6000 (Shimadzu Corporation) so that the long side of the cell was parallel to the direction of propagation of the excitation light (approximately 10 mm). The excitation light wavelength was set to 532 nm (bandwidth ±10 nm), the fluorescence wavelength to 435 nm (bandwidth ±15 nm), and the sensitivity to Low. The luminescence intensity was measured over time from the start of excitation light irradiation. The time from the emission peak until the luminescence was halved is shown in the table. Since the measurement was completed at 300 seconds, cells where the luminescence did not halve for more than 300 seconds were marked as >300.

[0133] [Evaluation of the degree of curing of the curable functional paste] 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 curable functional paste was placed on a glass slide, and a test specimen was prepared by sandwiching it with another glass slide. The specimens were then irradiated with visible light and ultraviolet light. For visible light irradiation, an LED light source (4-color LED light, manufactured by Alonefire) was used, with a height of 4 cm from the top surface of the glass slide, wavelength: 532 nm, irradiation intensity: 10 mW / cm². ２ The accumulated light intensity is 36 J / cm². ２ The material was continuously irradiated until the curing process was complete. To measure the degree of curing of the curable functional paste, the area ratio of the functional group peaks was used by the total internal reflection (ATR) method. The ATR spectrum was measured using an infrared spectrophotometer (Perkin Elmer Spectrum 3) equipped with an ATR stage. The slide glass on the irradiated side of the test specimen was removed, and the ATR spectrum of the cured surface was obtained. The degree of curing was defined as the percentage change in the C=C / C=O stretching vibration peak area ratio in the ATR spectrum of the cured material after irradiation with excitation light, relative to the C=C / C=O stretching vibration peak area ratio in the ATR spectrum of the curable functional paste.

[0134] [Dynamic Viscoelasticity Measurement] Two glass plates were prepared by applying a release agent and drying them. A curing function-enhancing paste was applied to one plate, and after setting a gap so that the film thickness was approximately 250 μm, it was sandwiched between the other glass plates. An LED type 525 nm irradiation device was used to irradiate one side at 20 mW / cm². ２ The material was irradiated with excitation light (wavelength 525 nm) for 1 hour. This was processed into a 40 mm x 5 mm specimen to be used as a test piece for dynamic viscoelasticity measurement (DMA). Using a viscoelasticity measuring device (DMS6100, manufactured by Seiko Instruments Inc.), DMA measurements were performed under the following conditions: measurement mode: tension, heating rate: 3 °C / min, measurement frequency: 10 Hz. The peak value of tanδ, the absolute value of the slope of the line passing through the peak value of tanδ and the tanδ value at a temperature of +20 °C or -20 °C from the peak temperature of tanδ, and the storage modulus at 25 °C were determined. When determining the absolute value of the slope, the tanδ value at the temperature with the smaller value, i.e., the tanδ value at the temperature with the larger absolute value of the slope, was adopted. Furthermore, when determining the peak value of tanδ, if tanδ follows a broad curve, the center value of the region of maximum tanδ obtained was taken as the peak value of tanδ. The results are shown in Table 1. Note that "-" in the table indicates that the value was not measured.

[0135]

[0136] The disclosure of Japanese Patent Application No. 2025-008098 (filing date: January 20, 2025) is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted to be incorporated by reference.

Claims

1. A curable functional paste comprising (A) a polymerizable compound, (B) a photopolymerization initiator, (C) a photosensitizer, and (D) a light emitter, wherein (A) the polymerizable compound comprises at least one polymerizable compound with a functional group equivalent of 105 or more, (C) the photosensitizer is a compound that absorbs light with a wavelength greater than 500 nm and can cause triplet-triplet energy transfer to (D) the light emitter, and (D) the light emitter can exhibit photon upconversion emission with a wavelength of 500 nm or less.

2. The curable function paste according to claim 1, wherein the polymerizable compound (A) comprises at least one polymerizable compound having at least one aliphatic group selected from the group consisting of a polyalkylene oxide group, an alkyl group having 6 or more carbon atoms, an alkylene group having 6 or more carbon atoms, a group derived from an alicyclic diol, and a group derived from a sugar alcohol.

3. The curable function paste according to claim 1 or 2, wherein the polymerizable compound (A) comprises a curing agent selected from the group consisting of a 2-4 functional thiol curing agent, a 2-4 functional phenol curing agent, a 2-4 functional acid anhydride curing agent, and a 2-4 functional amine curing agent.

4. The curable function paste according to any one of claims 1 to 3, wherein the (B) photopolymerization initiator can be activated by light with a wavelength of 500 nm or less.

5. A curable function-emerging paste according to any one of claims 1 to 4, for use in curing by irradiation with light with a wavelength exceeding 500 nm.

6. A curable function-emerging paste according to any one of claims 1 to 5, used as an adhesive, encapsulant, or coating agent for semiconductor devices or electronic components.

7. An adhesive, sealant, or coating agent comprising a curable function-exhibiting paste according to any one of claims 1 to 6.

8. A cured product obtained by curing a curable function-exhibiting paste according to any one of claims 1 to 6, or an adhesive, sealant, or coating agent according to claim 7.

9. A semiconductor device or electronic component comprising the cured product described in claim 8.

10. Use of the curable function-exhibiting paste according to any one of claims 1 to 6 for curing by irradiation with light with a wavelength greater than 500 nm.

11. A method for producing a cured product, comprising irradiating a curable function-exhibiting paste according to any one of claims 1 to 6, or an adhesive, encapsulant, or coating agent according to claim 7, with light having a wavelength greater than 500 nm.

12. A method for curing a curable functional paste, comprising irradiating the curable functional paste according to any one of claims 1 to 6 with light having a wavelength greater than 500 nm.

13. A method for bonding at least two components using a curable functional paste, comprising the steps of: applying the curable functional paste described in 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 curable functional paste, or both thereof with light having a wavelength greater than 500 nm.

14. A method for sealing gaps between or within parts using a curable functional paste, comprising the steps of: applying or injecting a curable functional paste according to any one of claims 1 to 6 into the gap between or within parts; and irradiating the curable functional paste with light having a wavelength greater than 500 nm.

15. A method for coating the surface of an object with a curable functional paste, comprising the steps of: applying the curable functional paste described in any one of claims 1 to 6 to the object; and irradiating the curable functional paste with light having a wavelength greater than 500 nm.

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