Curable function-expressing paste, adhesive, sealing material, coating agent, cured product, semiconductor device, electronic component, and curing, adhering, sealing, and coating methods using curable function-expressing paste

Abstract

The present invention addresses the problem of providing: a curable function-expressing paste that excels in deep portion curability in a method for curing by irradiating with light; an adhesive, sealing material, or coating agent containing this curable function-expressing paste; a cured product of this curable function-expressing paste; a semiconductor device or electronic component containing this cured product; and a curing method, an adhering method, a sealing method, and a coating method in which this curable function-expressing paste is used.　Provided is a curable function-expressing paste comprising a polymerizable compound (A), a polymerization initiator (B), a photosensitizer (C), and a light emitter (D). The polymerization initiator (B) contains at least a photoacid generator (B1) that can be directly activated by light having a wavelength of 500 nm or less, a thermal acid generator (B2) that can be indirectly activated by light having a wavelength of 500 nm or less in a state of being present in the curable function-expressing paste, or a combination thereof. Also provided are: an adhesive, a sealing material, or a coating agent containing this curable function-expressing paste; a cured product of this curable function-expressing paste; a semiconductor device or electronic component containing this cured product; and a curing method, an adhering method, a sealing method, and a coating method in which this curable function-expressing paste is used.

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, or if the gap between components is narrow, areas may be created in the adhesive where the UV irradiation light does not reach. In such cases, these areas remain uncured, making it difficult to obtain the desired degree of curing. Therefore, this type of adhesive is used in applications where areas where UV irradiation light does not reach 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. Furthermore, in order to achieve high adhesive strength and sealing properties, the light irradiation curing method for these pastes requires that curing can occur not only on the light-irradiated surface but also deep within the paste.

[0005] Therefore, the object of the present invention is to provide a curable function-emphasizing paste that exhibits excellent deep curing properties in a light-irradiation curing method, 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.

[0006] The specific means for solving the above problems are as follows. The aspects of the present invention include the following curable function-expressing paste, adhesive, encapsulant or coating agent, cured product, semiconductor device or electronic component, method for manufacturing a cured product, method for curing a curable function-expressing paste, use of a curable function-expressing paste, bonding method, encapsulation method and coating method. (1) A curable function-expressing paste comprising (A) a polymerizable compound, (B) a polymerization initiator, (C) a photosensitizer, and (D) a light-emitting element, wherein the (B) polymerization initiator comprises at least (B1) a photoacid generator that can be directly activated by light with a wavelength of 500 nm or less, (B2) a thermoacid generator that can be indirectly activated by light with a wavelength of 500 nm or less while present in the curable function-expressing paste, or a combination thereof. (2) The curable functional paste according to (1), wherein the (C) photosensitizer is present in the curable functional paste such that it absorbs light with a wavelength greater than 500 nm, causes triplet-triplet energy transfer to the (D) light emitter, and is decomposed by the acid generated from the (B1) photoacid generator and / or the (B2) thermoacid generator. (3) The curable functional paste according to (1) or (2), wherein the (D) light emitter can exhibit photon upconversion emission with a wavelength of 500 nm or less. (4) The curable functional paste according to any one of (1) to (3), wherein the (B) polymerization initiator includes the (B1) photoacid generator. (5) The curable functional paste according to any one of (1) to (4), wherein the (B) polymerization initiator includes the (B2) thermoacid generator. (6) The curable function-expressing paste according to any one of (1) to (5), wherein the (B) polymerization initiator comprises (B1) a photoacid generator, (B3) a photoradical polymerization initiator, (B4) a photobase generator, or any combination thereof. (7) The curable function-expressing paste according to any one of (1) to (6), wherein the total amount of the (B1) photoacid generator and the (B2) thermoacid generator is 0.01 to 20 parts by mass per 100 parts by mass of the (A) polymerizable compound. (8) The curable function-expressing paste according to any one of (1) to (7), which yields a cured product that does not exhibit upconversion luminescence and / or downconversion luminescence upon excitation light.(9) A curable function-granting paste according to any one of (1) to (8) above, which, by photocuring, gives a cured product in which the absorption of the wavelength used for curing is attenuated. (10) A curable function-granting paste according to any one of (1) to (9) above, for use in curing by irradiation with light with a wavelength of more than 500 nm. (11) A curable function-granting paste according to any one of (1) to (10) above, used as an adhesive, encapsulant, or coating agent for semiconductor devices or electronic components. (12) An adhesive, encapsulant, or coating agent containing the curable function-granting paste according to any one of (1) to (11) above. (13) A cured product obtained by curing the curable function-granting paste according to any one of (1) to (11) above, or the adhesive, encapsulant, or coating agent according to (12) above. (14) A semiconductor device or electronic component containing the cured product according to (13) above. (15) Use of the curable function-granting paste described in any one of (1) to (11) above for curing by irradiation with light having a wavelength greater than 500 nm. (16) A method for producing a cured product, comprising irradiating the curable function-granting paste described in any one of (1) to (11) above, or the adhesive, sealant, or coating agent described in (12) above, with light having a wavelength greater than 500 nm. (17) A method for curing a curable function-granting paste, comprising irradiating the curable function-granting paste described in any one of (1) to (11) above with light having a wavelength greater than 500 nm. (18) A method for bonding at least two parts with a photocurable resin composition, comprising the steps of: applying the curable function-granting paste described in any one of (1) to (11) above to at least one of the at least two parts; and irradiating at least one of the at least two parts, the curable function-granting paste, or both thereof, with light having a wavelength greater than 500 nm. (19) A method for sealing gaps between or within parts with a curable functional paste, comprising the steps of applying or injecting a curable functional paste according to any one of items (1) to (11) above into the gap between or within parts, and irradiating the curable functional paste with light having a wavelength greater than 500 nm.(20) A method for coating the surface of an object with a curable functional paste, comprising the steps of applying a curable functional paste described in any one of (1) to (11) above to the object, and irradiating the curable functional paste with light having a wavelength greater than 500 nm.

[0007] According to aspects of the present invention, a curable function-emphasizing paste exhibiting excellent deep curing properties in a light-irradiation curing method is provided, as well as an adhesive, 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. Due to its excellent deep curing properties, in a light-irradiation curing method, for example, it is possible to cure even deep inside places such as gaps between parts, or to cure a spread-out curable function-emphasizing paste deep inside regardless of the direction of light irradiation.

[0008] 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.

[0009] [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 polymerization initiator, (C) a photosensitizer, and (D) a light emitter, wherein the (B) polymerization initiator comprises at least (B1) a photoacid generator that can be directly activated by light with a wavelength of 500 nm or less, (B2) a thermoacid generator that can be indirectly activated by light with a wavelength of 500 nm or less while present in the curable functional paste, or a combination thereof. According to this aspect, a curable functional paste with excellent deep curing properties in a light-irradiation curing method can be provided. Due to the excellent deep curing properties, in a light-irradiation curing method, for example, it is possible to cure even deep inside places such as gaps between parts, or to cure the entire spread curable functional paste deep inside regardless of the direction of light irradiation.

[0010] From the perspective of improving productivity and considering applications to heat-sensitive components, there is a demand for curable functional pastes such as adhesives and sealants that can be cured solely by light irradiation. The 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 cure 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. Furthermore, in order to achieve high adhesive strength and sealing properties, the curing method of adhesives and sealants that exhibit curable function requires that the paste can be cured not only on the light-irradiated surface but also deep within. In other words, it is necessary to achieve high deep curing properties of adhesives and sealants that exhibit curable function using a light-irradiation curing method. When the amount of photon upconversion material in the curable function paste was increased to obtain a high photon upconversion emission amount in order to investigate how to improve deep curing properties, the deep curing results were worse. This is thought to be because the absorption of incident light by the photon upconversion material was excessive at the irradiated surface of the paste, and the light did not reach the depths of the paste. As a result of further investigation, it was surprisingly found that by including an acid generator in the curable function paste, the decomposition of the photosensitizer was induced by the acid generated by the acid generator, and the deep curing properties were improved. In technologies 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 observed. Therefore, the decomposition of the photosensitizer should generally be avoided.On the other hand, after or while triplet-triplet energy transfer occurs to the light emitter, the photosensitizer is moderately decomposed, causing the light emitter to receive energy transfer and emit light, while the incident light is no longer absorbed by the decomposed photosensitizer. As a result, the transmittance of incident light to the curable function-exhibiting paste increases, allowing the incident light to reach deep into the curable function-exhibiting paste. Consequently, photon upconversion emission is observed at both the light-irradiated surface and the deep interior of the curable function-exhibiting paste, directly and / or indirectly activating the polymerization initiator, promoting polymerization of the polymerizable compound, and resulting in a high curing depth. Furthermore, if the polymerizable compound includes a cationic polymerizable compound, the acid generated from the acid generator not only induces the decomposition of the photosensitizer but also initiates polymerization of the cationic polymerizable compound, thus promoting polymerization. When the polymerizable compound includes a radical polymerizable compound and / or an anionic polymerizable compound, including a radical polymerization initiator and / or a base generator as polymerization initiators activates these, and the resulting radicals and / or bases initiate polymerization of the radical polymerizable compound and / or anionic polymerizable compound. This embodiment was completed based on this new finding.

[0011] (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 a reactive group 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) can be appropriately selected from radical polymerizable compounds, cationic polymerizable compounds, anionic polymerizable compounds, or any combination thereof, depending on the type of polymerization initiator (B) described later.

[0012] 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).

[0013] 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 and promoting 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 (B3) photoradical polymerization initiator described later, or may only require a small amount of it. In other words, the maleimide compound also acts as a photoradical polymerization initiator. In this specification, a curable functional paste containing a maleimide compound but not containing the (B3) photoradical polymerization initiator described later is considered to be an embodiment containing the (A) polymerizable compound and the (B3) photoradical polymerization 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.

[0014] 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.

[0015] When a low room-temperature modulus is required for the cured product of a curable functional paste, bismaleimide having hydrocarbon groups derived from dimer acid can be used. Such bismaleimides are described, for example, in Japanese Patent Application Publication No. 2015-193725. Examples of commercially available bismaleimides having hydrocarbon groups derived from 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.

[0016] 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.

[0017] 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 alone or in combination of two or more. Examples of polyfunctional (meth)acrylate compounds include di(meth)acrylate of tris(2-hydroxyethyl) isocyanurate, tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, or 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; bispheno Examples of (meth)acrylate compounds include, but are not limited to, bisphenol A di(meth)acrylate; bisphenol F di(meth)acrylate; alkylene oxide-modified bisphenol A di(meth)acrylate; alkylene oxide-modified bisphenol F di(meth)acrylate; dihydrocyclopentadiethyl (meth)acrylate; as well as polyester (meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, ditrimethylolpropane poly(meth)acrylate, polyurethane having two or more (meth)acryloyl groups in one molecule, polyester having two or more (meth)acryloyl groups in one molecule, phenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, etc. Other (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.Examples include, but are not limited to, ditrimethylolpropanetetraacrylate (product name: EBECRYL140) manufactured by Daicel Ornex Co., Ltd., polyester acrylate (product name: Aronics M7100) manufactured by Toagosei Co., Ltd., dimethylol-tricyclodecanediaacrylate (product name: Light Acrylate DCP-A) manufactured by Kyoeisha Chemical Co., Ltd., and neopentyl glycol-modified trimethylolpropanediaacrylate (product name: Kayarad R-604) manufactured by Nippon Kayaku Co., Ltd.

[0018] 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.

[0019] 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 etherphenol resin (Gun-ei Chemical Examples include, but are not limited to, the FTC-AE series manufactured by Kogyo Co., Ltd., polyfunctional allylphenol resins (FATC series manufactured by Gun-ei Chemical Industry Co., Ltd.), allyl cyanurate derivatives (e.g., MA-DGIC, DAMGIC, MeDAIC, 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.

[0020] (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.

[0021] 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. 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. Also, ester residues composed of substituted hydrocarbon groups such as alkoxyalkyl groups and trialkylsilylalkyl groups can be used. Examples of the cyanoacrylate compound include alkyl and cycloalkyl cyanoacrylates such as methyl cyanoacrylate, ethyl cyanoacrylate, propyl cyanoacrylate, butyl cyanoacrylate, and cyclohexyl cyanoacrylate; alkenyl and cycloalkenyl cyanoacrylates such as allyl cyanoacrylate, methallyl cyanoacrylate, and cyclohexenyl cyanoacrylate; alkynyl cyanoacrylates such as propangyl cyanoacrylate; aryl cyanoacrylates such as phenyl cyanoacrylate and toluyl cyanoacrylate; methoxyethyl cyanoacrylate, ethoxyethyl cyanoacrylate, furfuryl cyanoacrylate, and trimethylsilylmethyl cyanoacrylate, trimethylsilylethyl cyanoacrylate, trimethylsilylpropyl cyanoacrylate, dimethylvinylsilylmethyl cyanoacrylate, etc. containing a hetero atom or silicon, but are not limited thereto. These may be used alone or in combination of two or more.

[0022] 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.

[0023] 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.

[0024] 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.

[0025] In a mixture of a compound having an unsaturated double bond and a thiol compound, the thiol compound is a compound containing at least one thiol group, and this thiol group can undergo a radical addition reaction (en-thiol reaction) with the unsaturated double bond of the compound having the unsaturated double bond. 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.

[0026] Any one radical polymerizable compound may be used, or two or more may be used in combination.

[0027] 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.

[0028] 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.

[0029] In this specification, a compound having an oxetanyl group is a compound having at least one oxetane ring (e.g., a 3-oxetanyl group) in 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.

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

[0031] 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, alkylene oxide-modified bisphenol A epoxy, alkylene oxide-modified bisphenol F epoxy, lauryl alcohol polyethylene glycol glycidyl ether, diglycidyl ether of alicyclic diols, diglycidyl ether of alkylene oxide adducts of alicyclic diols, bis[1-ethyl(3-oxyxet] 4,4'-bis[3-ethyl-(3-oxetanyl)methoxymethyl] oxymethyl ether (also known as (3-ethyl-3-(3-ethyloxetanyl-3-yl)methoxymethyl) oxymethyl oxymethyl ether), xylylene bisoxymethyl oxymethyl ether, 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-hydroxymethyl oxymethyl oxymethyl ether, 2 - Ethylhexyl oxetane, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-[(2-ethylhexyloxy)methyl]oxetane, 3-ethyl-3-(4-hydroxybutyl)oxymethyl oxetane, 3-ethyl-3-phenoxymethyl oxetane, 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.

[0032] 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 and 8400 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.

[0033] Any one cationic polymerizable compound may be used, or two or more may be used in combination.

[0034] 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.

[0035] The thiol compound mentioned above can be used as the thiol-based curing agent.

[0036] 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.

[0037] 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.

[0038] 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.).

[0039] (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.

[0040] 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.

[0041] 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).

[0042] (B) Polymerization initiator The curable function-exhibiting paste of this embodiment includes (B) a polymerization initiator (hereinafter also referred to as "component (B)"). In this embodiment, the polymerization initiator (B) includes at least (B1) a photoacid generator that can be directly activated by light with a wavelength of 500 nm or less, (B2) a thermoacid generator that can be indirectly activated by light with a wavelength of 500 nm or less while present in the curable function-exhibiting paste, or a combination thereof.

[0043] (B1) Photoacid Generator In this specification, (B1) photoacid generator is a photoacid generator that can be directly activated by light with a wavelength of 500 nm or less, and absorbs light with a wavelength of 500 nm or less to generate acid as an active species. In this embodiment, the photoacid generator can be activated by light with a wavelength of 500 nm or less, in particular by photon upconversion emission with a wavelength of 500 nm or less, as shown by the (D) emitter described later, and can generate acid as an active species. The (B1) photoacid generator is more preferably activated by light with a wavelength of 450 nm or less, even more preferably by light with a wavelength of 440 nm or less, and particularly preferably by light with a wavelength of 430 nm or less. By matching the absorption characteristics of the (B1) photoacid generator with the wavelength of light produced by the (D) emitter, the efficiency of the polymerization reaction can be increased. The acid generated from the photoacid generator promotes the polymerization of cationic polymerizable compounds (if present) and induces the decomposition of the (C) photosensitizer described below. This increases the transmittance of incident light to the curable function-expressing paste, allowing the incident light to reach deeper into the paste. As a result, photon upconversion emission is observed at both the light-irradiated surface and the deeper parts of the curable function-expressing paste, activating the polymerization initiator and promoting the polymerization of polymerizable compounds, resulting in a high curing depth. Furthermore, the decomposition of the (C) photosensitizer suppresses unintended upconversion emission and / or downconversion emission from the resulting cured product. If the cured product of the curable function-expressing paste contains undecomposed photosensitizer, irradiating the cured product with excitation light may cause upconversion emission and / or downconversion emission from the cured product. For example, when optical signals are used in semiconductor devices or electronic components, upconversion emission and / or downconversion emission from the cured product may adversely affect the processing of the optical signals. Therefore, in one embodiment, it is preferable that the curable function-expressing paste yields a cured product that does not exhibit upconversion luminescence and / or downconversion luminescence upon excitation light. Furthermore, it is preferable that the curable function-expressing paste yields a cured product in which the absorption of the wavelength used for curing is attenuated upon photocuring.Various compounds described in Japanese Patent Publication No. 2022-080366 can be used as the photoacid generator, and are not particularly limited. A preferred photoacid 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.

[0044] Examples of iodonium cations include iodonium ions such as diphenyliodonium, di-p-tolyliodonium, bis(4-dodecylphenyl)iodonium, bis(4-methoxyphenyl)iodonium, (4-octyloxyphenyl)phenyliodonium, bis(4-decyloxy)phenyliodonium, 4-(2-hydroxytetradecyloxy)phenylphenyliodonium, 4-isopropylphenyl(p-tolyl)iodonium, and 4-isobutylphenyl(p-tolyl)iodonium.

[0045] Examples of sulfonium ions include triphenylsulfonium, tri-p-tolylsulfonium, tri-o-tolylsulfonium, tris(4-methoxyphenyl)sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium, tris(4-fluorophenyl)sulfonium, tri-1-naphthylsulfonium, tri-2-naphthylsulfonium, tris(4-hydroxyphenyl)sulfonium, 4-(phenylthio)phenyldiphenylsulfonium, 4-(p-tolylthio)phenyldi-p-tolylsulfonium, 4-(4-methoxyphenylthio)phenylbis(4-methoxyphenyl)sulfonium, 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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.).

[0050] (B1) Any one type of photoacid generator may be used, or two or more types may be used in combination.

[0051] The content of (B1) photoacid generator in the curable function paste is preferably 0.01 to 30 parts by mass, more preferably 0.05 to 25 parts by mass, and even more preferably 0.1 to 20 parts by mass, per 100 parts by mass of (A) polymerizable compound.

[0052] (B2) Thermal Acid Generator In this specification, (B2) thermal acid generator is a thermal acid generator that can be indirectly activated by light with a wavelength of 500 nm or less while present in the curable function-expressing paste. "(B2) thermal acid generator can be indirectly activated by light with a wavelength of 500 nm or less while present in the curable function-expressing paste" means that the heat generated by the curing reaction of the curable function-expressing paste initiated by a photopolymerization initiator that is directly activated by light with a wavelength of 500 nm or less, particularly by photon upconversion emission with a wavelength of 500 nm or less as shown by the (D) emitter described later, can generate an acid (cation) as an active species. The acid generated from the thermal acid generator promotes polymerization of cationic polymerizable compounds (if present) and induces the decomposition of the (C) photosensitizer described later, increasing the transmittance of incident light to the curable function-expressing paste so that the incident light can reach deep into the curable function-expressing paste. As a result, photon upconversion emission is exhibited at both the light-irradiated surface and the deeper parts of the curable function-expressing paste, activating the polymerization initiator and promoting the polymerization of the polymerizable compound, thereby obtaining a high curing depth. In addition, (C) decomposition of the photosensitizer suppresses unintended upconversion emission and / or downconversion emission from the resulting cured product. If the cured product of the curable function-expressing paste contains an undecomposed photosensitizer, irradiating the cured product with excitation light may cause upconversion emission and / or downconversion emission from the cured product. For example, when optical signals are used in semiconductor devices or electronic components, upconversion emission and / or downconversion emission from the cured product may adversely affect the processing of the optical signals. Therefore, in some embodiments, it is preferable that the curable function-expressing paste provides a cured product that does not exhibit upconversion emission and / or downconversion emission when excited with excitation light. It is also preferable that the curable function-expressing paste provides a cured product in which the absorption of the wavelength used for curing is attenuated by photocuring.A photopolymerization initiator that can be directly activated by light with a wavelength of 500 nm or less and initiate the curing reaction of a curable functional paste can be appropriately selected from (B1) a photoacid generator, (B3) a photoradical polymerization initiator, (B4) a photobase generator, or any combination thereof. In this embodiment, (B2) a thermoacid generator is included in the curable functional paste in combination with (B1) a photoacid generator, (B3) a photoradical polymerization initiator, (B4) a photobase generator, or any combination thereof. BF is used as the (B2) thermoacid generator. 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. １Various 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.

[0053] The content of (B2) the thermal acid generator in the curable function paste is preferably 0.01 to 30 parts by mass, more preferably 0.05 to 25 parts by mass, and even more preferably 0.1 to 20 parts by mass, per 100 parts by mass of (A) the polymerizable compound.

[0054] (B3) Photoradical polymerization initiator In this embodiment, the (B) polymerization initiator may include the (B3) photoradical polymerization initiator. A photoradical polymerization initiator absorbs light and generates radicals as active species, thereby promoting the polymerization of a radically polymerizable compound. The (B3) photoradical polymerization initiator is preferably a photoradical polymerization initiator that can be activated by light with a wavelength of 500 nm or less, and can be activated by photon upconversion emission with a wavelength of 500 nm or less, as shown by the (D) light emitter described later. The (B3) photoradical polymerization initiator is more preferably activated by photon upconversion emission with a wavelength of 450 nm or less, even more preferably activated by photon upconversion emission with a wavelength of 440 nm or less, and particularly preferably activated by photon upconversion emission with a wavelength of 430 nm or less. By matching the absorption characteristics of the (B3) photoradical polymerization initiator with the wavelength of light produced by the (D) light emitter, the efficiency of the polymerization reaction can be increased. 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.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] 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).

[0059] 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.

[0060] (B3) Any one type of photoradical polymerization initiator may be used, or two or more types may be used in combination.

[0061] The content of (B3) 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 (A) polymerizable compound, from the viewpoint of photoirradiation reactivity.

[0062] (B4) Photobase Generator In this embodiment, (B) polymerization initiator may include (B4) photobase generator. A photobase generator absorbs light and generates anions as active species, thereby promoting the polymerization of anionic polymerizable compounds. Preferably, the (B4) photobase generator is a photobase generator that can be activated by light with a wavelength of 500 nm or less, and can be activated by photon upconversion emission with a wavelength of 500 nm or less, as shown by the (D) light emitter described later. More preferably, the (B4) photobase generator is activated by photon upconversion emission with a wavelength of 450 nm or less, even more preferably by photon upconversion emission with a wavelength of 440 nm or less, and particularly preferably by photon upconversion emission with a wavelength of 430 nm or less. By matching the absorption characteristics of the (B4) photobase generator with the wavelength of light produced by the (D) light emitter, the efficiency of the polymerization reaction can be increased. 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.

[0063] (B4) Any one type of photobase generator may be used, or two or more types may be used in combination.

[0064] The content of (B4) 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 (A) polymerizable compound.

[0065] (B5) Thermal base generator In this embodiment, (B) polymerization initiator may include (B5) thermal base generator. A thermal base generator is a compound that generates a base (anion) as an active species when heated, and is activated by the heat generated by the polymerization reaction initiated by the photopolymerization initiator, thereby promoting the polymerization of anionic polymerizable compounds.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] 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.).

[0070] A capillary-type 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 capillary-type thermal latent curing catalyst is "NISSOCURE TIC-188" (product name of Nippon Soda Co., Ltd.).

[0071] (B5) Any one type of thermal base generator may be used, or two or more types may be used in combination.

[0072] If a thermal base generator is included, the content of (B5) thermal base 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 (A) polymerizable compound.

[0073] (B6) Thermal radical polymerization initiator In this embodiment, (B) polymerization initiator may include (B6) thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals as active species when heated, and is activated by the heat generated by the polymerization reaction initiated by the photopolymerization initiator, thereby promoting the polymerization of radical polymerizable compounds.

[0074] 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.

[0075] (B6) Any one of the thermal radical polymerization initiators may be used, or two or more may be used in combination.

[0076] If a thermal radical polymerization initiator is included, the content of (B6) thermal radical 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 (A) polymerizable compound.

[0077] (B) In a curable functional paste of this embodiment in which the polymerization initiator comprises (B1) a photoacid generator and / or (B2) a thermal acid generator, (B) the polymerization initiator may include (B1) a photoacid generator, (B3) a photoradical polymerization initiator, (B4) a photobase generator, or any combination thereof, depending on the type of polymerizable compound (A) used. Furthermore, (B) the polymerization initiator may also include (B5) a thermal base generator and (B6) a thermal radical polymerization initiator, depending on the type of polymerizable compound (A) used.

[0078] (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.

[0079] 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.

[0080] 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.

[0081] (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.

[0082] 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 = 1:25 to 1:2000. In one embodiment, the molar ratio of photosensitizer to light emitter is photosensitizer:light emitter = 1:50 to 1:2000. In one embodiment, the molar ratio of the photosensitizer to the light emitter is photosensitizer:light emitter = 1:25 to 1:400. By appropriately selecting the combination of the photosensitizer and the light emitter, and the molar ratio, the photon upconversion emission emitted from the light emitter can be adjusted to include light with a wavelength of 500 nm or less when irradiated with light with a wavelength exceeding 500 nm.

[0083] 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).

[0084] In this embodiment, it is preferable that the photosensitizer is present in the curable function-expressing paste under conditions that it absorbs light with a wavelength greater than 500 nm, causing triplet-triplet energy transfer to the light emitter, and that its decomposition is induced by the acid generated from (B1) the photoacid generator and / or (B2) the thermoacid generator. Such conditions can be controlled, for example, by setting the amount of (B1) the photoacid generator and / or (B2) the thermoacid generator, the amount of (C) the photosensitizer, etc. in the curable function-expressing paste to a specific range. Since the acid generated from (B1) the photoacid generator and / or (B2) the thermoacid generator is a strong acid, it easily induces the decomposition of the photosensitizer. If the photosensitizer is decomposed by the acid before triplet-triplet energy transfer to the light emitter occurs, photon upconversion emission from the light emitter will not be observed. On the other hand, if the photosensitizer is not decomposed, the absorption of incident light by the photosensitizer becomes excessive at the irradiated surface of the curable function-expressing paste, preventing the incident light from reaching the depths of the curable function-expressing paste. As a result, photon upconversion emission is not observed in the depths of the curable function-expressing paste, and a high curing depth cannot be obtained. In technologies utilizing photon upconversion mechanisms, if the photosensitizer is decomposed, triplet-triplet energy cannot be transferred to the emitter, and photon upconversion emission from the emitter is not observed. Therefore, the decomposition of the photosensitizer should normally be avoided. However, if the photosensitizer is moderately decomposed after or while triplet-triplet energy transfer to the emitter is occurring, the 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 function-expressing paste increases, and the incident light reaches the depths of the curable function-expressing paste. As a result, photon upconversion emission is observed on both the light-irradiated surface and the deeper parts of the curable function-expressing paste, directly and / or indirectly activating the polymerization initiator, promoting polymerization of the polymerizable compound, and resulting in a high curing depth. In one embodiment, the total amount of (B1) photoacid generator and (B2) thermoacid generator is preferably 0.01 to 20 parts by mass, and more preferably 0.01 to 18 parts by mass, per 100 parts by mass of (A) polymerizable compound.In one embodiment, the total amount of (B1) photoacid generator and (B2) thermoacid generator is preferably 0.1 to 50,000 parts by mass, more preferably 0.5 to 30,000 parts by mass, and even more preferably 1.0 to 27,000 parts by mass, per 1 part by mass of (C) photosensitizer. In another embodiment, the total amount of (B1) photoacid generator and (B2) thermoacid generator is preferably 1 mol to 30,000 mol, more preferably 3 mol to 30,000 mol, even more preferably 3 mol to 25,000 mol, particularly preferably 7 mol to 20,000 mol, and most preferably 10 mol to 15,000 mol, per 1 part by mass of (C) photosensitizer. Whether or not "the photosensitizer is present in the curable functional paste such that its decomposition is induced by the acid generated from (B1) the photoacid generator and / or (B2) the thermoacid generator" can be confirmed, for example, by (1) the transmittance of incident light with a wavelength greater than 500 nm to the paste increasing over time, (2) the color of the curable functional paste fading upon irradiation with light with a wavelength greater than 500 nm, or (3) the cured product of the curable functional paste cured by irradiation with light with a wavelength greater than 500 nm does not exhibit upconversion emission and / or downconversion emission, or (4) the absorption of the wavelength used for curing is attenuated in the cured product of the curable functional paste cured by irradiation with light with a wavelength greater than 500 nm, or any combination thereof.

[0085] The presence of an appropriate amount of oxygen in the curable function-developing paste can help the photosensitizer to be appropriately decomposed by the acid generated from (B1) the photoacid generator and / or (B2) the thermoacid generator. Methods for including oxygen in the curable function-developing paste include, for example, handling the curable function-developing paste in the atmosphere, not subjecting each raw material of the curable function-developing paste and / or the manufactured curable function-developing paste to a degassing process and / or a reduced pressure process, or subjecting it to a light process, and not including an oxygen scavenger in the curable function-developing paste. Examples of degassing processes include bubbling the object with an inert gas such as nitrogen or argon, a heating process, a freeze-degassing process, a vacuum degassing process, or any combination thereof. The oxygen content in the curable function-developing 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.

[0086] 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.

[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 quiviate is included, the quiviate 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] As the rare earth element, there is no particular limitation as long as it is a rare earth element capable of up-conversion luminescence, but generally, rare earth elements that become 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 there is no particular limitation as long as it supports the rare earth elements in a state where up-conversion luminescence is possible. It may be an organic substance that reacts with the rare earth element to form a complex, dendrimer, etc., or an inorganic substance. From the viewpoint of easily containing the rare earth element in a luminescent state, it is preferably an inorganic substance.

[0102] As such an inorganic base material, a material having transparency to excitation light is preferable 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, the above. A coating material may be formed around a multi-photon excitation type photon up-conversion material having 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 a 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 manufactured 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 manufacturing 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] The viscosity of the curable functional paste according to this embodiment at 22±5°C immediately after preparation is preferably 0.01 to 100 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.

[0108] 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).

[0109] The method for producing the curable functional paste of this embodiment is not particularly limited. For example, components (A) to (D), and other optional components as needed, can be introduced simultaneously or separately into a suitable mixer, stirred and mixed to obtain a homogeneous composition, thereby obtaining the curable functional paste of this embodiment. 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. In one embodiment, the curable functional paste may be subjected to a degassing treatment and / or a reduced-pressure treatment to remove oxygen from the curable functional paste. In one embodiment, from the viewpoint of adjusting the reactivity of the curable functional paste, oxygen may be optionally included in the curable functional paste by not subjecting each raw material of the curable functional paste and / or the manufactured curable functional paste to the degassing and / or reduced-pressure treatment, or by subjecting it only lightly.

[0110] 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, for example, if we look at the relationship between the wavelength of the irradiated light and the penetration distance of the light on the silicon substrate, ultraviolet light below 380 nm penetrates the silicon substrate at a distance of several to tens of nanometers, while visible light between 380 and 780 nm penetrates at a distance of several hundred nanometers to several micrometers, and infrared light above 780 nm penetrates at a distance of tens of micrometers to the order of millimeters (e.g., 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 increasing the curing depth of the curable functional paste.

[0111] 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 ２This is possible. Depending on the desired degree of hardening, the integrated irradiation amount and irradiation intensity of the irradiation light can be adjusted as appropriate. 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 with light, or area irradiation, which irradiates a wide area with light. The light irradiation process may be carried out under atmospheric conditions or under an inert gas atmosphere such as nitrogen. In one embodiment, the hardening function-expressing paste may be irradiated with light with a wavelength of 500 nm or less and light with a wavelength exceeding 500 nm simultaneously or sequentially. Once the surface of the hardening function-expressing paste is hardened 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 hardening function-expressing paste without being affected by oxygen in the atmospheric conditions, making it easier to achieve both surface hardening and deep hardening of the hardening function-expressing 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.

[0112] 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.

[0113] When a curable functional paste is photocured as described above, if the resulting cured product contains an undegraded photosensitizer, irradiating the cured product with excitation light may cause upconversion emission and / or downconversion emission from the cured product. For example, when optical signals are used in semiconductor devices or electronic components, the upconversion emission and / or downconversion emission from the cured product may adversely affect the processing of the optical signals. Therefore, it is preferable that the curable functional paste provides a cured product that does not exhibit upconversion emission and / or downconversion emission when excited with light. Furthermore, it is preferable that the curable functional paste provides a cured product in which the absorption of the wavelength used for curing is attenuated by photocuring.

[0114] [Adhesives, encapsulants, or coatings] Another embodiment of the present invention includes a curable functional paste according to the above embodiment. This adhesive, encapsulant, or coating 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, encapsulant, or coating according to this embodiment can be cured by irradiation with long-wavelength light (e.g., more than 500 nm) and has excellent deep curing properties, resulting in high productivity and reliability, and is suitable for use, for example, in the manufacture of semiconductor devices and electronic components. For example, the adhesive, sealant, or coating agent of this embodiment can harden even in places such as gaps between parts. Also, for example, a spread adhesive, sealant, or coating agent can harden completely, regardless of the direction of light irradiation. Furthermore, for example, the adhesive, sealant, or coating agent of this embodiment can harden even if there are obstructions.

[0115] [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. In one embodiment, the cured product does not exhibit upconversion emission and / or downconversion emission when excited by excitation light. In one embodiment, the absorption of the wavelength used for curing in the cured product is attenuated compared to the absorption of the same wavelength in the curable functional paste before curing.

[0116] [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.

[0117] [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. Depending on the desired degree of hardening, the integrated irradiation amount and irradiation intensity of the irradiation light can be adjusted as appropriate. 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 with light, or area irradiation, which irradiates a wide area with light. The light irradiation process may be carried out under atmospheric conditions or under an inert gas atmosphere such as nitrogen. In one embodiment, the hardening function-expressing paste may be irradiated with light with a wavelength of 500 nm or less and light with a wavelength exceeding 500 nm simultaneously or sequentially. Once the surface of the hardening function-expressing paste is hardened 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 hardening function-expressing paste without being affected by oxygen in the atmospheric conditions, making it easier to achieve both surface hardening and deep hardening of the hardening function-expressing 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.

[0118] [Bonding Method] Another aspect of the present invention is a method for bonding at least two components using 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.

[0119] 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.

[0120] 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.

[0121] 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 cumulative irradiation amount and irradiation intensity of the irradiation light can be adjusted as appropriate according to the desired degree of curing. In this embodiment, either spot irradiation, which irradiates a local area with light, or area irradiation, which irradiates a wide area with light, can be performed. 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 to the curable function-expressing paste simultaneously or sequentially. 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 exceeding 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 exceeding 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. The curable functional paste used in this embodiment exhibits excellent deep curing properties and can cure even in gaps between parts and in shadowed areas of parts. Therefore, in the bonding method of this embodiment, light can be irradiated not only directly onto the curable functional paste but also through the parts. Furthermore, because the curable functional paste used in this embodiment exhibits excellent deep curing properties and can cure the entire spread of the curable functional paste to its depths regardless of the direction of light irradiation, light can be irradiated onto the object from any direction in the bonding method of this embodiment.

[0122] [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. The curable functional paste used in this aspect provides a high curing depth, so in the sealing method of this aspect, the curable functional paste located deep inside gaps where ultraviolet light is difficult to reach can be cured and sealed effectively. In addition, the curable functional paste used in this aspect has excellent deep curing properties, and the spread curable functional paste can be cured all the way to the back regardless of the direction of light irradiation, so in the sealing method of this aspect, light irradiation can be performed on the target object from any direction.

[0123] [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.), ceramics, or metals (e.g., copper, nickel, SUS), organic substrates (e.g., FR4, etc.), flexible printed circuit boards (FPC), etc. The coating method is the same as that in the bonding method described above. The light irradiation method is the same as that used in the bonding method described above.

[0124] 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.

[0125] [Preparation of Curable Functional Paste] Curable functional pastes for Examples 1-12, Comparative Examples 1-2, and Reference Examples 1-2 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, Comparative Examples, and Reference Examples are as follows.

[0126] • (A) Polymerizable compounds (A-1): Hydrogenated BisA type epoxy resin (Product name: YX8000, manufactured by Mitsubishi Chemical Corporation) (A-2): Polypropylene oxide modified bisphenol A type epoxy resin (Product name: AER9000, manufactured by Asahi Kasei Corporation) (A-3): Monofunctional epoxy compound (Product name: Adekaglycilol® ED-509S, manufactured by ADEKA Corporation) (A-4): 3,4-Epoxycyclohexylmethyl-3,4-Epoxycyclohexanecarboxylate (Product name: Celoxide® 2021P, manufactured by Daicel Corporation, alicyclic epoxy compound) (A-5): Oxetane resin (Product name: OXT-221, manufactured by Toagosei Co., Ltd.) (A-6): Dimethylol-tricyclodecanediaacrylate (Product name: Light acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd.) • (B) Polymerization initiators (B1-1): Sulfonium, tris[4-[(4-acetylphenyl)thio]phenyl]-,tetrakis(2,3,4,5,6-pentafluorophenyl) borate (product name: Omnirad 290, manufactured by IGM Resins B.V., photoacid generator) (B1-2): 4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl) borate (product name: Bluesil® PI2074 (manufactured by ELKEM SILICONES, photoacid generator) (B1-3): Iodonium salt-based photo / thermal acid generator (product name: IK-1FG, manufactured by Sunapro Co., Ltd.) (B2-1): Dimethylphenyl(4-methoxybenzyl)ammonium tetrakis(pentafluorophenyl) borate (product name: CXC1821, King (Manufactured by Industries, a thermal acid generator) (B3-1): 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)-butan-1-one (product name: Omnirad 379EG, manufactured by IGM Resins B.V., a photoradical polymerization initiator) (B3-2): bis(2,4,6-Trimethylbenzoyl)-phenylphosphine oxide (product name: Omnirad 819, manufactured by IGM Resins B.V.) • (C) Photosensitizer (C-1): Platinum(II) octaethylporphyrin (PtOEP) (manufactured by Sigma-Aldrich Japan) (C-2): Zinc(II) octaethylporphyrin (ZnOEP) (manufactured by Sigma-Aldrich Japan) • (D) Luminescent material (D-1): Diphenylanthracene (DPA) (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0127] In the examples, comparative examples, and reference examples, the properties of the curable function-exhibiting paste were measured as follows.

[0128] [Evaluation of curability and curing depth of curable functional pastes] In a dark place at a temperature of 22°C ± 5°C and a humidity of 50% ± 10%, the curable functional pastes of the examples, comparative examples, and reference examples were applied to the gaps between gap tapes of LCP substrates, with gap tapes measuring 2 mm wide, 5 mm long, and 150 μm thick attached at 2 mm intervals. A similar LCP substrate was placed on the surface where the curable functional paste was applied, and the LCP substrates were secured together with paper clips to prevent them from separating. A cover glass with a thickness of 0.18 mm was placed on the irradiation side of the curable functional paste sandwiched in the gap to prevent contact with air, and this was used as the measurement sample. Gap tape of the same thickness was attached to the bottom of the test piece to prevent resin leakage, and the curable functional paste was sandwiched between them. For the curable functional pastes of the examples and comparative examples, the above measurement samples were subjected to visible light irradiation and ultraviolet light irradiation, respectively. The visible light irradiation conditions were as follows: using an LED light source (high-power LED chip, 100W, manufactured by Chanzon), at a height of 4 cm from the top surface of the measurement sample, with a wavelength of 532 nm and an irradiation intensity of 1500 mW / cm². ２The samples were then continuously irradiated for 3 minutes. After the light irradiation was complete, the attached LCP substrates were peeled apart, and the length of the cured material formed in the gap between the gap tapes was measured. The curing performance by irradiation with light at a wavelength of 532 nm was evaluated in three stages: ○ for good curing performance, △ for curing performance but slow reaction rate, and × for poor curing performance. The ultraviolet light irradiation conditions were as follows: a single-wavelength UV LED light source (OmniCure® AC475, manufactured by Excelitas Technologies) was used, with a wavelength of 365 nm ultraviolet light and an irradiation intensity of 500 mW / cm², at a height of 4 cm from the top surface of the measurement sample to the light source. ２ The substrates were then continuously irradiated for 9 minutes. After the light irradiation was complete, the attached LCP substrates were peeled apart, and the length of the cured material formed in the gap between the gap tapes was measured. The results are shown in Table 1.

[0129] [Evaluation of Down-Conversion Emission from Cured Material] For the cured material obtained in the above evaluation of curing depth, an LED light source (4-color LED light, manufactured by Alonefire) was used, with a wavelength of 525 nm and an irradiation intensity of 800 mW / cm². ２ Light irradiation was performed to check whether the cured material exhibited the color of downconversion luminescence. The results were evaluated in two stages: ○ for no luminescence and × for strong luminescence. The results are shown in Table 1.

[0130] [Evaluation of discoloration of cured material] At a temperature of 22°C ± 5°C and a humidity of 50% ± 10% in the dark, 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 between another glass slide with a 300 μm gap tape attached. The specimens were then irradiated with visible light and infrared light, respectively. For visible light irradiation, an LED light source (4-color LED light, Alonefire) was used, with a wavelength of 532 nm and an irradiation intensity of 10 mW / cm², at a height of 4 cm from the top surface of the glass slide to the light source. ２ The material was then continuously irradiated for 10 minutes to obtain a cured product. The appearance of the obtained cured product was observed, and a circle (○) was used if the color of the photosensitizer was clearly reduced compared to before curing, and a cross (×) was used if the color of the sensitizer remained. The results are shown in Table 1.

[0131]

[0132]

[0133] In evaluating the curing depth of the curable functional pastes, the curing depth of the curable functional pastes in each example was clearly improved when cured by visible light irradiation compared to when cured by ultraviolet light irradiation. Although not shown in the table, even when the cover glass placed on the irradiation side of the curable functional paste was replaced with a 125 μm thick polyimide film that does not transmit ultraviolet light, a high curing depth was obtained under visible light irradiation conditions, but no cured product was obtained under ultraviolet light irradiation conditions. Also, although not shown in the table, a curable functional paste was prepared using components (A-1), (A-5), and (A-6) as polymerizable compounds, and it was confirmed that deep curing was possible by visible light irradiation. Also, although not shown in the table, it was confirmed that the curable functional pastes in each example had adhesive properties.

[0134] The disclosure of Japanese Patent Application No. 2025-008097 (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 polymerization initiator, (C) a photosensitizer, and (D) a light-emitting element, wherein the (B) polymerization initiator comprises at least (B1) a photoacid generator that can be directly activated by light with a wavelength of 500 nm or less, (B2) a thermoacid generator that can be indirectly activated by light with a wavelength of 500 nm or less while present in the curable functional paste, or a combination thereof.

2. The curable functional paste according to claim 1, wherein the (C) photosensitizer is present in the curable functional paste such that it absorbs light with a wavelength greater than 500 nm, causes triplet-triplet energy transfer to the (D) light emitter, and is decomposed by the acid generated from the (B1) photoacid generator and / or the (B2) thermoacid generator.

3. The curable functional paste according to claim 1 or 2, wherein the (D) light-emitting element can exhibit photon upconversion emission with a wavelength of 500 nm or less.

4. The curable function paste according to any one of claims 1 to 3, wherein the (B) polymerization initiator comprises (B1) photoacid generator.

5. The curable function paste according to any one of claims 1 to 4, wherein the polymerization initiator (B) comprises a thermal acid generator (B2).

6. The curable functional paste according to any one of claims 1 to 5, wherein the (B) polymerization initiator comprises (B1) a photoacid generator, (B3) a photoradical polymerization initiator, (B4) a photobase generator, or any combination thereof.

7. The curable function-exhibiting paste according to any one of claims 1 to 6, wherein the total amount of the photoacid generator (B1) and the thermoacid generator (B2) is 0.01 to 20 parts by mass per 100 parts by mass of the polymerizable compound (A).

8. A curable function-exhibiting paste according to any one of claims 1 to 7, which provides a cured product that does not exhibit upconversion luminescence and / or downconversion luminescence upon excitation light.

9. A curable function-exhibiting paste according to any one of claims 1 to 8, which provides a cured product in which the absorption of the wavelength used for curing is attenuated by photocuring.

10. A curable function-emerging paste according to any one of claims 1 to 9, for use in curing by irradiation with light with a wavelength exceeding 500 nm.

11. A curable function-emerging paste according to any one of claims 1 to 10, used as an adhesive, encapsulant, or coating agent for semiconductor devices or electronic components.

12. An adhesive, sealant, or coating agent comprising a curable function-exhibiting paste according to any one of claims 1 to 11.

13. A cured product obtained by curing a curable function-exhibiting paste according to any one of claims 1 to 11, or an adhesive, sealant, or coating agent according to claim 12.

14. A semiconductor device or electronic component comprising the cured product described in claim 13.

15. Use of the curable function-exhibiting paste according to any one of claims 1 to 11 for curing by irradiation with light with a wavelength greater than 500 nm.

16. A method for producing a cured product, comprising irradiating a curable function-exhibiting paste according to any one of claims 1 to 11, or an adhesive, sealant, or coating agent according to claim 12, with light having a wavelength greater than 500 nm.

17. A method for curing a curable functional paste, comprising irradiating the curable functional paste according to any one of claims 1 to 11 with light having a wavelength greater than 500 nm.

18. 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 claims 1 to 11 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.

19. 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 11 into the gap between or within parts; and irradiating the curable functional paste with light having a wavelength greater than 500 nm.

20. 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 11 to the object; and irradiating the curable functional paste with light having a wavelength greater than 500 nm.

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