Resin composition for sealing optical semiconductor, cured product, optical semiconductor device, and image display device

Abstract

To provide means enabling more suppression of deterioration of a quantum dot when LEDs are lightened.SOLUTION: A resin composition for sealing an optical semiconductor is provided, including resin (A), a quantum dot (B), and a blocked carboxylic acid (C) in which a carboxy group of a carboxylic acid is blocked by a vinyl ether compound.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition for sealing an optical semiconductor, a cured product, an optical semiconductor device, and an image display device. [Background technology]

[0002] Optical semiconductor devices using optical semiconductor elements such as light-emitting diodes (LEDs) have features such as long life, low power consumption, shock resistance, high-speed response, and the realization of light, thin, short, and small sizes, and are being developed in a wide range of applications, including backlighting for liquid crystal displays, mobile phones, information terminals, in-vehicle lighting, indoor and outdoor advertising, and indoor and outdoor lighting. Furthermore, as applications become more diverse, there is a demand for even higher efficiency, and in particular, research and development is being actively conducted to improve color reproducibility and increase the contrast ratio for display applications.

[0003] There are two types of display backlights: one in which LEDs are arranged directly below the display (direct type), and one in which they are arranged on the edge of the display and combined with a diffuser to illuminate the entire display (edge ​​type). Direct types can achieve a wide contrast ratio, but in recent years, in order to further increase the contrast ratio, research and development has been actively carried out on a technology called miniLED, in which small light-emitting elements are mounted on a substrate and the entire system is sealed with resin. With miniLED, the area of ​​the display illuminated by each light-emitting element is smaller, so the contrast of the image displayed on the display can be finely adjusted, resulting in images with clear differences in light and dark.

[0004] As an example of an encapsulating composition used to encapsulate such miniLEDs, Patent Document 1 discloses a light wavelength-converting composition comprising quantum dots including a core made of a first semiconductor compound, a shell covering the core and made of a second semiconductor compound different from the first semiconductor compound, and a ligand bonded to the surface of the shell, a compound having a heterocyclic group containing an oxygen atom, and a carboxylic acid that is not the ligand, wherein the compound having a heterocyclic group containing an oxygen atom is an epoxy compound with a silicone skeleton, the carboxylic acid has a carboxyl group equivalent weight of 50 or more and 5000 or less, and the carboxylic acid contains three or more carboxyl groups. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 6926515 Summary of the Invention [Problem to be solved by the invention]

[0006] Quantum dots tend to deteriorate due to moisture, oxygen, light, heat, etc., resulting in a decrease in luminous efficiency. This deterioration of quantum dots is particularly likely to occur due to light and heat generated when an LED is turned on. The technology described in Patent Document 1 above has the problem of insufficient prevention of quantum dot deterioration when the LED is turned on.

[0007] Therefore, an object of the present invention is to provide a means for further suppressing the deterioration of quantum dots when an LED is turned on. [Means for solving the problem]

[0008] The above-mentioned problems of the present invention can be solved by the following means: That is, the present invention provides a resin composition for encapsulating an optical semiconductor, comprising a resin (A), quantum dots (B), and a blocked carboxylic acid (C) in which the carboxy group of the carboxylic acid is blocked with a vinyl ether compound.

[0009] Another embodiment of the present invention is a cured product of the above-mentioned optical semiconductor encapsulating resin composition.

[0010] Yet another embodiment of the present invention is an optical semiconductor device in which an optical semiconductor element is encapsulated with the above-described cured product.

[0011] Yet another embodiment of the present invention is an image display device including the optical semiconductor device described above. [Effects of the Invention]

[0012] According to the present invention, a means is provided that can further suppress the deterioration of quantum dots when an LED is turned on. DETAILED DESCRIPTION OF THE INVENTION

[0013] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments and can be modified in various ways within the scope of the claims. The embodiments described in this specification can be combined in any way to form other embodiments. Unless otherwise specified, in this specification, operations and measurements of physical properties, etc. are performed under conditions of room temperature (20°C or higher and 25°C or lower) and a relative humidity of 40% RH or higher and 50% RH or lower.

[0014] [Resin composition for optical semiconductor encapsulation] One embodiment of the present invention is a resin composition for encapsulating an optical semiconductor, comprising a resin (A), quantum dots (B), and a blocked carboxylic acid (C) in which the carboxy group of the carboxylic acid is blocked with a vinyl ether compound. The optical semiconductor encapsulating resin composition according to the present invention having the above-described configuration can further suppress deterioration of the quantum dots when the LED is turned on.

[0015] The present inventors presume that the mechanism by which the optical semiconductor encapsulating resin composition having the above-described configuration solves the problems is as follows.

[0016] When a quantum dot-containing optical semiconductor encapsulating resin composition is applied to a miniLED for encapsulation and then turned on, the quantum dots deteriorate due to the light emitted during illumination and the heat generated by the miniLED and quantum dots. The optical semiconductor encapsulating resin composition according to the present invention contains a blocked carboxylic acid (C) in which the carboxy group of a carboxylic acid is blocked with a vinyl ether compound. When the LED is turned on, the quantum dots emit light and generate heat. The blocked carboxylic acid (C) releases the vinyl ether compound that serves as a protecting group only in the vicinity of the quantum dots that generate heat, generating a carboxylic acid having a polar carboxy group. This generated carboxylic acid protects the quantum dots, thereby further suppressing the deterioration of the quantum dots during LED illumination, and thereby extending the life of optical semiconductor elements and optical semiconductor devices, regardless of the type of resin contained in the composition.

[0017] The above mechanism is based on speculation, and its correctness does not affect the technical scope of the present invention. Similarly, the correctness of other speculations in this specification does not affect the technical scope of the present invention.

[0018] The constitution of the composition of the present invention will be described in more detail below. In this specification, the optical semiconductor encapsulating resin composition of the present invention will also be simply referred to as "the composition of the present invention," "the composition according to the present invention," or "the composition."

[0019] Resin (A) The resin (A) used in the present invention is not particularly limited, and may be any resin that has curability, such as a thermosetting resin, a photocurable resin, a condensation curable resin, etc. The resin (A) may be used alone or in combination of two or more kinds.

[0020] Among the resins (A), thermosetting resins are preferred from the viewpoint of being able to more effectively exhibit the effects of the present invention.Moreover, at least one selected from the group consisting of a thermosetting silicone resin having two or more thermosetting functional groups in one molecule, a thermosetting epoxy resin having two or more thermosetting functional groups in one molecule, and a thermosetting (meth)acrylic resin having two or more thermosetting functional groups in one molecule is more preferred.

[0021] Examples of thermosetting functional groups contained in thermosetting resins include epoxy groups, carboxy groups, hydroxy groups, alkenyl groups, hydrogensilyl groups, (meth)acryloyl groups, carbinol groups, mercapto groups, phenol groups, amide groups, amino groups, acid anhydride groups, (blocked) isocyanate groups, etc. Hereinafter, more preferred resins, namely, thermosetting silicone resins, thermosetting epoxy resins, and thermosetting (meth)acrylic resins, will be described.

[0022] <Thermosetting silicone resin> The thermosetting silicone resin is preferably a silicone resin having two or more thermosetting functional groups per molecule.Thermosetting silicone resins include self-curing resins that cure by heating without using a curing agent, and curing agent-curing resins that cure with a curing agent.The self-curing silicone resin, for example, includes a silicone resin that has a hydroxy group as a thermosetting functional group and undergoes a dehydration condensation reaction by heating, thereby curing.Furthermore, the curing agent-curing silicone resin, for example, includes a silicone resin that cures by adding a catalyst and heating, thereby undergoing a crosslinking reaction by a hydrocarbon group such as an alkenyl group.

[0023] The thermosetting silicone resin is not particularly limited, and examples thereof include those in which the resin skeleton is composed of a structure such as a silicone oligomer, organosiloxane, diorganosiloxane, organopolysiloxane, or diorganopolysiloxane, and the resin skeleton has two or more thermosetting functional groups. The skeleton of the thermosetting silicone resin may be linear, branched, or cyclic.

[0024] The thermosetting functional group of the thermosetting silicone resin is not particularly limited, and examples thereof include a hydroxy group, an alkenyl group, a hydrogensilyl group, a (meth)acryloyl group, an epoxy group, an amino group, a carbinol group, a mercapto group, a carboxy group, and a phenol group.

[0025] The thermosetting silicone resin may have functional groups such as alkyl groups and aromatic groups on the side chains in addition to the thermosetting reactive functional groups.

[0026] More specific examples of thermosetting silicone resins include cyclic siloxane compounds having two or more epoxy groups in the molecule. Examples of the epoxy group include a glycidyl group and an epoxycyclohexylethyl group. Furthermore, as the glycidyl group, a glycidoxypropyl group is preferred, and a 3-glycidoxypropyl group is more preferred. As the epoxycyclohexylethyl group, a 2,3-epoxycyclohexylethyl group is preferred. Examples of the cyclic siloxane skeleton include a cyclic dimethylsiloxane structure having a trimer to decamer.

[0027] The thermosetting silicone resin may be a synthetic product or a commercially available product, such as ADEKA RESIN (registered trademark, hereinafter the same) EP-3400L (manufactured by ADEKA Corporation); X-40-2670, X-22-4741, KF-1002, KF-1005, X-22-163, KF-105, X-22-163A, X-22-163B, X-22-163C, X-22-9002, X-22-169AS, X-22-169B, X-22-2046, KF-102, X-40-2669, X-40-2678, and KR-470 (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0028] <Thermosetting epoxy resin> The thermosetting epoxy resin is preferably an epoxy resin having two or more thermosetting functional groups in one molecule.

[0029] Specific examples of thermosetting epoxy resins include aliphatic epoxy resins, alicyclic epoxy resins, aromatic epoxy resins, hydrogenated epoxy resins, glycidyl ester compounds, glycidyl amine compounds, heterocyclic epoxy resins, modified epoxy resins, and epoxy compounds having a polymerizable functional group other than an epoxy group.

[0030] More specific examples of aliphatic epoxy resins include glycidyl ether compounds having an aliphatic structure, compounds obtained by epoxidizing unsaturated bonds, etc. More specific examples of aliphatic epoxy compounds include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, etc.

[0031] The aliphatic epoxy resin may be a synthetic product or a commercially available product. Examples of commercially available aliphatic epoxy resins include the Epolite (registered trademark, the same applies hereinafter) series (manufactured by Kyoeisha Chemical Co., Ltd.), the Denacol (registered trademark, the same applies hereinafter) series (manufactured by Nagase ChemteX Corporation), the YED series (manufactured by Mitsubishi Chemical Corporation), the Epotohto (registered trademark, the same applies hereinafter) series (manufactured by Nippon Steel Chemical & Material Co., Ltd.), Epolead (registered trademark, the same applies hereinafter) PB3600, and Epolead PB4700 (all manufactured by Daicel Corporation).

[0032] Examples of alicyclic epoxy resins include compounds having an alicyclic epoxy group, such as compounds having a cyclohexene oxide skeleton (epoxycyclohexyl group) and compounds in which an epoxy group is added to an alicyclic hydrocarbon directly or via a hydrocarbon group.

[0033] Specific examples of epoxy compounds having a cyclohexene oxide skeleton include cyclohexene oxide, (3,4,3',4'-diepoxy)bicyclohexyl, bis(3,4-epoxycyclohexylmethyl)ether, 1,2-epoxy-1,2-bis(3,4-epoxycyclohexan-1-yl)ethane, 2,2-bis(3,4-epoxycyclohexan-1-yl)propane, 1,2-bis(3,4-epoxycyclohexan-1-yl)ethane, alpha-pinene oxide, limonene monoxide, and limonene monoxide. Examples of epoxy groups include monene dioxide, 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, ε-caprolactone-modified 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, bis-(3,4-epoxycyclohexyl)adipate, 1,2-epoxy-4-vinylcyclohexane, butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl)-modified ε-caprolactone, and 3,4-epoxycyclohexylmethyl methacrylate.

[0034] Examples of the compound in which an epoxy group is added to the above-mentioned alicyclic hydrocarbon directly or via a hydrocarbon group include 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol.

[0035] The alicyclic epoxy resin may be a synthetic product or a commercially available product. Examples of commercially available alicyclic epoxy resins include CELLOXIDE (registered trademark, the same applies hereinafter) 8000, CELLOXIDE 8010, CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2000, EHPE3150, EHPE3150CE, EPOLEAD GT401, and CYCLOMER (registered trademark) M100 (all manufactured by Daicel Corporation); EPICLON (registered trademark, the same applies hereinafter) HP-7200L, EPICLON HP-7200, EPICLON HP-7200H, EPICLON HP-7200HH, and EPICLON HP-7200HHH (all manufactured by DIC Corporation); and the like.

[0036] Examples of aromatic epoxy resins include glycidyl compounds having a bisphenol skeleton, a fluorene skeleton, a biphenyl skeleton, or an aromatic ring such as a benzene ring, a naphthalene ring, or an anthracene ring.

[0037] More specific examples of aromatic epoxy resins include glycidyl ether compounds obtained by reacting the hydroxy group of a compound having a hydroxy group, such as phenol, bisphenol A, or bisphenol F, with epihalohydrin; glycidyl ether compounds obtained by reacting the hydroxy group of a compound having a hydroxy group, such as a novolak aralkyl glycidyl ether epoxy compound, phenyl glycidyl ether, or benzyl alcohol, with epihalohydrin; and glycidyl ether compounds obtained by reacting the hydroxy group of a compound having a hydroxy group, such as bisphenol A bis(ethylene glycol), with epihalohydrin.

[0038] The aromatic epoxy resin may also be a polymer obtained by reacting a plurality of polyol compounds with a plurality of epihalohydrins. Polymers obtained by reacting a plurality of polyol compounds with a plurality of epihalohydrins are generally called bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, etc.

[0039] Examples of the novolak-aralkyl type glycidyl ether epoxy compounds include glycidyl ether compounds obtained by reacting polyhydric phenols, such as phenol, cresol, and bisphenol A, with formaldehyde, acetaldehyde, and the like, and then reacting the resulting polyhydric phenols with epihalohydrin.

[0040] The aromatic epoxy resin may be a synthetic product or a commercially available product. Examples of commercially available products include Epolite 3002(N) (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol series (manufactured by Nagase ChemteX Corporation), jER (registered trademark) series (manufactured by Mitsubishi Chemical Corporation), Epotohto series (manufactured by Nippon Steel Chemical & Material Co., Ltd.), Oncoat series (all manufactured by Osaka Gas Chemicals Co., Ltd. and Nagase ChemteX Corporation), and EPICLON series (manufactured by DIC Corporation).

[0041] Specific examples of the hydrogenated epoxy compound include compounds in which the aromatic ring moiety of the above-mentioned aromatic epoxy resins is hydrogenated.

[0042] Specific examples of the glycidyl ester compounds include glycidyl ester epoxy resins such as diglycidyl phthalate and diglycidyl tetrahydrophthalate.

[0043] Specific examples of the glycidylamine compound include glycidylamine type epoxy resins such as tetraglycidyldiaminodiphenylmethane.

[0044] Specific examples of heterocyclic epoxy resins include isocyanurate-type epoxy resins such as triglycidyl isocyanurate, and hydantoin-type epoxy resins such as diglycidyl hydantoin and glycidyl glycidoxyalkyl hydantoin.

[0045] Examples of modified epoxy resins include urethane-modified epoxy resins, rubber-modified epoxy resins, and chelate-modified epoxy resins.

[0046] <Thermosetting (meth)acrylic resin> A thermosetting (meth)acrylic resin is a (meth)acrylic resin having two or more thermosetting functional groups in one molecule. The thermosetting functional group can be introduced into the thermosetting (meth)acrylic resin by using a vinyl monomer having a thermosetting functional group. The vinyl monomer having a thermosetting functional group may be a (meth)acrylic monomer (a monomer having a (meth)acryloyl group), or may be a vinyl monomer other than a (meth)acrylic monomer.

[0047] Examples of the thermosetting functional group contained in the thermosetting (meth)acrylic resin include an epoxy group, a carboxy group, a hydroxy group, an amide group, an amino group, an acid anhydride group, a (blocked) isocyanate group, etc. Among these, from the viewpoint of ease of production of the (meth)acrylic resin, the thermosetting functional group of the thermosetting (meth)acrylic resin is preferably at least one selected from the group consisting of an epoxy group, a carboxy group, and a hydroxy group.

[0048] Examples of vinyl monomers having an epoxy group as a thermosetting functional group include various chain epoxy group-containing monomers (e.g., glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, glycidyl vinyl ether, allyl glycidyl ether, etc.), various (2-oxo-1,3-oxolane) group-containing vinyl monomers (e.g., (2-oxo-1,3-oxolane)methyl (meth)acrylate, etc.), and various alicyclic epoxy group-containing vinyl monomers (e.g., 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3,4-epoxycyclohexylethyl (meth)acrylate, etc.).

[0049] Examples of vinyl monomers having a carboxy group as a thermosetting functional group include various carboxy group-containing monomers (e.g., (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, etc.), various monoesters of α,β-unsaturated dicarboxylic acids with monohydric alcohols having 1 to 18 carbon atoms (e.g., monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monoisobutyl fumarate, mono-tert-butyl fumarate, monohexyl fumarate, monooctyl fumarate, mono-2-ethyl fumarate), monohexyl maleate, monomethyl maleate, monoethyl maleate, monobutyl maleate, monoisobutyl maleate, mono-tert-butyl maleate, monohexyl maleate, monooctyl maleate, mono-2-ethylhexyl maleate, etc.), various monoalkyl itaconates (for example, monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, monoisobutyl itaconate, monohexyl itaconate, monooctyl itaconate, mono-2-ethylhexyl itaconate, etc.), and the like.

[0050] Examples of vinyl monomers having a hydroxy group as a thermosetting functional group include various hydroxy group-containing (meth)acrylates (e.g., 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, etc.), addition reaction products of the above-mentioned various hydroxy group-containing (meth)acrylates with ε-caprolactone, various hydroxy group-containing vinyl ethers (e.g., 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 4-hydroxybutyl vinyl ether, etc.), and the like. hydroxybutyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, etc.), addition reaction products of the above-mentioned various hydroxy group-containing vinyl ethers with ε-caprolactone, various hydroxy group-containing allyl ethers (for example, 2-hydroxyethyl(meth)allyl ether, 3-hydroxypropyl(meth)allyl ether, 2-hydroxypropyl(meth)allyl ether, 4-hydroxybutyl(meth)allyl ether, 3-hydroxybutyl(meth)allyl ether, 2-hydroxy-2-methylpropyl(meth)allyl ether, 5-hydroxypentyl(meth)allyl ether, 6-hydroxyhexyl(meth)allyl ether, etc.), addition reaction products of the above-mentioned various hydroxy group-containing allyl ethers with ε-caprolactone, etc.

[0051] Examples of (meth)acrylic monomers that do not have a thermosetting functional group and that serve as structural units of the thermosetting (meth)acrylic resin include (meth)acrylic acid alkyl esters (e.g., methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethyloctyl (meth)acrylate, dodecyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, etc.), various aryl (meth)acrylate esters (for example, benzyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, etc.), various alkyl carbitol (meth)acrylates (for example, ethyl carbitol (meth)acrylate, etc.). , various other (meth)acrylic acid esters (e.g., isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, etc.), various amino group-containing amide-based unsaturated monomers (e.g., N-dimethylaminoethyl (meth)acrylamide, N-diethylaminoethyl (meth)acrylamide, N-dimethylaminopropyl (meth)acrylamide, N-diethyl aminopropyl(meth)acrylamide, etc.), various dialkylaminoalkyl(meth)acrylates (for example, dimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate, etc.), various amino group-containing monomers (for example, tert-butylaminoethyl(meth)acrylate, tert-butylaminopropyl(meth)acrylate, aziridinylethyl(meth)acrylate, pyrrolidinylethyl(meth)acrylate, piperidinylethyl(meth)acrylate, etc.).

[0052] The thermosetting (meth)acrylic resin may be copolymerized with other vinyl monomers not having a thermosetting functional group in addition to the (meth)acrylic monomer. Examples of such other vinyl monomers include various α-olefins (e.g., ethylene, propylene, butene-1, etc.), various halogenated olefins (e.g., vinyl chloride, vinylidene chloride, etc.), various aromatic vinyl monomers (e.g., styrene, α-methylstyrene, vinyltoluene, etc.), various diesters of unsaturated dicarboxylic acids with monohydric alcohols having 1 to 18 carbon atoms (e.g., dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dioctyl fumarate, etc.), and the like. dimethyl maleate, diethyl maleate, dibutyl maleate, dioctyl maleate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, dioctyl itaconate, etc.), various acid anhydride group-containing monomers (e.g., maleic anhydride, itaconic anhydride, citraconic anhydride, (meth)acrylic anhydride, tetrahydrophthalic anhydride, etc.), various phosphate group-containing monomers (e.g., diethyl-2-(meth)acryloyloxyethyl phosphate, dibutyl-2-(meth)acryloyloxyethyl phosphate, -(meth)acryloyloxybutyl phosphate, dioctyl-2-(meth)acryloyloxyethyl phosphate, diphenyl-2-(meth)acryloyloxyethyl phosphate, etc.), various hydrolyzable silyl group-containing monomers (for example, γ-(meth)acryloyloxypropyltrimethoxysilane, γ-(meth)acryloyloxypropyltriethoxysilane, γ-(meth)acryloyloxypropylmethyldimethoxysilane, etc.), various aliphatic vinyl carboxylates (for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, branched aliphatic vinyl carboxylates having from 9 to 11 carbon atoms, vinyl stearate, etc.), various vinyl esters of carboxylic acids having a cyclic structure (for example, vinyl cyclohexanecarboxylate, vinyl methylcyclohexanecarboxylate, vinyl benzoate, vinyl p-tert-butylbenzoate, etc.).

[0053] <Curing agent> When the resin (A) is a thermosetting resin, the composition of the present invention may contain a curing agent for curing the thermosetting resin, and more preferably contains a curing agent.

[0054] The type of curing agent is not particularly limited, and any appropriate curing agent capable of curing a thermosetting resin can be used. In this specification, the above-mentioned thermosetting agent also includes a curing catalyst. The curing agent can be used alone or in combination of two or more.

[0055] From the viewpoint of further improving the heat resistance of the resulting cured product, it is preferable that the curing agent has an aromatic skeleton or an alicyclic skeleton. The curing agent preferably contains an amine curing agent (amine compound), an imidazole curing agent, a phenolic curing agent (phenolic compound), or an acid anhydride curing agent (acid anhydride), and more preferably contains a phenolic curing agent (phenolic compound) or an acid anhydride curing agent (acid anhydride). The acid anhydride curing agent preferably contains an acid anhydride having an aromatic skeleton, a water additive of the acid anhydride, or a modified product of the acid anhydride, or an acid anhydride having an alicyclic skeleton, a water additive of the acid anhydride, or a modified product of the acid anhydride.

[0056] Examples of the amine curing agent include dicyandiamide, imidazole compounds, diaminodiphenylmethane, and diaminodiphenylsulfone.

[0057] Examples of the imidazole curing agent include 2-undecylimidazole, 2-heptadecylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole, trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-dihydroxymethylimidazole, and the like.

[0058] Examples of phenol curing agents include phenol novolac, o-cresol novolac, p-cresol novolac, t-butylphenol novolac, dicyclopentadiene cresol, polyparavinylphenol, bisphenol A type novolac, xylylene-modified novolac, decalin-modified novolac, poly(di-o-hydroxyphenyl)methane, poly(di-m-hydroxyphenyl)methane, poly(di-p-hydroxyphenyl)methane, and the like.

[0059] Examples of acid anhydrides having an aromatic skeleton, water additives of such acid anhydrides, or modified products of such acid anhydrides include styrene / maleic anhydride copolymer, benzophenone tetracarboxylic anhydride, pyromellitic anhydride, trimellitic anhydride, 4,4'-oxydiphthalic anhydride, phenylethynylphthalic anhydride, glycerol bis(anhydrotrimellitate) monoacetate, ethylene glycol bis(anhydrotrimellitate), methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, and trialkyltetrahydrophthalic anhydrides.

[0060] The acid anhydride having an aromatic skeleton, the hydrate of the acid anhydride, or the modified product of the acid anhydride may be a synthetic product or a commercially available product. Examples of commercially available products include SMA (registered trademark, the same applies hereinafter) Resin EF30, SMA Resin EF40, SMA Resin EF60, and SMA Resin EF80 (all manufactured by Sartomer Japan); ODPA-M and PEPA (all manufactured by Manac Corporation); RIKACID (registered trademark, the same applies hereinafter) MTA-10, RIKACID MTA-15, RIKACID TMTA, RIKACID TMEG-100, RIKACID TMEG-200, RIKACID TMEG-300, RIKACID TMEG-500, RIKACID TMEG-S, RIKACID HT-1A, RIKACID MT-500, and RIKACID TDA-100 (all manufactured by New Japan Chemical Co., Ltd.); and EPICLON (registered trademark, the same applies hereinafter) B4400, EPICLON B650, and EPICLON B570 (all manufactured by DIC Corporation).

[0061] The acid anhydride having an alicyclic skeleton, the hydrated product of the acid anhydride, or the modified product of the acid anhydride is preferably an acid anhydride having a polyalicyclic skeleton, the hydrated product of the acid anhydride, or the modified product of the acid anhydride, or an acid anhydride having an alicyclic skeleton obtained by the addition reaction of a terpene compound with maleic anhydride, the hydrated product of the acid anhydride, or the modified product of the acid anhydride. The use of these curing agents further improves the flexibility, moisture resistance, and adhesion of the resulting cured product.

[0062] Examples of the acid anhydrides having an alicyclic skeleton, water-added products of the acid anhydrides, or modified products of the acid anhydrides include methylnadic acid anhydride, acid anhydrides having a dicyclopentadiene skeleton, or modified products of the acid anhydrides.

[0063] The acid anhydride having an alicyclic skeleton, the water additive of the acid anhydride, or the modified product of the acid anhydride may be a synthetic product or a commercially available product. Examples of commercially available products include RIKACID (registered trademark, the same applies hereinafter) MH-700, RIKACID MH-700G, RIKACID HH, RIKACID TH, RIKACID DDSA, RIKACID OSA, RIKACID HNA, and RIKACID HNA-100 (all manufactured by New Japan Chemical Co., Ltd.); jER Cure (registered trademark, the same applies hereinafter) YH306, jER Cure YH307, jER Cure YH308H, and jER Cure YH309 (all manufactured by Mitsubishi Chemical Corporation); and the like.

[0064] Examples of the curing catalyst include, for example, phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, and amine-based curing accelerators.

[0065] When the composition of the present invention contains a curing agent, the content of the curing agent in the composition is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, even more preferably 70 parts by mass or more, and particularly preferably 100 parts by mass or more, per 100 parts by mass of resin (A). The content of the curing agent in the composition is preferably 200 parts by mass or less, more preferably 170 parts by mass or less, and even more preferably 150 parts by mass or less, per 100 parts by mass of resin (A). When two or more curing agents are used, the above content represents the total amount.

[0066] When the content of the curing agent is equal to or greater than the lower limit, the composition can be sufficiently cured. When the content of the curing agent is equal to or less than the upper limit, excess heat curing agent that is not involved in curing is unlikely to be generated, and the heat resistance of the resulting cured product is increased.

[0067] [Quantum dots (B)] Quantum dots (semiconductor nanoparticles) (B) are semiconductor nanoparticles of a certain size that exhibit quantum confinement effects.

[0068] Quantum dots (semiconductor nanoparticles) can be synthesized by wet chemical processes, metalorganic chemical vapor deposition processes, molecular beam epitaxy processes, or other similar processes. Among these, wet chemical processes involve growing particles by adding precursor materials to an organic solvent.

[0069] In the wet chemical process, the organic solvent naturally coordinates with the surface of the quantum dot crystals as they grow, acting as a dispersant and regulating the growth of the crystals. Therefore, the wet chemical process allows for easier and lower cost control of the growth of semiconductor nanoparticles than gas phase deposition methods such as metal organic chemical vapor deposition (MOCVD) and molecular beam epitaxy (MBE).

[0070] By adjusting the size of quantum dots (semiconductor nanoparticles), the energy band gap can be adjusted, allowing light of various wavelengths to be obtained. Therefore, using quantum dots of different sizes enables displays that emit (or emit) light of multiple wavelengths. The size of quantum dots can be selected to emit red, green, and blue light, allowing the construction of color displays. In addition, the size of quantum dots can be combined to emit various colored lights to emit white light.

[0071] As quantum dots (semiconductor nanoparticles), semiconductor materials selected from the group consisting of II-VI group semiconductor compounds; III-V group semiconductor compounds; IV-VI group semiconductor compounds; IV group elements or compounds; and combinations thereof can be used.

[0072] The II-VI semiconductor compound is not particularly limited, but may be selected from the group consisting of binary compounds selected from the group consisting of CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, and mixtures thereof; ternary compounds selected from the group consisting of CdSeS, CdSeTe, CdSTe, ZnSeS, ZnTeSe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, and mixtures thereof; and quaternary compounds selected from the group consisting of CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, and mixtures thereof.

[0073] The III-V semiconductor compound is not particularly limited, and may be selected from the group consisting of binary compounds selected from the group consisting of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and mixtures thereof; ternary compounds selected from the group consisting of GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, and mixtures thereof; and quaternary compounds selected from the group consisting of GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and mixtures thereof.

[0074] The IV-VI semiconductor compound is not particularly limited, and may be selected from the group consisting of binary compounds selected from the group consisting of SnS, SnSe, SnTe, PbS, PbSe, PbTe, and mixtures thereof; ternary compounds selected from the group consisting of SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, and mixtures thereof; and quaternary compounds selected from the group consisting of SnPbSSe, SnPbSeTe, SnPbSTe, and mixtures thereof.

[0075] The Group IV element or compound is not particularly limited, but may be selected from the group consisting of mono-element compounds selected from the group consisting of Si, Ge, and mixtures thereof; and bi-element compounds selected from the group consisting of SiC, SiGe, and mixtures thereof.

[0076] Quantum dots may be composed of one type of compound or two or more types of compounds. They may also have a core-shell structure, for example, with a core made of a semiconductor compound and a shell made of a different semiconductor compound. The luminous efficiency of quantum dots can be improved by using a semiconductor compound constituting the shell with a higher band gap than the semiconductor compound constituting the core, so that excitons are confined in the core. Examples of core-shell structures (core / shell) with such a large-small band gap relationship include CdSe / ZnS, CdSe / ZnSe, CdSe / CdS, CdTe / CdS, InP / ZnS, CuInS / ZnS, ZnTeSe / ZnSe / ZnS, and InP / ZnSe / ZnS.

[0077] However, from the viewpoint of environmental pollution resistance, safety (toxicity) to living organisms, etc., it is more preferable that the quantum dots do not contain Cd (cadmium), Hg (mercury), arsenic (As), and Pb (lead) as constituent elements.

[0078] The particle size of quantum dots can be adjusted appropriately depending on the material that makes up the quantum dots so that light of the desired wavelength can be obtained. As the particle size of quantum dots decreases, the energy band gap increases. In other words, as the crystal size decreases, the emission of quantum dots shifts toward the blue side, i.e., toward higher energy. Therefore, by changing the size of quantum dots, the emission wavelength can be adjusted across the wavelength ranges of the ultraviolet, visible, and infrared regions of the spectrum.

[0079] For example, the average particle size (average diameter) of quantum dots (semiconductor nanoparticles) is not particularly limited, but is about 1 nm or more and 15 nm or less. From the viewpoint of light-emitting properties and dispersion stability of quantum dots, the particle size is preferably 7 nm or more and 15 nm or less. The average particle size of quantum dots can be obtained by measuring the particle size of quantum dots using TEM, SEM, XRD, etc., and calculating the volume-based average particle size.

[0080] Quantum dots may also be used that have organic ligands with coordinating groups coordinated to their surfaces. Adding organic ligands to the quantum dot raw material solution during quantum dot synthesis can prevent excessive crystal growth and yield quantum dots within the desired particle size range. Furthermore, quantum dots with a surface layer composed of organic ligands on their surface can prevent aggregation after synthesis.

[0081] The organic ligand is preferably an organic compound having a coordinating group that binds to the cation contained in the quantum dot. Examples of the coordinating group include a halogen atom, a carboxyl group, a carboxylic acid anhydride group, an amino group, an ammonium group, a mercapto group, a sulfide group, a sulfoxide group, a phosphine group, a phosphine oxide group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfonic acid group, a boronic acid group, and a heterocyclic group. Such organic ligands can be used alone or in combination of two or more.

[0082] Examples of halogen atom-containing compounds include halogenated alkyl compounds having a linear or branched alkyl group having from 1 to 30 carbon atoms. Specific examples of such halogenated alkyl compounds include methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, ethyl iodide, propyl chloride, propyl bromide, propyl iodide, butyl chloride, butyl bromide, butyl iodide, hexyl chloride, hexyl bromide, octyl chloride, octyl bromide, and decyl chloride.

[0083] Examples of carboxy group-containing compounds include linear or branched aliphatic carboxylic acid compounds having from 1 to 30 carbon atoms. Specific examples of such aliphatic carboxylic acid compounds include arachidonic acid, crotonic acid, trans-2-decenoic acid, erucic acid, 3-decenoic acid, cis-4,7,10,13,16,19-docosahexaenoic acid, 4-decenoic acid, allcis-5,8,11,14,17-eicosapentaenoic acid, allcis-8,11,14-eicosatrienoic acid, cis-9-hexadecenoic acid, trans-3-hexenoic acid, trans-2-hexenoic acid, 2-heptenoic acid, 3-heptenoic acid, 2-hexadecenoic acid, linolenic acid, linoleic acid, γ-linolenic acid, 3-nonenoic acid, 2-nonenoic acid, trans-2-octenoic acid, petroselinic acid, elaidic acid, oleic acid, and the like. Examples of suitable acids include carboxylic acid, 3-octenoic acid, trans-2-pentenoic acid, trans-3-pentenoic acid, ricinoleic acid, sorbic acid, 2-tridecenoic acid, cis-15-tetracosenoic acid, 10-undecenoic acid, 2-undecenoic acid, acetic acid, butyric acid, behenic acid, cerotic acid, decanoic acid, arachidic acid, heneicosanoic acid, heptadecanoic acid, heptanoic acid, hexanoic acid, heptacosanoic acid, lauric acid, myristic acid, melissic acid, octacosanoic acid, nonadecanoic acid, nonacosanoic acid, n-octanoic acid, palmitic acid, pentadecanoic acid, propionic acid, pentacosanoic acid, nonanoic acid, stearic acid, lignoceric acid, tricosanoic acid, tridecanoic acid, undecanoic acid, and valeric acid.

[0084] Examples of the amino group-containing compound include aliphatic amine compounds having a linear or branched alkyl group having from 1 to 30 carbon atoms. Specific examples of such aliphatic amine compounds include 1-aminoheptadecane, 1-aminononadecane, heptadecane-9-amine, stearylamine, oleylamine, 2-n-octyl-1-dodecylamine, allylamine, amylamine, 2-ethoxyethylamine, 3-ethoxypropylamine, isobutylamine, isoamylamine, 3-methoxypropylamine, 2-methoxyethylamine, 2-methylbutylamine, neopentylamine, n-propylamine, and the like. amine, methylamine, ethylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-octadecylamine, tri(n-hexyl)amine, tri(n-octyl)amine, tri(n-decyl)amine, and the like.

[0085] Examples of the mercapto group-containing compound include hexyl mercaptan, octyl mercaptan, and lauryl mercaptan.

[0086] Examples of the sulfide group-containing compound include dialkyl sulfides such as dibutyl sulfide.

[0087] Examples of the sulfoxide group-containing compound include dialkyl sulfoxides such as dimethyl sulfoxide and dibutyl sulfoxide.

[0088] Examples of the phosphine group-containing compound include trialkylphosphines such as tripropylphosphine, tributylphosphine, trihexylphosphine, and trioctylphosphine.

[0089] Examples of the phosphine oxide group-containing compound include trialkylphosphine oxides such as tripropylphosphine oxide, tributylphosphine oxide, trihexylphosphine oxide, trioctylphosphine oxide, and tridecylphosphine oxide.

[0090] Examples of heterocyclic group-containing compounds include nitrogen-containing heterocyclic compounds such as pyridine, lutidine, collidine, and quinolines; sulfur-containing heterocyclic compounds such as thiophene; and the like.

[0091] Among these organic ligands, at least one selected from the group consisting of alkyl halide compounds, mercapto group-containing compounds, and aliphatic carboxylic acid compounds is preferred from the viewpoint of dispersion stability of quantum dots, etc. Furthermore, the organic ligand is more preferably at least one selected from the group consisting of oleic acid, heptanoic acid, hexanoic acid, heptacosanoic acid, lauric acid, hexyl mercaptan, octyl mercaptan, and lauryl mercaptan.

[0092] The content of the organic ligand in the quantum dots is not particularly limited, but is preferably 0.5% by mass to 15% by mass, with the total mass of the quantum dots and the organic ligand being 100% by mass.

[0093] Quantum dots having organic ligands having coordinating groups coordinated on the surface can be synthesized by methods described in, for example, J. Am. Chem. Soc., 115, pp. 8706-8715 (1993), J. Phys. Chem., 101, pp. 9463-9475 (1997), Nature volume 575, pp. 634-638 (2019), etc. Commercially available quantum dots can also be suitably used.

[0094] Furthermore, quantum dots coated with a coating layer made of glass may be used as the quantum dots. The coating layer made of glass may be composed of a sintered body of glass powder. The yield point of the glass powder may be 380°C or less, 300°C or less, or 200°C or less. On the other hand, the lower limit of the yield point of the glass powder is not particularly limited, but may be 100°C or more, or 120°C or more. Here, the yield point refers to the point at which a test piece shows maximum elongation in measurement using a thermal expansion measurement (TMA) device, i.e., the value at which the test piece stops elongating.

[0095] As the glass powder, Sn- and P-based glasses such as SnO-P2O5-based glass, SnO-P2O5-B2O3-based glass, and SnO-P2O5-F-based glass, which have low deformation points, are preferred. Among these, it is preferable to use SnO-P2O5-F-based glass, which is easy to lower the deformation point. The specific composition of SnO-P2O5-F-based glass is, in cation %, Sn 2+ 10-90%, P 5+ 10-70%, anion % and O 2- 30~99.9%, F - Examples of SnO-P2O5-based glasses include those containing, in mole percent, 50-80% SnO, 5-25% P2O5 (but excluding 25%), 0-3% ZrO2, 0-10% Al2O3, 0-10% B2O3, 0-10% Li2O, 0-10% Na2O, 0-10% K2O, 0-10% Li2O + Na2O + K2O, 0-10% MgO, 0-3% CaO, 0-2.5% SrO, 0-2% BaO, 0-11% MgO + CaO + SrO + BaO, and 0-10% ZrO2 + Al2O3 + MgO, with an SnO / P2O5 ratio of 1.6 to 4.8.

[0096] Furthermore, quantum dots coated with a polymeric compound may be used as the quantum dots. Examples of such polymeric compounds include copolymers containing acid groups or maleic anhydride groups, such as maleic anhydride (MA)-olefin copolymers, acrylic-olefin copolymers, styrene-maleic anhydride copolymers, and polyethylene oxide; polystyrene derivatives; poly(meth)acrylate esters; ethylene-norbornene copolymers; urethane acrylate oligomers (including polyester, polyether, polybutadiene, and polycaprolactone types); and the like.

[0097] The content of quantum dots (B) in the composition of the present invention is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and even more preferably 0.1 parts by mass or more, per 100 parts by mass of resin (A) (if a curing agent is included, the total of 100 parts by mass of resin (A) and curing agent). Furthermore, the content of quantum dots (B) in the composition of the present invention is preferably 3 parts by mass or less, more preferably 2 parts by mass or less, and even more preferably 1 part by mass or less, per 100 parts by mass of resin (A) (if a curing agent is included, the total of 100 parts by mass of resin (A) and curing agent). That is, the content of quantum dots (B) in the composition of the present invention is preferably 0.01 parts by mass or more and 3 parts by mass or less, more preferably 0.05 parts by mass or more and 2 parts by mass or less, and even more preferably 0.1 parts by mass or more and 1 part by mass or less, per 100 parts by mass of resin (A) (if a curing agent is included, the total of 100 parts by mass of resin (A) and curing agent). When two or more types of quantum dots (B) are used, the above content represents the total amount.

[0098] [Blocked Carboxylic Acid (C)] The blocked carboxylic acid (C) contained in the composition of the present invention is a reaction product of a compound (c1) selected from a carboxylic acid and a carboxylic acid anhydride with a vinyl ether compound (c2) serving as a blocking agent, and is a compound in which the carboxy group of the carboxylic acid is protected by the blocking agent.

[0099] In other words, "blocking" of blocked carboxylic acid (C) refers to protecting the carboxy group (-COOH) derived from compound (c1) by addition reaction with the vinyl ether group (-O-CH=CH2) or vinyl thioether group (-S-CH=CH2) of vinyl ether compound (c2). Blocked carboxylic acid (C) is dissociated again into compound (c1) and vinyl ether compound (c2) by heating.

[0100] In blocked carboxylic acid (C), the carboxyl group of the carboxylic acid is protected by a blocking agent, so the activation ability based on the carboxyl group of the carboxylic acid becomes latent during heat history during the manufacturing process, making it inactive against thermosetting resins. On the other hand, when the LED is turned on, the quantum dots generate heat, and during this heat generation, the vinyl ether compound (c2), which is the blocking agent, dissociates to generate carboxylic acid, which protects the quantum dots.

[0101] Here, examples of the reaction between the compound (c1) and the vinyl ether compound (c2) include a mode in which a carboxylic acid compound is reacted with a vinyl ether compound; a mode in which a carboxylic acid anhydride is reacted with a hydroxyvinyl ether compound; a mode in which a reaction product of a carboxylic acid anhydride and a polyhydric alcohol is addition polymerized with a divinyl ether compound; and a mode in which a dicarboxylic acid is addition polymerized with a divinyl ether compound.

[0102] (Compound (c1)) The compound (c1) used to produce the blocked carboxylic acid (c) may be a monofunctional carboxylic acid, a polyfunctional carboxylic acid, or a carboxylic acid anhydride. Examples of the monofunctional carboxylic acid include linear or branched saturated aliphatic monofunctional carboxylic acids such as acetic acid, propionic acid, butyric acid, and lauric acid; linear or branched unsaturated aliphatic monofunctional carboxylic acids such as acrylic acid and methacrylic acid; and aromatic monofunctional carboxylic acids such as benzoic acid and 2-phenoxybenzoic acid.

[0103] Examples of polyfunctional carboxylic acids include linear, branched, or cyclic saturated aliphatic bifunctional carboxylic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, glutaric acid, 2,4-diethylglutaric acid, 2,4-dimethylglutaric acid, pimelic acid, azelaic acid, sebacic acid, and cyclohexanedicarboxylic acid; linear or branched unsaturated aliphatic bifunctional carboxylic acids such as maleic acid, fumaric acid, and itaconic acid; and diglycolic acid. Examples of polyfunctional carboxylic acids also include trifunctional or higher carboxylic acids such as trimellitic acid and pyromellitic acid.

[0104] Specific examples of carboxylic acid anhydrides include succinic anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, phthalic anhydride, diglycolic anhydride, and glutaric anhydride.

[0105] The compound (c1) is preferably a polyfunctional carboxylic acid, more preferably a bifunctional carboxylic acid, and even more preferably a saturated aliphatic bifunctional carboxylic acid.

[0106] (Vinyl ether compound (c2)) The vinyl ether compound (c2) used to produce the blocked carboxylic acid (C) is not particularly limited as long as it is a compound having a vinyl ether group (-O-CH=CH2) or a vinyl thioether group (-S-CH=CH2), and examples thereof include aliphatic vinyl ethers, aliphatic vinyl thioethers, cyclic vinyl ethers, and cyclic vinyl thioethers.

[0107] Specific examples of aliphatic vinyl ethers include monovinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, 2-ethylhexyl vinyl ether, and cyclohexyl vinyl ether; divinyl ether compounds such as butanediol divinyl ether, cyclohexanediol divinyl ether, cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, ethylene glycol divinyl ether, and hexanediol divinyl ether; trivinyl ether compounds such as trimethylolpropane trivinyl ether; and tetravinyl ether compounds such as pentaerythritol tetravinyl ether. Examples of aliphatic vinyl thioethers include thio compounds corresponding to the above-mentioned examples of aliphatic vinyl ethers.

[0108] Specific examples of cyclic vinyl ethers include 2,3-dihydrofuran, 3,4-dihydrofuran, 2,3-dihydro-2H-pyran, 3,4-dihydro-2H-pyran, 3,4-dihydro-2-methoxy-2H-pyran, 3,4-dihydro-4,4-dimethyl-2H-pyran-2-one, 3,4-dihydro-2-ethoxy-2H-pyran, and sodium 3,4-dihydro-2H-pyran-2-carboxylate. Examples of cyclic vinyl thioethers include thio compounds corresponding to the above-mentioned examples of cyclic vinyl ethers.

[0109] The vinyl ether compound (c2) may also be a hydroxyvinyl ether compound used in the reaction with a carboxylic acid anhydride. Specific examples of such hydroxyvinyl ether compounds include hydroxymethyl vinyl ether, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxypentyl vinyl ether, hydroxyhexyl vinyl ether, hydroxyheptyl vinyl ether, hydroxyoctyl vinyl ether, hydroxynonyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, 3-hydroxycyclohexyl vinyl ether, 2-hydroxycyclohexyl vinyl ether, cyclohexanedimethanol monovinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, and tetraethylene glycol monovinyl ether.

[0110] The vinyl ether compound (c2) is preferably a vinyl ether, more preferably an alkyl vinyl ether.

[0111] The blocked carboxylic acid (C) may be a reaction product of any combination of the above-mentioned compound (c1) and the above-mentioned vinyl ether compound (c2). However, a reaction product (hemiacetal ester) of the compound (c1) with a vinyl ether is preferred, and a reaction product of a saturated aliphatic bifunctional carboxylic acid with an alkyl vinyl ether is more preferred.

[0112] The method for synthesizing the blocked carboxylic acid (C) using the above-mentioned compound (c1) and vinyl ether compound (c2) is not particularly limited, and can be carried out according to a conventional method for addition reaction.

[0113] The blocked carboxylic acid (C) may be a synthetic product or a commercially available product, such as Santacid (registered trademark, the same applies hereinafter) D-2, Santacid G, Santacid H, Santacid I, Nofcure (registered trademark, the same applies hereinafter) TN-1, Nofcure TN-2, Nofcure TN-5, and Nofcure TN-6 (all manufactured by NOF Corporation).

[0114] The blocked carboxylic acids (C) can be used singly or in combination of two or more.

[0115] The content of the blocked carboxylic acid (C) in the composition of the present invention is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, even more preferably 2 parts by mass or more, and particularly preferably 3 parts by mass or more, per 100 parts by mass of resin (A) (if a curing agent is included, the total of 100 parts by mass of resin (A) and curing agent). Furthermore, the content of the blocked carboxylic acid (C) in the composition of the present invention is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, and particularly preferably 15 parts by mass or less, per 100 parts by mass of resin (A) (if a curing agent is included, the total of 100 parts by mass of resin (A) and curing agent). That is, the content of the blocked carboxylic acid (C) in the composition of the present invention is preferably from 0.1 to 50 parts by mass, more preferably from 1 to 30 parts by mass, even more preferably from 2 to 20 parts by mass, and particularly preferably from 3 to 15 parts by mass, per 100 parts by mass of resin (A) (100 parts by mass of resin (A) and curing agent combined, if a curing agent is included). When two or more types of blocked carboxylic acids (C) are used, the above content represents the total amount.

[0116] [Optional ingredients] The composition of the present invention may contain optional components within the scope of not impairing the effects of the present invention. Examples of optional components include the above-mentioned curing agent, as well as thermal acid generators, thermal base generators, ultraviolet absorbers, inorganic fillers (particularly silica), antioxidants, antistatic agents, flame retardants, adhesion promoters, dispersants, antifoaming agents, matting agents, light stabilizers, dyes, pigments, fluorescent substances, sensitizers, surfactants, organic solvents, etc. The optional components may be used alone or in combination of two or more. The thermal acid generators, thermal base generators, inorganic fillers, and organic solvents will be described below.

[0117] <Thermal acid generator> The composition of the present invention may further contain a thermal acid generator. A thermal acid generator is a compound that generates an acid by bond cleavage caused by heat. By including a thermal acid generator, the curing of the composition of the present invention can be further accelerated.

[0118] Examples of the cation moiety of the thermal acid generator include arylsulfonium ions (particularly monoarylsulfonium ions) such as 4-hydroxyphenyl-methyl-benzylsulfonium ion, 4-hydroxyphenyl-methyl-(2-methylbenzyl)sulfonium ion, 4-hydroxyphenyl-methyl-1-naphthylmethylsulfonium ion, and p-methoxycarbonyloxyphenyl-benzyl-methylsulfonium ion. Examples of the anion moiety of the thermal acid generator include [(Y) s B(Phf)4 s ] (wherein Y represents a phenyl group or a biphenylyl group; Phf represents a phenyl group in which at least one hydrogen atom is substituted with at least one selected from a perfluoroalkyl group, a perfluoroalkoxy group, and a halogen atom; and s is an integer of 0 to 3), BF4, [(Rf) n PF 6-n ] (Rf: an alkyl group in which 80% or more of the hydrogen atoms are substituted with fluorine atoms, and n is an integer of 0 or more and 5 or less), AsF6, SbF6, pentafluorohydroxyantimonate, and the like.

[0119] The thermal acid generator may be a synthetic product or a commercially available product. Examples of commercially available products include TA-60, TA-60B, TA-100, TA-100FG, and TA-120 (all manufactured by San-Apro Co., Ltd.); CI-2639 and CI-2624 (both manufactured by Nippon Soda Co., Ltd.); CXC-1612 and CXC-1738 manufactured by King Industries Co., Ltd. (both manufactured by King Industries Co., Ltd.); San-Aid (registered trademark, the same applies hereinafter) SI-60, San-Aid SI-80, San-Aid SI-100, San-Aid SI-200, San-Aid SI-110, San-Aid SI-145, San-Aid SI-150, San-Aid SI-60L, San-Aid SI-80L, San-Aid SI-100L, San-Aid SI-110L, San-Aid SI-145L, San-Aid SI-150L, ​​and San-Aid SI-160L, San-Aid SI-180L (both manufactured by Sanshin Chemical Industry Co., Ltd.), etc.

[0120] The thermal acid generators can be used alone or in combination of two or more.

[0121] When the composition of the present invention contains a thermal acid generator, the content of the thermal acid generator in the composition of the present invention is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and even more preferably 0.1 parts by mass or more, per 100 parts by mass of resin (A) (or, if a curing agent is included, the total of 100 parts by mass of resin (A) and curing agent). Furthermore, the content of the thermal acid generator in the composition of the present invention is preferably 3 parts by mass or less, more preferably 2 parts by mass or less, and even more preferably 1 part by mass or less, per 100 parts by mass of resin (A) (or, if a curing agent is included, the total of 100 parts by mass of resin (A) and curing agent). That is, the content of the thermal acid generator in the composition of the present invention is preferably 0.01 parts by mass or more but 3 parts by mass or less, more preferably 0.05 parts by mass or more but 2 parts by mass or less, and even more preferably 0.1 parts by mass or more but 1 part by mass or less, per 100 parts by mass of resin (A) (or, if a curing agent is included, the total of 100 parts by mass of resin (A) and curing agent). When two or more types of thermal acid generators are used, the above content represents the total amount thereof.

[0122] <Thermal base generator> The composition of the present invention may further contain a thermal base generator. A thermal base generator is a compound that generates a base by bond cleavage caused by heat. By including a thermal base generator, the curing of the composition of the present invention can be further accelerated.

[0123] The thermal base generator can be any compound that generates a base by heating as described above, and examples thereof include 1,8-diazabicyclo[5.4.0]undecene-7 (DBU) or a salt thereof (e.g., phenol salt, octylate salt, p-toluenesulfonate, formate salt, tetraphenylborate salt, etc.); 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) or a salt thereof (e.g., phenol salt, octylate salt, p-toluenesulfonate, formate salt, tetraphenylborate salt, etc.); salts, etc.); tertiary amines such as benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and N,N-dimethylcyclohexylamine; imidazoles such as 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole; phosphate esters, phosphines such as triphenylphosphine; phosphonium compounds such as tetraphenylphosphonium tetra(p-tolyl)borate; organic metal salts such as zinc octoate and tin octoate; and metal chelates.

[0124] The thermal base generator may be a synthetic product or a commercially available product. Examples of commercially available products include U-CAT (registered trademark, the same applies hereinafter) SA1, U-CAT SA102, U-CAT SA102-50, U-CAT SA106, U-CAT SA112, U-CAT SA506, U-CAT SA603, U-CAT 1000, U-CAT 1102, U-CAT 2000, U-CAT 2024, U-CAT 2026, U-CAT 2030, U-CAT 2110, U-CAT 2313, U-CAT 651M, U-CAT 660M, U-CAT 18X, U-CAT 201G, U-CAT 202, U-CAT 420A, and U-CAT 130 (all manufactured by San-Apro Co., Ltd.).

[0125] The thermal base generators can be used alone or in combination of two or more.

[0126] When the composition of the present invention contains a thermal base generator, the content of the thermal base generator in the composition of the present invention is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and even more preferably 0.3 parts by mass or more, per 100 parts by mass of resin (A) (or, if a curing agent is included, the total of 100 parts by mass of resin (A) and curing agent). Furthermore, the content of the thermal base generator in the composition of the present invention is preferably 3 parts by mass or less, more preferably 2 parts by mass or less, and even more preferably 1 part by mass or less, per 100 parts by mass of resin (A) (or, if a curing agent is included, the total of 100 parts by mass of resin (A) and curing agent). That is, the content of the thermal base generator in the composition of the present invention is preferably 0.01 parts by mass or more and 3 parts by mass or less, more preferably 0.1 parts by mass or more and 2 parts by mass or less, and even more preferably 0.3 parts by mass or more and 1 part by mass or less, per 100 parts by mass of resin (A) (or, if a curing agent is included, the total of 100 parts by mass of resin (A) and curing agent). When two or more types of thermal base generators are used, the above content represents the total amount thereof.

[0127] <Inorganic filler> If necessary, an inorganic filler can be added to the composition of the present invention, which can improve various physical properties of the resulting cured product, such as strength, hardness, elastic modulus, thermal expansion coefficient, thermal conductivity, heat dissipation, electrical properties, light reflectance, flame retardancy, fire resistance, gas barrier properties, and thixotropy.

[0128] The inorganic filler is not particularly limited as long as it is an inorganic substance or a compound containing an inorganic substance, and specific examples include silica-based inorganic fillers such as quartz, fumed silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, and ultrafine amorphous silica, as well as alumina, zircon, iron oxide, zinc oxide, titanium oxide, silicon nitride, boron nitride, aluminum nitride, silicon carbide, glass fiber, glass flakes, alumina fiber, carbon fiber, mica, graphite, carbon black, ferrite, graphite, diatomaceous earth, clay, clay, talc, aluminum hydroxide, calcium carbonate, manganese carbonate, magnesium carbonate, barium sulfate, potassium titanate, calcium silicate, inorganic balloons, and silver powder. These inorganic fillers can be used alone or in combination of two or more.

[0129] The inorganic filler may be subjected to a suitable surface treatment, such as alkylation, trimethylsilylation, silicone treatment, or treatment with a silane coupling agent, but is not particularly limited thereto.

[0130] The inorganic filler may be in various shapes, such as crushed, flake, spherical, or rod-like. The average particle size and particle size distribution of the inorganic filler are not particularly limited, but the average particle size is preferably 0.001 μm or more and 100 μm or less, and more preferably 0.005 μm or more and 70 μm or less. Similarly, the BET specific surface area of ​​the inorganic filler is not particularly limited, but is preferably 70 μm or less. 2 / g or more, and 100m 2 / g or more is more preferable, and 200m 2 It is particularly preferable that the saturation coefficient is 1 / g or more.

[0131] Among these, the inorganic filler is preferably silica. The silica may be a synthetic product or a commercially available product. Examples of commercially available silica include the Aerosil (registered trademark, the same applies hereinafter) series manufactured by Nippon Aerosil Co., Ltd. (Aerosil R972, Aerosil R974, Aerosil R9200, Aerosil R976, Aerosil R976S, Aerosil RX50, Aerosil NAX50, Aerosil NX90, Aerosil RX200, Aerosil R8200, Aerosil RX300, Aerosil R812, Aerosil R812S, Aerosil RY50, Aerosil NY50, Aerosil RY200S, Aerosil R202, Aerosil RY200, Aerosil RY300, Aerosil R104, Aerosil R10). 6, Aerosil NA50H, Aerosil NA50Y, Aerosil RA200H, Aerosil RA200HS, Aerosil NA200Y, Aerosil R805, Aerosil R816, Aerosil RM50, Aerosil R711, Aerosil R7200, Aerosil OX50, Aerosil 50, Aerosil 90G, Aerosil 130, Aerosil 150, Aerosil 200, Aerosil 300, Aerosil 380, etc.), and QS102, MT10, DM10, DM20S, DM30, DM30S, KS20S, KS30S, HM20S, PM20, PM20S, ZD30S, etc. manufactured by Tokuyama Corporation. These silicas can be used alone or in combination of two or more.

[0132] When the composition of the present invention contains silica, the content of silica in the composition is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and even more preferably 3 parts by mass or more, per 100 parts by mass of resin (A) (if a curing agent is included, the total of 100 parts by mass of resin (A) and curing agent). Furthermore, the content of silica is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less, per 100 parts by mass of resin (A) (if a curing agent is included, the total of 100 parts by mass of resin (A) and curing agent).

[0133] <Thixotropy> According to a preferred embodiment, the composition of the present invention has thixotropy. The thixotropy of the composition of the present invention increases the fluidity (high fluidity) when shear force is applied to the composition during coating, thereby improving workability and productivity. On the other hand, when the composition is allowed to stand and harden after coating, the viscosity is sufficiently high (low fluidity), and there is little or no spontaneous casting, allowing a cured product of the desired shape to be obtained.

[0134] The thixotropy index, which is an index of the thixotropy of the composition of the present invention, is preferably from 2 to 10. In this specification, the thixotropy index is defined as the value calculated by V1 / V2, where V1 is the viscosity of the composition measured using an E-type viscometer at a temperature of 25°C and a rotation speed of 0.5 rpm, and V2 is the viscosity of the composition measured using an E-type viscometer at a temperature of 25°C and a rotation speed of 5 rpm.

[0135] If the thixotropy index is within the above range, the above effects (high fluidity during application and low fluidity during standing and curing) can be efficiently obtained.

[0136] The composition of the present invention can be imparted with thixotropy by adding an inorganic filler, and the thixotropy index can be controlled by appropriately selecting the type and amount of inorganic filler added.

[0137] <Organic solvents> The composition of the present invention may contain an organic solvent. The type of organic solvent is not particularly limited as long as it can dissolve or disperse the components (A) to (C) and any optional components contained as needed. The organic solvent may be used alone or in combination of two or more.

[0138] Examples of the organic solvent include hydrocarbon solvents, ester solvents, alcohol solvents, ketone solvents, ether solvents, and nitrogen-containing solvents.

[0139] Examples of hydrocarbon solvents include aliphatic hydrocarbon solvents such as n-pentane, n-hexane, and cyclohexane, and aromatic hydrocarbon solvents such as benzene, toluene, and xylene.

[0140] Examples of ester-based solvents include carbonate-based solvents such as diethyl carbonate, acetate monoester-based solvents such as methyl acetate and ethyl acetate, lactone-based solvents such as γ-butyrolactone, polyhydric alcohol partial ether carboxylate-based solvents such as diethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate, and lactate-based solvents such as methyl lactate and ethyl lactate.

[0141] Examples of alcohol solvents include monoalcohol solvents such as methanol, ethanol, and n-propanol, and polyalcohol solvents such as ethylene glycol and 1,2-propylene glycol.

[0142] Examples of the ketone solvent include chain ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and cyclic ketone solvents such as cyclohexanone.

[0143] Examples of ether solvents include chain ether solvents such as n-butyl ether, polyhydric alcohol ether solvents such as cyclic ether solvents such as tetrahydrofuran, and polyhydric alcohol partial ether solvents such as diethylene glycol monomethyl ether.

[0144] Examples of nitrogen-containing solvents include chain nitrogen-containing solvents such as N,N-dimethylacetamide, and cyclic nitrogen-containing solvents such as N-methyl-2-pyrrolidone.

[0145] However, from the viewpoint of ensuring thixotropy, etc., it is preferable that the content of the organic solvent in the composition of the present invention is as small as possible. Specifically, the content of the organic solvent in the composition of the present invention is preferably 10% by mass or less, relative to the total mass of the composition (100% by mass). It is more preferably 5% by mass or less, further preferably 1% by mass or less, and particularly preferably 0% by mass, ie, no organic solvent is included.

[0146] [Method for preparing the composition] The method for preparing the composition of the present invention is not particularly limited, and examples thereof include a method of mixing the components at room temperature or at elevated temperature using a mixer such as a homodisper, a homomixer, a rotation-revolution mixer, a universal mixer, a planetarium mixer, a kneader, a three-roll mill, a bead mill, etc. The order in which the components are mixed is also not particularly limited, and the components may be mixed sequentially or all at once.

[0147] [Cured product] The composition of the present invention is cured by heating to form a cured product. That is, the present invention provides a cured product of the resin composition for encapsulating optical semiconductor elements of the present invention. The heating temperature (curing temperature) during curing is preferably 60°C or higher and 200°C or lower. The heating time (curing time) is preferably 1 minute or higher and 120 minutes or lower.

[0148] The shape of the cured product obtained by curing the composition of the present invention is not particularly limited, and examples thereof include a sheet, a film, a convex lens, a concave lens, a Fresnel lens, a truncated cone, a truncated square pyramid, etc. The cured product of the present invention can be handled alone, but can also be handled in a state in which it is used to cover, seal, or adhere an optical semiconductor element or the like.

[0149] [Optical semiconductor devices, image display devices] According to one embodiment of the present invention, there is provided an optical semiconductor device in which an optical semiconductor element is encapsulated with a cured product of the above-described composition of the present invention.

[0150] As described above, the composition and cured product of the present invention are particularly useful for encapsulating optical semiconductor elements (LED elements) such as blue LEDs (light-emitting diodes), red LEDs, green LEDs, white LEDs, and ultraviolet LEDs. Optical semiconductor devices in which such optical semiconductor elements are encapsulated are suitable for use in various lighting devices, electronic bulletin boards, traffic lights, backlights for liquid crystal display devices, LED displays, and the like. Furthermore, an image display device can be produced by combining the backlight with a display panel.

[0151] When an optical semiconductor element such as an LED is encapsulated with the composition of the present invention, the LED element can be encapsulated with a cured product of the composition of the present invention by, for example, applying the composition of the present invention onto an LED element mounted in a pre-molded package made of a thermoplastic resin and curing the composition on the LED element.

[0152] The optical semiconductor encapsulating resin composition of the present invention and its cured product can be preferably used when the optical semiconductor device is a mini LED display device or a micro LED display device.Furthermore, it can also be used in an optical semiconductor device that is used in a folded state, such as a foldable image display device (flexible display) (particularly, a foldable image display device (foldable display)).

[0153] Although the embodiments of the present invention have been described in detail, it is clear that this is for illustrative and exemplary purposes only and not for limitation, and that the scope of the present invention should be interpreted by the appended claims.

[0154] The present invention encompasses the following aspects and configurations: 1. A resin composition for encapsulating an optical semiconductor, comprising a resin (A), quantum dots (B), and a blocked carboxylic acid (C) in which a carboxy group of a carboxylic acid is blocked with a vinyl ether compound; 2. The resin composition for encapsulating an optical semiconductor according to the above item 1, wherein the content of the blocked carboxylic acid (C) is 0.1 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the resin (A); 3. The resin composition for encapsulating an optical semiconductor according to 1. or 2. above, further comprising a curing agent; 4. The resin composition for encapsulating an optical semiconductor according to 3. above, wherein the content of the blocked carboxylic acid (C) is 0.1 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the resin (A) and the curing agent combined; 5. The optical semiconductor encapsulating resin composition according to any one of 1. to 4. above, wherein the resin (A) is at least one selected from the group consisting of a thermosetting silicone resin having two or more thermosetting functional groups in one molecule, a thermosetting epoxy resin having two or more thermosetting functional groups in one molecule, and a thermosetting (meth)acrylic resin having two or more thermosetting functional groups in one molecule; 6. The resin composition for encapsulating an optical semiconductor according to any one of 1. to 5. above, which has thixotropy; 7. The optical semiconductor encapsulating resin composition according to 6. above, wherein the viscosity of the optical semiconductor encapsulating resin composition measured using an E-type viscometer at a temperature of 25°C and a rotation speed of 0.5 rpm is V1, and the viscosity of the optical semiconductor encapsulating resin composition measured using an E-type viscometer at a temperature of 25°C and a rotation speed of 5 rpm is V2, and the thixotropy index defined as V1 / V2 is 2 or more and 10 or less; 8. A cured product of the optical semiconductor encapsulating resin composition according to any one of 1. to 7. above; 9. An optical semiconductor device in which an optical semiconductor element is encapsulated with the cured product according to 8. above; 10. An image display device comprising the optical semiconductor device described in 9 above. [Example]

[0155] The present invention will be described in more detail using the following examples and comparative examples, but the technical scope of the present invention is not limited to the following examples.

[0156] [Preparation of Resin Composition for Encapsulating Optical Semiconductors] (Examples 1 to 4, Comparative Examples 1 to 4) The components were blended to obtain the compositions shown in Table 1 below, and mixed for 3 minutes at 25°C using a centrifugal mixer (Thinky Mixer ARE-310) to prepare optical semiconductor encapsulating resin compositions 1 to 4 and comparative optical semiconductor encapsulating resin compositions 1 to 4. The details of each component are as follows: <Composition> KR-470: KR-470, alicyclic epoxy group-containing cyclic siloxane tetrafunctional oligomer, manufactured by Shin-Etsu Chemical Co., Ltd. EP-3400L: Cyclic siloxane compound, manufactured by ADEKA Corporation Cel8010: Celloxide 8010, 2,3'-bi(7-oxabicyclo[4.1.0]heptane), manufactured by Daicel Corporation EHPE3150: 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, manufactured by Daicel Corporation MH-700G: Rikacid MH-700G, an acid anhydride hardener, a mixture of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride, manufactured by New Japan Chemical Co., Ltd. Santacid G: Santacid G, blocked carboxylic acid, bifunctional carboxylic acid hemiacetal ester, manufactured by NOF Corporation R202: AEROSIL R202, silica, manufactured by Nippon Aerosil Co., Ltd. R976S: AEROSIL 976S, silica, manufactured by Nippon Aerosil Co., Ltd. TA-100FG: Sulfonium salt type thermal acid generator, manufactured by San-Apro Co., Ltd. SA603: U-CAT SA603, formate salt of 1,8-diazabicyclo[5.4.0]undecene-7, a thermal base generator, manufactured by San-Apro Co., Ltd. Quantum dots: InP, manufactured by Hansol.

[0157] <Fabrication of light-emitting device> A light-emitting device was prepared, comprising a substrate (20 mm long and wide, 1 mm high) coated with a reflective material, a blue LED element with an emission peak wavelength of 450 nm, and an electrode layer to which the blue LED element was electrically connected via solder. The optical semiconductor encapsulating resin compositions of each Example and Comparative Example were applied to the prepared light-emitting device using a Jet dispenser manufactured by Micronic Technologies, Inc., so that the composition formed a lens shape. The optical semiconductor encapsulating resin composition was then cured by heating at 190°C for 5 minutes, yielding a light-emitting device in which the blue LED element was covered with the cured product of the composition.

[0158] [evaluation] (thixotropy index) The viscosity was measured at 25°C at rotation speeds of 0.5 rpm and 5 rpm using an E-type viscometer (cone rotor 3° x R9.7) manufactured by Toki Sangyo Co., Ltd. The viscosity of the optical semiconductor encapsulating resin composition at a rotation speed of 0.5 rpm was defined as V1 (unit: Pa s), and the viscosity of the optical semiconductor encapsulating resin composition at a rotation speed of 5 rpm was defined as V2 (unit: Pa s). The thixotropy index was calculated by dividing V1 by V2 (V1 / V2).

[0159] (curable) The surface of the optical semiconductor encapsulating resin composition cured by heating on a blue LED element was rubbed with ethanol, and the curability was evaluated according to the following criteria: ◯: No change in the cured product, and no quantum dot components adhered to the wiping side ×: Scratch marks remain on the surface of the cured product, or quantum dot components adhere to the wiped side.

[0160] (Brightness maintenance rate) A power of about 22 mW was applied to the light-emitting device obtained above to cause it to emit light, and the initial luminance was measured. This was taken as the pre-test luminance (unit: cd / m 2 After that, the lamp was allowed to emit light continuously for 100 hours, and the luminance was measured. This was taken as the post-test luminance (unit: cd / m 2The luminance maintenance rate (unit: %) was calculated from the obtained pre-test luminance and post-test luminance values ​​using the formula (post-test luminance / pre-test luminance) x 100. The luminance meter used was a Topcon UA-20C (measurement conditions: measurement distance 600 mm, wide-angle lens (f = 12 mm), ≦500 nm cut filter*).

[0161] The compositions and evaluation results of the optical semiconductor encapsulating resin compositions of Examples 1 to 4 and Comparative Examples 1 to 4 are shown in Table 1 below. Note that blank spaces in the composition column of Table 1 indicate that the component was not used. The composition of each component in Table 1 is expressed in parts by mass.

[0162] [Table 1]

[0163] As is clear from Table 1 above, the compositions of Examples 1 to 4 were found to have higher luminance maintenance rates than the compositions of Comparative Examples 1 to 4. This demonstrates that the compositions of the present invention can further suppress the deterioration of quantum dots when the LED is turned on, and can further extend the life of optical semiconductor elements and optical semiconductor devices.

Claims

1. Resin (A), Quantum dots (B), a blocked carboxylic acid (C) in which the carboxy group of a carboxylic acid is blocked with a vinyl ether compound; A resin composition for sealing an optical semiconductor, comprising:

2. 2. The resin composition for encapsulating an optical semiconductor according to claim 1, wherein the content of the blocked carboxylic acid (C) is 0.1 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the resin (A).

3. The optical semiconductor encapsulating resin composition according to claim 1 , further comprising a curing agent.

4. 4. The resin composition for encapsulating an optical semiconductor according to claim 3, wherein a content of the blocked carboxylic acid (C) is 0.1 parts by mass or more and 50 parts by mass or less relative to a total of 100 parts by mass of the resin (A) and the curing agent.

5. 4. The optical semiconductor encapsulating resin composition according to claim 1, wherein the resin (A) is at least one selected from the group consisting of a thermosetting silicone resin having two or more thermosetting functional groups in one molecule, a thermosetting epoxy resin having two or more thermosetting functional groups in one molecule, and a thermosetting (meth)acrylic resin having two or more thermosetting functional groups in one molecule.

6. The optical semiconductor encapsulating resin composition according to claim 1 or 3, which has thixotropy.

7. The viscosity of the optical semiconductor encapsulating resin composition measured using an E-type viscometer at a temperature of 25° C. and a rotation speed of 0.5 rpm is defined as V1, When the viscosity of the optical semiconductor encapsulating resin composition measured using an E-type viscometer at a temperature of 25° C. and a rotation speed of 5 rpm is defined as V2, 7. The optical semiconductor encapsulating resin composition according to claim 6, wherein a thixotropy index defined by V1 / V2 is 2 or more and 10 or less.

8. A cured product of the optical semiconductor encapsulating resin composition according to claim 1 or 3.

9. An optical semiconductor device comprising an optical semiconductor element encapsulated with the cured product according to claim 8.

10. An image display device comprising the optical semiconductor device according to claim 9.

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