JP2012126756A - Curable resin composition, and light-emitting device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition which provides a cured product having a high refractive index, excellent transparency, and also excellent heat resistance, stably disperses a fluorescence substance, changes the hue of the cured product by only changing the kind of the fluorescence substance, and to provide a light-emitting device obtained by employing the same.SOLUTION: The curable resin composition contains: (A) at least one kind of polymer selected from a siloxane-based polymer, a titanoxane-based polymer, and a copolymer of these; (B) at least one kind of metal oxide particles selected from the group consisting of zirconium oxide, titanium oxide, zinc oxide, tantalum oxide, indium oxide, hafnium oxide, tin oxide, niobium oxide, and composites thereof; and (C) a fluorescent substance. The light-emitting device includes: a laminate (light-emitting element) composed of a base plate 2, a first electrode 3, a light-emitting layer 4, and a second electrode 5; and a cured film 1 which is the cured product of the curable resin composition formed around the laminate.

Description

  The present invention relates to a curable resin composition and a light emitting device obtained using the same.

  A light emitting element such as a light emitting diode (LED) element is usually covered with a sealing material in order to protect the light emitting element or change the color. In particular, it is known that the light extraction efficiency is increased by coating the light emitting element with a material having a high refractive index.

  Conventionally, an epoxy resin has been generally used as a resin for this sealing material, but in an LED element using a blue LED element or an ultraviolet LED element as a light emitting element, a near ultraviolet light or an ultraviolet LED emitted from the blue LED element is used. The ultraviolet light emitted from the element has a problem that the sealing material made of an epoxy resin is yellowed in the vicinity of the light emitting element or is thermally deteriorated due to heat generation of the light emitting element. In particular, in applications that require high luminance such as electric lamps, the amount of light emitted from blue LED elements and ultraviolet LED elements is large, and yellowing and thermal degradation are likely to occur.

  For this reason, a sealing material made of a silicone resin has been studied as a sealing material that does not cause yellowing due to near-ultraviolet light or ultraviolet light even in a high-luminance environment and has heat resistance. However, a silicone resin made of dimethylsiloxane has a low refractive index, and it is difficult to efficiently extract light emitted from the LED element.

  Patent Documents 1 and 2 disclose a silicone resin composition containing a silicone resin having an alkenyl group bonded to a silicon atom and an organohydrogenpolysiloxane having a Si—H bond. In Patent Documents 1 and 2, this silicone resin composition is crosslinked by a hydrosilylation reaction to form a cured product. However, this cured product has a problem that the refractive index is low.

JP 2004-186168 A JP 2004-221308 A

  The present invention solves the problems of the prior art as described above, and has a high refractive index, excellent transparency, can stably disperse phosphors, and further has excellent heat resistance. An object of the present invention is to provide a curable resin composition capable of obtaining a body and capable of changing the hue of a cured body simply by changing the type of phosphor, and a light-emitting device obtained using the same And

In order to achieve the above-mentioned object, the present inventors have conducted intensive research and have developed a curable composition containing a specific polymer such as a siloxane polymer, particles of a specific metal oxide such as zirconium oxide, and a phosphor. It was found that the above-mentioned object can be achieved by using the above, and the present invention was completed.
That is, the present invention provides the following [1] to [11].
[1] A curable resin composition containing the following components (A) to (C).
(A) At least one polymer selected from siloxane polymers, titanoxane polymers, and copolymers thereof (B) zirconium oxide, titanium oxide, zinc oxide, tantalum oxide, indium oxide, hafnium oxide, oxidation Particles of at least one metal oxide selected from the group consisting of tin, niobium oxide, and composites thereof (C) Phosphor [2] The blending amount of component (B) is 100 masses of component (A). Curable resin composition as described in said [1] which is 50-1,000 mass parts with respect to a part.
[3] The curable resin composition according to [1] or [2], wherein the amount of the component (C) is 10 to 500 parts by mass with respect to 100 parts by mass of the component (B).
[4] The curability according to any one of [1] to [3], wherein the amount of the component (C) is 10 to 500 parts by mass with respect to 100 parts by mass of the component (A). Resin composition.
[5] The curable resin composition according to any one of [1] to [4], further including (D) an organic solvent.
[6] The blending amount of the component (D) is 1 to 500 parts by mass with respect to 100 parts by mass of the total amount of the components excluding the component (D) in the curable resin composition. Curable resin composition.
[7] In the above [5] or [6], the blending amount of the component (D) is 10 to 50 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). The curable resin composition described.
[8] The curable resin composition according to any one of [1] to [7], wherein the number average primary particle size of the component (B) is 1 to 100 nm.
[9] The curable resin composition according to any one of [1] to [8], wherein the number average primary particle size of the component (C) is 0.1 to 100 μm.
[10] The curable resin composition according to any one of [1] to [9], which is used for coating a light emitting element.
[11] A light-emitting device comprising: a light-emitting element; and a cured film formed on the surface of the light-emitting element, which is a cured body of the curable resin composition according to [10].

The cured product of the curable resin composition of the present invention has a high refractive index, excellent transparency, and excellent heat resistance.
The curable resin composition of the present invention can stably disperse the phosphor.
In the curable resin composition of the present invention, it is possible to easily change the hue of the obtained cured product by changing the type of the starting phosphor. In this case, if used as a material for covering the surface of a light emitting element such as an LED element, the hue of light emitted from the light emitting element can be changed.

It is sectional drawing which shows notionally the light-emitting device coat | covered with the hardening body which consists of curable resin composition of this invention.

The curable resin composition of the present invention comprises (A) at least one polymer selected from siloxane-based polymers, titanoxane-based polymers, and copolymers thereof, (B) zirconium oxide, titanium oxide, and zinc oxide. Tantalum oxide, indium oxide, hafnium oxide, tin oxide, niobium oxide, and at least one metal oxide particle selected from the group consisting of these composites, and (C) a phosphor.
Hereinafter, each component used in the present invention will be described in detail.

[Component (A): at least one polymer selected from siloxane-based polymers, titanoxane-based polymers, and copolymers thereof]
Examples of at least one polymer selected from a siloxane-based polymer, a titanoxane-based polymer, and a copolymer thereof include, for example, a compound represented by the following general formula (1) and a general formula (2) below. A polymer formed by condensation of at least one compound selected from compounds can be exemplified.
(R ¹ ) _p Si (X) _4-p (1)
(In the general formula (1), R ¹ is a non-hydrolyzable organic group having 1 to 12 carbon atoms, X is a hydrolyzable group, and p is an integer of 0 to 3.)
(R ¹ ) _p Ti (X) _4-p (2)
(In the general formula (2), R ¹ is a non-hydrolyzable organic group having 1 to 12 carbon atoms, X is a hydrolyzable group, and p is an integer of 0 to 3.)
The hydrolyzable group represented by X in the general formulas (1) and (2) is usually in the temperature range of room temperature (25 ° C.) to 100 ° C. in the presence of non-catalyst and excess water. By heating, a hydrolyzable group such as an alkoxy group can be hydrolyzed to produce a silanol group or a titanol group. The hydrolyzable group can be further condensed after hydrolysis to form a siloxane condensate or titanoxane condensate.
The subscript p in the general formula (1) is an integer of 0 to 3, preferably an integer of 0 to 2.

It is preferable that at least one polymer selected from siloxane-based polymers, titanoxane-based polymers, and copolymers thereof includes at least one of silanol groups and titanol groups. The number of hydroxyl groups contained in at least one of the silanol group and titanol group is preferably 15 to 300%, more preferably 30 to 250%, based on the total number of silicon atoms and titanium atoms in the polymer. Especially preferably, it is 50 to 200%. When the number of hydroxyl groups contained in at least one of the silanol group and the titanol group is within the above range with respect to the total number of silicon atoms and titanium atoms in the polymer, the dispersibility of the metal oxide particles was excellent. A curable resin composition is obtained, and a cured film (cured body of the composition) having a high refractive index and excellent transparency, heat resistance, crack resistance, and light resistance is obtained.
The siloxane-based polymer, titanoxane-based polymer, and copolymers thereof may have some unhydrolyzed hydrolyzable groups remaining. The siloxane polymer, titanoxane polymer, and copolymers thereof may be partial condensates in which some silanol groups, titanol groups, or hydrolyzable groups are condensed.

R ¹ in the general formulas (1) and (2) is a non-hydrolyzable organic group having 1 to 12 carbon atoms. Here, the non-hydrolyzable in R ¹ means a property that exists stably as it is under the condition that the hydrolyzable group X is hydrolyzed.
Examples of R ¹ include a hydrocarbon group having 1 to 12 carbon atoms and a halogenated hydrocarbon group having 1 to 12 carbon atoms. R ¹ may be linear, branched, cyclic, or a combination thereof. R ¹ may have a structural unit containing a hetero atom. Examples of such a structural unit include an ether bond, an ester bond, and a sulfide bond. Examples of R ¹ containing such a bond include a group having an epoxy group such as an oxetanyl group and an oxiranyl group, and a group having a (meth) acryloyloxy group.
In R ¹ , the hydrocarbon group having 1 to 12 carbon atoms is preferably a hydrocarbon group having 1 to 8 carbon atoms from the viewpoint of reactivity and crack resistance of the cured film to be obtained. More preferably, it is a hydrocarbon group. Specifically, aliphatic hydrocarbon groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl Examples thereof include alicyclic hydrocarbon groups such as a group, and aromatic hydrocarbon groups such as a phenyl group, a methylphenyl group, an ethylphenyl group, and a benzyl group. Among these, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a t-butyl group, a phenyl group, and a methylphenyl group are preferable, and a methyl group and an ethyl group are more preferable.

Examples of the halogenated hydrocarbon group having 1 to 12 carbon atoms in R ¹ include a fluorinated hydrocarbon group, a chlorinated hydrocarbon group, and a brominated hydrocarbon group, and a fluorinated hydrocarbon group is preferable. The number of carbon atoms of the halogenated hydrocarbon group is preferably 1 to 4 from the viewpoint of reactivity and crack resistance of the resulting cured film.
Specifically, chloromethyl group, dichloromethyl group, trichloromethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, perfluoro-n-propyl Group, perfluoroisopropyl group, perfluoro-n-butyl group, perfluoroisobutyl group, perfluoro-t-butyl group and the like. Of these, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a pentafluoroethyl group, a perfluoro-n-propyl group, a perfluoroisopropyl group, and a perfluoro-t-butyl group are preferable. , Fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, and pentafluoroethyl group are more preferable.

  Examples of the hydrolyzable group X in the general formula (1) and the general formula (2) include a hydrogen atom, a halogen atom, an alkoxy group having 1 to 12 carbon atoms, a halogenated alkoxy group having 1 to 12 carbon atoms, and 2 carbon atoms. -12 acyloxy groups, C2-C12 halogenated acyloxy groups, and the like. Preferable examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like. Preferable examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group and an ethoxy group. Preferable examples of the acyloxy group having 2 to 12 carbon atoms include an acetoxy group, a propionyloxy group, and a butyroyloxy group.

Specific examples of the hydrolyzable silane compound represented by the general formula (1) (hereinafter sometimes abbreviated as silane compound) will be described.
Examples of the silane compound having four hydrolyzable groups include tetrachlorosilane, tetraaminosilane, tetraacetoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrabenzyloxysilane, trimethoxysilane, trimethoxysilane, An ethoxysilane etc. are mentioned.

Examples of silane compounds having three hydrolyzable groups include methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyl trimethoxysilane, pentafluorophenyl trimethoxysilane, phenyltrimethoxysilane, d 3 _- methyltrimethoxysilane, nonafluorobutyl ethyl trimethoxysilane, trifluoromethyl trimethoxy silane, and the like.

Examples of the silane compound having two hydrolyzable groups include dimethyldichlorosilane, dimethyldiaminosilane, dimethyldiacetoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, and dibutyldimethoxysilane.
Examples of the silane compound having one hydrolyzable group include trimethylchlorosilane, hexamethyldisilazane, trimethylsilane, tributylsilane, trimethylmethoxysilane, and tributylethoxysilane.

Specific examples of the hydrolyzable titanium compound represented by the general formula (2) (hereinafter sometimes abbreviated as titanium compound) will be described.
Titanium compounds having four hydrolyzable groups include tetrachlorotitanium, tetraaminotitanium, tetraacetoxytitanium, tetramethoxytitanium, tetraethoxytitanium, tetrabutoxytitanium, tetraphenoxytitanium, tetrabenzyloxytitanium, trimethoxytitanium. , Triethoxy titanium and the like.

Titanium compounds having three hydrolyzable groups include methyltrichlorotitanium, methyltrimethoxytitanium, methyltriethoxytitanium, methyltributoxytitanium, ethyltrimethoxytitanium, ethyltriisopropoxytitanium, ethyltributoxytitanium, butyl Examples include trimethoxy titanium, pentafluorophenyl trimethoxy titanium, phenyl trimethoxy titanium, d ₃ -methyl trimethoxy titanium, nonafluorobutyl ethyl trimethoxy titanium, trifluoromethyl trimethoxy titanium, and the like.

Examples of the titanium compound having two hydrolyzable groups include dimethyldichlorotitanium, dimethyldiaminotitanium, dimethyldiacetoxytitanium, dimethyldimethoxytitanium, diphenyldimethoxytitanium, dibutyldimethoxytitanium and the like.
Examples of the titanium compound having one hydrolyzable group include trimethylchlorotitanium, trimethyltitanium, tributyltitanium, trimethylmethoxytitanium, and tributylethoxytitanium.

The molecular weight of at least one polymer selected from the (A) component siloxane-based polymer, titanoxane-based polymer, and copolymers thereof will be described. Such molecular weight can be measured as a polystyrene-reduced weight average molecular weight using gel permeation chromatography (hereinafter sometimes abbreviated as GPC) using tetrahydrofuran as a mobile phase.
The weight average molecular weight of at least one polymer selected from siloxane-based polymers, titanoxane-based polymers, and copolymers thereof is preferably 500 to 100,000, more preferably 800 to 30,000, and still more preferably. 1,000 to 5,000. If the value is less than 500, the crack resistance during the formation of the cured film tends to decrease. When the value exceeds 100,000, the dispersibility of the metal oxide particles as the component (B) tends to decrease.

The catalyst used in obtaining at least one polymer selected from siloxane-based polymers, titanoxane-based polymers, and copolymers thereof is at least one selected from metal chelate compounds, acidic compounds, and basic compounds. It is preferable that it is a compound of this, and it is more preferable that it is an acidic compound.
(D-1) Metal Chelate Compound A metal chelate compound that can be used as a catalyst is represented by the following general formula (3).
R ¹⁵ _e M (OR ¹⁶ ) _fe (3)
(In the general formula (3), R ¹⁵ represents a chelating agent, M represents a metal atom, R ¹⁶ represents an alkyl group or an aryl group, f represents a valence of the metal atom M, and e represents an integer of 1 to f. Show.)

Here, the metal atom M is preferably at least one metal atom selected from a group 13 metal (aluminum, gallium, indium, thallium) and a group 4 metal (titanium, zirconium, hafnium). Zirconium is more preferred.
Examples of the chelating agent represented by R ¹⁵ include CH ₃ COCH ₂ COCH ₃ and CH ₃ COCH ₂ COOC ₂ H ₅ .
Examples of the alkyl group or aryl group represented by R ¹⁶ include the alkyl group or aryl group represented by R ¹ in the general formula (1).
Preferred specific examples of the metal chelate _{compound, (CH 3 (CH 3)} HCO) 4-t Ti (CH 3 COCH 2 COCH 3) t, (CH 3 (CH 3) HCO) 4-t Ti (CH 3 _{COCH 2 COOC 2 H 5) t} , (C 4 H 9 O) 4-t Ti (CH 3 COCH 2 COCH 3) t, (C 4 H 9 O) 4-t Ti (CH 3 COCH 2 COOC 2 H 5 ) _T , (C ₂ H ₅ (CH ₃ ) HCO) _4-t Ti (CH ₃ COCH ₂ COCH ₃ ) _t , (C ₂ H ₅ (CH ₃ ) HCO) _4-t Ti (CH ₃ COCH ₂ COOC _{2) H 5) t, (CH 3} (CH 3) HCO) 4-t Zr (CH 3 COCH 2 COCH 3) t, (CH 3 (CH 3) HCO) 4-t Zr (CH 3 COCH 2 COOC _{H 5) t, (C 4} H 9 O) 4-t Zr (CH 3 COCH 2 COCH 3) t, (C 4 H 9 O) 4-t Zr (CH 3 COCH 2 COOC 2 H 5) t, ( _{C 2 H 5 (CH 3)} HCO) 4-t Zr (CH 3 COCH 2 COCH 3) t, (C 2 H 5 (CH 3) HCO) 4-t Zr (CH 3 COCH 2 COOC 2 H 5) t _{, (CH 3 (CH 3)} HCO) 3-t Al (CH 3 COCH 2 COCH 3) t, (CH 3 (CH 3) HCO) 3-t Al (CH 3 COCH 2 COOC 2 H 5) t, ( _{C 4 H 9 O) 3-} t Al (CH 3 COCH 2 COCH 3) t, (C 4 H 9 O) 3-t Al (CH 3 COCH 2 COOC 2 H 5) t, (C 2 H 5 (CH ₃₎ HCO) _{3- Al (CH 3 COCH 2 COCH 3} ) t, (C 2 H 5 (CH 3) HCO) 3-t Al (CH 3 COCH 2 COOC 2 H 5) t , and the like.
T in these chemical formulas represents an integer of 0 to 4.

The amount of the metal chelate compound is preferably 0.0001 to 10 parts by mass, more preferably 0.001 to 5 parts by mass with respect to 100 parts by mass (as calculated as a complete hydrolysis condensate) of the silane compound and the titanium compound. It is. When the amount is less than 0.0001 part by mass, the coating property may be inferior when the composition of the present invention is applied to a substrate or the like by a spin coating method or the like. When the amount exceeds 10 parts by mass, polymer growth cannot be controlled and gelation may occur.
When hydrolyzing and condensing at least one of a silane compound and a titanium compound in the presence of a metal chelate compound, 0.5 to 20 mol of water is used per mol of the total amount of at least one of the silane compound and the titanium compound. It is particularly preferable to use 1 to 10 mol of water. If the amount of water is less than 0.5 mol, the hydrolysis reaction does not proceed sufficiently, which may cause problems in coating properties and storage stability. If the amount exceeds 20 mol, hydrolysis and condensation will occur. During the reaction, polymer precipitation or gelation may occur. Moreover, it is preferable that water is added intermittently or continuously.
These metal chelate compounds can be used individually by 1 type or in combination of 2 or more types.

(D-2) Acidic compound Examples of the acidic compound that can be used as the catalyst include organic acids and inorganic acids.
Examples of organic acids include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid Acid, butyric acid, meritic acid, arachidonic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfone Acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, maleic anhydride, fumaric acid, itaconic acid, succinic acid, mesaconic acid, Citraconic acid, malic acid, malonic acid, hydrolyzed glutaric acid, hydrolyzed maleic anhydride Object can include hydrolysis products of phthalic anhydride.
Examples of inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.
Of these, organic acids are preferred in that there is little risk of polymer precipitation or gelation during the reaction of hydrolysis condensation (hydrolysis and subsequent condensation). Among organic acids, a compound having a carboxyl group is more preferable.
Among compounds having a carboxyl group, acetic acid, oxalic acid, maleic acid, formic acid, malonic acid, phthalic acid, fumaric acid, itaconic acid, succinic acid, mesaconic acid, citraconic acid, malic acid, malonic acid, glutaric acid, maleic anhydride Acid hydrolysates and the like are particularly preferred.
These acidic compounds can be used alone or in combination of two or more.

The amount of the acidic compound is preferably 0.0001 to 10 parts by mass, more preferably 0.001 to 5 parts by mass with respect to 100 parts by mass (in terms of complete hydrolysis condensate) of the total amount of the silane compound and the titanium compound. is there. When the amount is less than 0.0001 part by mass, the coating property may be inferior when the composition of the present invention is applied to a substrate or the like by a spin coating method or the like. If the amount exceeds 10 parts by mass, the hydrolytic condensation reaction may suddenly proceed to cause gelation.
When hydrolyzing and condensing at least one of a silane compound and a titanium compound in the presence of an acidic compound, it is preferable to use 0.5 to 20 mol of water per mol of the total amount of at least one of the silane compound and the titanium compound. It is particularly preferred to use 1-10 moles of water. If the amount of water is less than 0.5 mol, the hydrolysis reaction does not proceed sufficiently, which may cause problems in applicability and storage stability. When the amount of water exceeds 20 mol, polymer precipitation or gelation may occur during the hydrolysis condensation reaction. Moreover, it is preferable that water is added intermittently or continuously.

(D-3) Basic compound Examples of basic compounds that can be used as a catalyst include methanolamine, ethanolamine, propanolamine, butanolamine, N-methylmethanolamine, N-ethylmethanolamine, and N-propylmethanolamine. N-butylmethanolamine, N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N, N-dimethylmethanolamine, N, N-diethylmethanolamine, N, N-dipropylmethanolamine, N, N-dibutylmethanolamine, N-methyldimethanolamine, N-ethyldimethanolamine, N-propyldimethanolamine, N-butyldimethanolamine, N- (aminomethyl) methanolamine, N- (aminomethyl) D Tanolamine, N- (aminomethyl) propanolamine, N- (aminomethyl) butanolamine, methoxymethylamine, methoxyethylamine, methoxypropylamine, methoxybutylamine, N, N-dimethylamine, N, N-diethylamine, N, N-dipropylamine, N, N-dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide , Tetramethylethylenediamine, tetraethylethylenediamine, tetrapropylethylenediamine, ammonia, sodium hydroxide, potassium hydroxide, water Of tetramethyl ammonium, tetraethyl ammonium hydroxide, tetra -n- propyl ammonium hydroxide, tetra -n- butyl ammonium hydroxide, tetramethylammonium bromide, tetramethylammonium chloride, tetraethylammonium bromide, and the like.
The amount of the basic compound is preferably 0.00001 to 10 mol, more preferably 0.00005 to 5 mol with respect to 1 mol of the total amount of hydrolyzable groups in the silane compound and the titanium compound. If the amount is less than 0.00001 mol, hydrolysis condensation may not proceed sufficiently. When the amount exceeds 10 mol, the storage stability of the obtained hydrolysis condensate may be inferior.

[Component (B): Metal Oxide Particles]
In the present invention, zirconium oxide, titanium oxide, zinc oxide, tantalum oxide, indium oxide, hafnium oxide, tin oxide are used as metal oxide particles in order to improve the refractive index of the cured film obtained from the curable resin composition. Further, metal oxide particles such as niobium oxide and composites thereof (hereinafter also referred to as “metal oxide particles”) are used. The titanium oxide is not particularly limited as long as it has a TiO ₂ structure, and examples thereof include an anatase type, a rutile type, and a brookite type.
Of these metal oxide particles, zirconium oxide and titanium oxide are preferable, and zirconium oxide is more preferable.
These metal oxide particles are used alone or in combination of two or more.
The refractive index of light having a wavelength of 400 nm at 25 ° C. of the cured film obtained from the curable resin composition containing the metal oxide particles is preferably 1.55 or more, more preferably 1.60 or more, and particularly preferably 1. .70 or more.

The number average primary particle diameter of the metal oxide particles is preferably 1 to 100 nm, more preferably 3 to 70 nm, and particularly preferably 5 to 50 nm. When the number average primary particle diameter is within the above range, a cured film with more excellent transparency can be obtained.
The metal oxide particles as the component (B) may be in a powder form or a solvent-dispersed sol before mixing with the component (A) and the component (C). As the solvent, for example, an organic solvent is used. Examples of the organic solvent include 2-butanol, methanol, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, propylene glycol monomethyl ether, and the like.
(B) The compounding quantity of a component becomes like this. Preferably it is 50-1,000 mass parts with respect to 100 mass parts of (A) component, More preferably, it is 100-800 mass parts, More preferably, it is 150-500 mass parts. If the amount is less than 50 parts by mass, the refractive index of the cured film may decrease, and the light emission efficiency of the light-emitting device may decrease. If the amount exceeds 1,000 parts by mass, the cured film has sufficient crack resistance. May not have.
In addition, when (B) component is solvent dispersion | distribution sol, the compounding quantity of (B) component means the mass which does not contain a solvent. Moreover, when (B) component is a solvent dispersion | distribution sol, the quantity of the organic solvent as a solvent of (B) component shall comprise a part of compounding quantity of the organic solvent which is (D) component.

[(C) component; phosphor]
Next, the phosphor contained in the curable resin composition of the present invention will be described.
The phosphor used in the present invention is not particularly limited, and for example, generally known inorganic phosphors and organic phosphors can be used, and one or more of these are used in any ratio and combination. be able to.
By using an arbitrary phosphor, the hue of the obtained cured product can be changed. For example, the hue of light emitted from the light emitting element can be changed by forming a cured film that is a cured body of the curable resin composition of the present invention on the surface of the light emitting element.
Hereinafter, specific examples of the phosphor will be exemplified, but in the illustrated general formula, phosphors that are different only in a part of the structure are appropriately omitted. For example, “Y ₂ SiO ₅ : Ce ³⁺ ”, “Y ₂ SiO ₅ : Tb ³⁺ ” and “Y ₂ SiO ₅ : Ce ³⁺ , Tb ³⁺ ” are changed to “Y ₂ SiO ₅ : Ce ³⁺ , Tb ³⁺ ”, “ “La ₂ O ₂ S: Eu”, “Y ₂ O ₂ S: Eu” and “(La, Y) ₂ O ₂ S: Eu” are collectively shown as “(La, Y) ₂ O ₂ S: Eu”. ing. Omitted parts are separated by commas (,).

As a phosphor preferably used in the present invention, for example, a group consisting of M ₃ SiO ₅ , MS, MGa ₂ S ₄ , MAlSiN ₃ , M ₂ Si ₅ N ₈ , and MSi ₂ N ₂ O ₂ as a base crystal (however, , M represents at least one selected from the group consisting of Ca, Sr, and Ba.) And contains at least one selected from Cr, Mn, Fe, Bi, Ce as an activator , Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, and a phosphor containing at least one selected from the group consisting of Yb.

Specific examples of the phosphor include, for example, Ba ₃ SiO ₅ : Eu, (Sr _1-a Ba _a ) ₃ SiO ₅ : Eu, Sr ₃ SiO ₅ : Eu, CaS: Eu, SrS: Eu, BaS: Eu. _{, CaS: Ce, SrS: Ce} , BaS: Ce, CaGa 2 S 4: Eu, SrGa 2 S 4: Eu, BaGa 2 S 4: Eu, CaGa 2 S 4: Ce, SrGa 2 S 4: Ce, BaGa 2 _{S 4: Ce, CaAlSiN 3:} Eu, SrAlSiN 3: Eu, (Ca 1-a Sr a) AlSiN 3: Eu, CaAlSiN 3: Ce, SrAlSiN 3: Ce, (Ca 1-a Sr a) AlSiN 3: Ce _{, Ca 2 Si 5 N 8:} Eu, Sr 2 Si 5 N 8: Eu, Ba 2 Si 5 N 8: Eu, (Ca 1-a Sra) 2 Si _{N 8: Eu, Ca 2 Si} 5 N 8: Ce, Sr 2 Si 5 N 8: Ce, Ba 2 Si 5 N 8: Ce, (Ca 1-a Sr a) 2 Si 5 N 8: Ce, CaSi 2 N ₂ O ₂ : Eu, SrSi ₂ N ₂ O ₂ : Eu, BaSi ₂ N ₂ O ₂ : Eu, CaSi ₂ N ₂ O ₂ : Ce, SrSi ₂ N ₂ O ₂ : Ce, BaSi ₂ N ₂ O ₂ : Ce, (Ba, Sr, Ca) ₂ SiO ₄ : Eu, Ba ₃ Si ₆ O ₉ N ₄ : Eu (for the above, a satisfies 0 ≦ a ≦ 1) and the like.
In addition to the above phosphors, other phosphors can be used depending on the purpose, such as improved durability and improved dispersibility. Such no particular limitation on the composition of the _phosphor, Y ₂ O _3, Zn ₂ metal oxide represented by SiO ₄ and the _like, a metal nitride typified by Sr 2 _Si 5 _{N 8} or the like, Ca ₅ A host crystal composed of a phosphate represented by (PO ₄ ) ₃ Cl and the like and a sulfide represented by ZnS, SrS, CaS and the like is added to Ce, Pr, Nd, Pm, Sm, Eu, Tb, Dy. , Ho, Er, Tm, Yb and other rare earth metal ions and Ag, Cu, Au, Al, Mn, Sb and other metal ions are preferably combined as the activator or coactivator.

Preferable examples of the material of the parent crystal include, for example, sulfides such as (Zn, Cd) S, SrGa ₂ S ₄ , SrS, and ZnS, oxysulfides such as Y ₂ O ₂ S, and (Y, Gd) _{3. A l5 O1 2, YAlO 3,} BaMgAl 10 O 17, (Ba, Sr) (Mg, Mn) Al 10 O 17, (Ba, Sr, Ca) (Mg, Zn, Mn) Al 10 O 17, BaAl 12 O ₁₉ , CeMgAl ₁₁ O ₁₉ , (Ba, Sr, Mg) O · Al ₂ O ₃ , BaAl ₂ Si ₂ O ₈ , SrAl ₂ O ₄ , Sr ₄ Al ₁₄ O ₂₅ , Y ₃ Al ₅ O _12, etc. Salt, silicate such as Y ₂ SiO ₅ and Zn ₂ SiO ₄ , oxide such as SnO ₂ and Y ₂ O ₃ , borate such as GdMgB ₅ O ₁₀ and (Y, Gd) BO ₃ , Ca ₁₀ (PO ₄ ) _{6 F, Cl) 2, (Sr} , Ca, Ba, Mg) 10 (PO 4) such as _{6 C l2 halophosphate,} Sr ₂ P ₂ O _7, the (La, Ce) phosphate PO _4, etc. etc. Can be mentioned.

However, the parent crystal and the activator element or coactivator element are not particularly limited in element composition, and can be partially replaced with elements of the same family. The obtained phosphor can be used as long as it absorbs light in the near ultraviolet to visible region and emits visible light.
Specifically, the following phosphors can be used, but these are merely examples, and phosphors that can be used in the present invention are not limited to these.

(Orange to red phosphor)
Examples of phosphors that emit orange to red fluorescence (hereinafter also referred to as “orange to red phosphors”) include the following.
The emission peak wavelength of the orange to red phosphor is preferably 580 to 780 nm, more preferably 585 to 700 nm. Examples of such orange to red phosphors include europium composed of broken particles having a red fracture surface and emitting red region (Mg, Ca, Sr, Ba) ₂ Si ₅ N ₈ : Eu. The activated alkaline earth silicon nitride-based phosphor is composed of growing particles having a substantially spherical shape as a regular crystal growth shape, and emits light in the red region (Y, La, Gd, Lu) ₂ O ₂ S: Examples include europium-activated rare earth oxychalcogenide phosphors represented by Eu. Furthermore, the oxynitride and / or oxysulfide containing at least one element selected from the group consisting of Ti, Zr, Hf, Nb, Ta, W, and Mo described in JP-A-2004-300247 A phosphor containing an oxynitride having an alpha sialon structure in which a part or all of the Al element is substituted with a Ga element can also be used in the present invention. These are phosphors containing oxynitride and / or oxysulfide.

Other orange or red phosphors include Eu-activated oxysulfide phosphors such as (La, Y) ₂ O ₂ S: Eu, Y (V, P) O ₄ : Eu, Y ₂ O ₃ : Eu-activated oxide phosphor such as Eu, (Ba, Sr, Ca, Mg) ₂ SiO ₄ : Eu, Mn, (Ba, Mg) ₂ SiO ₄ : Eu, Mn-activated silicate fluorescence such as Eu, Mn Eu-activated tungstate such as LiW ₂ O ₈ : Eu, LiW ₂ O ₈ : Eu, Sm, Eu ₂ W ₂ O ₉ , Eu ₂ W ₂ O ₉ : Nb, Eu ₂ W ₂ O ₉ : Sm Phosphor, Eu-activated sulfide phosphor such as (Ca, Sr) S: Eu, Eu-activated aluminate phosphor such as YAlO ₃ : Eu, LiY ₉ (SiO ₄ ) ₆ O ₂ : Eu, Ca _{2 Y 8 (SiO 4) 6 O} 2: Eu, (Sr, Ba, Ca) 3 SiO 5: E , _Sr 2 BaSiO _5: Eu-activated silicate phosphors such as _{Eu, (Y, Gd) 3} Al 5 O 12: Ce, (Tb, Gd) 3 Al 5 O 12: Ce -activated aluminate such as Ce Phosphor, Eu such as (Mg, Ca, Sr, Ba) ₂ Si ₅ N ₈ : Eu, (Mg, Ca, Sr, Ba) SiN ₂ : Eu, (Mg, Ca, Sr, Ba) AlSiN ₃ : Eu Activated nitride phosphor, Ce activated nitride phosphor such as (Mg, Ca, Sr, Ba) AlSiN ₃ : Ce, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, Eu, Mn-activated halophosphate phosphor such as Mn, Ba ₃ MgSi ₂ O ₈ : Eu, Mn, (Ba, Sr, Ca, Mg) ₃ (Zn, Mg) Si ₂ O ₈ : Eu, Mn, etc. Eu, Mn activated silicate phosphor, 3.5MgO · 0.5MgF _2. GeO ₂ : Mn-activated germanate phosphor such as Mn, Eu-activated oxynitride phosphor such as Eu-activated α-sialon, (Gd, Y, Lu, La) ₂ O ₃ : Eu, Bi, etc. Eu, Bi-activated oxide phosphor, (Gd, Y, Lu, La) ₂ O ₂ S: Eu, Bi-activated oxysulfide phosphor such as Eu, Bi, (Gd, Y, Lu, La) VO ₄ : Eu, Bi-activated vanadate phosphors such as Eu and Bi, SrY ₂ S ₄ : Eu and Ce-activated sulfide phosphors such as Eu and Ce, and CaLa ₂ S ₄ : Ce-activated such as Ce Sulfide phosphor, (Ba, Sr, Ca) MgP ₂ O ₇ : Eu, Mn, (Sr, Ca, Ba, Mg, Zn) ₂ P ₂ O ₇ : Eu, Mn activated phosphoric acid such as Eu, Mn Salt phosphor, (Y, Lu) ₂ WO ₆ : Eu, Mo activated tungstate phosphor such as Eu, Mo, (B a, Sr, Ca) _x Si _{y Nz} : Eu, Ce (where x, y, z represent an integer of 1 or more. Eu, Ce activated nitride phosphors such as (Ca, Sr, Ba, Mg) ₁₀ (PO ₄ ) ₆ (F, Cl, Br, OH) ₂ : Eu, Mn activated halophosphorus such as Eu, Mn Acid salt phosphor, ((Y, Lu, Gd, Tb) _1-xy Sc _x Ce _y ) ₂ (Ca, Mg) _1-r (Mg, Zn) _{2 + r} Siz _-q Ge _q O _{12 + δ} It is also possible to use a Ce-activated silicate phosphor or the like.

  Further, as an orange to red phosphor, a red organic phosphor comprising a rare earth element ion complex having an anion such as β-diketonate, β-diketone, aromatic carboxylic acid, or Bronsted acid as a ligand, a perylene pigment (For example, dibenzo {[f, f ′]-4,4 ′, 7,7′-tetraphenyl} diindeno [1,2,3-cd: 1 ′, 2 ′, 3′-lm] perylene), anthraquinone Pigment, lake pigment, azo pigment, quinacridone pigment, anthracene pigment, isoindoline pigment, isoindolinone pigment, phthalocyanine pigment, triphenylmethane basic dye, indanthrone pigment, indophenol It is also possible to use a pigment, a cyanine pigment, a dioxazine pigment or the like.

Of the orange to red phosphors, those having a peak wavelength of preferably 580 to 620 nm, more preferably 590 to 610 nm can be suitably used as the orange phosphor. Examples of such orange phosphors include Eu-activated silicate phosphors such as (Sr, Ba, Ca) ₃ SiO ₅ : Eu, Sr ₂ BaSiO ₅ : Eu, (Sr, Mg) ₃ (PO ₄ ). ₂ : Sn-activated phosphate phosphors such as Sn ^{2+ and the} like.

Any one of the orange to red phosphors exemplified above may be used alone, or two or more may be used in any combination and ratio.
Among the above examples, as the red phosphor, (Ca, Sr, Ba) AlSiN ₃ : Eu, (Ca, Sr, Ba) AlSiN ₃ : Ce, (La, Y) ₂ O ₂ S: Eu are preferable, (Sr, Ca) AlSiN ₃ : Eu and (La, Y) ₂ O ₂ S: Eu are particularly preferable.
Moreover, among the above examples, (Sr, Ba) ₃ SiO ₅ : Eu is preferable as the orange phosphor.

(Green phosphor)
Examples of the phosphor emitting green fluorescence (hereinafter also referred to as “green phosphor”) include the following. The emission peak wavelength of the green phosphor is preferably 490 to 560 nm, more preferably 510 to 540 nm, and particularly preferably 515 to 535 nm.

As such a green phosphor, for example, a europium-activated alkali represented by (Mg, Ca, Sr, Ba) Si ₂ O ₂ N ₂ : Eu that is composed of fractured particles having a fracture surface and emits light in the green region. Europium-activated alkaline earth silicate composed of earth silicon oxynitride-based phosphors, broken particles having fractured surfaces, and emitting in the green region (Ba, Ca, Sr, Mg) ₂ SiO ₄ : Eu System phosphors and the like.

Other green phosphors include Eu-activated aluminate phosphors such as Sr ₄ Al ₁₄ O ₂₅ : Eu, (Ba, Sr, Ca) Al ₂ O ₄ : Eu, and (Sr, Ba) Al _2. Si ₂ O ₈ : Eu, (Ba, Mg) ₂ SiO ₄ : Eu, (Ba, Sr, Ca, Mg) ₂ SiO ₄ : Eu, (Ba, Sr, Ca) ₂ (Mg, Zn) Si ₂ O ₇ : Eu, (Ba, Ca, Sr, Mg) ₉ (Sc, Y, Lu, Gd) ₂ (Si, Ge) ₆ O ₂₄ : Eu-activated silicate phosphor such as Eu, Y ₂ SiO ₅ : Ce, Ce, Tb activated silicate phosphors such as Tb, Sr ₂ P ₂ O ₇ —Sr ₂ B ₂ O ₅ : Eu activated boric acid phosphors such as Eu, Sr ₂ Si ₃ O _8-2 SrCl ₂ : Eu-activated halo silicate phosphor such as _Eu, Zn 2 _SiO 4: M such as Mn Activated silicate _{phosphors, CeMgAl 11 O 19: Tb,} Y 3 Al 5 O 12: Tb -activated aluminate phosphors such as _{Tb, Ca 2 Y 8 (SiO} 4) 6 O 2: Tb, La 3 Ga ₅ SiO ₁₄ : Tb-activated silicate phosphor such as Tb, (Sr, Ba, Ca) Ga ₂ S ₄ : Eu, Tb, Sm-activated thiogallate phosphor such as Eu, Tb, Sm, Y ₃ (Al, Ga) ₅ O ₁₂ : Ce, (Y, Ga, Tb, La, Sm, Pr, Lu) ₃ (Al, Ga) ₅ O ₁₂ : Ce-activated aluminate phosphor such as Ce, Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce, Ca ₃ (Sc, Mg, Na, Li) ₂ Si ₃ O ₁₂ : Ce activated silicate phosphor such as Ce, Ce activated oxide phosphor such as CaSc ₂ O ₄ : Ce, SrSi ₂ O ₂ N ₂ : Eu, (Mg, Sr, B a, Ca) Si ₂ O ₂ N ₂ : Eu-activated oxynitride phosphor such as Eu-activated β sialon such as Eu, BaMgAl ₁₀ O ₁₇ : Eu, Mn-activated aluminate phosphor such as Eu and Mn Eu-activated aluminate phosphors such as SrAl ₂ O ₄ : Eu, Tb-activated oxysulfide phosphors such as (La, Gd, Y) ₂ O ₂ S: Tb, LaPO ₄ : Ce, Tb, etc. Ce, Tb-activated phosphate phosphor, sulfide phosphor such as ZnS: Cu, Al, ZnS: Cu, Au, Al, (Y, Ga, Lu, Sc, La) BO ₃ : Ce, Tb, Na ₂ Gd ₂ B ₂ O ₇ : Ce, Tb, (Ba, Sr) ₂ (Ca, Mg, Zn) B ₂ O ₆ : Ce, Tb-activated borate phosphor such as K, Ce, Tb, Ca ₈ Mg (SiO ₄ ) _{4 Cl 2} : Eu, Mn activated halosilicate phosphor such as Eu, Mn, etc. (Sr, Ca, Ba) (Al, Ga, In) ₂ S ₄ : Eu-activated thioaluminate phosphor such as Eu, thiogallate phosphor, (Ca, Sr) ₈ (Mg, Zn) (SiO ₄ ) ₄ C _l2: Eu, Eu such as Mn, Mn-activated halo silicate _{phosphor, MSi 2 O 2 N 2:} Eu, M 3 Si 6 O 9 N 4: Eu, M 2 Si 7 O 10 N 4: Eu ( Here, M represents an alkaline earth metal element. It is also possible to use Eu-activated oxynitride phosphors such as

  Further, as a green phosphor, it is also possible to use a pyridine-phthalimide condensed derivative, a benzoxazinone-based, a quinazolinone-based, a coumarin-based, a quinophthalone-based, a naltalimide-based fluorescent pigment, or an organic phosphor such as a terbium complex. .

(Blue phosphor)
Examples of phosphors emitting blue fluorescence (hereinafter also referred to as “blue phosphors”) include the following. The emission peak wavelength of the blue phosphor is preferably 420 to 490 nm, more preferably 430 to 470 nm, and particularly preferably 440 to 460 nm.

As such a blue phosphor, a europium-activated barium magnesium aluminate system represented by BaMgAl ₁₀ O ₁₇ : Eu, which is composed of growing particles having a substantially hexagonal shape as a regular crystal growth shape and emits light in a blue region. Europium activated halo represented by (Ca, Sr, Ba) ₅ (PO ₄ ) ₃ Cl: Eu, which is composed of phosphors and growing particles having a substantially spherical shape as a regular crystal growth shape, and emits light in a blue region. Calcium phosphate phosphor, composed of growing particles having a cubic shape as a regular crystal growth shape, emits light in the blue region, and is activated by europium represented by (Ca, Sr, Ba) ₂ B ₅ O ₉ Cl: Eu Consists of alkaline earth chloroborate-based phosphors and fractured particles with fractured surfaces. (Sr, Ca, Ba) Al ₂ O ₄ : Eu or (Sr, Ca, Ba) ₄ Al ₁₄ O ₂₅ : Europium activated alkaline earth aluminate-based phosphor represented by Eu.

Other blue phosphors include Sn-activated phosphate phosphors such as Sr ₂ P ₂ O ₇ : Sn, (Sr, Ca, Ba) Al ₂ O ₄ : Eu, (Sr, Ca, Ba). ₄ Al ₁₄ O ₂₅ : Eu, BaMgAl ₁₀ O ₁₇ : Eu, BaAl ₈ O ₁₃ : Eu-activated aluminate phosphors such as Eu, SrGa ₂ S ₄ : Ce, CaGa ₂ S ₄ : Ce-activated such as Ce Thiogallate phosphor, (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, BaMgAl ₁₀ O ₁₇ : Eu-activated aluminate phosphor such as Eu, Tb, Sm, (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, Eu such as Mn, Mn-activated aluminate _{phosphor, (Sr, Ca, Ba,} Mg) 10 (PO 4) 6 C l2: Eu, (Ba, Sr, Ca) 5 (PO 4) 3 (Cl, F , Br, OH): Eu-activated halophosphate phosphors such as Eu, Mn, Sb, BaAl ₂ Si ₂ O ₈ : Eu, (Sr, Ba) ₃ MgSi ₂ O ₈ : Eu-activated silicates such as Eu Phosphor, Eu-activated phosphate phosphor such as Sr ₂ P ₂ O ₇ : Eu, sulfide phosphor such as ZnS: Ag, ZnS: Ag, Al, Ce-activated silicic acid such as Y ₂ SiO ₅ : Ce Salt phosphor, tungstate phosphor such as CaWO ₄ , (Ba, Sr, Ca) BPO ₅ : Eu, Mn, (Sr, Ca) ₁₀ (PO ₄ ) ₆ .nB ₂ O ₃ : Eu, 2SrO · 0 .84P ₂ O ₅ .0.16B ₂ O ₃ : Eu, Mn-activated borate phosphor such as Eu, Eu-activated halosilicate phosphor such as Sr ₂ Si ₃ O ₈ .2SrCl ₂ : Eu, etc. It is also possible to use.

Further, as the blue phosphor, for example, naphthalic acid imide-based, benzoxazole-based, styryl-based, coumarin-based, pyrazoline-based, triazole-based compound fluorescent pigments, organic phosphors such as thulium complexes, and the like can be used.
Among the above examples, as the blue phosphor, BaMgAl ₁₀ O ₁₇ : Eu, (Ba, Ca, Mg) ₂ SiO ₄ : Eu, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu is preferred, and BaMgAl ₁₀ O ₁₇ : Eu is particularly preferred.

(Yellow phosphor)
Examples of phosphors that emit yellow fluorescence (hereinafter also referred to as “yellow phosphors”) include the following. The emission peak wavelength of the yellow phosphor is preferably 530 to 620 nm, more preferably 540 to 600 nm, and particularly preferably 550 to 580 nm.

Examples of such yellow phosphors include various oxide-based, nitride-based, oxynitride-based, sulfide-based, and oxysulfide-based phosphors.
In particular, RE ₃ M ₅ O ₁₂ : Ce (where RE represents at least one element selected from the group consisting of Y, Tb, Gd, Lu, and Sm, and M represents Al, Ga, and Sc. And Ma ₃ Mb ₂ Mc ₃ O ₁₂ : Ce (where Ma is a divalent metal element, Mb is a trivalent metal element, and Mc is tetravalent). A garnet phosphor having a garnet structure represented by AE ₂ MdO ₄ : Eu (where AE is selected from the group consisting of Ba, Sr, Ca, Mg, and Zn) At least one kind of element, Md represents Si and / or Ge), etc., and an acid obtained by substituting a part of oxygen of the constituent element of the phosphor of these systems with nitrogen Nitride phosphor, AE lSiN _3: Ce (., where, AE is, Ba, Sr, Ca, Mg and represents at least one element selected from the group consisting of Zn) of the nitride-based fluorescent material or the like having a CaAlSiN ₃ structure, such as Ce And the phosphor activated in step (b).

Other yellow phosphors include sulfide-based fluorescence such as CaGa ₂ S ₄ : Eu, (Ca, Sr) Ga ₂ S ₄ : Eu, (Ca, Sr) (Ga, Al) ₂ S ₄ : Eu. It is also possible to use a phosphor activated with Eu such as an oxynitride phosphor having a SiAlON structure such as a body, Ca _x (Si, Al) ₁₂ (O, N) ₁₆ : Eu. Examples of yellow phosphors include brilliant sulfoflavine FF (Color Index Number 56205), basic yellow HG (Color Index Number 46040), eosine (Color Index Number 45Gd), 45G Etc. can also be used.

Although there is no restriction | limiting in particular in the particle size of (C) fluorescent substance used for this invention, Usually, a number average primary particle diameter is 0.1-100 micrometers, Preferably it is 2-50 micrometers, More preferably, it is 10-25 micrometers. If the number average primary particle size is too small, the brightness of the cured product of the curable resin composition may be reduced, or the phosphor may aggregate in the curable resin composition. On the other hand, if the number average primary particle size is too large, coating unevenness or blockage of a dispenser may occur.
In addition, the particle size distribution (QD) of the phosphor (C) is preferably smaller in order to make the dispersed state of particles in the curable resin composition uniform, but is usually 0.03 to 0.4, preferably 0.8. It is 05-0.3, More preferably, it is 0.07-0.2. In addition, the shape of the phosphor (C) is not particularly limited, and an arbitrary shape can be used.

(C) The compounding quantity of a component becomes like this. Preferably it is 10-500 mass parts with respect to 100 mass parts of (B) component, More preferably, it is 15-200 mass parts, More preferably, it is 20-100 mass parts. If the amount is less than 10 parts by mass, the efficiency with which the cured film changes color may be reduced. When the amount exceeds 500 parts by mass, sufficient storage stability and crack resistance may not be obtained.
Moreover, the compounding quantity of (C) component becomes like this. Preferably it is 10-500 mass parts with respect to 100 mass parts of (A) component, More preferably, it is 20-300 mass parts, More preferably, it is 50-200 mass parts. If the amount is less than 10 parts by mass, the efficiency with which the cured film changes color may be reduced. When the amount exceeds 500 parts by mass, sufficient storage stability and crack resistance may not be obtained.

The curable resin composition of the present invention may further contain (D) an organic solvent. (D) By adding an organic solvent, the storage stability of the composition can be improved and an appropriate viscosity can be imparted.
Examples of the organic solvent (D) include ether organic solvents, ester organic solvents, ketone organic solvents, hydrocarbon organic solvents, alcohol organic solvents, and the like. Of these, it is preferable to use an organic solvent having a boiling point under atmospheric pressure in the range of 50 to 250 ° C. and capable of uniformly dissolving each component.
Examples of such organic solvents include aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, monoalcohol solvents, polyhydric alcohol solvents, ketone solvents, ether solvents, ester solvents, nitrogen-containing solvents. And sulfur-containing solvents. These organic solvents are used singly or in combination of two or more.
Among these (D) organic solvents, ketones and alcohols are preferable. This is because the storage stability of the composition can be further improved. More preferable organic solvents include at least one compound selected from the group consisting of 2-heptanone, propylene glycol monomethyl ether, ethyl lactate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, and 2-butanol. It is done.

  In addition, the type of (D) organic solvent is preferably selected in consideration of the coating method of the composition. For example, since a cured product having a uniform thickness can be easily obtained, a spin coating method can be used. Examples of the organic solvent used in this case include ethylene glycol monoethyl ether and propylene glycol monomethyl ether. Glycol ethers; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate; Esters such as ethyl lactate and ethyl 2-hydroxypropionate; Diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol Diethylene glycols such as ethyl methyl ether; methyl ethyl ketone, methyl isobutyl ketone, 2-heptano , Cyclohexanone, ketones such as methyl amyl ketone; .gamma.-butyrolactone are preferable, and ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, ethyl lactate, methyl ethyl ketone, methyl isobutyl ketone, and methyl amyl ketone preferred.

The blending amount of the component (D) is preferably 1 to 500 parts by weight, more preferably 3 to 200 parts by weight, and even more preferably 5 to 100 parts by weight with respect to 100 parts by weight of the total amount of components excluding the component (D). Especially preferably, it is 10-30 mass parts. If the blending amount is within the above preferred range, the dispersion stability of the phosphor can be improved and an appropriate viscosity can be imparted.
The blending amount of the component (D) is preferably 10 to 50 parts by mass, more preferably 15 to 45 parts by mass, and still more preferably 100 parts by mass of the total amount of the component (A) and the component (B). It is 18-40 mass parts, Most preferably, it is 20-35 mass parts. If the blending amount is within the above preferred range, the dispersion stability of the phosphor can be improved and an appropriate viscosity can be imparted.
The method for adding the component (D) is not particularly limited. For example, the component (D) may be added when the component (A) is produced, or when the dispersion of the component (B) is prepared. You may add and may add when mixing (A) component and (B) component.

(E) Dispersant In the composition of the present invention, various dispersants can be used for improving the dispersibility of the metal oxide particles.
As the dispersant, for example, an aluminum compound can be used. Examples of the aluminum compound include aluminum alkoxide, aluminum β-diketonate complex and the like. Specifically, alkoxide compounds such as triethoxyaluminum, tri (n-propoxy) aluminum, tri (i-propoxy) aluminum, tri (n-butoxy) aluminum, tri (sec-butoxy) aluminum, aluminum tris (methylacetate) Examples include β-diketonate complexes such as acetate), aluminum tris (ethyl acetoacetate), tris (acetoacetonato) aluminum, aluminum monoacetylacetonatobis (methyl acetate), aluminum monoacetylacetonatobis (ethyl acetate). Commercial products of aluminum compounds include AIPD, PADM, AMD, ASBD, aluminum ethoxide, ALCH, ALCH-50F, ALCH-75, ALCH-TR, ALCH-TR-20, aluminum chelate M, aluminum chelate D, aluminum chelate A (W), surface treatment agent OL-1000, algomer, algomer 800AF, algomer 1000SF (manufactured by Kawaken Fine Chemical Co., Ltd.) and the like can be used.

The curable resin composition of the present invention can further contain a nonionic dispersant. When a nonionic dispersant is included, dispersibility can be improved. The nonionic dispersant used in the present invention is preferably a phosphate ester type nonionic dispersant having a polyoxyethylene alkyl structure.
The curable resin composition of the present invention can further contain a dispersion aid in order to enhance dispersibility. As the dispersion aid, one or more selected from acetylacetone and N, N-dimethylacetoacetamide can be suitably used.

(F) Surfactant When the composition of the present invention is applied to a substrate or the like by a spin coat method or the like, it is preferable to incorporate a surfactant in order to obtain a uniform coating film.
Examples of the surfactant that can be used in the present invention include silicon-based surfactants and fluorine-based surfactants, and silicon-based surfactants are preferred.

Examples of silicon surfactants include, for example, SH28PA (Toray Dow Corning, dimethylpolysiloxane polyoxyalkylene copolymer), Paintad 19, 54 (Toray Dow Corning, dimethylpolysiloxane polyoxyalkylene copolymer). Coalescence), SF8428 (manufactured by Toray Dow Corning, dimethylpolysiloxane polyoxyalkylene copolymer (containing side chain OH)), BYKUV3510 (manufactured by BYK Japan, dimethylpolysiloxane-polyoxyalkylene copolymer), DC57 ( Toray Dow Corning Silicone, dimethylpolysiloxane-polyoxyalkylene copolymer), DC190 (Toray Dow Corning Silicone, dimethylpolysiloxane-polyoxyalkylene copolymer), Silap FM-4411, FM-4421, FM-4425, FM-7711, FM-7721, FM-7721, FM-0411, FM-0421, FM-0425, FM-DA11, FM-DA21, FM-DA26, FM0711, FM0721, FM-0725, TM-0701, TM-0701T (manufactured by Chisso), UV3500, UV3510, UV3530 (manufactured by Big Chemie Japan), BY16-004, SF8428 (manufactured by Toray Dow Corning Silicone), VPS-1001 (made by Wako Pure Chemical Industries) etc. are mentioned. Among these, Silaplane FM-7711, FM-7721, FM-7725, FM-0411, FM-0421, FM-0425, FM0711, FM0721, FM-0725, and VPS-1001 are preferable.
Moreover, as a commercial item of the silicon-type surfactant which has an ethylenically unsaturated group, TegoRad2300, 2200N (made by Tego Chemie) etc. can be mentioned, for example.

  Examples of the fluorosurfactant include, for example, Megafac F-114, F410, F411, F450, F493, F494, F443, F444, F445, F446, F470, F471, F472SF, F474, F475, R30, F477, F478. F479, F480SF, F482, F483, F484, F486, F487, F172D, F178K, F178RM, ESM-1, MCF350SF, BL20, R08, R61, R90 (manufactured by DIC).

  The compounding amount of the component (F) in the composition of the present invention is usually 0 to 10% by mass, preferably 0.1 to 5% by mass, when the total amount of the components excluding the organic solvent is 100% by mass. Preferably it is 0.5-3 mass%. When the amount of component (F) exceeds 10% by mass, the refractive index of the cured film may be lowered.

The curable resin composition of the present invention can also contain a dehydrating agent. Thus, by adding a dehydrating agent, the radiation curing reaction of the composition can be promoted, and the storage stability of the composition can be further improved.
The dehydrating agent used in the curable resin composition of the present invention does not affect the radiation curable property and storage stability by a compound that is converted into a substance other than water by a chemical reaction, or physical adsorption or inclusion. Defined as a compound. That is, by containing such a dehydrating agent, it is possible to improve contradictory characteristics such as storage stability and radiation curability without impairing the light resistance and heat resistance of the cured film. The reason for this is that the dehydrating agent effectively absorbs water entering from the outside, thereby improving the storage stability of the composition. On the other hand, in the condensation reaction, which is a radiation curing reaction, the generated water is sequentially introduced. It is considered that the radiation curability of the composition is improved by effectively absorbing the dehydrating agent.

  Various additives other than the above can be blended with the curable resin composition of the present invention within a range not impairing the effects of the present invention. Examples of such additives include curable compounds other than the above components, antioxidants, ultraviolet absorbers, and the like.

The curable resin composition of the present invention can be used for coating a light emitting device. Specifically, a light emitting device or the like in which a curable resin composition is applied on the surface of a light emitting element by a spin coating method or the like, and a cured film that is a cured body is formed by heat and / or radiation.
Next, an example of the light emitting device of the present invention will be described. In FIG. 1, a laminated body (light emitting element) including a first electrode 3, a light emitting layer 4, and a second electrode 5 is formed on a substrate 2. A cured film 1 obtained by curing the curable resin composition of the present invention is coated around the laminate. 1 is a light-emitting device according to the present invention.

“Parts” in the following synthesis examples, examples and comparative examples represent “parts by mass” unless otherwise specified.
(Synthesis Example 1)
To a reactor equipped with a reflux condenser and a stirrer, 100 parts of a silicone alkoxy oligomer (manufactured by Shin-Etsu Chemical Co., Ltd., X-40-9227), 304 parts of propylene glycol monomethyl ether, and 13 parts of a 0.7% oxalic acid aqueous solution were added. After mixing, the mixture was heated to 75 ° C. with stirring and reacted for 4 hours. After cooling, 304 parts of propylene glycol monomethyl ether was added, the solvent was removed by distillation under reduced pressure, and the reaction mixture was concentrated to 200 parts. The same operation was performed once again to obtain 200 parts of a solution containing the silicone oligomer (A-1) in which the alkoxy site was hydrolyzed.
(Synthesis Example 2)
To a reactor equipped with a reflux condenser and a stirrer, 100 parts of a silicone alkoxy oligomer (X-40-9247 manufactured by Shin-Etsu Chemical Co., Ltd.), 304 parts of propylene glycol monomethyl ether, and 13 parts of a 0.7% aqueous oxalic acid solution were added. After mixing, the mixture was heated to 75 ° C. with stirring and reacted for 4 hours. After cooling, 304 parts of propylene glycol monomethyl ether was added, the solvent was removed by distillation under reduced pressure, and the reaction mixture was concentrated to 200 parts. The same operation was performed once again to obtain 200 parts of a solution containing the silicone oligomer (A-2) in which the alkoxy site was hydrolyzed.

(Preparation of composition 1)
15.9 parts of fine particles of zirconium oxide (number average primary particle diameter: 15 nm), 1.9 parts of PLAADD ED-151 (compound name: polyoxyethylene alkyl phosphate ester), tri (sec-butoxy) aluminum 2. 2 parts, 0.9 parts of acetylacetone, 2.3 parts of 2-butanol, and 54.3 parts of methyl ethyl ketone are added to a container, and 300 parts of zirconia beads having a particle diameter of 0.1 mm (made by Nikkato) are added to the container. The mixture was stirred at 1,500 rpm for 10 hours to disperse the fine particles of zirconium oxide.
196 parts of "A-1" (including 98 parts of solid), 173 parts of propylene glycol monomethyl ether, dimethylpolysiloxane-polyoxyalkylene copolymer in 600 parts of the dispersion containing fine particles of zirconium oxide obtained. By adding 0.3 part and distilling the mixture under reduced pressure to remove the solvent, 122 parts of zirconium oxide fine particle dispersion “J-1” (solid content = 82%, viscosity = 10,000 mPa · s) was obtained. Obtained.

(Preparation of composition 2)
125 parts of zirconium oxide fine particle dispersion “J-2” (solid content concentration = 80%, viscosity = 1, similar to “Preparation of composition 1” except that the amount of propylene glycol monomethyl ether and the like was changed. 100 mPa · s) was obtained.
(Preparation of composition 3)
Except for changing the amount of propylene glycol monomethyl ether or the like, 135 parts of the zirconium oxide fine particle dispersion “J-3” (solid content concentration = 74%, viscosity = 170 mPa · s) was obtained.

(Preparation of composition 4)
Except for changing the amount of propylene glycol monomethyl ether and the like, 123 parts of the zirconium oxide fine particle dispersion “J-4” (solid content concentration = 81%, viscosity = 9, 000 mPa · s).
(Preparation of composition 5)
133 parts of zirconium oxide fine particle dispersion liquid as described in “Preparation of composition 1” except that “A-1” was changed to “A-2” and the amount of fine particles of zirconium oxide was changed. “J-5” (solid content concentration = 75%, viscosity = 220 mPa · s) was obtained.

Example 1
71 parts of the zirconium oxide fine particle dispersion “J-1” prepared in “Preparation of composition 1” and 29 parts of yttrium / aluminum / garnet phosphor are placed in a container, and a rotating / revolving mixer (made by THINKY; product name) : Awatori Netaro ARE-250; the same mixer was also used in the following examples and comparative examples.) The mixture was stirred and dispersed at 2,000 rpm for 5 minutes and 2,200 rpm for 5 minutes to obtain a curable resin. A composition was obtained.

(Example 2)
83 parts of the zirconium oxide fine particle dispersion “J-1” produced in “Preparation of composition 1” and 17 parts of yttrium / aluminum / garnet-based phosphor are placed in a container, and 5 parts at 2,000 rpm with a rotating / revolving mixer. The mixture was stirred and dispersed for 5 minutes at 2,200 rpm to obtain a curable resin composition.

(Example 3)
91 parts of the zirconium oxide fine particle dispersion “J-1” produced in “Preparation 1 of composition” above and 9 parts of yttrium / aluminum / garnet phosphor are placed in a container, and 5 parts at 2,000 rpm with a rotating / revolving mixer. The mixture was stirred and dispersed for 5 minutes at 2,200 rpm to obtain a curable resin composition.

(Example 4)
71 parts of the zirconium oxide fine particle dispersion “J-2” produced in “Preparation 2 of composition” above and 29 parts of yttrium / aluminum / garnet-based phosphor are placed in a container, and 5 parts at 2,000 rpm with a rotating / revolving mixer. The mixture was stirred and dispersed for 5 minutes at 2,200 rpm to obtain a curable resin composition.

(Example 5)
73 parts of the zirconium oxide fine particle dispersion “J-3” produced in “Preparation of composition 3” described above and 27 parts of yttrium / aluminum / garnet phosphor are placed in a container, and 5 parts at 2,000 rpm with a rotating / revolving mixer. The mixture was stirred and dispersed for 5 minutes at 2,200 rpm to obtain a curable resin composition.

(Example 6)
84 parts of the zirconium oxide fine particle dispersion “J-3” produced in “Preparation of composition 3” described above and 16 parts of yttrium / aluminum / garnet-based phosphor are placed in a container, and 5 parts at 2,000 rpm with a rotating / revolving mixer. The mixture was stirred and dispersed for 5 minutes at 2,200 rpm to obtain a curable resin composition.

(Example 7)
92 parts of the zirconium oxide fine particle dispersion “J-3” produced in “Preparation of composition 3” above and 8 parts of yttrium / aluminum / garnet-based phosphor are placed in a container, and 5 parts at 2,000 rpm with a rotating / revolving mixer. The mixture was stirred and dispersed for 5 minutes at 2,200 rpm to obtain a curable resin composition.

(Example 8)
71 parts of the zirconium oxide fine particle dispersion “J-4” produced in “Preparation of composition 4” above and 29 parts of yttrium / aluminum / garnet phosphor are placed in a container, and 5 parts at 2,000 rpm with a rotating / revolving mixer. The mixture was stirred and dispersed for 5 minutes at 2,200 rpm to obtain a curable resin composition.

Example 9
92 parts of the zirconium oxide fine particle dispersion “J-4” produced in “Preparation of composition 4” above and 8 parts of yttrium / aluminum / garnet-based phosphor are placed in a container, and 5 parts at 2,000 rpm with a rotating / revolving mixer. The mixture was stirred and dispersed for 5 minutes at 2,200 rpm to obtain a curable resin composition.

(Example 10)
71 parts of the zirconium oxide fine particle dispersion “J-5” produced in “Preparation of composition 5” above and 29 parts of yttrium / aluminum / garnet-based phosphor are placed in a container, and 5 parts at 2,000 rpm in a rotating / revolving mixer. The mixture was stirred and dispersed for 5 minutes at 2,200 rpm to obtain a curable resin composition.

(Example 11)
92 parts of the zirconium oxide fine particle dispersion “J-5” produced in “Preparation 5 of composition” above and 8 parts of yttrium / aluminum / garnet phosphor were put in a container, and 5 parts at 2,000 rpm with a rotating / revolving mixer. The mixture was stirred and dispersed for 5 minutes at 2,200 rpm to obtain a curable resin composition.

(Comparative Example 1)
Both ends silanol dimethyl silicone oil (Momentive Performance Materials Japan GK, XC96-723) 385 g, methyltrimethoxysilane 10.28 g, and zirconium tetraacetylacetonate powder 0.791 g as a catalyst were stirred. The solution was weighed in a 500 ml three-necked Kolben equipped with a blade, a fractionating tube, a Dimroth condenser, and a Liebig condenser, and stirred at room temperature for 15 minutes until the coarse particles of the catalyst were dissolved. Thereafter, the temperature of the reaction solution was raised to 100 ° C. to completely dissolve the catalyst, and initial hydrolysis was performed while stirring at 500 rpm for 30 minutes at 100 ° C. under total reflux.
Subsequently, the distillate was connected to the Liebig condenser side, nitrogen was blown into the liquid with SV20, and the methanol, water, and low-boiling silicon components of by-products were distilled off accompanying nitrogen, and the temperature was increased to 100 ° C. and 500 rpm. And stirred for 1 hour. While nitrogen was blown into the liquid with SV20, the temperature was further raised to 130 ° C., and the polymerization reaction was continued for 5.5 hours while maintaining this temperature to obtain a reaction liquid having a viscosity of 389 mPa · s. Here, “SV” is an abbreviation for “Space Velocity” and refers to the volume of blown volume per unit time. Therefore, SV20 means blowing nitrogen (N ₂ ) in a volume 20 times that of the reaction liquid in one hour.
Nitrogen blowing was stopped and the reaction solution was once cooled to room temperature, then transferred to an eggplant-shaped flask, and remained in a trace amount on an oil bath at 120 ° C. and 1 kPa for 20 minutes using a rotary evaporator. Methanol, moisture, and low boiling silicon components were distilled off to obtain a silicone material “A-3” having a viscosity of 584 mPa · s.
Put the silicone material “A-3” and hydrophobic fumed silica (Aerosil RX-200, manufactured by Nippon Aerosil Co., Ltd.) 0.12 g, yttrium / aluminum / garnet phosphor into a container, and put it into a rotating / revolving mixer. The mixture was stirred and dispersed at 2,000 rpm for 5 minutes and at 2,200 rpm for 5 minutes to obtain a curable resin composition.

<Production of cured film>
Zirconium oxide fine particle dispersions “J-1” to “J-5” obtained in “Preparation of composition 1” to “Preparation of composition 5” above on a fused silica or silicon substrate having a diameter of 4 inches or comparison The silicone material “A-3” obtained in Example 1 is supplied, spin-coated to a thickness of about 1 μm, and heated at 120 ° C. for 1 minute and 150 ° C. for 60 minutes to form a cured film (Film thickness: 1 μm) was produced.

<Characteristic evaluation of cured film>
The cured film was evaluated by measuring the following characteristics. The results are shown in Table 1.
(1) Transparency The transmittance (%) at a wavelength of 400 nm of the cured film was measured using a spectrophotometer manufactured by JASCO Corporation.
(2) Refractive index The refractive index of the said cured film in 23 degreeC and wavelength 633nm was measured using the prism coupler by a metricon company.
(3) Heat resistance The cured film was heat-treated at a temperature of 270 ° C for 5 minutes using an oven. The transmittance (%) of the cured film after the treatment was measured.
The results are shown in Table 1.

<Production of cured film>
A curable resin composition obtained in Examples 1 to 7 and Comparative Example 1 was supplied onto a fused quartz or silicon substrate having a diameter of 4 inches and spin-coated to a thickness of about 1 μm. A cured film (film thickness: 1 μm) was prepared by heating at 150 ° C. for 1 minute and at 150 ° C. for 60 minutes.

<Characteristic evaluation of cured film>
The cured film was evaluated by measuring the following characteristics. The results are shown in Table 2.
(4) Curability The surface of the cured film was touched with a finger, and “O” indicates that there is no stickiness, and “X” indicates that there is stickiness. The results are shown in Table 2.
(5) Crack resistance The appearance of the cured film was visually observed, and “◯” indicates that there was no crack, and “X” indicates that there was a crack. The results are shown in Table 2.
(6) Presence / absence of pores The cross section of the cured film was observed with an SEM, and those having no pores were designated as “◯” and those having pores as “x”. The results are shown in Table 2.
(7) Storage stability After leaving the curable resin composition obtained in Examples 1 to 11 and Comparative Example 1 for 2 hours and for 8 hours, the presence or absence of phosphor settling visually. Evaluated. The case where the sedimentation of the phosphor was observed after standing for 2 hours was “x”, and the sedimentation of the phosphor was not observed after standing for 2 hours, but the sedimentation of the phosphor was observed after standing for 8 hours. The evaluation was evaluated as “Δ”, and the case where sedimentation of the phosphor was not observed after standing for 8 hours was evaluated as “◯”. The results are shown in Table 2.

DESCRIPTION OF SYMBOLS 1 Cured film 2 Board | substrate 3 1st electrode 4 Light emitting layer 5 2nd electrode

Claims (11)

A curable resin composition containing the following components (A) to (C).
(A) At least one polymer selected from siloxane polymers, titanoxane polymers, and copolymers thereof (B) zirconium oxide, titanium oxide, zinc oxide, tantalum oxide, indium oxide, hafnium oxide, oxidation Particles of at least one metal oxide selected from the group consisting of tin, niobium oxide, and composites thereof (C) Phosphor   The curable resin composition of Claim 1 whose compounding quantity of the said (B) component is 50-1,000 mass parts with respect to 100 mass parts of said (A) component.   The curable resin composition of Claim 1 or 2 whose compounding quantity of the said (C) component is 10-500 mass parts with respect to 100 mass parts of said (B) component.   The curable resin composition of any one of Claims 1-3 whose compounding quantity of the said (C) component is 10-500 mass parts with respect to 100 mass parts of said (A) component.   Furthermore, (D) Curable resin composition of any one of Claims 1-4 containing the organic solvent.   The curable resin according to claim 5, wherein the blending amount of the component (D) is 1 to 500 parts by mass with respect to 100 parts by mass of the total amount of the components excluding the component (D) in the curable resin composition. Composition.   The curable resin composition of Claim 5 or 6 whose compounding quantity of the said (D) component is 10-50 mass parts with respect to 100 mass parts of total amounts of the said (A) component and the said (B) component. object.   The number average primary particle diameter of the said (B) component is 1-100 nm, The curable resin composition of any one of Claims 1-7.   The curable resin composition of any one of Claims 1-8 whose number average primary particle diameter of the said (C) component is 0.1-100 micrometers.   The curable resin composition according to claim 1, which is used for coating a light emitting element.   A light-emitting device comprising: a light-emitting element; and a cured film that is formed on the surface of the light-emitting element and is a cured body of the curable resin composition according to claim 10.

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