TW201139563A - Curable resin composition and light emitting device - Google Patents

Abstract

Disclosed is a curable resin composition which has high refractive index, excellent transparency, excellent heat resistance and the like. Specifically disclosed is a curable resin composition which contains (A) a siloxane polymer that is obtained from a silane compound containing a compound represented by general formula (1): (R1)PSi(X)4-P (wherein R1 represents a polymerizable organic group having 2-12 carbon atoms; X represents a hydrolyzable group; and p represents an integer of 1-3), (B) metal oxide particles, and (C) an organic solvent. The curable resin composition contains 50-2,000 parts by mass of the component (B) per 100 parts by mass of the component (A). The curable resin composition is a material for a cured film (2) that covers a light emitting element (1).

Description

[Technical Field] The present invention relates to a curable resin composition and an apparatus for obtaining the same. [Prior Art] A light-emitting device such as a light-emitting diode (LED) is generally constructed by coating a light-emitting element in order to protect a light-emitting element such as a polar body (LED) element or to change color. Further, it is known that a high refractive index material light-emitting element can improve light extraction efficiency. In the past, epoxy resin was generally used as the material of the package material, and the blue LED element or the ultraviolet LED element was used as the light-emitting LED. The epoxy resin (package material) in the vicinity of the light-emitting element was caused by the near-ultraviolet light emitted from the LED element or from the ultraviolet LED. The element emits light and is yellow, and there is a problem of thermal deterioration due to heat generation of the light-emitting element. In applications requiring high brightness such as electric lamps, the amount of light emitted from the blue LED element or the LED element is large, and yellowing or thermal deterioration is likely to occur. Accordingly, as an encapsulating material which is not required to be yellowed by light or ultraviolet light and which is hard to be thermally deteriorated, for example, an fluorenone resin formed of dimethyl polyoxyalkylene is used in applications requiring high brightness. Constituting it. However, the problem with this package is that the refractive index is low and it is difficult to effectively emit light from the LED elements. Patent Documents 1 and 2 disclose that a luminescent light-emitting system comprising an oxime resin having an oxime resin bonded to a ruthenium atom and an organic hydrogen polyoxyalkylene having a Si-H bond is coated with a sealant. However, the component is from the ultraviolet of the blue light. In particular, UV near UV has been developed for packaging materials to be taken from the base of the composition 201139563. The fluorenone resin composition is crosslinked by hydroquinone alkylation reaction to obtain a cured product. However, the cured product has a problem of a low refractive index. [PRIOR ART DOCUMENT] Patent Document 1: JP-A-2004-1861, JP-A-2006-1995 The object of the present invention is to provide a curable resin composition having a high refractive index, excellent transparency, heat resistance, and the like, and a light-emitting device having excellent luminous efficiency. [Means for Solving the Problems] The inventors of the present invention conducted active research to achieve the above object, and found that a curable resin composition containing a metal oxide particle such as a siloxane-based polymer having a specific structure and an oxidation pin is used. Further, the present invention can be obtained by obtaining a film having a high refractive index, excellent transparency and heat resistance, and excellent crack resistance. That is, the present invention provides the following [1] to [9]. Π] A method of producing a light-emitting device, comprising the steps of: (a) coating a light-emitting element with a curable resin composition, the hardenable resin composition comprising: (A) containing the following general formula (1)矽alkylation of the compound -6-201139563 Hydrate-derived polymer: (R')pSi(X)4-p (1) [In the formula (1), R1 is a carbon number of 2 to 12 a polymerizable organic group, X is a hydrolyzable group, and P is an integer of 1 to 3, (B) a metal oxide particle, and (C) an organic solvent, and the amount of the component (B) is relative to the above ( a) a component of 50 parts by mass to 2,000 parts by mass, and (^) a step of heating the above-mentioned light-emitting element. [2] The method for producing a light-emitting device according to the above [1], comprising the step (b) of irradiating the curable resin composition with ultraviolet rays before the step (c). [3] A light-emitting device comprising: a light-emitting element; and a cured film of a cured product of a curable resin composition formed on a surface of the light-emitting element, wherein the curable resin composition contains (A) (1) A siloxane compound obtained by a decane compound of the compound: (R1) pSi(X)4.p (1) [In the formula (1), R1 is a polymerizable organic group having a carbon number of 2 to 12 a group, X is a hydrolyzable group, and p is an integer of 1 to 3, and (B) a metal oxide particle, and the amount of the component (B) is 50 to 2,000 based on 100 parts by mass of the component (A). Parts by mass. [4] A curable resin composition comprising (A) a fluorene-based polymer obtained from a decane compound containing a compound represented by the following formula (1), 201139563 (R1) pSi(X)4-P (1) [In the formula (1), R1 is a polymerizable organic group having 2 to 2 carbon atoms, x is a hydrolyzable group, and p is an integer of 1 to 3], (B) metal oxide particles, and (C) In the organic solvent, the amount of the component (B) is 50 to 2,000 parts by mass based on 100 parts by mass of the component (A). [5] The curable resin composition according to the above [4], wherein the decane compound further contains a compound represented by the following formula (2), (R2)qSi(X)4-q (2) [ In (2), R2 is a non-polymerizable organic group having 1 to 12 carbon atoms, X is a hydrolyzable group, and q is an integer of 〇3 to 3). [6] The curable resin composition according to the above [4], wherein the compound represented by the above formula (1) and the compound represented by the above formula (2) are in the above-mentioned manner. The mass ratio of the compound represented by the formula (1) is 10 to 1% by mass. [7] The curable resin composition according to any one of the above [4], wherein the component (B) is a microparticle having a number average primary particle diameter of from 1 to 100 nm. [8] The curable resin composition according to any one of the above [4] to [7], which is used for coating a light-emitting element. [9] A method for producing a curable resin composition, characterized by mixing (A) a fluorene-based polymer obtained from a decane compound containing a compound represented by the following formula (!) in (C) an organic solvent; And (B) a metal oxide particle, the curable tree 201139563 lipid composition according to any one of the above [4] to [8], (R1) pSi(X)4-p (1) [formula ( In 1), R1 is a polymerizable organic group having 2 to 12 carbon atoms, X is a hydrolyzable group, and p is an integer of 1 to 3). [Effect of the Invention] The curable resin composition of the present invention has a high refractive index and is excellent in transparency, heat resistance, crack resistance, and light resistance. The curable resin composition of the present invention is suitably used as a material for forming a cured film on the surface of a light-emitting element. A light-emitting device in which a cured film of a cured product of the curable resin composition of the present invention is formed on the surface of a light-emitting element has high luminous efficiency. [Embodiment] Each component used in the present invention will be described in detail. [(A) component: specific alkoxycarbon-based polymer] The methane-alkyl polymer of the component (A) is prepared by containing a compound represented by the following formula () and optionally having the following formula (2) (R)pSi(X)4-p. (1) [In the formula (1), R is a polymerizable organic group having 2 to 12 carbon atoms, and X is a hydrolyzable group, and P is an integer from 1 to 3], (R )qSi(X)4.q (2)

In the formula (2), R is a non-polymerizable organic group of carbon number, X 201139563 is a hydrolyzable group, and q is an integer of 0 to 3]. The hydrolyzable group represented by X in the general formulae (1) and (2) generally means that it can be heated at a temperature ranging from room temperature (25 ° C) to 100 ° C in the absence of a catalyst and in the presence of excess water. The alkoxy group is hydrolyzed to form a stanol group. Further, the hydrolyzable group may be further condensed after hydrolysis to form a decane oxygen condensate. The additional word P in the general formula (1) is an integer of 1 to 3, preferably an integer of 1 to 2, and the additional word q in the general formula (2) is an integer of 0 to 3, preferably 0 to 2 The polyoxyalkylene-based polymer may be one in which at least two hydrolyzable decane compounds are condensed. The a naphthenic polymer may also remain a part of the unhydrolyzed hydrolyzable group. Further, the siloxane-based polymer may be a partial condensate in which a part of the stanol group or the hydrolyzable group is condensed with each other. The hydrolyzable group X in the general formulae (1) and (2) is exemplified by a hydrogen atom, a halogen atom, an alkoxy group having 1 to 12 carbon atoms, a halogenated alkoxy group having a carbon number of 12, and a carbon number of 2 to 12. An oxy group, a halogenated fluorenyl group having 2 to 12 carbon atoms, and the like. Preferable examples of the alkoxy group having 1 to 12 carbon atoms are methoxy group, ethoxy group and the like. Preferred examples of the halogenated alkoxy group of the carbon number 12 are a trifluoromethoxy group, a trichloromethoxy group, a pentafluoroethoxy group, a pentachloroethoxy group and the like. Preferred examples of the halogen atom are fluorine, chlorine, bromine, iodine and the like. Preferred examples of the decyloxy group having 2 to 12 carbon atoms are ethoxycarbonyl, propyloxy, butanoxy and the like. Preferred examples of the halogenated oxy group having 2 to 12 carbon atoms are trifluoroacetoxy, trichloroacetoxy, pentafluoropropoxy, and pentachloropropoxycarbonyl heptafluorobutoxy , heptachlorobutoxy group and the like. -10- 201139563 The polymerizable organic group R1 in the formula (1) is non-hydrolyzable, and is preferably organic of either a radical polymerizable functional group and a cationically polymerizable functional group in the molecule. base. Further, the term "non-hydrolyzable" means a property which is still stable under the condition that the hydrolyzable group X is hydrolyzed. The functional group of the radical polymerizable property is exemplified by an alkenyl group having 2 to 10 carbon atoms and an alkynyl group having 2 to 10 carbon atoms. The cationically polymerizable functional group is exemplified by an epoxy group such as oxiranyl or oxetane. By introducing such a functional group into the organic group R1, the curable resin composition can be hardened more rapidly by radical polymerization or cationic polymerization. The compound of the formula (1) can be exemplified by 2-(meth)acryloxyethyltrimethoxydecane, 2-(methyl)propenyloxyethyltriethoxydecane, 3-(methyl Propylene methoxy propyl trimethoxy decane, 3-(methyl) propylene methoxy propyl triethoxy decane, 3-(methyl) propylene methoxy propyl methyl dimethoxy cleavage 3-(Methyl)allyloxypropyltriisopropoxy oxane 'vinyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyl A Diethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, [3-[(3-ethyl-3-oxetanyl)methoxy] Propyltrimethoxydecane, 3-(3-methyl-3-oxetanylmethoxy)propyltrimethoxydecane, oxetanyltrimethoxydecane, and the like. The polymerizable organic group R2 in the formula (2) is a non-hydrolyzable group and is a non-polymerizable organic group having 1 to 12 carbon atoms. The organic group R2 is exemplified by a hydrocarbon group having 1 to 12 carbon atoms, a halogenated hydrocarbon having 1 to 12 carbon atoms, and a base such as 201139563. The organic group R1 may be linear, branched, cyclic or a combination thereof. Further, the organic group R1 may also be a structure containing a hetero atom. These structural units can be exemplified by an ether bond, an ester bond, a thioether bond or the like. The hydrocarbon group of the carbon number 12 in the organic group R1 is preferably a hydrocarbon group having 1 to 8 carbon atoms, more preferably a hydrocarbon group having 1 to 4 carbon atoms, from the viewpoint of reactivity and crack resistance of the obtained film. Specific examples thereof include aliphatic hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and t-butyl groups, cyclopropyl, cyclobutyl and cyclopentyl groups. An aromatic hydrocarbon group such as an alicyclic hydrocarbon group such as a cyclohexyl group, a phenyl group, a methylphenyl group, an ethylphenyl group or a benzyl group, preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group or a t-butyl group. Phenyl, methylphenyl, more preferably methyl or ethyl. Further, the hydrocarbon group having 1 to 12 carbon atoms which is substituted by a halogen atom in the organic group R1 is a fluorinated hydrocarbon group, a chlorinated hydrocarbon group or a brominated hydrocarbon group, and preferably a fluorinated hydrocarbon group. The carbon number of the hydrocarbon group is preferably from 1 to 4 from the viewpoint of reactivity and crack resistance of the obtained film. Specific examples thereof include chloromethyl, dichloromethane, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, and all. Fluorylpropyl, perfluoroisopropyl, perfluoro-n-butyl, perfluoroisobutyl, perfluoro-tert-butyl, preferably fluoromethyl, difluoromethyl, trifluoromethyl, 2,2 , 2-trifluoroethyl, pentafluoroethyl, perfluoro-n-propyl, perfluoroisopropyl, perfluoro-t-butyl, more preferably fluoromethyl, difluoromethyl, trifluoromethyl, 2 , 2,2-trifluoroethyl, pentafluoroethyl. Specific examples of the hydrolyzable decane compound represented by the general formula (2) - 201139563 The decane compound having four hydrolyzable groups is exemplified by tetrachlorodecane, tetraaminodecane, tetraethoxydecane, tetramethoxy A decyl alkane, a tetraethoxy decane, a tetrabutoxy decane, a tetraphenoxy decane, a tetrabenzyloxy decane, a trimethoxy decane, a triethoxy decane, or the like. The decane compound having three hydrolyzable groups is exemplified by methyltrichlorodecane, methyltrimethoxydecane, methyltriethoxydecane, methyltributoxydecane, ethyltrimethoxydecane, ethyltri Isopropoxydecane, ethyltributoxydecane, butyltrimethoxydecane, pentafluorophenyltrimethoxydecane, phenyltrimethoxydecane, d3-methyltrimethoxydecane, nonafluorobutyl Ethyltrimethoxydecane, trifluoromethyltrimethoxydecane, and the like. The decane compound having two hydrolyzable groups is exemplified by dimethyldichlorodecane, dimethyldiaminodecane, dimethyldiethoxydecane, dimethyldimethoxydecane, diphenyldimethyl Oxydecane, methylphenyldimethoxydecane, dibutyldimethoxydecane, and the like. The decane compound having one hydrolyzable group is exemplified by trimethylchlorodecane, hexamethyldioxane, trimethyldecane, tributyldecane, trimethylmethoxydecane, tributylethoxysilane, and the like. . The naphthenic polymer of the component (A) will be described. The molecular weight can be measured by using a gel permeation chromatograph (hereinafter abbreviated as GPC) in terms of a weight average molecular weight in terms of polystyrene using a tetrahydrofuran as a mobile phase. The weight average molecular weight of the decane-based polymer is preferably from 50,000 to 100,000 Å, more preferably from 800 to 30,000 Å, still more preferably from 1, 〇〇〇 to 5,000. When the enthalpy is less than 50,000, the crack resistance at the time of formation of a cured film tends to decrease. When the cerium exceeds 100,000, the dispersibility of the metal oxide particles -13 to 201139563 of the component (B) tends to decrease. The mass ratio of the compound represented by the formula (1) to the compound represented by the formula (1) in the total amount of the compound represented by the formula (1) is preferably from 10 to 1% by mass. More preferably, it is 2 0 to 1 〇〇 mass%, preferably 3 0 to 1 0 0% by mass, and the ratio is less than 10% by mass, and crack resistance is deteriorated. The above-mentioned oxane-based polymer is usually hydrolyzed and condensed by a decane compound containing a compound represented by the above formula (1) and optionally a compound represented by the following formula (2) in the presence of a catalyst. obtain. The catalyst for obtaining the siloxane polymer is preferably at least one compound selected from the metal chelating compound, the acidic compound, and the basic compound, and more preferably an acidic compound. (a) Metal chelating compound The metal chelating compound which can be used as a catalyst is represented by the following general formula (3). R15eM(OR16)fe ......(3) (wherein R15 is a chelating agent, Μ is a metal atom, Ri6 represents an alkyl group or a square group' f represents the valence of gold iridium, and e represents 1~ The integer of f). The metal ruthenium is preferably at least one metal selected from the group consisting of lanthanum metals (aluminum, gallium, indium, molybdenum) and IV lanthanum metals (titanium, pin, feed), more preferably titanium, aluminum or zirconium. The honey-binding agent represented by R15 may be exemplified by CH3C〇CH2C〇c:H3, CH3COCH2COOC2H5, etc., and the substituents represented by R16 are listed as methyl, ethyl, n-propyl, isopropyl-14-201139563, n-butyl. And an isobutyl group and a tributyl group, and examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a benzyl group and the like. Preferred examples of the metal chelate compound are (CH3 (CH3) HCO) 4-t Ti (CH3COCH2COCH3), '(CH3(CH3) HCO) 4-tTi(CH3COCH2CO〇C2H5) , '(C4H9O) 4-tTi -( CH3COCH2COCH3 ) t , ( C4H9O ) 4-tTi ( CH3COCH2COOC2H5 ) t ' ( C2H5 ( CH3 ) CO ) 4-tTi ( CH3COCH2COCH3 ) t ' ( C2H5 ( CH3 ) CO ) 4.tTi ( CH3COCH2COOC2H5 ) t ' ( CH3 ( CH3 ) HCO ) 4-tZr ( CH3COCH2COCH3 ) t ' ( CH3 ( CH3 ) HCO ) 4-tZr ( CH3COCH2COOC2H5 ) . ' ( C4H9O ) 4-tZr ( CH3COCH2COCH3 ) t , ( C4H9O ) 4-tZr ( CH3COCH2COOC2H5 ) t ' ( C2H5 ( CH3 ) CO ) 4-tZr ( CH3COCH2COCH3 ) t ' ( C2H5 ( CH3 ) CO ) 4-«Zr ( CH3COCH2COOC2H5 ) t ' ( CH3 ( CH3 ) HCO ) 3-tAl ( CH3COCH2COCH3 ) t ' ( CH3 ( CH3 ) HCO ) 3., A1 ( CH3COCH2COOC2H5 ) « , ( C4H9O ) 3-tAl ( CH3COCH2COCH3 ) t ' ( C4H9O ) 3,, A1 ( CH3COCH2COOC2H5 ) t ' ( C2H5 ( CH3 ) CO ) 3-tAl ( CH3COCH2COCH3 ) t ' ( C2H5 (CH3) CO) 3-tAl (CH3COCH2COOC2H5) t and the like. The amount of the metal chelate compound is preferably from 0.001 to 10,000 parts by mass, more preferably from 0.001 to 5 parts by mass, per 100 parts by mass of the total amount of the decane compound (in terms of the fully hydrolyzed condensate). When the amount is less than 0.000 1 part by mass, the coating property of the coating film may be deteriorated when the coating amount is -15-201139563. When the amount exceeds 0 mass%, the growth of the polymer cannot be controlled, and gelation may occur. When the hydrolyzable decane compound is hydrolyzed and contracted in the presence of a metal honey compound, the total amount of the sand compound is preferably from 0 to 20 moles per 1 mole. It is preferred to use 1 to 10 moles of water. When the amount of water is less than 5%, the hydrolysis reaction cannot be sufficiently carried out, and there are problems in coating properties and storage stability. When it exceeds 20 m, the polymer precipitates or gels during hydrolysis and condensation. The situation. And the water is preferably added intermittently or continuously. (b) Acid compound The acidic compound which can be used as a catalyst can be exemplified by an organic acid or an inorganic acid, preferably an organic acid. The organic acid may, for example, be acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, azelaic acid. , gallic acid, butyric acid, Mellitic acid, arachidonic acid, shikimic acid, ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid (linolenic acid), salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, hydrazine chloroacetic acid, trifluoroacetic acid, formic acid, malonic acid , sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, maleic anhydride, fumaric acid, itaconic acid, morphic acid, mesaconic acid, citraconic acid, malic acid, malonic acid, glutaric acid Hydrolyzate of acid, hydrolyzate of maleic anhydride, hydrolyzate of phthalic anhydride, and the like. The inorganic acid may, for example, be hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, scale-16-201139563 acid or the like. Among them, an organic acid is preferred from the viewpoint of precipitation or gelation of the polymer in the hydrolysis condensation (hydrolysis and subsequent condensation) reaction, and among them, it is more preferably a compound having a carboxyl group. Among the 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, An organic acid such as malonic acid, glutaric acid or a hydrolyzate of maleic anhydride. These acidic compounds may be used singly or in combination of two or more kinds of the hydrazine acidic compound in an amount of 100 parts by mass based on the total amount of the decane compound (in terms of the fully hydrolyzed condensate), preferably 〇. 〇〇〇1~1 〇 The mass fraction is more preferably 1 to 5 parts by mass. When the amount is less than 0.1 part by mass, the coating property of the coating film may be deteriorated. When the amount is more than 10 parts by mass, the hydrolysis condensation reaction may rapidly proceed to cause gelation. When the hydrolyzable decane compound is hydrolyzed and condensed in the presence of an acidic compound, the total amount of the decane compound is preferably 0.5 to 20 moles of water per 1 mole, preferably 1 to 10 moles of water. When the amount of water is less than 0.5 mol, the hydrolysis reaction may not proceed sufficiently, and there may be problems in coatability and storage stability. When the amount exceeds 20 mol, the polymer in the hydrolysis condensation reaction may precipitate or gel. Happening. Moreover, the water is preferably added intermittently or continuously. (c) Basic compound The basic compound which can be used as a catalyst is exemplified by, for example, methanolamine, B-17-201139563 Alcoholamine, propanolamine, butanolamine, N-methylmethanolamine, N-ethylmethanol N -propylmethanolamine, N-butylmethanolamine, N-methylethanolamine, N-ethanolamine, N-propylethanolamine, N,N-dimethylmethanolamine, hydrazine, hydrazine-diethanolamine, hydrazine, hydrazine- Dipropylmethanolamine, hydrazine, hydrazine-dibutylmethanolamine, hydrazine-methylmethanolamine, hydrazine-ethyldimethanolamine, hydrazine-propyldimethylethanolamine, hydrazine-butylolamine, hydrazine-(amine group Methyl)methanolamine, Ν-(aminomethyl)ethanol hydrazine-(aminomethyl)propanolamine, Ν-(aminomethyl)butanolamine, methylmethylamine, methoxyethylamine , methoxypropylamine, methoxybutyl hydrazine, hydrazine-dimethylamine, hydrazine, hydrazine-diethylamine, hydrazine, hydrazine-dipropylamine, hydrazine, hydrazine-amine, trimethyl Amine, triethylamine, tripropylamine, tributylamine, tetramethylammonium chloride, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydrogen, tetramethylethylenediamine, Tetraethylethylenediamine, tetrapropylethyl, ammonia, sodium hydroxide 'potassium hydroxide, tetramethylammonium hydroxide, Hydrogen oxyethylammonium, tetra-n-propylammonium hydroxide, tetra-n-butylammonium hydroxide, bromomethylammonium, tetramethylammonium chloride, tetraethylammonium bromide. The amount of the basic compound is 1 mole based on the hydrolyzable group in the decane compound, preferably 0.0000 1 to 1 Torr, more preferably 0.00005 Å. [(Β) component: metal oxide particles] In the present invention, a metal oxide having a high refractive index is used to obtain a cured product of a refractive index. These microparticles are as long as 25. (The refractive index of the light of 40 〇 nm is preferably 丨55 or more, more preferably 丨6 〇, more preferably 1.70 or more of the fine particles, and is not particularly limited, for example, an amine, an ethyl methyl group Dimethylamine, oxyamine, dibutoxide, oxidative diamine, tetracycline, tetracycline, ～5, δ-18, 201139563 pin, titanium oxide, zinc oxide, oxidized giant, indium oxide, oxidation, Metal oxide particles such as tin oxide, cerium oxide, and the like, and fine particles of cerium oxide (Zr 〇 2) are preferred. The titanium oxide is not particularly limited as long as it has a structure of T i Ο 2, and is For example, an anatase type, a rutile type, a brookite type. The metal oxide particles may be used singly or in combination of two or more. (B) The metal oxide particles of the component have a good average primary particle diameter. It is 1 to 100 nm, more preferably 3 to 70 nm, and most preferably 5 to 50 nm. The number average primary particle diameter of the metal oxide particles can be measured as a number average particle diameter by, for example, transmission electron microscope observation. When the particles are not spherical, Taking the average of the long axis and the short axis as When the ratio of the particle diameter to the major axis/minor axis is 2 or more, the short axis is used as the particle diameter. When the number average primary particle diameter is within the above range, a cured product excellent in transparency can be obtained. (B) Metal oxide particles of the component Before mixing with the component (A) and the component (C), it may be in the form of a powder or a solvent-dispersed sol. For example, an organic solvent may be used as the solvent. The organic solvent is exemplified by, for example, 2-butanol, methanol, methyl b. Ketone, methyl isobutyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, propylene glycol monomethyl ether, etc. The amount of the component (B) is 50 parts by mass relative to the (A) component. ～2,000 parts by mass, preferably 100 to 1,500 parts by mass, more preferably 150 to 1,000 parts by mass. When the amount exceeds 2,000 parts by mass, sufficient crack resistance cannot be obtained, and the amount is not When the amount is 50 parts by mass, the refractive index of the cured film (the cured product of the composition) is lowered, and the luminous efficiency of the light-emitting device is lowered by -19-201139563. Further, when the component (B) is a solvent-dispersed sol, The blending amount of the component (B) means the mass without solvent. Further, the component (b) is solvent dispersion. In the case of the sol, the amount of the organic solvent as the solvent of the component (B) is one of the components of the organic solvent constituting the component (C). [(C) component: organic solvent] The present invention can improve the composition by formulating an organic solvent. The organic solvent is exemplified by an ether-based organic solvent, an ester-based organic solvent, a ketone-based organic solvent, a hydrocarbon-based organic solvent, an alcohol-based organic solvent, etc. The organic solvent is preferably used as an organic solvent. The organic solvent which can uniformly disperse each component in the range of 50 to 25 (at a range of TC) at atmospheric pressure (l, 013 hPa) is exemplified by, for example, an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, and a single solvent. An alcohol solvent, a polyol solvent, a ketone solvent, an ether solvent, an ester solvent, a nitrogen-containing solvent, a sulfur-containing solvent, or the like. These organic solvents may be used alone or in combination of two or more. In the organic solvent, a monool solvent, a polyol solvent, and a ketone solvent are preferred from the viewpoint of further improving the storage stability of the composition. Examples of preferred compounds of such solvents are propylene glycol monomethyl ether, ethyl lactate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl amyl ketone, methanol, ethanol, 2- Butanol and the like. These preferred compounds may be used alone or in combination of two or more. In the present invention, the type of the organic solvent is preferably selected in consideration of the coating method of the composition -20-201139563. For example, in order to easily obtain a cured film having a uniform thickness (hardened product of a composition) and using a spin coating method, a glycol ether such as ethylene glycol monoethyl ether or propylene glycol monomethyl ether is preferably used as the organic solvent; Ethylene glycol alkyl ether acetate such as ethyl cellosolve acetate, propylene glycol methyl ether acetate or propylene glycol ethyl ether acetate; esters such as ethyl lactate and ethyl 2-hydroxypropionate; Diethylene glycol such as diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether; methyl ethyl ketone, methyl isobutyl ketone, 2 g Ketones such as ketone, cyclohexanone and methyl amyl ketone; γ-butyrolactone and the like. The most preferred organic solvents are ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, ethyl lactate, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl. Ketones, etc. The compounding amount of the component (c) (organic solvent) is preferably from 50 to 20,000 parts by mass, more preferably from 100 to 1,000 parts by mass, per 100 parts by mass of the total of the components of the composition other than the organic solvent. If it is within the above preferred range, the storage stability of the composition can be improved, and the appropriate viscosity can be imparted, and a high refractive index cured film having a uniform thickness can be easily formed. The method of adding the component (c) is not particularly limited. For example, it may be added during the production of the (Α) component, or may be added during the preparation of the dispersion containing the (β) component, or may be mixed with the component (A) and (Β). Add when ingredients. [(D) component: dispersant] The curable resin composition of the present invention can use various dispersants to increase the dispersibility of the metal oxide particles. As the dispersant, for example, a bromine compound can be used. Examples of the tin compound -21 - 201139563 are alkane alumina, aluminum β-diketonate complex, and the like. Specifically, it may be an alkylene such as triethoxyaluminum, tri(n-propoxy)aluminum, tris(isopropoxy)aluminum, tri(n-butoxy)aluminum or tris(t-butoxy)aluminum. Oxygen compound, aluminum ginseng (methyl acetamidine acetate), aluminum ginseng (ethyl acetoacetate), ginseng (acetyl acetonate) aluminum 'aluminum monoethyl phthalate pyruvate bis (methyl acetate Ester), β-diketonate complex of aluminum monoethyl phthalate bis (ethyl acetate). Commercially available aluminide products can use AIPD' PADM, AMD, ASBD, ethoxylated 'ALCH' ALCH-50F, ALCH-75, ALCH-TR, ALCH-TR-20, aluminum chelate M, aluminum chelate D, aluminum chelate A (W), surface treatment agent OL-1 000, ALUGOMER, ALUGOMER 800AF, ALUGOMER 1000SF (above is manufactured by Chuanxiong Precision Chemical Co., Ltd.). A nonionic dispersant can be used as the dispersant. The dispersibility can be improved by using a nonionic dispersant. The nonionic dispersing agent used in the present invention is preferably a phosphate-based nonionic dispersing agent having a polyoxyethylene alkyl structure. The amount of the dispersing agent is not particularly limited. However, when the dispersing agent is contained, the total amount of the constituent components excluding the organic solvent is, for example, 0.1 to 20% by mass. [(E) component: dispersing aid] The curable resin composition of the present invention may further contain a dispersing aid to improve dispersibility. The dispersing aid may suitably be one or more selected from the group consisting of etidylacetone and N,N_:methylacetamidoacetamide. -22- 201139563 The amount of the dispersing aid is not particularly limited. However, when the dispersing aid is used, the total amount of the constituent components other than the organic solvent is, for example, 0.1 to 10% by mass. [(F) component: surfactant] When the curable resin composition of the present invention is applied to a substrate or the like by spin coating, it is preferable to prepare a surfactant in terms of obtaining a coating film having a uniform thickness. . The surfactant used in the present invention is exemplified by an anthrone-based surfactant, a cross-linking surfactant, and the like. Among them, a ketene-based surfactant is preferred. Examples of the anthrone-based surfactants include, for example, SH28P A (manufactured by Tor ay Dow Corning Co., Ltd., dimethyl polyoxyalkylene polyoxyalkylene copolymer), PEINTADO 19, 54 (manufactured by Toray Dow Corning Co., Ltd., Methyl polyoxyalkylene polyoxyalkylene copolymer), FM0411 (SILAPLANE, manufactured by CHISSO), SF 8428 (manufactured by Toray Dow Corning, dimethyl polyoxyalkylene polyoxyalkylene copolymer (side chain) Contains OH ) ), BYKUV3510 (manufactured by BYK, Japan, dimethyl polyoxyalkylene-polyoxyalkylene copolymer), DC5 7 (manufactured by Toray Dow Corning, dimethyl polyoxyalkylene-polyoxyalkylene) Base copolymer), DC190 (manufactured by Toray Dow Corning, dimethyl polyoxetane-polyoxyalkylene copolymer), SILAPLANE FM-4411, FM-442 1 , FM-4425, FM-771 1, FM-772 1, FM-7 72 5, FM-041 1, FM-042 1, FM-042 5, FM-DA11, FM-DA21, FM-DA26, FM071 1, FM072 1, FM-0725, TM- 070 1 , TM-070 1 T ( -23- 201139563 CHISSO company), UV3500, UV3510, UV3 5 3 0 (manufactured by BY本 BYK), BY1 6-004, SF8428 ( Toray Dow

Made by Corning, VPS-1001 (made by Wako Pure Chemical Industries, etc.). The best example is awkward! 1 For SILAPLANE FM-771 1, FM-772 1, FM-7725, FM-0411, FM-042 1, FM-0425, FM0711, FM072 1, FM-0725, VPS-1001, etc. Further, commercially available products of an anthranone compound having an ethylenically unsaturated group may, for example, be Tego Rad 2300 or 2200 N (manufactured by TEGO Chemical Co., Ltd.). Fluorine-based surfactants are exemplified by, for example, Megafac F-1 1 4, F4 1 0, F411, F45 0, F493, F494, F443, F444, F445, F446, F470 'F471, F472SF, F474, F475, R30, F477' F478, F479, F480SF, F482, F48 3, F484, F486, F487, F172D, F178K, F178RM, ESM-1, MCF3 5 0SF, BL20, R08, R61, R90 (manufactured by DIC Corporation). The blending ratio of the component (F) is preferably from 0 to 10% by mass, more preferably from 0.1 to 5% by mass, and most preferably from 0.5 to 3% by mass, based on 100% by mass of the total of the components of the composition other than the organic solvent. When the amount exceeds 10% by mass, the refractive index of the cured product of the composition may decrease. [(G) component: dehydrating agent] The curable resin composition of the present invention may further contain a dehydrating agent. By adding a dehydrating agent', the radiation hardening reaction of the composition can be promoted while the storage stability of the composition is further improved. The dehydrating agent used in the present invention is defined as a compound which converts water into a substance other than water by using a chemical reaction, or by physical adsorption or inclusion, which converts water into radiation hardening property and storage stability. Compound. By containing a dehydrating agent, the two properties of storage stability and radiation hardenability are improved without impairing the light resistance or heat resistance of the composition. As for the reason, it is considered that the dehydrating agent effectively absorbs water invaded from the outside to improve the storage stability of the composition, and on the other hand, in the condensation reaction of the radiation hardening reaction, 'the water generated by the dehydrating agent is successively absorbed, The radiation hardenability of the composition is improved. _ [(Η) component: polymerization initiator] The curable resin composition of the present invention may further contain a polymerization initiator. The polymerization initiator is defined as a compound which can cause an active species (free radical or acid) which polymerizes a component (Α) by light irradiation or heating. The term "light irradiation" as used herein means irradiation of ionizing radiation such as infrared rays, visible light, ultraviolet rays, and X-rays, electron beams, alpha rays, beta rays, and gamma rays. The photoradical polymerization initiator which can generate radicals by light irradiation is exemplified by, for example, acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2. -Phenylacetophenone, xanthone, anthrone, benzaldehyde, hydrazine, hydrazine, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4' -dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michael's ketone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl condensate Ketone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-hydroxy-l-{4-[4-(2-hydroxy-2-methyl- Propionyl)-benzyl]-phenyl b-2--25- 201139563 methyl-propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, Diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1-[4-(methylthio)phenyl]_2·morpholinyl-propan-1 -ketone, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethylpentyl oxidation Phosphine and the like. Among them, 1-hydroxycyclohexyl phenyl ketone or the like is preferably used from the viewpoint of transparency, polymerization rate, and solution stability. Commercial products are listed, for example, as Irgacure 127, 184, 369, 3 79, 651, 500, 819, 907, 784, 2959, CGI-1700, -1750, -1850, CG24-61, Darocur 1116, 1173 (above Bart is manufactured by Chemical Company; Lucirin TPO, LR8 893, LR8970 (above is manufactured by BASF); UBECRYL P36 (manufactured by UCB). The photoradical polymerization initiator may be used singly or in combination of two or more. In the curable resin composition, the blending ratio of the photoradical polymerization initiator is 100% by mass, preferably 0.1 to 10% by mass, more preferably 0.2 to 7 by mass based on the total solid content of the curable resin composition. %, more preferably 0.5 to 5 mass%. When the above-mentioned blending ratio is less than 〇1. ii%, the hardening cannot be sufficiently performed, and there is a case where a cured product having sufficient reliability cannot be obtained. Moreover, the above ratio is more than 1 〇. /. At the time, the photopolymerization initiator has a possibility of adversely affecting the long-term characteristics of the cured product. In addition, the photoacid generator which generates an acid by light irradiation may, for example, be an onium salt (first group compound) having a structure represented by the formula (4) or a sulfonic acid derivative having a structure represented by the formula (5). (Second Group Compound-26-201139563 [R2aR3bR4〇R5dW]m + [MZm + n]m' (4) [In the general formula (4), 'cation is a key ion' w is S, Se, Te, P, As, Sb, Bi, Ο, I, Br, Cl or -N = N, R2, R3, R4 and R5 are the same or different organic groups, and a, b, c and d are integers of 〇~3, respectively ( a + b + c + d) - η is the valence of W, etc. Further, Μ is a metal or metalloid which constitutes a halide complex [the central atom of MXm + d] such as ruthenium, osmium, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn or Co. Z is a halogen atom or an aryl group such as F, Cl, Br, and m is a halide complex ion. Net charge, n is the atomic price of M].

Qs-[S( = 〇)2-R6], (5) [In the formula (5), Q is a monovalent or divalent organic group, and R6 is a one-valent organic group having a carbon number of 1 to 12, and an additional word s For 〇 or 1, the additional word t is 1 or 2]. First, the key salt of the first group of compounds is a compound which can release an acid active material by receiving light. Among the first group of compounds, a more effective key salt is an aromatic gun salt, and preferably a diaryl sulfonium salt represented by the following formula (6). [R7-Ar 1 -I + -Ar2-R8] [Y ] (6) [In the formula (6), R7 and R8 are each a monovalent organic group, which may be the same or different, and at least one of R7 and R8 is An alkyl group having a carbon number of 4 or more, and Ar1 and Ar2 are each an aromatic group, and may be the same or different, and γ· is a monovalent anion' is a fluorinated anion of Group 3 or Group 5 of the periodic table or C104·, CF3- S03 · Selected anion]. Further, 'when the second group of compounds is exemplified by the 'sulfonic acid derivative represented by the formula (5)', it can be exemplified as diterpenoids, disulfonyldiazomethanes, -27-201139563 disulfonyl group. Methane, sulfonyl benzhydryl methane, sulfhydrazine sulfonate, benzoin sulfonate, 1-oxy-2-hydroxy-3-propanol sulfonate, ortho-benzene Trisphenol trisulfonates, benzyl sulfonates. Further, among the sulfonic acid derivatives represented by the formula (5), more preferably an imine sulfonate, more preferably a trifluoromethanesulfonate derivative of the sulfhydrazine sulfonate. The addition amount (content ratio) of the photoacid generator will be described. The amount of the photo-acid generator to be added is not particularly limited. However, the total amount of the solid content of the curable resin composition is preferably 100 parts by mass, and usually it is preferably within 15 parts by mass. When the amount is more than 15 parts by mass, the weather resistance or heat resistance of the obtained cured product tends to decrease. [Component (I): Other Additives] The curable resin composition of the present invention may contain various additives other than the above insofar as the effects of the present invention are not impaired. These additives are exemplified by curable compounds other than the above components, antioxidants, ultraviolet absorbers, and the like. [Method for Producing Curable Resin Composition] The curable resin composition of the present invention can be prepared by mixing the above components (A) to (C) and optionally other optional components. In general, the component (A) specific azoxyalkylene polymer and the component (B) metal oxide particles and any other components added thereto may be mixed in a specific ratio in a (C) organic solvent, whereby the curable resin composition is prepared. . -28-201139563 [Cured film] The cured film of the cured product of the composition of the present invention preferably has a refractive index of preferably 1.6 or more. When the refractive index is 1.6 or more, the light-emitting efficiency of the light-emitting device is increased. 膜 The film thickness of the cured film is not particularly limited, but may be suitably set within a range of, for example, 50 nm to ΙΟΟμηι depending on the type of the light-emitting element. [Application] The curable resin composition of the present invention is not particularly limited, and can be used for, for example, a light-emitting element such as a light-emitting diode, a semiconductor laser 'photodiode, a photoelectric crystal, an electroluminescence element, a CCD, or a CMOS image sensor. Among the optical members used in the film, the antireflection film of the solar cell, and the like, it is preferably used in a light-emitting element such as a light-emitting diode, a semiconductor laser, a photodiode, a photoelectric crystal, or an electroluminescence element. [Light-emitting device and method of manufacturing the same] The light-emitting device of the present invention is not particularly limited, and is exemplified by, for example, a light-emitting diode 'semiconductor laser, a photodiode, a photo-crystal' electroluminescence element, a CCD, a C-MOS, and a solar cell. Wait. The light-emitting device of the present invention can be produced by coating a curable resin composition of the present invention and curing it to form a cured film, followed by encapsulation in a package as needed. The method of coating (coating) the curable resin composition of the present invention is not particularly limited, and may be selected from spin coating, dipping -29-201139563 coating, impregnation, ink jetting, etc., in consideration of the shape of the light-emitting device. A conventional method can be used for the hardening method. Specifically, it is a method of heating at 30 to 250 ° C for 1 minute to 24 hours. When the curable resin composition of the present invention contains a photoacid generator, it is preferred to carry out light irradiation before the above heating step. The light irradiation at this time is preferably irradiated with ultraviolet rays at an energy of, for example, 1 〇〇 to 5,000 mJ/cm 2 . The light-emitting device shown in Fig. 1 is a structure in which a cured film 2' formed of a curable resin composition of the present invention is formed on the surface of a light-emitting element 1, and is packaged by a sealing material 5. In Fig. 1, reference numerals 3a and 3b denote electrode portions, 4a and 4b denote fine metal wires, and 6 denotes an insulating substrate. When the light-emitting device is a light-emitting diode, a light-emitting diode element manufactured using a compound such as GaAs, GaAlAs, A]GaInP, GaP, GaAsP, ZnSe, ZnS, GaN, or nnGaN can be used. Further, the luminescent color of the light-emitting diode is not particularly limited, and examples thereof include red, green, blue, yellow, orange, yellow-green, and white. EXAMPLES Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited by the examples. [Preparation of component (A)] [Synthesis Example 1] Glycidoxypropyltrimethoxydecane (47-52 g) and tetraethoxysilane (l?.47 g) were added to a flask equipped with a stirrer and a reflux tube. -30- 201139563 Propylene glycol monomethyl ether (27.49g) and oxalic acid (0.04g) were heated to 60 °C. Then, 'distilled water (P, after the completion of the dropwise addition, the solution was stirred at 80 ° C for 2 hours. Then, concentrated, and the final solid content was adjusted to 30% by mass, obtained) was made of propylene glycol monomethyl ether. Solution. Call it "A-Ι". In addition, "A-2" to "A-5" are 21.0 g of zirconium oxide (number average 15 nm) and 29.7 g (solid content: 8.9 g) of (B) component using East Asia Synthesis Co., Ltd. [Preparation of composition 1]. "A-1", propylene glycol monomethyl ether having a total weight of 70 g was fed into a container, and zirconia beads having a particle diameter of 0.1 mm (manufactured by Nikkato Co., Ltd.) were added, and the beads were honed to 15 The mixture was stirred at rpm for 10 hours to disperse the oxidized scorpion (component (B)). The composition "J-1" was obtained by adding a dimethyl alkane-polyoxyalkylene copolymer 〇_1〇g ' to the dispersion of the obtained zirconia fine particles.

In addition, the composition "b2", "]-3", "J-6", "J" were prepared in addition to the composition of the components shown in Table 1.

[Preparation of Composition 2] 15.91 g of chromium oxide fine particles as (B) component (several particle diameter: 15 nn 〇, 1.91 g of PLADD ED-151 (compound oxyethylene alkyl phosphate), three (second butyl)氧基)Aluminum 2.2〇g After stirring [•48g) Under reduced pressure (A manufacturer particle size: machine solvent in which 3 50g - particulate polyoxo® "J-1 average one = poly, acetonitrile - 31 - 201139563 0.55 g of acetone, 2.30 g of 2-butanol, and 70.00 g of methyl ethyl ketone were fed into a container, and 305 g of zirconia beads (manufactured by Nikkato Co., Ltd.) having a particle diameter of 0.1 mm was added thereto, and beads were used. After granulating, the mixture was stirred at 150 ° rpm for 10 hours to disperse the fine particles of zirconia (component (B)). Add 7.73 § "A_4", dimethyl to 93.18 g of the obtained dispersion of oxidized pin microparticles. The polyoxyalkylene-polyoxyalkylene copolymer O.lg was obtained to obtain the composition "J-4". [Preparation of the composition 3] 15.9 1 g was used as the oxidized pin fine particles of the component (B) Particle size: 15 nm), 1.91 g of PLADD ED-151, 3 (second butoxy) aluminum 2.20 g, acetamidine acetone 0.85 g, 2-butanol 2.30 g 'methyl ethyl ketone 70.00 g Into the vessel, 350 g of zirconia beads (manufactured by Nikkato Co., Ltd.) having a particle diameter of 0.1 mm was added thereto, and the mixture was stirred by a bead granule at 1500 rpm for 10 hours to disperse the zirconia fine particles (component (B)). To 93.18 g of the dispersion of the oxidized pin microparticles, 5.73 g of "A-5" and 1.0 g of Irgacure 1 84 (manufactured by BASF Corporation) as a photopolymerization initiator, dimethylpolyoxane-polyoxyalkylene was added. The base copolymer 〇.lg 'obtains the composition "]-5". -32- 201139563 tl® 卜 23.90 6.00 70.00 0.10 100.00 VO ηΛ 29.90 70.00 0.10 100.00 in 5.73 15.91 2.30 70.00 1.91 2.20 0.85 0.10 1.00 100.00 6.73 15.91 2.30 70.00 1.91 2.20 0.85 0.10 100.00 rn 8.90 21.00 70.00 0.10 100.00 (N 8.90 21.00 70.00 0.10 100.00 8.90 21.00 70.00 0.10 100.00 Unit: parts by mass 1 Al (solid content) A-2 m &lt; A-4 &lt; Zirconia ί 1-methoxy Base-2-propanol 2-butanol methyl ethyl ketone PLAAD ED-151 gin. (second butoxy) aluminum acetoacetone dimethyl polyoxy siloxane - polyoxyalkylene copolymer Uz ο σ3 Total composition &lt; 0Q u Q ω pH X as-xo^^IE^ls^冏M : inch-v 0(N-ISas-xoNBilt?«i1§^55M:rn-v o(N-Hsas -xo^^陌&lt;^1s&lt;ln55K:CN-v μομ§8 Ανοα ΛνΉΟΗ(las0v-NBtfi?«i1s&lt;infflM :,v -33- 201139563 For each of the above-mentioned compositions "Jl"~"J-7" Evaluation was carried out as follows: (Evaluation of characteristics of the composition) (1) Dispersion particle size The volume average particle at 25 ° C was measured for the fine particles in the obtained composition by a dynamic light scattering type particle size distribution measuring apparatus manufactured by Horiba, Ltd. path. When the volume average particle diameter is less than 50 nm, it is "〇", and those of 50 nm or more and less than 100 nm are "△_!, and those of 100 nm or more are "X". The results are shown in Table 2. <Preparation of cured film> Compositions "J-1" to "J-4", "J-6", and "J-7" The composition for formation was distributed on a fused silica or tantalum substrate having a diameter of 4 inches. The thickness was set to about 1 μm by spin coating, heated at 1200 ° C for 1 minute, and heated at 150 ° C for 60 minutes to prepare a cured film. • Composition "J-5" The composition was placed on a fused silica or ruthenium substrate having a diameter of 4 inches, spin-coated to a thickness of about 1 μm, and heated at 120 ° C for 1 minute. Subsequently, ultraviolet rays were irradiated in the atmosphere at an exposure amount of 2000 mJ/cm 2 using a contact mask analyzer, followed by heating at 150 ° C for 60 minutes to prepare a cured film. <Evaluation of Characteristics of Cured Film> The following characteristics were measured and evaluated for the cured film produced as described above. Conclusion -34- 201139563 The results are shown in Table 2. (2) Sturability The surface of the cured film obtained as described above was touched with a finger, and it was judged as "〇" if it was not sticky, and "X" when it was sticky. (3) Crack resistance The appearance of the cured film obtained above was visually observed, and those without cracks were judged as "〇", and those having cracks were judged as "X". (4) Transparency

The cured film obtained by the above-mentioned spectrophotometer manufactured by JASCO Corporation was used to measure the transmittance (%) of the film having a thickness of 1 μη〇 at a wavelength of 400 nm. When the transmittance was 90% or more, it was judged as "〇", and when it was less than 90%, It was judged that the X (5) refractive index was measured using a 稜鏡 coupler manufactured by METORICON Co., Ltd., and the refractive index at 63 ° C and a wavelength of 63 3 nm was measured. When the refractive index was 1.6 or more, it was judged as "〇", which was less than 1.6. (6) Heat resistance The oven was treated at a temperature of 200 ° C for 60 minutes using an oven. The decrease in the transmittance of the cured film before and after the treatment (the ratio of the decrease in transmittance) was less than 1 When 〇% is determined to be "〇", it is judged as "X" when it exceeds 1%. (7) Light resistance The light resistance of the cured film obtained above was evaluated using a light source system (REX-1000) manufactured by Asahi Laser Co., Ltd. The same light source was irradiated for 10 hours (irradiation illuminance 1.5 W/cm2, cut-off light other than 405 nm-35-201139563, test temperature 2 3 t:) 'visual observation of the appearance of the cured film before and after the test' unchanged It is judged as "〇", and it is judged by a slight discoloration. It is judged as "△" and the yellowing is judged as "X". [Table 2] Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Composition surface J-1 J-2 J-3 J-4 J-5 J-6 J-7 Evaluation of dispersed particle size 〇〇〇Δ Δ 〇〇 hardenability 〇〇〇〇〇〇〇 crack resistance 〇〇〇〇〇〇〇 transparency 〇〇〇 〇〇〇〇Refractive index 〇〇〇〇〇 XX heat resistance 〇〇〇〇〇〇〇 light resistance 〇〇〇〇〇〇〇 It can be understood from Table 2 that the cured product of the composition of the present invention has excellent transparency, High refractive index, high heat resistance, and high light resistance, it is known that efficient use of radiation from a light-emitting device including a light-emitting element such as an LED element can be expected. [Simplified Schematic] FIG. 1 is a commemorative display. Sectional view of an example of a light-emitting device of the invention [Description of main components] 1 : Light-emitting element - 36 - 201139563 2 : Cured film 3 a : Electrode portion 3 b : Electrode portion 4 a : Metal thin wire 4 b : Metal thin wire 5 : Package Material 6: Insulating substrate

Claims (1)

201139563 VII. Patent application scope: 1. A method for manufacturing a light-emitting device, comprising the steps of: (a) coating a light-emitting element with a curable resin composition, wherein the curable resin composition contains: (A) containing the following The azide-based polymer (R1) obtained by the decane compound of the formula (1) is a polymer of (R1) pSi(X)4.p (1) [In the formula (1), R1 is a polymerization of carbon number 2 to 12 The organic group, X is a hydrolyzable group, and P is an integer of 1 to 3], (B) metal oxide particles, and (C) an organic solvent, r and the amount of the above component (B) is relative to the above (A) The component is used in an amount of 50 to 2,000 parts by mass, and (c) a step of heating the above-mentioned light-emitting element. 2. The method of producing a light-emitting device according to the first aspect of the invention, comprising the step (b) of irradiating the curable resin composition with ultraviolet rays before the step (c). 3. A light-emitting device comprising a light-emitting element and a cured film of a cured product of a curable resin composition formed on a surface of the light-emitting element, the curable resin composition containing (A) containing the following formula (1) a pyrithione-based polymer (R 丨) pSi(X)4.p (1) obtained by a decane compound of the compound (in the formula (1), R1 is a polymerizable organic group having a carbon number of 2 to 12, X is a hydrolyzable group, and P is an integer of 1 to 3, and -38-201139563 (B) metal oxide particles 'and the amount of the component (B) is 5 parts by mass based on 100 parts by mass of the component (A) 2,000~2,000 parts by mass. 4. A curable resin composition which contains (A) a fluorene-based polymer obtained from a squalane compound containing a compound represented by the following formula (1), (R1) pSi ( X) 4-p (1) [In the formula (1), R1 is a polymerizable organic group having a carbon number 'X is a hydrolyzable group, and P is an integer of 1 to 3', (B) metal oxide particles, and C) The organic solvent, and the amount of the component (B) is 50 to 2,000 parts by mass based on 100 parts by mass of the component (A). 5. The curable resin composition of claim 4, wherein the decane compound further contains a compound j (R2) qSi(X) 44 (2) represented by the following formula (2) [Formula (2) In the above, R2 is a non-polymerizable organic group having 1 to 12 carbon atoms, X is a hydrolyzable group, and q is an integer of 0 to 3). 6. The curable resin composition of claim 4, wherein the compound represented by the above formula (1) and the compound represented by the above formula (2) are in the above formula ( 1) The mass ratio of the compound to be expressed is 1 〇 to 1 〇〇 mass%. 7. The curable resin composition according to any one of claims 4 to 6, wherein the component (B) is a microparticle having an average number average primary particle diameter of from 1 to 100 nm. The sclerosing resin composition as described in any one of claims 4 to 7 is a coating for a light-emitting element. A method for producing a curable resin composition, characterized by mixing (a) a pyrithione-based polymer obtained from a decane compound containing a compound represented by the following formula (1) in (C) an organic solvent, and (B) a metal oxide particle, which is a curable resin composition according to any one of claims 4 to 8, (R,) pSi(X)4-p (1) [in the formula (1) 'R1 is a polymerizable organic group having 2 to 12 carbon atoms, X is a hydrolyzable group, and p is an integer of 1 to 3). -40-