TW201247792A - Composition for reflective film of light emitting element, light emitting element, and method for producing light emitting element - Google Patents

Abstract

A light emitting element including a light emitting layer, a substrate that allows light transmission, and a reflective film that reflects light from the light emitting layer in this order, wherein the reflective film includes metal nano-particles, and the light-emitting element is optionally provided with a reinforcing film that includes binder.

Description

[Technical Field] The present invention relates to a composition for a reflective film which is applied to a light-emitting element, a light-emitting element which is manufactured by using the composition for a reflective film of a light-emitting element, and a light-emitting element Manufacturing method. Specifically, the present invention is provided with a light-emitting element having a light-emitting layer, a light-transmitting substrate, and a reflective film that reflects light emitted from the light-emitting layer, and a reflective film that can efficiently reflect light emitted from the light-emitting layer. And its manufacturing method. [Prior Art] In recent years, light-emitting elements, particularly LED light sources, have been used in various fields with high brightness and the like. In particular, since a white LED light source can be realized and used for backlights of lighting fixtures and liquid crystal displays, etc., in order to further improve the brightness of the LED light source, etc., it is possible to efficiently apply light emission from LED elements, and to disclose a method. The present invention includes a substrate, an LED element mounted on the support substrate, and a sealing agent containing a fluorescent agent, and an ore-containing Ag electrode film for reflecting the light emission of the LED element between the substrate and the LED element, and is coated with Ag An LED light source having a titanium thin film on the electrode film (Patent Document 1). The LED light source efficiently reflects light from the illuminator by providing a reflective film layer between the substrate and the LED element to increase the illuminating intensity. Here, the Ag film and the titanium film are formed by a plating method or a vacuum film forming method. -5- 201247792 In general, the electro-mine method is expected to be a cumbersome step and the generation of waste liquid, and the vacuum film-forming method is costly in order to maintain and operate a large-scale vacuum film forming apparatus. The above-mentioned LED light source is thermally degraded or photo-degraded only by the Ag-plated electrode film, so that a titanium film is required to be formed by electroplating and vacuum film formation. According to the present invention, a light-emitting element having a light-emitting layer, a light-transmitting substrate, and a reflection film that reflects light from the light-emitting layer is provided in order, and a reflective film is not present between the light-emitting layer and the light-transmitting substrate. . In such a configuration, thermal deterioration or photodegradation occurs only in accordance with a conventional shovel Ag electrode film, and therefore, plating method and vacuum film formation method are required. [Patent Document 1] JP-A-2009-23 1 5 68 SUMMARY OF THE INVENTION The present invention has been made in an effort to solve the above problems. It is an object of the present invention to provide a thin film forming method for a reflective film which has a function of reflecting light emitted from a light-emitting element and having an electrode, thereby suppressing deterioration of the reflective film due to heat and the environment, and simplifying the manufacturing steps. A light-emitting element capable of greatly improving the running cost and a method of manufacturing the same. The present invention relates to a composition for a reflective film which is suitable for use in a light-emitting element, which is suitable for the above-mentioned problems, and is suitable for a composition for a reinforcing film of a light-emitting element and a light-emitting element. The first aspect of the present invention is a composition for a reflective film which is applied to a light-emitting element, and the light-emitting element is provided with a light-emitting layer, a light-transmitting substrate, and a reflective film for reflecting light emitted from the light-emitting layer. A composition for a reflective film of a light-emitting element-6 to 201247792, characterized in that the composition for a reflective film contains metal nanoparticles. The composition for a reflective film according to the second aspect of the present invention is a composition for a reflective film which is applied to a light-emitting device as in the first aspect, and further contains an additive. The composition for a reflection film according to the third aspect of the present invention is a composition for a reflection film which is applied to a light-emitting element in the first or second aspect, and further contains a dispersion medium. The fourth aspect of the present invention is a composition for a reinforcing film which is applied to a light-emitting element, and the light-emitting element includes, in order, a light-emitting layer, a light-transmitting substrate, a reflective film that reflects light emitted from the light-emitting layer, and a reinforcing film. A film for a reinforcing film composition for a light-emitting element, characterized in that the composition for a reinforcing film contains a binder. The composition for a reinforcing film according to the fifth aspect of the present invention is the composition for a reinforcing film which is applied to a light-emitting element according to the fourth aspect, and further contains a selected from the group consisting of cerium oxide-based particles, cericate particles, and metal particles. And one or more kinds of fine particles or flat particles composed of a group of metal oxide particles. According to a sixth aspect of the present invention, in a light-emitting device, a light-emitting element including a light-emitting layer, a light-transmitting substrate, and a reflective film that reflects light emitted from the light-emitting layer is provided, and the reflective film contains a metal. Nano particles. A light-emitting device according to a seventh aspect of the invention is the light-emitting device according to the sixth aspect, wherein the reflective film further contains an additive. The light-emitting element of the eighth aspect of the present invention, wherein the light-emitting element according to the sixth or seventh aspect of the present invention has a reinforcing film, and the light-emitting layer, the light-transmitting substrate, and the reflective film are sequentially provided. And the reinforcing film, wherein the reinforcing film contains a binder. According to a ninth aspect of the invention, in the light-emitting device of the eighth aspect, the reinforced film further comprises a component selected from the group consisting of cerium oxide particles, ceric acid particles, metal particles, and metal oxide particles. One or two or more kinds of fine particles or flat particles of the group. The light-emitting element of the tenth aspect of the invention is the light-emitting element of any one of the sixth to ninth aspects, wherein the reflective film is produced by a wet coating method. The light-emitting element of the first aspect of the present invention is the light-emitting element according to the eighth or ninth aspect, wherein the reinforcing film is produced by a wet coating method, and the light-emitting element of the first aspect of the invention The light-emitting element of any one of the above-mentioned 6th to 1st-type states, wherein the thickness of the reflective film is 0 · 0 5 〜1. 0 // m 第 the 13th type of the invention is a luminescence In the method for producing a device, a composition for a reflective film containing metal nanoparticles and an additive is applied onto a light-transmitting substrate by a wet coating method, and then a reflective film is formed by sintering or hardening. And forming a light-emitting layer on the opposite surface of the reflective film of the light-transmitting substrate. In the method for producing a light-emitting device, the composition for forming a reflective film of the present invention which is applied to a light-emitting device can be used. A method for producing a light-emitting device according to a thirteenth aspect of the present invention is the method for producing a light-emitting device according to the eighth aspect of the present invention, wherein after the reflecting film is formed, the light-emitting layer is further formed by wet In the coating method, a composition for a reinforcing film containing a binder is applied onto a reflective film, and then a reinforced film is formed by sintering or hardening. In the method for producing a light-emitting device, the composition for forming a reinforcing film to be applied to a light-emitting device of the present invention can be used. Advantageous Effects of Invention According to the present invention, a composition for forming a reflective film which is applied to a light-emitting element can improve heat resistance and corrosion resistance even by a high-output light-emitting element by using metal nanoparticles, and can provide a suppression A high-life light-emitting element that is degraded by a heat generated by a light-emitting layer or a reflective film. The reflective film can be applied to various light sources, and is particularly suitable for LED light sources. Further, since the reflective film can be produced by a wet coating method, the manufacturing steps can be simplified and the cost can be reduced. Further, according to the present invention, a light-emitting element having higher heat resistance or corrosion resistance can be provided. According to the light-emitting element of the present invention, the light-transmitting substrate and the light-emitting layer have high adhesion, and the reliability of the light-emitting element can be improved. Further, the light-emitting element of the present invention having a reinforced film has high heat resistance and corrosion resistance, and can suppress deterioration of the reflective film due to heat or environment generated from the light-emitting layer, so that it can have a long life. According to the method for producing a light-emitting device of the present invention, a light-emitting element having high heat resistance and high corrosion resistance can be obtained at a low cost. 201247792 [Embodiment] Hereinafter, the present invention will be specifically described based on the embodiments. % is % when it is not specifically indicated, and in the case other than the number. [Composition for a reflective film of a light-emitting element] The composition for a reflective film to be applied to a light-emitting device (hereinafter referred to as a composition for a reflective film) is preferably provided with a light-emitting layer and a light-transmitting property. A composition for a reflection film of a light-emitting element of a substrate and a reflection film that reflects light emitted from the light-emitting layer, wherein the composition for a reflection film contains metal nanoparticles. The metal nanoparticles are provided to reflect the light reflected from the light emitted from the light-emitting layer to a composition for a reflective film after sintering or curing, that is, a reflective film. The metal nanoparticles may be one or a mixture of two or more selected from the group consisting of silver, gold, platinum, palladium, rhodium, nickel, copper, tin, indium, zinc, iron, chromium, and manganese. Or the alloy composition is preferably silver or gold from the viewpoint of reflectivity and conductivity. The average particle diameter of the metal nanoparticles is preferably from 10 to 50 nm. Here, the average particle diameter is measured by a specific surface area and measured by a BET method. For example, the specific surface area can be determined by QUANTACHROME AUTOSORB-1 from Quantachrome Instruments. The shape of the metal nanoparticles is spherical or plate-shaped, and is preferable from the viewpoint of dispersibility and reflectivity. The composition for a reflective film preferably contains an additive from the viewpoint of adhesion and reflectivity of the reflective film. The additive contains at least one selected from the group consisting of an organic polymer, a metal oxide, a metal hydroxide, an organometallic compound, and eucalyptus-10-201247792, and is a viewpoint of reflectivity and adhesion. Especially good. The organic polymer used as the additive is at least one selected from the group consisting of a copolymer of polyvinylpyrrolidone and polyvinylpyrrolidone, and a water-soluble cellulose, from the viewpoint of reflectivity. It is better. As the copolymer of polyvinylpyrrolidone, a PVP-methacrylate copolymer, a PVP-styrene copolymer, a PVP-vinyl acetate copolymer or the like can be used. Further, as the water-soluble cellulose, a cellulose ether such as hydroxypropylmethylcellulose, methylcellulose or hydroxyethylmethylcellulose can be used. The metal oxide used as an additive preferably contains a material selected from the group consisting of aluminum, ruthenium, titanium, zirconium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium, and antimony. At least one oxide or composite oxide of the group. The composite oxide may specifically include 1τ〇 containing the above metal (

Indium Tin Oxide: Antimony-doped Tin Oxide, IZO (Indium-doped Zinc Oxide), AZO (Aluminum-doped Zinc Oxide) Aluminium oxide zinc oxide). The metal hydroxide used as an additive preferably contains a material selected from the group consisting of Jinlu, Sha, Qin, Wrong, Luo, Zhong, Iron, Ming, Zhen, Silver, Copper, Bismuth, Molybdenum, Tin, Indium, and Bismuth At least one hydroxide of the group consisting of. The organometallic compound used as an additive preferably contains at least 1 selected from the group consisting of sand, titanium, pin, indium, lanthanum, iron, cobalt, cerium, silver, copper, cerium, lanthanum, and tin. A hydrolysate of a metal soap, a metal complex, an alkoxylated metal or an alkoxylated metal. For example, the metal soap may be acetic acid 201247792 chromium, manganese formate, iron citrate, cobalt formate, nickel acetate, silver citrate, copper acetate, copper citrate, tin acetate, zinc acetate, zinc oxalate, molybdenum acetate or the like. Further, examples of the metal complex include acetamylacetone zinc complex, acetamylacetone chromium complex, acetamacetone nickel complex, and the like. Further, as the alkoxide metal, titanium isopropoxide, methyl silicate, isocyanate propyl trimethoxide, alan propyl trimethoxide or the like can be used. As the eucalyptus oil as an additive, both pure eucalyptus oil and modified eucalyptus oil can be used. In the modified eucalyptus oil, a part of the side chain of the polyoxyalkylene (lateral chain type) may be further introduced, and the organic group may be introduced into both ends of the polyoxyalkylene (both end type), and the organic group may be used. One of the two ends of the polyoxyalkylene (single-terminal type) and the organic group introduced into a part of the side chain of the polyoxyalkylene and both ends (both side chain type). Modified eucalyptus oil, reactive eucalyptus oil and non-reactive eucalyptus oil, both of which can be used as additives for the present invention. The term "reactive eucalyptus" means amine modification, epoxy modification, carboxy modification, methanol modification, hydrazine modification, and modification of heterogeneous functional groups (eg, epoxy group, amine group, polyether group), non-reactive The eucalyptus oil refers to polyether modification, methyl styrene modification, alkyl modification, higher fatty acid ester modification, fluorine modification, and hydrophilic special modification. Further, the composition for a reflective film preferably contains a dispersion medium from the viewpoint of coatability. The dispersion medium contains 1% by mass or more, preferably 2% by mass or more, and 2% by mass or more, preferably 3% by mass or more of water-soluble solvent with respect to 100% by mass of the entire dispersion medium. For example, it contains an alcohol. For example, when the dispersion medium is composed only of water and an alcohol, when 2% by mass of water is contained, 98% by mass of the alcohol is contained, and when 2,700% by mass of the alcohol is contained in 201247792, the content is 98% by mass. water. Further, the dispersion medium, i.e., the protective molecule which chemically reforms on the surface of the metal nanoparticles, contains either or both of a hydroxyl group (-OH) and a carbonyl group (-C = 0). The content of water is preferably in the range of 1% by mass or more based on 1% by mass of the entire dispersion medium. When the content of water is less than 2% by mass, the film obtained by coating the composition for a reflective film by a wet coating method is difficult to be sintered at a low temperature. Further, the reflectance of the reflective film after sintering is also lowered. When the hydroxyl group (-OH) is contained in the protective agent for chemically modifying the metal nanoparticles such as silver nanoparticles, the dispersion stability of the composition for the reflective film can be improved, and the low-temperature sintering of the coating film can be effectively performed. effect. In addition, when a carbonyl group (-C = 0) is contained in the protective agent for chemically modifying the metal nanoparticles such as silver nanoparticles, the dispersion stability of the composition for a reflective film can be improved as described above. Low temperature sintering of the film can also be effective. The water-miscible solvent used in the dispersion medium is preferably an alcohol. Among them, the above alcohols, particularly preferably selected from the group consisting of methanol, ethanol 'propanol, butanol, ethylene glycol 'propylene glycol, diethylene glycol, glycerin, isodecyl hexanol and erythritol One or two or more. The metal nanoparticle is preferably 75 parts by mass or more, and more preferably 80 parts by mass or more, from the viewpoint of reflectivity, with respect to 100 parts by mass of the composition for the reinforced reflective transparent film which is obtained by subtracting the dispersion medium. Further, from the viewpoint of the adhesion of the reflective film, it is preferably 95 parts by mass or less, and particularly preferably 80 parts by mass or more. When the conductivity is imparted to the reflective film, it is preferably 75 parts by mass or more, and particularly preferably 80 parts by mass or more, based on 1 part by mass of the reflective film. -13-201247792 The dispersion medium is preferably 50 to 99 parts by mass with respect to 100 parts by mass of the composition for a reflective film, from the viewpoint of coatability. Further, as the composition for a reflective film, it is preferred to add a low-resistance agent or a water-soluble cellulose derivative depending on the components to be used. The low-resistance agent is preferably one or more selected from the group consisting of mineral salts and organic acid salts of cobalt, iron, indium, nickel, lead, tin, titanium, and zinc. For example, a mixture of nickel acetate and ferric chloride, a mixture of zinc naphthenate, a mixture of tin octoate and cerium chloride, a mixture of indium nitrate and lead acetate, a mixture of titanium acetate and cobalt octoate, or the like can be used. The low-resistance agent is preferably 0.2 to 15 parts by mass with respect to the composition for a reflective film: 100 parts by mass. A water-soluble cellulose derivative which is a non-ionic surfactant and has a high ability to disperse metal nanoparticles even when added in a small amount compared with other surfactants. Further, it is made of a water-soluble cellulose derivative. The addition can also enhance the reflectivity of the formed enhanced reflective film. The water-soluble cellulose derivative may, for example, be hydroxypropylcellulose or hydroxypropylmethylcellulose. The water-soluble cellulose derivative is preferably a composition for a reflective film of 100 parts by mass of the composition for a reinforcing reflective film: within a range not detracting from the object of the present invention. Further, anti-oxidants, flat agents, rheological viscosity reducers, enamel fillers, stress relieving agents, and other additives may be further formulated as necessary. [Composition for reinforcing film] A composition for a reinforcing film for a light-emitting element (hereinafter referred to as a composition for a reinforcing film) is preferably applied to a light-emitting layer or a light-transmitting substrate.

S -14 - 201247792 A composition for a reinforcing film which is used for a light-emitting element and a reinforcing film for reflecting light emitted from a light-emitting layer, and a reinforcing film composition containing a binder. The reinforcing film composition can form a reinforcing film, and when the reflecting film has pores, it penetrates into the reflecting film and contains a binder at the interface between the pores of the reflecting film and/or the reflecting film and the reinforcing reflective transparent film, which can be improved. The strength of the reflective film itself or the adhesion strength of the reflective film to the enhanced reflective transparent film. The binder 'preferably contains an organic or inorganic matrix material of a polymer type binder which is hardened by irradiation with ultraviolet rays or heat or ultraviolet rays, and an inorganic matrix material of a non-polymer type binder. Either or both. The organic matrix material of the polymer binder preferably contains an epoxy resin-based, urethane-based, urethane-based, epoxy-acrylic, cellulose-based, and oxime-containing material. One or two or more of the group consisting of alkane-based polymers. As the acrylic binder, an acrylic polymer obtained by adding a photopolymerization initiator to an acrylic monomer and irradiating ultraviolet rays (UV) to the mixture to carry out photopolymerization can be used. The acrylic monomer may be selected from the group consisting of 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, neopentyl glycol diacrylate, tetramethylol mesyl tetraacrylate, and tetraacrylic acid di( a group consisting of trimethylol)propane ester, bismuth diacrylate, 9-decanediol ester, tripropylene glycol diacrylate, epoxidized isocyanuric acid triacrylate and tetramethylol mesyl tetraacrylate Kinds or more than two single monomers or mixed monomers. Among these monomers, a solvent such as MIBK (methyl isobutyl ketone), PGME (1-methoxy-2-propane) or pGMEA (propylene glycol monomethyl ether acetate) is preferably added. However, as long as the general organic -15-201247792 solvent capable of dissolving the above monomers can be used, ethanol, methanol, benzene, toluene, di NMP (N-methylpyrrolidone), acrylonitrile, acetonitrile THF (4) can be used. , ethyl acetate, MEK (butanone), butyl carbitol, butyl acetate, 2-butoxyethanol, 2-butoxyethyl acetate, ethyl carbitol carbitol acetate, IpA (Isopropanol), acetone, DMF (methylamine), DMSO (dimethyl sulfoxide), piperidine, phenol, and the like. As the photopolymerization initiator, 1 hydroxy-cyclohexyl-phenyl ketone, 2-methyl-1-phenyl-propane-1 ketone, 2-hydroxy-1-[4-[4-(2- Hydroxy-propenyl)-benzyl]-phenyl]-2-methyl-propan-1-one, 1-[4-(oxy)-phenyl]-2-hydroxy-2-methyl-1 - Propane-1-one and the like. The propylene can be used by being diluted by any of the above solvents to be easily coated. The photopolymerization initiator is added in an amount of from 1 to 30 parts by mass based on the acrylic monomer 100. When the amount of photopolymerization added is less than the amount by mass based on 100% by mass of the acrylic monomer, the curing is insufficient, and when it exceeds 30 parts by mass, the cured film ( ) may be discolored or residual stress may cause adhesion failure. Therefore. In this way, the photopolymerization initiator is added to the acrylic monomer and stirred to obtain a matrix liquid for the composition for reinforcing the film. When the solvent and the photoinitiator are added to the acrylic monomer and the resulting mixture is stirred, it can be heated to about 40 °C. As the epoxy-based adhesive, an epoxy-based polymer obtained by adding a solvent to an epoxy resin, adding a thermal curing agent to the mixed solution, and stirring the mixture, and heating the obtained liquid can be used. The epoxy resin may, for example, be an epoxy resin, a cresol novolac type epoxy resin, a bisphenol A type epoxy toluene, a hydrofuran carbitol, an ethylene dimethyl group, and a benzyl-2-2-methyl group. -2-glycolic acid single viscosity mass part starting agent 0.1 type reinforcing film polymerizes the solvent mixture to form a uniform resin mixture, and the biphenyl resin is mixed.

S -16- 201247792 Bisphenol F type epoxy resin, naphthalene type epoxy resin, etc. Further, as the solvent, BCA (butyl carbitol acetate), ECA (ethyl carbitol acetate), B C (butyl carbitol), or the like can be used. In addition, as long as the general organic solvent capable of dissolving the above epoxy resin can be used, ethanol, methanol, benzene, toluene, xylene, PGME (1-methoxy-2-propane), PGMEA (propylene glycol monomethyl ether) can be used. Acetate), NMP (N-methylpyrrolidone), mIBK (methyl isobutyl ketone), acrylonitrile, acetonitrile, THF (tetrahydrofuran), ethyl acetate, MEK (butanone), butyl carbitol , butyl carbitol acetate, 2-butoxyethanol, 2-butoxyethyl acetate, ethyl carbitol, ethyl carbitol acetate, IPA (isopropanol), acetone, DMF ( Dimethylformamide), DMSO (dimethyl sulfoxide), piperidine, phenol, and the like. Further, the thermosetting agent may be 2-ethyl-4-methylimidazole, boron fluoride-monoethanolamine, DICY (dicyanoguanamine), diethylaminopropylamine, isophoradiamine, Diaminodiphenylmethane, piperidine, 2,4,6-tris-(dimethylaminomethyl)phenol, 2-methylimidazole, hexahydrophthalic anhydride, 7,11-octadecane Diene-1,1 8-dicarbon oxime, and the like. The epoxy resin can be used by being diluted with any of the above solvents to adjust the viscosity to be easily applied. The heat-hardening agent is added in an amount of 5 to 20 parts by mass based on 100 parts by mass of the epoxy resin. When the amount of the heat hardener added is less than 0.5 parts by mass relative to the mass part of the epoxy resin, the hardening is insufficient, and when it exceeds 20 parts by mass, the cured film (reinforcing film) is large. Internal stress causes poor adhesion. In this manner, a solvent and a thermosetting agent are added to the epoxy resin and stirred to obtain a mixed solution, which can be used as a matrix liquid for a composition for reinforcing a film. When the solvent and the heat hardener are added to the epoxy resin and the mixture is stirred and the mixture is not uniform, it can be heated to 40 °C from •17 to 201247792. The cellulose-based binder can be obtained by adding a solvent to a cellulose-based polymer and stirring, adding gelatin to the mixture, stirring, and heating the resulting mixture. As the cellulose polymer, hydroxypropylcellulose, hydroxypropylmethylcellulose, methylcellulose, hydroxyethylmethylcellulose or the like of a water-soluble cellulose derivative can be used. Further, as the solvent, IPA (isopropyl alcohol), ethanol, methanol, PGM E (l-methoxy-2-propane), PGMEA (propylene glycol monomethyl ether acetate), MIBK (methyl isobutyl ketone), Acetone, etc. The cellulose-based polymer can be used by being diluted with any of the above solvents to adjust the viscosity to be easily applied. The gelatin is added in an amount of 0.1 to 20 parts by mass based on 1 part by mass of the cellulose polymer. When the amount of the gelatin added is less than 0.1 part by mass or more than 20 parts by mass based on 1 part by mass of the cellulose-based polymer, the viscosity suitable for coating cannot be obtained. Thus, a mixture of a solvent and gelatin added to a cellulose-based polymer and stirred can be used as a matrix liquid for a composition for reinforcing a film. Further, by adding a solvent and gelatin to the cellulose-based polymer and heating to about 30 ° C and stirring, the mixture can be made uniform. The urethane-based adhesive of a thermosetting urethane resin can be prepared as follows. First, an excess amount of a polyisocyanate compound represented by toluene diisocyanate (TDI) 'biphenylmethane isocyanate (MDI) or the like, and a polyol represented by a polyol compound such as trimethylolpropane or neopentyl glycol are used. The components are reacted to obtain a urethane prepolymer having an active isocyanate group at the end. Next, a phenolic compound represented by methylphenol, a lactone represented by s-butyrolactone, or a thiol represented by butanone oxime, etc., 18-201247792, is contained in the terminal. The reactive isocyanate urethane prepolymer is reacted. As the solvent, ketones, alkylbenzenes, cellosolves, esters, alcohols and the like can be used. Specific examples of the ketones include acetone and methyl ethyl ketone. Specific examples of the alkyl benzenes include benzene and toluene. Specific examples of the cellosolve include 2-methoxyethanol and 2-butoxyethanol. Specific examples of the esters include 2-butoxyethyl acetate and butyl acetate, and specific examples of the alcohols. Examples thereof include isopropyl alcohol, butanol, and the like. On the other hand, a polyamine can be used as the thermal hardener (reagent). Specific examples of the polyamine include N-octyl-N-aminopropyl-Ν'-aminopropylpropanediamine, N-dodecyl-N-aminopropyl-Ν'-aminopropylpropyl Diamine, Ν-tetradecyl-Ν-aminopropyl-Ν'-aminopropylpropanediamine, Ν-octyl-Ν-aminopropyl-Ν', Ν'-bis(aminopropyl)-propyl Diamine and the like. The urethane prepolymer containing a reactive isocyanate group at the terminal obtained by reacting the above polyol component with an isocyanate compound is subjected to block formation by a blocking agent to prepare a block polyisocyanate. . The equivalent ratio of the amine group of the polyamine to the isocyanate group of the block polyisocyanate is preferably before and after 1 (in the range of 0.7 to 1.1). This is because when the equivalent ratio of the amine group of the polyamine to the isocyanate group of the block polyisocyanate is less than 0.7 or exceeds 1.1, one of the block polyisocyanate and the polyamine is increased. The reaction is not sufficiently carried out, and the hardening is insufficient. The urethane polymer ' can be used by being diluted with any of the above solvents to adjust the viscosity to be easily coated. Acrylic urethane-based adhesive containing an urethane acrylate-based oligomer and cured by ultraviolet (UV) irradiation, and can be used in violet UV-3310B or violet UV-6100B (manufactured by Nippon Synthetic Co., Ltd.). -19-201247792 or an urethane urethane-based polymer such as EBECRYL4 82 0 or EBECRYL 2 84 (manufactured by Daicel Cytec Co., Ltd.), U-4HA or UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.). Further, a photopolymerization initiator (for example, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2.methyl-1-phenyl-propane-1-) used in the acrylate system may be added as necessary. Ketones, etc., to improve the hardenability. Further, as the solvent, ketones, alkylbenzenes, cellosolves, esters, alcohols and the like can be used. Specific examples of the ketones include acetone and methyl ethyl ketone. Specific examples of the alkyl benzenes include benzene and toluene. Specific examples of the cellosolve include 2-methoxyethanol and 2-butoxyethanol. Specific examples of the esters include 2-butoxyethyl acetate and butyl acetate, and specific examples of the alcohols. Examples thereof include isopropyl alcohol, butanol, and the like. In addition, the photopolymerization initiator may be added in an amount of 0.1 to 30 parts by mass based on 100 parts by mass of the urethane acrylate polymer, if necessary. When the amount of the photopolymerization initiator to be added is less than 0.1 part by mass, the hardening is insufficient, and when it exceeds 30 parts by mass, the reinforcing film generates a large internal stress and causes poor adhesion. Further, the urethane urethane monomer can be used by being diluted with any of the above solvents to adjust the viscosity to be easily applied. As the epoxy acryl-based adhesive, an epoxy acryl-based polymer can be used. As the epoxy acryl-based polymer, bisphenol A type epoxy acrylate (for example, NK oligomer EA-1 020 manufactured by Shin-Nakamura Chemical Co., Ltd.) or 1,6-hexanediol diglycidyl ether diacrylate can be used. (for example, NK oligomer EA-552 1 manufactured by Shin-Nakamura Chemical Industry Co., Ltd.). Further, Neopol 8318 or Neopol 8355 manufactured by Japan U-PICA Co., Ltd. may be used. As the solvent, ketones, alkylbenzenes, cellosolves, esters, alcohols and the like can be used. Specific examples of the ketones are exemplified by acetone, methyl ethyl ketone, etc., and specific examples of the alkyl benzenes include benzene and toluene. Specific examples of the cellosolve include 2-methoxyethanol and 2-butoxyethanol. Specific examples of the esters include 2-butoxyacetate and butyl acetate. Specific examples of the alcohols include isopropyl alcohol and butanol. An epoxy acrylic polymer may be added with a thermal hardener or a photopolymerization initiator as necessary. By heat hardening or photopolymerization initiator, heat hardening or UV hardening or UV hardening can be carried out after heat hardening. Further, the epoxy acrylate polymer can be used by being diluted with any of the above solvents to adjust the viscosity to be easily applied. As the siloxane-based binder, a siloxane-based polymer can be used. As the fluorene-based polymer, polydimethyl siloxane, polymethylhydroquinone, polymethylphenyl siloxane or the like can be used. Further, as the a naphthenic polymer shown here, both pure eucalyptus oil and modified eucalyptus oil can be used. In the modified eucalyptus oil, a part of the side chain of the polyoxyalkylene (lateral chain type) may be further introduced, and the organic group may be introduced into both ends of the polyoxyalkylene (both end type), and the organic group may be used. One of the two ends of the polyoxyalkylene (single-terminal type) and a part of the side chain of the polyoxyalkylene and the both ends (the two-terminal type of the side chain) are introduced. Modified eucalyptus oil, reactive eucalyptus oil and non-reactive eucalyptus oil, both of which can be used. The term "reactive eucalyptus" means amine modification, epoxy modification, carboxy modification, methanol modification, hydrazine modification, or modification of heterogeneous functional groups (eg, epoxy group, amine group, polyether group), non-reaction Sexual eucalyptus oil, which means polyether modification, methyl styrene modification, alkyl modification, higher fatty acid ester modification, fluorine modification, and hydrophilic special modification. As the solvent, ketones, alkylbenzenes, cellosolves, esters, alcohols and the like can be used. Specific examples of the ketones include -21 - 201247792, and acetone, methyl ethyl ketone and the like are listed. Specific examples of the alkylbenzenes include benzene and toluene. Specific examples of the cellosolve include 2-methoxyethanol and 2-butoxyethanol. Specific examples of the esters include 2-butoxyethyl acetate and butyl acetate. Specific examples of the alcohols include isopropyl alcohol and butanol. The siloxane polymer may be added with a thermosetting agent or a photopolymerization initiator as needed. However, when the film is cured without adding a thermosetting agent, it is not necessary to add a curing agent. Further, the siloxane-based polymer can be used by being diluted with any of the above solvents to adjust the viscosity to be easily applied. The inorganic matrix material of the polymer binder preferably contains one or more selected from the group consisting of metal soaps, metal complexes, alkoxylated metals, and hydrolyzed metal alkoxides. The inorganic matrix material of these polymer binders can be changed from an organic system to an inorganic matrix material by heating. That is, a film having a property of an inorganic matrix material can be formed by sintering. The metal contained in the hydrolyzate of the metal soap, the metal complex, the alkoxylated metal or the alkoxylated metal is preferably one or two selected from the group consisting of aluminum, ruthenium, titanium, zirconium and tin. the above. As the metal soap, chromium acetate, manganese formate, iron citrate, cobalt formate, nickel acetate, silver citrate, copper acetate, copper citrate, tin acetate, zinc acetate, zinc oxalate, molybdenum acetate or the like can be used. As the metal complex, an acetoacetate zinc complex, an acetophenone chromium complex, an acetamacetone nickel complex or the like can be used. As the alkoxide metal, titanium isopropoxide, methyl silicate, isocyanate propyl trimethoxane, amine propyl trimethoxane, etc. may be used. On the other hand, an inorganic matrix material of a non-polymer type binder may be used. Use Si〇2 binder. The Si〇2 binder can be produced by 201247792 by one of the following examples. First, HC1 was dissolved in pure water while stirring to prepare an aqueous solution of HC1. Next, tetraethoxyoxane and ethanol are mixed, and the above HC aqueous solution is added to the mixed solution, followed by heating to cause a reaction. This produces a SiO 2 bonding agent. Further, the non-polymer type binder preferably contains a hydrolyzate selected from the group consisting of metal soaps, metal complexes, metal alkoxides, metal alkoxides, halodecanes, 2-alkoxyethanols, non-diones, and One type or two or more types of the group consisting of alkyl acetates. The hydrolyzate of the alkoxylated metal ' contains a sol gel. Further, the metal contained in the hydrolyzate of the metal soap, the metal complex, the alkoxylated metal or the alkoxylated metal is preferably one selected from the group consisting of aluminum, ruthenium, titanium, chromium and tin or 2 or more types. As the metal soap, chromium acetate, manganese formate, iron citrate, cobalt formate, nickel acetate, silver citrate, copper acetate, copper citrate, tin acetate, zinc acetate, zinc oxalate, molybdenum acetate or the like can be used. As the metal complex, acetyl acetonate zinc complex, acetamyl acetonate complex, acetoacetate nickel complex or the like can be used, and the alkoxide metal can be used as the titanium isopropoxide or the methyl citrate 'isocyanate. Propyl trimethoprim, amine propyl trimethoxane, and the like. As the halodecane, chlorodecane, bromodecane, flurazepam or the like can be used. As the 2-oxoethanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol or the like can be used. As the dot-diketone, 2,4-pentanedione, 1,3-biphenyl-1,3-propanedione or the like can be used. As the alkyl acetate, ethylene glycol monomethyl ether acetate vinegar, propylene glycol monomethyl ether acetate or the like can be used. In addition, the composition for a reinforcing film may contain one or two or more selected from the group consisting of a decane coupling agent, an aluminum coupling agent, and a titanium coupling agent. The composition for reinforcing the film can further improve the adhesion of the reinforcing film to the reflecting film by containing a decane coupling agent or an aluminum coupling agent. Therefore, in the i-ray through -23-201247792, the camera is stepped back from the cut layer. By using each of the ^ for the cutting of the separation when the stripping is carried out, the strip is cut into layers, and the light splitting film is formed into a layered surface. The inverse number is obtained from the multi-layer film. In the case of the film, the composition for a reinforcing film may contain one or more selected from the group consisting of cerium oxide particles, ceric acid particles, metal particles, and metal oxide particles. Particles or flat particles. For example, the composition for a reinforcing film may contain one or more kinds of fine particles or flat selected from the group consisting of colloidal cerium oxide, fumed cerium oxide particles, cerium oxide particles, mica particles, and swelled stone particles. particle. The colloidal cerium oxide is a colloid of SiO 2 or the hydrate, and has an average particle diameter of 1 to 10 nm, preferably 5 to 50 nm, and does not have a certain structure. The fumed cerium oxide particles are obtained by vaporizing cerium chloride and oxidizing it in a gas phase in a high-temperature flame, and have an average particle diameter of 1 to 50 nm, preferably 5 to 30 nm. The cerium oxide particles are particles having an average particle diameter of 1 to 100 nm, preferably 5 to 50 nm. The mica particles are particles having an average particle diameter of from 10 Å to 50,000 nm produced by a synthesis method, and are preferably flat particles having an average diameter of from 1 to 20/zm and an average thickness of 10 to 1 〇〇 nm. The type of the ion-exchange layered phthalate compound having a crystal structure in which the surfaces formed by the ionic bond or the like are superposed in parallel with each other with a weak bonding force, and the average particle diameter is iOMOOOOOnmi particles. It is preferably a flat particle having an average diameter of 1 to 20 μm and an average thickness of 10 to 10 nm. The composition for reinforcing the film can further increase the hardness of the reinforcing film by containing colloidal cerium oxide, fumed cerium oxide particles or the like. Therefore, after the separation groove is formed by cutting, even if the burrs or residues remaining on the separation groove are removed by an air knife or the like, since the abrasion resistance of the reinforced film is good, the abrasion resistance and impact resistance are good. The edge of the separation groove of the reinforced membrane is notched. The amount of addition is preferably from 0.1 to 30 parts by mass, particularly preferably parts by mass, per 100 parts by mass of the reinforcing film. When it is less than 0.1 part by mass, it is difficult to obtain an effect. When the amount is more than 30 parts by mass, the adhesion is liable to lower. In the present invention, the average particle diameter of each of the fine particles is measured in the following manner. It is measured by a lightning/scattering particle size distribution measuring apparatus (LA-95 0 manufactured by Horiba, Ltd.), and the average particle diameter (D5G) is calculated from the particle diameter standard. The number of reference average particle diameters calculated from the laser diffraction/scattering particle size distribution, and the image observed by a scanning micromirror (manufactured by Hitachi High Technologies, I 4300SE and S-900) In the meantime, the average particle diameter when the particle diameter was measured at any 50 points was almost the same. Further, the average diameter and the average thickness of the above-mentioned particles and the average thickness of the flat particles described later were also measured in the same manner as described above. The average particle size of the colloidal cerium oxide is limited to 1 to 10 nm because the colloidal cerium oxide is unstable and contains less than 1 nm. When it exceeds 100 nm, the particle size increases and cannot become a dispersion. Therefore, if the size of the fumed cerium oxide particles, the cerium oxide particles, and the mica particle particles is limited to the above range, the size of the oxidized cerium oxide particles, the cerium dioxide particles, or the film (reflecting film) which is not lower than the lower layer is formed. The range of sizes. Further, the composition for reinforcing film may contain a composition selected from the group consisting of gold, platinum rhodium, nickel, copper, tin, indium, zinc 'iron, chromium, manganese and aluminum, and does not produce a composition of 0.2-20. Diffraction model: 50% of the measured electronic display: S-particles are flat and flat. In addition, one or more metals having a larger particle size, a palladium group, a group of -25-201247792, or a fine particle or flat particle containing the metal oxide. The average particle diameter of these fine particles is set in the range of 1 to 50,000 nm, preferably 100 to 5,000 nm. The average diameter of the flat particles is preferably 50,000 nm, and the average thickness of the flat particles is preferably from 100 to 20,000 nm. The composition for a reinforcing film can further impart flexibility to the reinforcing film by containing fine particles such as gold or platinum or flat particles. Therefore, even if the reinforcing film is stressed during cutting, the stress can be alleviated by the ductility and malleability of the reinforcing film. Here, the size of the metal fine particles is limited to the above range, and since the size of the obtained fine particles is limited, the size of the flat metal fine particles is limited to the above range, and is set so as not to exceed the thickness of the reflective film. The range of sizes. The amount of such fine particles or flat particles added is preferably 0.1 to 30 parts by mass, particularly preferably 0.2 to 20 parts by mass. When the amount is less than 0.1 part by mass, the effect is not easily obtained. On the other hand, when it exceeds 30 parts by mass, the adhesion is liable to lower. Further, the content of the metal or metal oxide in the fine particles or the flat fine particles is set to 70% by mass or more, preferably 80 to 100% by mass. This is because when the amount is less than 70% by mass, the workability of the reinforced film is lowered. The composition for reinforcing the film may further be formulated with an antioxidant, a flattening agent, a rheological viscosity reducing agent, a ceramium filler, a stress relieving agent, and other additives, as long as the object of the present invention is not impaired. [Light-emitting element] The light-emitting element of the present invention is provided with a light-emitting element including a light-emitting layer, a light-transmitting substrate, and a reflection film that reflects light emitted from the light-emitting layer, -26-201247792, which is characterized in that the reflective film contains Metal nanoparticles. Fig. 1 is a cross-sectional view showing an example of a light-emitting element. The light-emitting element 1 is provided with a reflective film 10, a light-transmitting substrate 20, and a light-emitting layer 30 in this order. Usually, the reflective film 10 is bonded to the support substrate 60 by the adhesive layer 50, and the desired wiring is formed on the light-emitting layer 30, and then sealed by the sealing material 40. FIG. 2 is a cross-sectional view showing a preferred example of the light-emitting element. . When the light-emitting element 2 is provided with the reinforcing film 12, the reflective film 11, the substrate 21, and the light-emitting layer 31 in this order, the heat-resistant and corrosion-resistant properties of the reflective film 11 can be improved by the reinforcing film 12, and the light-transmitting substrate can be further improved. The adhesion of the reflective film is preferable, and the peeling of the reflective film 11 from the substrate 2 1 can be suppressed in the cutting step, which is preferable. When the reinforcing film 12 contains a binder, it can be produced by a wet coating method, which is particularly preferable. However, even if it is produced by a vacuum film forming method or the like, the heat resistance and corrosion resistance of the reflecting film 11 can be improved. . In the configuration shown in Fig. 2, the reinforcing film 12 is bonded to the support substrate 61 by the adhesive layer 51, and the desired wiring is formed on the light-emitting layer 31, and then sealed with the sealing material 41. <<Reflective Film>> The reflective film reflects light passing through the light-emitting layer of the substrate. The reflective film contains metal nanoparticles, and preferably further contains an additive. The metal nanoparticles and additives are as described above. The content ratio of the additive is preferably 0.1 to 25 parts by mass, particularly preferably 0.2 to 10 parts by mass, per 100 parts by mass of the transparent conductive film. When the amount is 0.1 part by mass or more, the adhesion to the transparent conductive film is good, and when it is 25 parts by mass or less, film unevenness is less likely to occur at the time of film formation. -27- 201247792 The thickness of the reflective film is preferably from 0.05 to 1.0 Å in terms of reflectivity and conductivity, and more preferably 〇.1 to 〇.5 ym. The average pore diameter of the pores on the surface of the reflective film on the side of the light-transmitting substrate is 100 nm or less, the average depth is 10 nm or less, and the number density is 30 / / m 2 , and the wavelength is in the range of 380 to 780 nm. It is preferable to achieve a high diffuse reflectance of 80% or more of the theoretical reflectance. In general, the reflection spectrum shows a project having a high reflectance on the long wavelength side and a low on the short wavelength side. When the average diameter of the pores exceeds 100 nm, the inflection point at which the reflectance starts to decrease is further shifted to the long wavelength side, and a good reflectance is not obtained, so that the average diameter of the pores is preferably 100 nm or less. Further, when the average depth of the pores exceeds 10 Onm, the gradient (slope) of the reflection spectrum becomes large, and a good reflectance cannot be obtained, so the average depth of the pores is preferably 100 nm or less. When the number density of the pores exceeds 30 / / m 2 , the reflectance on the long wavelength side is lowered - a good reflectance is not obtained, so the number density of the pores is preferably 30 / ym 2 or less. The film Λ3Α-strongly reinforced film can improve the heat resistance and corrosion resistance of the reflective film, and can suppress the peeling of the reflective film when cutting is employed in the manufacturing step of the light-emitting element. The reinforcing film contains a binder 'adhesive as described above. For example, when a polymer-based binder is contained, it may contain an acrylic polymer, an epoxy polymer, an urethane polymer, an urethane polymer, and an epoxy acryl polymerization. A species or two of the group consisting of a cellulose, a cellulose polymer, and a siloxane polymer are -28-201247792. Or an inorganic matrix material which may contain an inorganic matrix material or a non-polymer binder of a polymer binder. In addition, as described in the composition for a reinforced film, one or more selected from the group consisting of cerium oxide particles, ceric acid particles, metal particles, and metal oxide particles may be contained. Particles or flat particles. The thickness of the reinforced film is preferably 0 · 0 1 to 0.5 / / m from the viewpoint of heat resistance and corrosion resistance, and particularly preferably 〇 · 〇 1 〇 〇 2 v m. [Manufacturing Method of Light-Emitting Element] The method for producing a light-emitting element of the present invention is characterized in that a composition for a reflective film containing metal nanoparticles and an additive is applied onto a light-transmitting substrate by a wet coating method. Thereafter, a reflective film is formed by sintering or hardening, and the light-emitting layer is formed on the opposite surface of the reflective film of the light-transmitting substrate. First, a composition for a reflective film containing metal nanoparticles, preferably containing an additive, is applied to a light-transmitting substrate by a wet coating method. The coating here is preferably such that the thickness after sintering is 0.05 to 1.0 μm, particularly preferably 0.1 to 0.5 &quot; m. Next, the coating film is dried at a temperature of 120 to 350 ° C, preferably 15 0 to 2 50 ° C, for 5 to 60 minutes, preferably 15 to 40 minutes. The reflective film is thus formed. The light-transmitting substrate is not particularly limited as long as it can form a light-emitting layer, and is preferably a sapphire substrate from the viewpoint of light transmittance and heat dissipation. The composition for the reflective film can be blended with a desired material by a paint shaker, a ball mill, a sand mill, a centrimill, a three roll, etc. according to a general method, and a light-transmitting adhesive, and a case It is produced by dispersing different transparent conductive particles or the like. Of course, it can also be produced by a usual stirring operation. Further, it is preferable to mix the components of the metal nanoparticles to be mixed with the dispersion medium containing the metal nanoparticles which are previously dispersed, and it is easy to obtain a homogeneous composition for a reflective film. The wet coating method is preferably a spray coating method, a dispensing coating method, a spin coating method, a knife coating method, a slit coating method, an inkjet coating method, a screen printing method, or a lithography method. And any of the die-casting method, but it is not limited thereto, and any method can be applied. The spray coating method is applied to a light-transmitting substrate by forming a composition for enhancing the reflective film into a mist by compressed air, or by applying a dispersion to the dispersion itself to form a mist. The method of the substrate, the dispensing method, for example, the composition for enhancing the reflective film is placed in a syringe, and by pressing the piston of the syringe, the dispersion is discharged from the fine nozzle at the tip of the syringe, and is applied to the light-transmitting Method of a substrate. In the spin coating method, the composition for enhancing the reflective film is dropped onto a light-transmissive substrate which is rotated, and the composition for enhancing the reflective film after dripping is diffused to the periphery of the light-transmitting substrate by the centrifugal force, and the doctor blade is applied. The baffle plate is provided so as to be movable in the horizontal direction by a light-transmissive substrate having a predetermined gap between the tip end of the blade, and the composition for enhancing the reflective film is supplied from the blade to the light-transmitting substrate on the upstream side, and then A method in which a light-transmitting substrate is horizontally moved toward a downstream side. The slit coating method is a method in which a composition for enhancing a reflective film is applied from a narrow slit to a light-transmissive substrate, and the inkjet coating method is used to fill the composition for a reinforcing reflective film. The ink jet of a commercially available ink jet printer is ink jet printed on a light transmissive base -30-201247792. The screen printing method is a method of transferring a composition for an enhanced reflection film to a light-transmitting substrate by using a tissue as a pattern indicating material and using the plate image produced above. The lithographic method is a composition for a reinforcing reflective film attached to a plate, which is not directly attached to a light-transmitting substrate, but is transferred from a plate to a rubber sheet, and then transferred from a rubber sheet to a light-transmitting substrate. A printing method for applying water repellency of a composition for enhancing a reflective film. The die-casting method is a method of dispensing a composition for an enhanced reflection film supplied to a die-casting mold by a manifold, and pressing it from the slit onto the film to coat the surface of the traveling light-transmitting substrate. method. The die casting method has a slit coating method, a slant plate coating method, and a curtain coating method. Finally, the light-transmissive substrate having the reflective coating film is preferably in the range of 130 to 250 ° C, particularly preferably 180 to 20 ° C, in the atmosphere or in an inert gas atmosphere such as nitrogen or helium. The sintering is carried out for 5 to 60 minutes, preferably 1 to 5 minutes. When the binder reacts due to hydrolysis or the like, it can be hardened at a lower temperature. When the sintering temperature of the light-transmitting substrate having a coating film is set in the range of 130 to 2 50 °C, the lack of hardening of the reflective film occurs when the temperature is less than 30 °C. In addition, when it exceeds 250 °C, the advantages of production in low-temperature processes cannot be utilized. That is, the manufacturing cost rises and the productivity is lowered. Further, when the light-emitting layer is previously formed and loaded on the light-transmitting substrate, the light-bearing layer is relatively weak in heat resistance, and the light-emitting efficiency is lowered by the sintering step. The sintering time of the light-transmitting substrate having a coating film is set in the range of 5 to 60 minutes because when the sintering time is less than the lower limit -, the absence of sintering of the adhesive on the reflective film -31 - 201247792 occurs. . When the sintering time exceeds the upper limit 値, the manufacturing cost rises more than necessary, resulting in a decrease in productivity, and in addition, a decrease in luminous efficiency of the light-emitting layer is also caused. The method of forming the light-emitting layer on the opposite surface of the light-transmitting substrate from the reflective film is not particularly limited, and may be a generally known organic metal chemical vapor phase growth method (MOCVD) or a halogenated vapor phase epitaxial growth method ( HVPE), molecular beam epitaxy growth method (MBE) and the like. As described above, in the production method of the present invention, by using the wet coating method, the vacuum process such as the vacuum distillation method or the sputtering method can be eliminated as much as possible, so that the reflective film can be manufactured more inexpensively, and the method can be easily and inexpensively performed. A light-emitting element having high heat resistance and corrosion resistance of the present invention is produced. When the light-emitting element is bonded to another member, when the reflective film is directly bonded by Au_Sn solder of high-temperature solder, the reflective film may be eroded by Au-Sn solder, which is not preferable. Further, after the formation of the reflective film, before the formation of the light-emitting layer, the composition for the reinforcing film containing the binder is applied onto the reflective film by a wet coating method, and then the film is formed by sintering or hardening. Further, the heat resistance and the corrosion resistance of the light-emitting element can be further improved, and further, it is preferable to prevent the peeling of the reflective film during the step of manufacturing the light-emitting element by cutting. As described above, the binder for the reinforced film is the same as the composition for the reflective film, and the composition for the reinforced film is preferably 0.01 to 0.5 after sintering. // m, especially preferably 0.01~0.2 em. The heating method for curing or the ultraviolet irradiation method can be appropriately selected depending on the type of the binder of the composition for reinforcing the film. Adding the above-mentioned necessary additives such as particles, fine particles, and flat fine particles to the substrate liquid of the composition for reinforcing the film of sr-32-201247792, and dispersing the additives in the matrix liquid, the basis of the stirring of the mixer, etc. Dispersion by blade agitation, or shear dispersion of a planetary agitation or a three-roll honing machine, or dispersion using a bead mill or a bead containing a paint shaker. Further, a method of mixing the solvent component in which the additive is dispersed in the matrix liquid by the above method may be employed. Further, when the additive itself has been dispersed as a dispersion by a suitable solvent, in addition to the above method, a liquid mixing method based on ultrasonic homogenizer or ultrasonic vibration can be used. As described above, by using the wet coating method, the transparent conductive film can be manufactured more inexpensively, and the light-emitting element having high heat resistance and corrosion resistance can be produced simply and at low cost. [Examples] Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited thereto. [Example 1] First, a composition for a reflective film was produced. In the following, the production step "Production of a composition for a reflective film" is shown in which silver nitrate is dissolved in deionized water to prepare a metal salt aqueous solution. Further, sodium citrate was dissolved in deionized water to prepare a sodium citrate aqueous solution having a concentration of 26% by mass. The granulated -33-201247792 ferrous sulfate was directly added to the aqueous sodium citrate solution and dissolved in a nitrogen gas stream maintained at 35 ° C to prepare a citrate ion in a molar ratio of 3:2. An aqueous solution of a reducing agent with ferrous ions. Next, the above-mentioned nitrogen gas stream was maintained at 35 t, and the stirring material of the magnetic stirrer was placed in a reducing agent aqueous solution, and the aqueous metal salt solution was dropped into the reducing agent aqueous solution while stirring at a rotation speed of the stirring member: 100 rpm. Here, the concentration of each solution is adjusted such that the amount of the metal salt aqueous solution added to the reducing agent aqueous solution is 1/10 or less of the amount of the reducing agent aqueous solution, and even if the metal salt aqueous solution is dropped into the room temperature, The reaction temperature was maintained at 40 °C. Further, the mixing ratio of the reducing agent aqueous solution and the metal salt aqueous solution is set to be citrate ion and ferrous ion of the reducing agent aqueous solution, and the molar ratio of the total atomic valence of the metal ion in the aqueous metal salt solution is three times Moor. After the aqueous solution of the metal salt is dropped into the aqueous solution of the reducing agent, the mixture is continuously stirred for 15 minutes, thereby producing silver nanoparticles in the mixed solution, thereby obtaining a silver nanoparticle dispersion in which silver nanoparticles are dispersed. . The pH of the silver nanoparticle dispersion was 5.5, and the stoichiometric amount of the silver nanoparticles in the dispersion was 5 §/liter. The obtained silver nanoparticle dispersion was allowed to stand at room temperature, whereby the silver nanoparticles in the dispersion were sedimented, and the precipitated silver nanoparticle aggregates were separated by decantation. The deionized water was added to the separated silver nanoparticle aggregate to form a dispersion, which was subjected to desalting treatment by ultrafiltration, and then washed with methanol, and the content of the metal (silver) was 50% by mass. Then, using a centrifugal separator, the centrifugal force of the centrifugal separator is adjusted to separate relatively large silver particles having a particle diameter exceeding l 〇〇 nm, thereby adjusting the number to

The S-34-201247792 volume average contains 71% of silver nanoparticles with a primary particle size in the range of ίο~50nm. That is, the ratio of the silver nanoparticles in the range of 10 to 50 nm in the range of 10 to 50 nm is 7.1% relative to the total silver nanoparticles, and the silver nanometer is obtained. Particle dispersion. The obtained silver nanoparticles were chemically modified with a protective agent of sodium citrate. Then, 10 parts by mass of the obtained metal nanoparticles were mixed and mixed with 90 parts by mass of a mixed solution containing water, ethanol and methanol to prepare a composition for a reflective film. The metal nanoparticles constituting the composition for a reflective film contain 75 mass% or more of metal nanoparticles. With respect to the composition for a reflective film, a reflective coating film was formed on a glass substrate by a spin coating method, and baked at 200 ° C for 20 minutes in a nitrogen atmosphere to obtain a reflective film having a thickness of 200 nm. Here, the film thickness was measured by a scanning electron microscope (SEM, device name: S-4300, SU-8000) manufactured by Hitachi High Technologies, Inc., and observed by cross-sectional observation. In the other examples and comparative examples, the film thickness was also measured in the same manner. [Example 2] After preparing a silver nanoparticle dispersion liquid in the same manner as in Example 1, 10 parts by mass of the obtained metal nanoparticles were mixed and mixed in a mixed solution containing water, ethanol and methanol: 90 parts by mass and borrowed In this dispersion, polyvinylpyrrolidone (PVP, molecular weight: 3,60,000) and tin acetate were added to the dispersion to obtain a ratio of metal nanoparticles: 96 parts by mass and PVP: 4 parts by mass. Composition. The metal natriene-35-201247792 m particles constituting the composition for a reflective film contain 75 mass% or more of metal nanoparticles. Then, in the same manner as in Example 1, a reflective film having a thickness of 100 nm was produced. [Example 3] After the silver nanoparticle dispersion liquid was produced in the same manner as in Example 1, 10 parts by mass of the obtained metal nanoparticle was added and mixed in a mixed solution containing water, ethanol and methanol: 90 parts by mass and borrowed In the dispersion, zinc acetate was added to the dispersion to obtain a composition for a reflective film in a ratio of 95 parts by mass of metal nanoparticles to 5 parts by mass of zinc acetate, and then produced in the same manner as in Example 1. Thickness: 200 nm reflective film. Next, a composition for a reinforcing film was produced. The production steps are shown below. <<Preparation of composition for reinforcing film>> Using neopentyl glycol diacrylate as a raw material monomer, l〇g was dissolved in PGME: 100 cm3, and 0.5 g of 1-hydroxy-cyclohexyl-phenyl-ketone was added. The acrylic resin was synthesized while maintaining the temperature at 50 ° C while maintaining vigorous stirring for 1 hour. The acrylic resin was diluted with ethanol to have a solid content concentration of 1% by mass to prepare a composition for a reinforcing film. The composition for the reinforcing film was formed on the reflective film by a spin coater. It was then sintered at 150 ° C for 10 minutes to obtain a reinforced film. [Example 4] After preparing a silver nanoparticle dispersion liquid in the same manner as in Example 1, 10 parts by mass of the obtained metal nanoparticles were mixed and mixed in a mixed solution containing water, ethanol, and -36-201247792 methanol: 90 The dispersion was dispersed in this manner, and the dispersion was prepared into a composition for a reflective film at a ratio of 95 parts by mass to the amount of metal nanoparticles. The same was made, and a reflective film having a thickness of 150 nm was produced. Next, SiO 2 as a composition for a reinforcing film was placed in a four-necked flask made of 500 cm 3 glass, 140 g and 140 g of ethanol were added thereto, and stirred, and a solution in which an acid was dissolved in 120 g of pure water was added at a time, and then at 50 ° C. And made it out. The transparent conductive film composition was spin-coated at 160 ° C for 30 minutes by spin coating to obtain a thick conductive film. [Examples 5 to 6, 17] Examples 5 to 6 and 17 were produced in the same manner as the composition described in the first table and the film thickness of Example 4. The Si〇2 binder was used in the same manner as in Example 4; [Examples 7 to 16, 18 to 20] The composition was the same as the composition described in Table 1, and the film thickness was the same as in Example 3. Examples 7 to 16, 18 to 20. The acrylic type used in the composition used dipropyl ester, and the bisphenol A type epoxy resin was used as the epoxy type, and the copper acetate was added to the copper acetate: 5 and the binder of Example 1 was used. Tetraethoxy decane 1.7 g of 60% nitrate was reacted for 3 hours to form a film on a reflective film: 100 Å, and the other 与SiO 2 adhesive used in Example 5, and others, reinforced epoxide As the diol, methyl fiber-37-201247792 was used as the cellulose system, and diphenylmethane isocyanate and methylphenol were used as the urethane system. [Example 21] Example 21 was produced in the same manner as in Example 2 except that the composition and film thickness described in Table 1 were used. For the SiO 2 bonding agent used in this example, the SiO 2 bonding agent used in Example 4 was used. [Comparative Example 1] A silver thin film having a thickness of 100 nm was formed on a glass substrate by a sputtering method by a vacuum film formation method. [Comparative Example 2] A silver thin film having a thickness of 100 nm was formed on a glass substrate by a sputtering method, and then a titanium thin film having a thickness of 30 nm was formed by sputtering. [Measurement of reflectance] Examples 1 to 2 1 and Comparative Example 1 The evaluation of the reflectance of 2 is a measurement of the diffuse reflection of the reflective film at a wavelength of 450 nm by a combination with an ultraviolet visible spectrophotometer and an integrating sphere. rate. In addition, the heat treatment test was carried out at 200 ° C for 1 000 hours, and the corrosion resistance test was carried out under the conditions of hydrogen sulfide: 10 ppm, temperature: 25 ° C, relative humidity: 75 ° / «) RH, and 594 hours. Vulcanization test' and measure the reflectance after each test. The first table shows the results of these. -38- 201247792 [Adhesion evaluation] For the adhesion evaluation, the tape was tested on the tape test (JIS K-5600), and the tape was adhered to the film after the reflectance was measured in Examples 2 and 5. When peeling off again, the degree of peeling or curling of the film to be formed is evaluated in three stages of excellent and acceptable. The film formation is not attached to the tape side, and only the adhesive tape is peeled off, and it is preferable that the peeling of the adhesive tape and the state in which the photoelectric conversion layer of the substrate is exposed are mixed. The peeling of the adhesive tape makes it impossible to fully expose the surface of the photoelectric conversion layer which becomes the substrate. Example 2 is OK, and Example 5 is excellent.

S -39- 201247792 [Table 1] Reflective film protective film thickness [nm] Reflectance [%] (45〇11111) Metal nanoparticle additive Binder Reflective film Reinforcement die After initial heat treatment Vulcanization test 0 Example 1 Ag 100 质fl% - - 200 - 85 75 29 ΕΓ Example 2 Ag 96 fl fl% PVP 4 质 S% - 100 - 86 76 30 苡 Example 3 Ag 95 质: % Zn 5 fl fl: % Acrylic 200 10 82 79 74 Face 4 Ag95 Fifi Acetic acid Cu 5 flfl% Si02 binder 150 100 84 78 82 0 Example 5 Ag99 A% PVP 0.9 Fl% SiO20. Tannin 11% Si〇 2Adhesive system 100 50 86 85 84 苡Example 6 Ag95 质fl% PVP 4 质fl% ITO 1 s% 〇% Si〇2 binder system 120 70 83 82 82 苡Example 7 Ag 95 MR% PVP 4 质 S % ATO 1 S% Epoxy 260 200 85 83 77 K Example 8 Ag95 Mfl% PVP 4 Fifi Ti021 Titanium 2% Epoxy 740 340 81 80 77 Surface Example 9 Ag 95 Flu 1% PVP 4 g% Fe203 1 quality fl% cellulose system 70 100 85 82 80 ET Example 10 Ag 90 quality fl% PVP 9 quality fl% Al203 1 quality fi% cellulose system 90 160 84 83 79 decoration example 11 Ag 95 quality fl% PVP 4 quality fl% Zn(OH)2 1 quality fi% cellulose system 580 190 82 80 76 Example 12 Ag 95 mass fl; % PVP 4 mass fi% A! (OH) 3 1 Wfl: % Acrylic 370 310 82 81 80 苡 Example 13 Ag 95 质fi% PVP 4 质g% acetic acid Sn 1% by mass Urethane 750 430 84 82 78 Η Example 14 Ag 95 质fl% PVP 4 质fi% methyl phthalate 丨 mass % urethane system 350 200 86 84 79 Η Example 15 Ag 95 Quality fl% PVP 4 quality fl; % formic acid Co 1 substance g% epoxy system 310 140 85 82 80 fl Example 16 Ag 95.9 quality fi% PVP 4 substance fl% citric acid FeO.l mass 0 / 〇 acrylic 270 80 81 80 75 Example 17 Ag 92 mass fi; % Cu 4 mass fl; % PVP 3 mass S% acetic acid Sn 1 mass % Si〇 2 binder system 170 100 86 84 82 Example 18 Ag 95.8 WR% Fe 0.2 quality fi % methylcellulose 4% by mass Acrylic 550 60 82 81 77 Surface Example 19 Ag 96.8 Quality fi% Mn 0.2 Mass g% PVP-methyl propyl dimethyl urethane ethyl ester 2% by mass Acetic acid Sn 1% by mass Fiber Prime system 400 40 83 81 79 ΗExample 20 Ag 96.8% by mass In 0.22 flfl% PVP 2 质fl% Acetate Ni fl fl:% Cellulose 50 430 81 80 79 Case 21 Ag 99 Flu: % PVP 0_9 ϋ%% Si02 0.1 质fi% - 100 50 79 77 75 Comparative Example 1 - - - 100 - 87 66 14 Comparative Example 2 - - - 100 30 80 78 65 sr -40- 201247792 It can be seen from the first table that in Examples 1 and 2, the reflectances at the initial stage and after the heat treatment are high, and after the vulcanization test The reflectivity is also about 30%. On the other hand, in Comparative Example 1 produced by the sputtering method, the initial reflectance was high, but the deterioration after the heat treatment was large, and the reflectance after the vulcanization test was greatly reduced to 14%. Further, in Examples 3 to 21, the reflectances at the initial stage, after the heat treatment, and after the vulcanization test were extremely high, and it was found that the heat resistance and the corrosion resistance were extremely high, and it was possible to produce a light-emitting layer with respect to high output. A light-emitting element that is less deteriorated in terms of temperature rise. On the other hand, in Comparative Example 2 produced by the sputtering method, the reflectance after the vulcanization test was as low as 65%. In the light-emitting device of the present invention, a reflective film containing metal nanoparticles is provided between the light-transmitting substrate and the light-emitting layer, whereby heat resistance and corrosion resistance can be improved even with a high-output light-emitting element. The deterioration of the reflective film caused by heat generated by the light-emitting layer or the environment is suppressed. Since the reflective film can be produced by a wet coating method, the manufacturing steps can be simplified and the cost can be reduced. Further, a transparent conductive film containing a light-transmitting adhesive is further provided between the light-emitting layer and the reflective film, whereby heat resistance and light resistance can be further improved, which is extremely useful. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an example of a light-emitting element of the present invention. Fig. 2 is a cross-sectional view showing a preferred example of the light-emitting element of the present invention - 41 - 201247792 [Explanation of main component symbols] 1, 2: light-emitting element 10, 1 1 : reflective film 1 2 : reinforcing film 2 0 : Photonic substrate 2 1 : Substrate 30, 31 : Light-emitting layer 40, 41 : Sealing material 50, 51 : Adhesive layer 60, 61 : Support substrate - 42-

Claims (1)

201247792 VII. Patent Application Range: 1. A composition for a reflective film suitable for a light-emitting element, which is suitable for a light-emitting element having a light-emitting layer, a light-transmitting substrate, and a reflective film for reflecting light from the light-emitting layer. A composition for a reflective film, characterized in that the composition for a reflective film contains metal nanoparticles. 2. The composition for a reflective film of the light-emitting element according to the first aspect of the patent application, further comprising an additive. 3. The composition for a reflective film which is applied to a light-emitting element according to claim 1 or 2, further comprising a dispersion medium. 4. A composition for a reinforcing film suitable for a light-emitting element, which is suitable for reinforcing a light-emitting element, which is provided with a light-emitting layer, a light-transmitting substrate, a reflective film that reflects light from the light-emitting layer, and a reinforcing film. A composition for a film, characterized in that the composition for a reinforcing film contains a binder. 5. The composition for a reinforcing film for a light-emitting element according to the fourth aspect of the invention, further comprising a group selected from the group consisting of cerium oxide particles, cerium particles, metal particles, and metal oxide particles. One or two or more kinds of fine particles or flat particles. A light-emitting element comprising a light-emitting layer, a light-transmitting substrate, and a light-emitting element that reflects a light-emitting layer from the light-emitting layer, wherein the reflective film contains metal nanoparticles. 7. The light-emitting element of claim 6, wherein the reflective film further contains an additive. The light-emitting device of the sixth or seventh aspect of the invention, further comprising a reinforced film, wherein the light-emitting layer, the light-transmitting substrate, the reflective film, and the reinforcing film are provided in this order. The reinforcing film described above contains a binder. 9. The light-emitting element of claim 8, wherein the reinforcing film further contains one or two selected from the group consisting of cerium oxide particles, silicate particles, metal particles, and metal oxide particles. More than one type of particles or flat particles. 10. The light-emitting element according to claim 6 or 7, wherein the above-mentioned reflective film is produced by a wet coating method. 11. The light-emitting element of claim 8 wherein the reflective film and/or the reinforcing film are produced by a wet coating method. 12. The light-emitting element of claim 6 or 7 wherein the thickness of the reflective film is 0.05-1.0 // m. 13. The light-emitting element of claim 8 wherein the thickness of the reflective film is 0.05 to 1.0/m. A method for producing a light-emitting device, characterized in that a composition for a reflective film containing metal nanoparticles and an additive is applied onto a light-transmitting substrate by a wet coating method, followed by sintering or hardening A reflective film is formed, and the light-emitting layer is formed on the opposite surface of the reflective film of the light-transmitting substrate. The method for producing a light-emitting device according to claim 14, wherein after forming the reflective film, the composition of the reinforcing film containing the adhesive is further coated by a wet coating method before forming the light-emitting layer. After being coated on the reflective film, the reinforced film is formed by sintering or hardening. S -44-