TWI537346B - Composition for reflective film of light emitting element, light emitting element, and method for producing light emitting element - Google Patents

Description

Composition for reflective film suitable for light-emitting element, light-emitting element, and method for producing light-emitting element

The present invention relates to a composition for a reflective film which is applied to a light-emitting device, a light-emitting device which is produced by using the composition for a reflective film of a light-emitting device, and a method for producing the light-emitting device. 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.

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, it is used for lighting devices and backlights of liquid crystal displays.

In order to further improve the brightness of the LED light source, etc., it is possible to efficiently apply the light emission from the LED element, and to disclose a substrate, an LED element mounted on the support substrate, and a seal containing a fluorescent agent. The mixture is provided with an Ag-plated electrode film for reflecting the light emission of the LED element between the substrate and the LED element, and an LED light source having a titanium thin film on the Ag-plated electrode film (Patent Document 1).

In the LED light source, light from the illuminator is efficiently reflected 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.

In general, the electroplating method envisions cumbersome steps and the generation of waste liquid, and the vacuum film forming method consumes a large amount of cost in order to maintain and operate a large-scale vacuum film forming apparatus. The LED light source is thermally degraded or photodegraded only by the Ag-plated electrode film. Therefore, 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 Ag-plated electrode film, and therefore, a plating method and a vacuum film formation method are used in combination.

[Patent Document 1] JP-A-2009-231568

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 applied to a light-emitting device which solves the above-described problems by the configuration described below, and is applied to a composition for a reinforcing film of a light-emitting device and a light-emitting device.

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. Light-emitting element A composition for a reflective film, 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 in the first aspect, and further contains an additive.

The composition for a reflective film of the third aspect of the present invention is a composition for a reflective 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 element according to a seventh aspect of the present invention is the light-emitting device of the sixth aspect, wherein the reflective film further contains an additive.

The light-emitting element of the eighth aspect of the present invention is as described above in the sixth or seventh type The light-emitting element further includes a reinforcing film, and the light-emitting layer, the light-transmitting substrate, the reflective film, and the reinforcing film are sequentially provided, and 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 according to any one of the sixth to ninth aspects of the present invention, wherein the reflective film is produced by a wet coating method.

The light-emitting element of the eleventh aspect of the invention is the light-emitting element of the eighth or ninth aspect, wherein the reinforcing film is produced by a wet coating method.

In a light-emitting device according to a twelfth aspect of the present invention, the light-emitting device of any one of the sixth to eleventh aspects, wherein the reflective film has a thickness of 0.05 to 1.0 μm.

According to a thirteenth aspect of the present invention, in a method of producing a light-emitting 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. 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.

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 of manufacturing a light-emitting element of a fourteenth aspect of the present invention is as described above In a method of producing a light-emitting device according to a thirteenth aspect, after the formation of the reflective film, a composition for a reinforcing film containing a binder is further applied onto a reflective film by a wet coating method before forming the light-emitting layer. The 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.

According to the composition for forming a reflective film of the present invention, the metal nanoparticle can improve heat resistance and corrosion resistance even with a high-output light-emitting element, and can provide a light-shielding layer A high-life light-emitting element that produces deterioration of the reflective film caused by heat or the environment. 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 corrosion resistance can be obtained easily and at low cost.

Hereinafter, the present invention will be specifically described based on the embodiments. % is not particularly indicated, and is in the case of a mass % other than the numerical value.

[Composition for a reflective film for a light-emitting element]

The composition for a reflective film of the present invention (hereinafter referred to as a composition for a reflective film) is preferably provided with a light-emitting layer, a light-transmitting substrate, and a reflection reflecting the light emitted from the light-emitting layer. A composition for a reflective film of a light-emitting device of a film, characterized in that the composition for a reflective film contains metal nanoparticles.

The metal nanoparticles impart reflectivity to 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 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 using 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 an organic polymer, a metal oxide, a metal hydroxide, an organometallic compound, and an eucalyptus oil. At least one of the groups formed is particularly preferable from the viewpoint of reflectivity and adhesion.

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, lanthanum, 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. Specific examples of the composite oxide include ITO (Indium Tin Oxide) containing the above metal, ATO (Antimony-doped Tin Oxide), and IZO (Indium-doped Zinc Oxide). Zinc oxide), AZO (Aluminum-doped Zinc Oxide), and the like.

The metal hydroxide used as an additive preferably contains a material selected from the group consisting of aluminum, lanthanum, titanium, zirconium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium, and antimony. At least one hydroxide of the group.

The organometallic compound used as an additive preferably contains at least one selected from the group consisting of ruthenium, titanium, zirconium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, and tin. a hydrolysate of a metal soap, a metal complex, an alkoxylated metal or an alkoxylated metal. For example, metal soap can use acetic acid Chromium, manganese formate, ferric citrate, cobalt formate, nickel acetate, silver citrate, copper acetate, copper citrate, tin acetate, zinc acetate, zinc oxalate, molybdenum acetate, and the like. Further, examples of the metal complex include acetamylacetone zinc complex, acetamylacetate chromium complex, acetamacetone nickel complex, and the like. Further, as the alkoxide metal, titanium isopropoxide, methyl silicate, isocyanate propyl trimethoxide, amine 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 Sexual 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 it contains 2% by mass of water, it contains 98% by mass of an alcohol, including When there is 2% by mass of an alcohol, it contains 98% by mass of water. Further, the dispersion medium, that is, the protective molecule chemically modified on the surface of the metal nanoparticles, contains either or both of a hydroxyl group (-OH) and a carbonyl group (-C=O). The content of water is preferably in the range of 1% by mass or more based on 100% 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=O) 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. Wherein, the above alcohols, particularly preferably selected from the group consisting of methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, glycerin, isodecylhexanol 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 enhanced reflection transparent film from which the dispersion medium is subtracted. Moreover, 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, per 100 parts by mass of the reflective film.

The dispersion medium is preferably from 50 to 99 parts by mass per 100 parts by mass of the composition for a reflective film, and is preferable 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 based on 100 parts by mass of the composition for a reflective film. 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 a water-soluble cellulose derivative. The addition can also enhance the reflectivity of the formed enhanced reflective film. Examples of the water-soluble cellulose derivative include hydroxypropylcellulose and hydroxypropylmethylcellulose. The water-soluble cellulose derivative is preferably 0.2 to 5 parts by mass based on 100 parts by mass of the composition for a reinforcing reflection film.

The composition for a reflective film may further be formulated with an antioxidant, a flattening agent, a rheological viscosity reducing agent, a filler, a stress relieving agent, and other additives, as long as the object of the present invention is not impaired.

[Reinforcing film composition]

A composition for a reinforcing film for a light-emitting element (hereinafter referred to as a composition for a reinforcing film) is preferably provided with a light-emitting layer or a light-transmitting substrate. A reflective film for reflecting light emitted from the light-emitting layer and a reinforcing film for a reinforcing film composition for a light-emitting element, wherein the composition for a reinforcing film contains a binder. The reinforcing film composition can form a reinforcing film. Further, 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 reflective film and the enhanced reflecting 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 acrylic, epoxy, 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 adhesive, 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, 1,9-nonanediol diacrylate, tripropylene glycol diacrylate, epoxidized triacetyl urethane and tetramethylolmethacrylate 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. But as long as it can dissolve the general organic of the above monomers Either solvent, ethanol, methanol, benzene, toluene, xylene, NMP (N-methylpyrrolidone), 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, as the photopolymerization initiator, 1-hydroxy-cyclohexyl-phenyl-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-hydroxy-1-[4- [4-(2-Hydroxy-2-methyl-propenyl)-benzyl]-phenyl]-2-methyl-propan-1-one, 1-[4-(2-hydroxyethoxy) -Phenyl]-2-hydroxy-2-methyl-1-propan-1-one and the like. The acrylic monomer can be used by being diluted with any of the above solvents to adjust the viscosity to be easily applied. The photopolymerization initiator is added in an amount of 0.1 to 30 parts by mass based on 100 parts by mass of the acrylic monomer. When the amount of the photopolymerization initiator added is less than 0.1 part by mass relative to 100% by mass of the acrylic monomer, the hardening is insufficient, and when it exceeds 30 parts by mass, the cured film (reinforcing film) may be discolored or residual stress. And caused the poor adhesion. In this manner, a solvent and a photopolymerization initiator are added to the acrylic monomer 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 photopolymerization initiator are added to the acrylic monomer and stirred to obtain a uniformity, the mixture 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 and stirring the mixture, adding a thermal curing agent to the mixed solution, and stirring the mixture, and heating the resulting mixture, can be used. Examples of the epoxy resin include a biphenyl type epoxy resin, a cresol novolac type epoxy resin, and a bisphenol A type epoxy resin. Bisphenol F type epoxy resin, naphthalene type epoxy resin, and the like. Further, as the solvent, BCA (butyl carbitol acetate), ECA (ethyl carbitol acetate), BC (butyl carbitol), or the like can be used. Further, as long as a general organic solvent capable of dissolving the above epoxy resin is 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 sulfonium), piperidine, phenol, and the like. Further, the thermosetting agent may be 2-ethyl-4-methylimidazole, boron fluoride-monoethanolamine, DICY (dicyandiamide), diethylaminopropylamine, isophorone diamine, Diaminodiphenylmethane, piperidine, 2,4,6-tris-(dimethylaminomethyl)phenol, 2-methylimidazole, hexahydrophthalic anhydride, 7,11-octadecane Diene-1,18-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 thermosetting agent is added in an amount of 0.5 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 100 parts by mass of the epoxy resin, the hardening is insufficient, and when it exceeds 20 parts by mass, the cured film (reinforcing film) generates a large internal stress. And caused the 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 a solvent and a heat hardener are added to the epoxy resin and stirred to form a mixture which is not uniform, Warm to 40 ° C.

The cellulose-based binder can be obtained by adding a solvent to a cellulose-based polymer, 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, the solvent may be IPA (isopropyl alcohol), ethanol, methanol, PGME (1-methoxy-2-propane), PGMEA (propylene glycol monomethyl ether acetate), MIBK (methyl isobutyl ketone), acetone. Wait. 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 100 parts 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 100 parts by mass of the cellulose-based polymer, the viscosity suitable for coating cannot be obtained. In this manner, a solvent and gelatin are added to the cellulose-based polymer and stirred to obtain a mixed solution, which can be used as a matrix liquid for a composition for reinforcing a film. Further, the solvent and gelatin are added to the cellulose-based polymer and heated to about 30 ° C and stirred to form a uniform mixture.

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 phenol system represented by methylphenol, a lactone system represented by β-butyrolactone, or a guanidine system represented by butanone oxime, etc. The blocker is reacted with a urethane prepolymer having an active isocyanate group at the end. 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, 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-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 (reactive agent). Specific examples of the polyamine include N-octyl-N-aminopropyl-N'-aminopropylpropanediamine, N-dodecyl-N-aminopropyl-N'-aminopropylpropyl Diamine, N-tetradecyl-N-aminopropyl-N'-aminopropylpropanediamine, N-octyl-N-aminopropyl-N', N'-di(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 applied.

The urethane acrylate-based adhesive contains an urethane acrylate-based oligomer and is cured by ultraviolet (UV) irradiation, and violet UV-3310B or violet UV-6100B (made by Nippon Synthetic Co., Ltd.) can be used. ) Or an urethane urethane-based polymer such as EBECRYL4820 or EBECRYL 284 (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, 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-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 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-1020 manufactured by Shin-Nakamura Chemical Co., Ltd.) or 1,6-hexanediol diglycidyl ether diacrylate (for example) can be used. For example, NK oligomer EA-5521 manufactured by Shin-Nakamura Chemical Industry Co., Ltd., and the like. 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. Ketone Specific examples thereof include 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-butoxyethyl acetate 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 acryl-based polymer can be used by being diluted by 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 decane-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-end type) and a part of the side chain of the polyoxyalkylene and the both ends (both side chain type) 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 refers to 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 ketones, 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-based polymer may be added with a thermal curing agent or a photopolymerization initiator as necessary, but it is not necessary to add a thermosetting agent when the film is cured without adding a thermosetting 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 a hydrolyzate of a metal soap, a metal complex, an alkoxylated metal, and an alkoxylated metal. 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 the 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 acetaminophen zinc complex, an acetoacetate chromium complex, an acetamacetone nickel complex or the like can be used. As the alkoxide metal, titanium isopropoxide, methyl silicate, isocyanate propyl trimethoxide, amine propyl trimethoxane or the like can be used.

On the other hand, as the inorganic matrix material of the non-polymer type binder, a SiO ₂ binder can be used. The SiO ₂ binder can be produced by one of the examples shown below. First, HCl was dissolved in pure water while stirring to prepare an aqueous HCl solution. Next, tetraethoxyoxane and ethanol were mixed, and the above aqueous HCl solution was added to the mixed solution, followed by heating to cause a reaction. Thereby, a SiO ₂ binder was produced. 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, β-diketones, 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, zirconium 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, an acetonitrile zinc complex, an acetoacetate chromium complex, an acetonitrile nickel complex, or the like can be used, and the alkoxide metal can be a titanium isopropoxide, a methyl citrate or an isocyanate. Propyltrimethoxydecane, aminopropyltrimethoxydecane, and the like. As the halodecane, chlorodecane, bromodecane, fluorodecane, or the like can be used. As the 2-alkoxyethanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol or the like can be used. As the β-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, 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 a reinforcing film can further improve the adhesion of the reinforcing film to the reflecting film by containing a decane coupling agent, an aluminum coupling agent or the like. Therefore, in 1 piece When a plurality of light-emitting layers are formed on the optical substrate, when the step of dividing into the light-emitting layers by forming a dividing groove on the light-transmitting substrate from the side of the reflecting film is performed, the reinforcing film can be prevented from being peeled off from the reflecting film. situation.

In addition, the composition for a reinforcing film may contain one or two or more kinds of fine particles or flat particles selected from the group consisting of cerium oxide particles, ceric acid particles, metal particles, and metal oxide 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 100 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 in a gas phase under 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 10 to 50,000 nm which are produced by a synthesis method, and are preferably flat particles having an average diameter of 1 to 20 μm and an average thickness of 10 to 100 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 10~. The particles of 100,000 nm are preferably flat particles having an average diameter of 1 to 20 μm and an average thickness of 10 to 100 nm. The composition for the reinforced film can further increase the hardness of the reinforced 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, the reinforced film is separated because the abrasion resistance and impact resistance of the reinforced film are good. The groove does not create a missing edge at the edge. The amount of the addition is preferably from 0.1 to 30 parts by mass, particularly preferably from 0.2 to 20 parts by mass, per 100 parts by mass of the composition for a reinforcing film. When it is less than 0.1 part by mass, it is difficult to obtain an effect. On the other hand, when it exceeds 30 mass parts, adhesiveness will fall easily. In the present invention, the average particle diameter of each particle and each particle is measured in the following manner. It is measured by a laser diffraction/scattering particle size distribution measuring device (manufactured by Horiba, Ltd., model: LA-950), and the 50% average particle diameter (D ₅₀ ) calculated from the particle diameter standard is counted. . The value of the number of reference average particle diameters calculated by the laser diffraction/scattering type particle size distribution measuring apparatus was measured by a scanning electron microscope (manufactured by Hitachi High Technologies, Model: S-4300SE and S-900). In the observed image, the average particle diameter when the particle diameter was actually measured for any 50 particles was almost the same. Further, the average diameter and the average thickness of the above flat particles and the average diameter and average thickness of each of the flat fine particles described later were also measured in the same manner as described above.

When the average particle diameter of the colloidal cerium oxide is limited to the range of 1 to 100 nm, the colloidal cerium oxide is unstable and easily aggregates when it is less than 1 nm, and when it exceeds 100 nm, the particle diameter increases and the dispersion cannot be formed. Therefore. Further, the size of the fumed cerium oxide particles, the cerium oxide particles, the mica particles, and the nanite particles is limited to the above-described range because the particle size is available or the film is not lower than the lower layer (reflecting film) ) The thickness of the larger range of sizes.

Further, the composition for reinforcing the film may contain a group selected from the group consisting of gold, platinum, palladium, rhodium, nickel, copper, tin, indium, zinc, iron, chromium, manganese, and aluminum. One or two or more kinds of metals, or fine particles or flat particles containing such metal oxides. 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 from 1 to 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 a reinforcing film may further be formulated with an antioxidant, a flattening agent, a rheological viscosity reducing agent, a 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 reflective film that reflects light emitted from the light-emitting layer. It 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 with the sealing material 40.

Fig. 2 is a cross-sectional view showing a preferred example of a 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 21 can be suppressed in the cutting step, which is preferable. When the reinforcing film 12 contains a binder, it is preferably produced by a wet coating method. 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 a 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.

The thickness of the reflective film is preferably from 0.05 to 1.0 μm, particularly preferably from 0.1 to 0.5 μm, from the viewpoint of reflectivity and conductivity.

The pores of the surface of the reflective film on the side of the light-transmitting substrate have an average diameter of 100 nm or less, an average depth of 100 nm or less, and a number density of 30/μm ² , and a theoretical reflection can be achieved in a wavelength range of 380 to 780 nm. A high diffusion reflectance of 80% or more is preferable. 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 toward the long wavelength side, and a good reflectance cannot be obtained. Therefore, the average diameter of the pores is preferably 100 nm or less. Further, when the average depth of the pores exceeds 100 nm, 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 / μm ² , the reflectance on the long wavelength side is lowered, and a good reflectance cannot be obtained, so the number density of the pores is preferably 30 / μm ² or less.

"Reinforcing film"

The reinforced film can improve the heat resistance and the 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, and the binder is 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, or an epoxy acrylic polymer. One or two of a group consisting of a cellulose, a cellulose polymer, and a siloxane polymer on. 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 reinforcing film, one or two 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 from 0.01 to 0.5 μm, particularly preferably from 0.01 to 0.2 μm, from the viewpoint of heat resistance and corrosion resistance.

[Method of Manufacturing Light-Emitting Element]

A method for producing a light-emitting device of the present invention, 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.

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, and particularly preferably 0.1 to 0.5 μm. The coating film is then dried at a temperature of 120 to 350 ° C, preferably 150 to 250 ° 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 mixed with the desired components by a coating shaker, a ball mill, a sand mill, a centrimill, a three roll, etc. according to a general method. The light-transmitting adhesive and the transparent conductive particles which are different in the case are dispersed and produced. Of course, it can also be manufactured by a usual stirring operation. Further, it is preferable to mix the components of the metal nanoparticles and to mix them 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 an inkjet coating method is used to fill a composition for a reinforcing reflective film. Inkjet printers sold in inkjet printers, and inkjet printing on light-transmitting substrates The method on the board. 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 maintained at 130 to 250 ° C, particularly preferably at a temperature of 180 to 220 ° C, in the atmosphere or in an inert gas atmosphere such as nitrogen or argon. Sintering is carried out for 5 to 60 minutes, preferably 15 to 40 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 250 ° C, the loss of insufficient hardening occurs on the reflective film when it is less than 130 ° C. In addition, when it exceeds 250 ° C, the production advantages of the low temperature process 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-emitting 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 the sintering time is not reached when the sintering time is less than the lower limit. There will be a lack of sintering of the binder. When the sintering time exceeds the upper limit value, 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 deposition 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. Μm, especially preferably 0.01 to 0.2 μm. 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 particles The method of reinforcing the matrix liquid of the composition for a film and dispersing the additive in the substrate liquid may be a dispersion by a blade agitation such as stirring by a mixer, or a shear of a planetary agitation or a three-roll mill. Cut and disperse, or use a bead mill or a dispersion of beads 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 according to an ultrasonic homogenizer or ultrasonic vibration may be used.

As described above, by using the wet coating method, the transparent conductive film can be manufactured more inexpensively, and a 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 described in detail by way of examples, but the invention is not limited thereto.

[Example 1]

First, a composition for a reflective film was produced. The production steps are shown below.

"Production of Compositions for Reflective Films"

Silver nitrate was 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. Granular in a nitrogen gas stream maintained at 35 ° C Ferrous sulfate was directly added to the aqueous sodium citrate solution and dissolved to prepare an aqueous solution of a reducing agent containing citrate ions and ferrous ions in a molar ratio of 3:2.

Next, the nitrogen gas stream was kept at 35 ° C, and a stirring material of a magnetic stirrer was placed in a reducing agent aqueous solution while stirring at a rotation speed of the stirring member: 100 rpm, and the aqueous metal salt solution was dropped into the reducing agent aqueous solution and mixed. 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 was dropped into the aqueous solution of the reducing agent, the mixture was continuously stirred for 15 minutes to produce silver nanoparticles in the mixed solution, thereby obtaining a silver nanoparticle dispersion in which silver nanoparticles were dispersed. The pH of the silver nanoparticle dispersion was 5.5, and the stoichiometric amount of the silver nanoparticles in the dispersion was 5 g/liter.

The obtained silver nanoparticle dispersion liquid was allowed to stand at room temperature, whereby silver nanoparticle particles in the dispersion liquid were sedimented, and the aggregated silver nanoparticle particles after sedimentation 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 of more than 100 nm, thereby adjusting the number to The amount average meter contains 71% of silver nanoparticles having a primary particle diameter in the range of 10 to 50 nm. That is, the silver nanoparticle particles having a primary particle diameter in the range of 10 to 50 nm in a range of 10 to 50 nm are 71% in proportion to the total silver nanoparticle particles, and a silver nanoparticle dispersion liquid is obtained. The obtained silver nanoparticle is chemically modified by 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% by 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.

[Embodiment 2]

After the silver nanoparticle dispersion liquid was prepared in the same manner as in the example 1, 10 parts by mass of the obtained metal nanoparticle was mixed and mixed in a mixed solution containing water, ethanol, and methanol: 90 parts by mass, and dispersed. Vinylpyrrolidone (PVP, molecular weight: 360,000) and tin acetate were added to the dispersion to obtain a composition for a reflective film, which was a ratio of metal nanoparticles: 96 parts by mass and PVP: 4 parts by mass. Metal naphthalene constituting a composition for a reflective film The rice particles contain 75% by 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 the 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 the acetic acid was dispersed. Zinc 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. Next, in the same manner as in Example 1, a reflective film having a thickness of 200 nm was produced.

Next, a composition for a reinforcing film was produced. The production steps are shown below.

"Production of Composition for Reinforcing Film"

Using neopentyl glycol diacrylate as a raw material monomer, 10 g was dissolved in PGME: 100 cm ³ , and 0.5 g of 1-hydroxy-cyclohexyl-phenyl-ketone was added thereto, and kept at 50 ° C while maintaining vigorous stirring. An acrylic resin was synthesized in 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 the silver nanoparticle dispersion liquid was prepared in the same manner as in Example 1, 10 parts by mass of the obtained metal nanoparticle was mixed and mixed with water and ethanol. In a mixed solution of methanol: 90 parts by mass and dispersed in the dispersion, copper 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 copper acetate. Next, in the same manner as in Example 1, a reflective film having a thickness of 150 nm was produced.

Next, using a SiO ₂ binder as a composition for a reinforcing film, a four-necked flask made of 500 cm ³ glass was used, and 140 g of tetraethoxy decane and 140 g of ethanol were added thereto, and stirred, and 1.7 g of 60 was added at a time. % nitric acid was dissolved in 120 g of a solution of pure water and then reacted at 50 ° C for 3 hours to produce.

The transparent conductive film composition was formed on a reflective film by a spin coating method, and sintered at 160 ° C for 30 minutes, thereby obtaining a transparent conductive film having a thickness of 100 nm.

[Examples 5 to 6, 17]

Examples 5 to 6 and 17 were produced in the same manner as in Example 4 except that the composition and film thickness described in the first table were used. Embodiment SiO ₂ binding agent as used in Example 5, the system embodiment using SiO 4 used in Example ₂ of binder.

[Examples 7 to 16, 18 to 20]

Examples 7 to 16 and 18 to 20 were produced in the same manner as in Example 3 except that the composition and film thickness described in the first table were used. Here, the acrylic used in the composition for a reinforcing film is neopentyl glycol diacrylate, and bisphenol A epoxy resin is used as the epoxy system, and methyl fiber is used. As the cellulose system, diphenylmethane isocyanate and methylphenol are 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. SiO ₂ binding agent used in the examples of the present embodiment, using embodiments based SiO ₂ binder used in the Example 4.

[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]

The reflectances of Examples 1 to 21 and Comparative Examples 1 and 2 were evaluated by the combination of an ultraviolet visible light spectrophotometer and an integrating sphere to measure the diffuse reflectance of the reflective film at a wavelength of 450 nm. In addition, a 1000-hour heat treatment test was carried out at 200 ° C, and a vulcanization test as a corrosion resistance test was carried out under the conditions of hydrogen sulfide: 10 ppm, temperature: 25 ° C, relative humidity: 75% RH, and 504 hours, and various measurements were performed. Reflectance after the test. The first table shows the results of these.

[Adhesion evaluation]

The adhesion evaluation was carried out according to the method of the tape test (JIS K-5600). For the examples 2 and 5 after the reflectance was measured, the film was adhered to the film and then peeled off. The degree of peeling or curling is evaluated in three stages of excellent and unrecognizable. The film formation is not attached to the tape side, and it is preferable that only the adhesive tape is peeled off, and the peeling of the adhesive tape and the state in which the photoelectric conversion layer to be the substrate is exposed are mixed, because 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.

As can be seen from the first table, in Examples 1 and 2, the reflectances at the initial stage and after the heat treatment were high, and the reflectance after the vulcanization test was 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.

1, 2‧‧‧Lighting elements

10,11‧‧·reflective film

12‧‧‧ reinforcing film

20‧‧‧Transmissive substrate

21‧‧‧Substrate

30, 31‧‧‧Lighting layer

40, 41‧‧‧ sealing materials

50, 51‧‧‧ adhesive layer

60, 61‧‧‧ support substrate

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.

2‧‧‧Lighting elements

11‧‧‧Reflective film

12‧‧‧ reinforcing film

21‧‧‧Substrate

31‧‧‧Lighting layer

41‧‧‧Filled materials

51‧‧‧Adhesive layer

61‧‧‧Support substrate

Claims (12)

A composition for a reflective film which is applied to a light-emitting element, and is suitable for a composition for a reflective film comprising a light-emitting element, a light-transmitting substrate, and a light-emitting element that reflects a light-emitting layer from the light-emitting layer. The composition for a reflective film contains a metal nanoparticle and an additive, and the composition for the reflective film contains 92 to 99% by mass of the silver naphthalene with respect to 100% by mass of the total of the metal nanoparticle and the additive. Rice particles. A composition for a reflective film which is applied to a light-emitting element according to the first aspect of the patent application, further comprising a dispersion medium. A composition for a reinforcing film suitable for a light-emitting element, which is suitable for a reinforcing film suitable for a light-emitting element, comprising a light-emitting layer, a light-transmitting substrate, a reflective film for reflecting light emitted from the light-emitting layer, and a reinforcing film In the composition for a reinforcing film, the composition for a reinforcing film contains a binder, and the composition for the reinforcing film contains 0.1 to 30 parts by mass of the cerium oxide-based particles, based on 100 parts by mass of the composition for the reinforcing film. One or two or more kinds of fine particles or flat particles in which a group of citrate particles, metal particles or metal oxide particles are grouped. A light-emitting element comprising a light-emitting element, 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 and an additive. The reflective film contains 92 to 99% by mass of silver nanoparticles, based on 100% by mass of the total of the metal nanoparticles and the additive. The light-emitting element of claim 4, further comprising a reinforcing film comprising the light-emitting layer, the light-transmitting substrate, the reflective film, and the reinforcing film, wherein the reinforcing film contains a binder. The light-emitting element according to claim 5, wherein the reinforcing film further contains one or more kinds of particles selected from the group consisting of cerium oxide particles, ceric acid particles, metal particles, or metal oxide particles. Or flat particles. The light-emitting element of claim 4, wherein the reflective film is produced by a wet coating method. The light-emitting element of claim 5, wherein the reflective film and/or the reinforcing film are produced by a wet coating method. The light-emitting element of claim 4, wherein the reflective film has a thickness of 0.05 to 1.0 μm. The light-emitting element of claim 5, wherein the reflective film has a thickness of 0.05 to 1.0 μm. 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, and then formed by sintering or hardening. The reflective film is formed on the opposite surface of the reflective film of the light-transmitting substrate; and the composition for the reflective film contains 92 to 99% by mass based on 100% by mass of the total of the metal nanoparticles and the additive. Silver nanoparticle child. The method for producing a light-emitting device according to claim 11, wherein after the formation of the reflective film, a composition for a reinforcing film containing a binder is further applied by a wet coating method before the formation of the light-emitting layer. After the reflective film is formed, a reinforced film is formed by sintering or hardening.