CN102651441A - Composition for reflective film of light emitting element, light emitting element, and method for producing light emitting element - Google Patents
Composition for reflective film of light emitting element, light emitting element, and method for producing light emitting element Download PDFInfo
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- CN102651441A CN102651441A CN2012100410651A CN201210041065A CN102651441A CN 102651441 A CN102651441 A CN 102651441A CN 2012100410651 A CN2012100410651 A CN 2012100410651A CN 201210041065 A CN201210041065 A CN 201210041065A CN 102651441 A CN102651441 A CN 102651441A
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- light
- emitting component
- reflectance coating
- film composition
- reflection
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/44—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the coatings, e.g. passivation layer or anti-reflective coating
- H01L33/46—Reflective coating, e.g. dielectric Bragg reflector
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
- H01L2933/0008—Processes
- H01L2933/0025—Processes relating to coatings
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Led Device Packages (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
A light-emitting element comprises a light-emitting layer, a light-transmitting substrate and a reflecting film which reflects light emitted from the light-emitting layer. The reflecting film contains metal nano particles. The light-emitting element can further have a strengthening film with adhesive.
Description
Technical field
The light-emitting component that the present invention relates to be used for the reflection film composition of light-emitting component, makes through this reflection film composition that is used for light-emitting component and the manufacturing approach of light-emitting component.More particularly, relate to possess successively reflection of light film that luminescent layer, light-transmitting substrate and reflection sent by luminescent layer, possess the light-emitting component that reflects the reflection of light layer that sends by luminescent layer effectively and the manufacturing approach of light-emitting component.
Background technology
In recent years, light-emitting component, led light source are especially wherein followed high brightnessization etc., are used in the various fields.Particularly, therefore be used in the purposes such as ligthing paraphernalia, backlight liquid crystal display owing to can realize White LED light source.
For the brightness that further improves led light source etc.; Study from the luminous of LED element more effectively being used to; A kind of led light source is disclosed; This led light source has substrate, carry the LED element on supporting substrate and contain the sealant of fluorescer, between substrate and LED element, possesses the luminous plating Ag electrode film of reflection LED element, has titanium film (patent documentation 1) plating on the Ag electrode film.
In this led light source,, reflect the light of self-luminous body effectively and increase luminous intensity through between substrate and LED element, reflective coating being set.Wherein, Ag film and titanium film form through galvanoplastic and vacuum film formation method.
Usually, mention galvanoplastic and can be contemplated to miscellaneous operation, the generation of waste liquid, mention the vacuum film formation method,, need very big cost in order to keep and turn round large-scale vacuum film formation apparatus.In above-mentioned led light source, because plating Ag electrode film is only arranged, can produce thermal degradation when, light deterioration, therefore need the titanium film, and need and with galvanoplastic and vacuum film formation method.
In addition, this invention is an object with the light-emitting component of the reflection of light film that possesses luminescent layer, light-transmitting substrate and reflection successively and sent by luminescent layer, between luminescent layer and light-transmitting substrate, does not have reflectance coating.In this formation,, can produce thermal degradation when, light deterioration, therefore need and with galvanoplastic and vacuum film formation method because plating Ag electrode film is only arranged usually.
Patent documentation 1: TOHKEMY 2009-231568 communique
Summary of the invention
The present invention is a problem to address the above problem.The objective of the invention is to; Light that is sent by light-emitting component through reflection and the film forming method that improves the reflectance coating with electrode effect are provided, can suppress because the heat of reflectance coating and deterioration that environment brings and make manufacturing process easy, significantly improve the manufacturing approach of the light-emitting component and the light-emitting component of operating cost.
The present invention relates to through the technical scheme shown in following solve above-mentioned problem the reflection film composition that is used for light-emitting component, be used for the reinforcement film composition and the light-emitting component of light-emitting component.
The 1st scheme of the present invention is the reflection film composition that is used for light-emitting component, is used for possessing successively the light-emitting component of the reflection of light film that luminescent layer, light-transmitting substrate and reflection sent by luminescent layer, and the reflection film composition contains metal nanoparticle.
The 2nd scheme of the present invention is the reflection film composition that is used for light-emitting component that above-mentioned the 1st scheme relates to, and then contains additive.
The 3rd scheme of the present invention is the reflection film composition that is used for light-emitting component that the above-mentioned the 1st or the 2nd scheme relates to, and then contains decentralized medium.
The 4th scheme of the present invention is the reinforcement film composition that is used for light-emitting component, and the reflection of light film that be used for possessing luminescent layer successively, light-transmitting substrate, reflection is sent by luminescent layer and the light-emitting component of strengthening membrane are strengthened film composition and contained adhesive.
The 5th scheme of the present invention is the reinforcement film composition that is used for light-emitting component that above-mentioned the 4th scheme relates to; Wherein, and then contain one or more particulate or the flat particle that is selected from silica-based particle, silicate particles, metallic or the metal oxide particle.
The 6th scheme of the present invention is a light-emitting component, possesses the reflection of light film that luminescent layer, light-transmitting substrate and reflection are sent by luminescent layer successively, and reflectance coating contains metal nanoparticle.
The 7th scheme of the present invention is the light-emitting component that above-mentioned the 6th scheme relates to, said reflectance coating and then contain additive.
The 8th scheme of the present invention is the light-emitting component that the above-mentioned the 6th or the 7th scheme relates to, and then possesses strengthening membrane, possesses said luminescent layer, said light-transmitting substrate, said reflectance coating and said strengthening membrane successively, and said strengthening membrane contains adhesive.
The 9th scheme of the present invention is the light-emitting component that above-mentioned the 8th scheme relates to, and wherein, said strengthening membrane and then contain is selected from one or more particulate or the flat particle in silica-based particle, silicate particles, metallic or the metal oxide particle.
The 10th scheme of the present invention is the light-emitting component that arbitrary scheme relates in the above-mentioned the 6th～the 9th, and said reflectance coating can be made through the wet type rubbing method.
The 11st scheme of the present invention is the light-emitting component that the above-mentioned the 8th or the 9th scheme relates to, and said strengthening membrane is made through the wet type rubbing method.
The 12nd scheme of the present invention is the light-emitting component that arbitrary scheme relates in the above-mentioned the 6th～the 11st, and the thickness of said reflectance coating is 0.05～1.0 μ m.
The 13rd scheme of the present invention is the manufacturing approach of light-emitting component; Wherein, After utilizing the coating of wet type rubbing method to contain the reflection film composition of metal nanoparticle and additive on the light-transmitting substrate; Through burning till or solidify to form reflectance coating, form luminescent layer at the opposing face of the reflectance coating of light-transmitting substrate.
In the manufacturing approach of above-mentioned light-emitting component, can use the reflectance coating that is used for light-emitting component of the present invention to form and use composition.
The 14th scheme of the present invention is the manufacturing approach of the light-emitting component that relates to of above-mentioned the 13rd scheme; After forming above-mentioned reflectance coating, form before the luminescent layer; And then after utilizing the coating of wet type rubbing method to contain the reinforcement film composition of adhesive on the reflectance coating, through burning till or solidify to form strengthening membrane.
In the manufacturing approach of above-mentioned light-emitting component, can use the strengthening membrane that is used for light-emitting component of the present invention to form and use composition.
The reflectance coating that is used for light-emitting component according to the present invention forms uses composition; Pass through metal nanoparticle; Even be the light-emitting component of high-output power; Also can improve thermal endurance, corrosion resistance, the high life light-emitting component of the deterioration of the reflectance coating that the heat that can suppress to be produced by luminescent layer or environment bring can be provided.This reflectance coating can be used for various light sources, is specially adapted to led light source.In addition, this reflectance coating can be made through the wet type rubbing method, so manufacturing process is easy, can be with the low cost manufacturing.In addition, according to the present invention, thermal endurance, light-emitting component that corrosion resistance is higher can be provided.
According to light-emitting component of the present invention, can improve the adaptation of light-transmitting substrate and luminescent layer, improve the reliability of light-emitting component.
In addition, possess the light-emitting component of the present invention of strengthening membrane, thermal endurance, corrosion resistance are high, the deterioration of the reflectance coating that heat that suppresses to be produced by luminescent layer or environment bring, and the life-span is high.
According to the manufacturing approach of light-emitting component of the present invention, can be easily obtain thermal endurance, light-emitting component that corrosion resistance is high with low cost.
Description of drawings
Fig. 1 is the sectional view of an example of expression light-emitting component of the present invention.
Fig. 2 is the sectional view of a preferred example of expression light-emitting component of the present invention.
Embodiment
Below the present invention is carried out bright specifically based on execution mode.And, only if % represent especially, otherwise except the intrinsic situation of numerical value, be quality %.
[the reflection film composition that is used for light-emitting component]
The reflection film composition that is used for light-emitting component of the present invention (below be called the reflection film composition) is characterised in that; It is the reflection film composition that is used for possessing successively the light-emitting component of the reflection of light film that luminescent layer, light-transmitting substrate and reflection sent by luminescent layer, and the reflection film composition contains metal nanoparticle.
Metal nanoparticle to burn till or solidify after the reflection film composition, promptly give the reflection of light property of sending by luminescent layer to reflectance coating.As metal nanoparticle, can enumerate one or more mixing composition or the alloy composition that is selected from silver, gold, platinum, palladium, ruthenium, nickel, copper, tin, indium, zinc, iron, chromium and the manganese, consider to be preferably silver, gold from the viewpoint of reflectivity, conductivity.The average grain diameter of metal nanoparticle is preferably 10～50nm.Wherein, average grain diameter uses the BET method to measure through specific area measuring.For example, in specific area measuring, can use the QUANTACHROME AUTOSORB-1 of Quantachrome Instruments.The shape of metal nanoparticle is considered to be preferably spherical, tabular from dispersed, reflexive viewpoint.
The reflection film composition is considered from the adaptation of reflectance coating, reflexive viewpoint, is preferably contained additive.As additive, consider from the viewpoint of reflectivity, adaptation, more preferably contain and be selected from least a in organic polymer, metal oxide, metal hydroxides, organo-metallic compound and the silicone oil.
As as the organic polymer of additive, consider from reflexive viewpoint, be preferably at least a in the copolymer that is selected from polyvinylpyrrolidone, polyvinylpyrrolidone and the water-soluble cellulose.As the copolymer of polyvinylpyrrolidone, can enumerate PVP-methacrylate copolymer, PVP-styrol copolymer, PVP-vinyl acetate copolymer etc.In addition, as water-soluble cellulose, can enumerate cellulose ethers such as HPMC, methylcellulose, HEMC.
Metal oxide as as additive is preferably and contains at least a oxide or the composite oxides that are selected from aluminium, silicon, titanium, zirconium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium and the antimony.Composite oxides specifically can be enumerated the ITO (Indium Tin Oxide, tin-doped indium oxide) that contains above-mentioned metal, ATO (Antimony-doped Tin Oxide, antimony-doped tin oxide), IZO (Indium-doped Zinc Oxide, indium doping zinc-oxide), AZO (Aluminum-doped Zinc Oxide, aluminium-doped zinc oxide) etc.
Metal hydroxides as as additive is preferably and contains at least a hydroxide that is selected from aluminium, silicon, titanium, zirconium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium and the antimony.
Organo-metallic compound as as additive is preferably and contains the hydrolysate that is selected from least a metallic soap, metal complex, metal alkoxide or metal alkoxide in silicon, titanium, zirconium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum and the tin.For example, as metallic soap, can enumerate chromium acetate, formic acid manganese, ironic citrate, cobaltous formate, nickel acetate, silver citrate, copper acetate, copper citrate, tin acetate, zinc acetate, zinc oxalate, acetate molybdenum etc.In addition, as metal complex, can enumerate acetylacetone,2,4-pentanedione Zn complex, acetylacetone,2,4-pentanedione chromic compound, acetylacetone,2,4-pentanedione nickel complex etc.In addition, as metal alkoxide, can enumerate isopropyl titanate, methyl silicate, isocyanic acid propyl trimethoxy silicane, TSL 8330 etc.
As as the silicone oil of additive, can use pure silicon oil (Straight silicone oil) and modified silicon oil the two.As modified silicon oil, can and then use the part of the side chain of polysiloxanes import organic group silicone oil (side chain type), import the silicone oil (single tip type) of organic group and at the part of the side chain of polysiloxanes and the silicone oil (side chain two tip type) of two terminal importing organic groups two terminal any sides that import in the silicone oil (two tip type) of organic groups, two ends of polysiloxanes at polysiloxanes.Responding property silicone oil and non-reactive silicone oil in the modified silicon oil can be used these two kinds simultaneously as additive of the present invention.And; Reactive silicone oil is represented amino-modified silicone oil, epoxy radicals modified silicon oil, carboxy-modified silicone oil, methyl alcohol modified silicon oil, sulfhydryl modified silicone oil and xenogenesis functional group modification (epoxy radicals, amino, polyether-based) silicone oil, and non-reactive silicone oil is represented polyether modified silicon oil, methyl styrene base modified silicon oil, alkyl modified silicon oil, high-grade aliphatic ester modified silicon oil, fluorine modified silicon oil and hydrophilic special modified silicon oil.
In addition, consider that the reflection film composition preferably contains decentralized medium from the viewpoint of coating.Decentralized medium contains water and 2 quality % solvent, the for example alcohols with water compatible above, that preferred 3 quality % are above that 1 quality % is above, preferred 2 quality % are above and suits with respect to whole decentralized medium 100 quality %.For example, decentralized medium only comprises water and pure time-like, contains the alcohols of 98 quality % when containing the water of 2 quality %, and the pure time-like that contains 2 quality % contains the water of 98 quality %.Further, decentralized medium, the protection molecule that promptly surfaces of metal nanoparticles carried out chemical modification contain hydroxyl (OH) or carbonyl (any side or both sides C=O).With respect to whole decentralized medium 100 quality %, the content of water is preferably more than the 1 quality %.This is because the content of water during less than 2 quality %, is difficult to the film that sintering at low temperatures obtains through wet type rubbing method coating reflection film composition.And be because can cause the reflectivity of the reflectance coating after burning till to reduce.In addition, (OH) as if containing metal nanoparticles such as Nano silver grain are being carried out in the protective agent of chemical modification, the dispersion stabilization that then reflects film composition is excellent, and the low-temperature sintering of filming is also had effective function for hydroxyl.In addition, (C=O) as if containing metal nanoparticles such as Nano silver grain are being carried out in the protective agent of chemical modification, then same as described abovely, the dispersion stabilization of reflection film composition is excellent, and the low-temperature sintering of filming is also had effective function for carbonyl.As that use in the decentralized medium and solvent water compatible, be preferably alcohols.Wherein, as above-mentioned alcohols, more preferably use is selected from one or more in methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol, propane diols, diethylene glycol (DEG), glycerine, isobornyl hexanol and the erythrite.
With respect to reflection film composition 100 mass parts of removing decentralized medium, if then consider more than metal nanoparticle 75 mass parts from reflexive viewpoint preferred, if more than 80 mass parts then more preferably.In addition, if below 95 mass parts, then consider from the viewpoint of the adaptation of reflectance coating preferred, if more than 80 mass parts then more preferably.And if when wanting to give conductivity to reflectance coating, with respect to reflectance coating 100 mass parts, metal nanoparticle is preferably more than 75 mass parts, more preferably more than 80 mass parts.
With respect to reflection film composition 100 mass parts, consider that from the viewpoint of coating preferred decentralized medium is 50～99 mass parts.
In addition, the reflection film composition preferably adds low resistance agent (low opposingization drug), water-soluble cellulose derivative according to the composition that uses.As the low resistance agent, more preferably be selected from the inorganic acid salt of cobalt, iron, indium, nickel, lead, tin, titanium and zinc and in the acylate one or more.Can enumerate mixture of for example mixture, acetyl group acetate titanium and the cobalt octoate of mixture, indium nitrate and the lead acetate of mixture, naphthalene acid zinc, tin octoate and the antimony chloride of nickel acetate and iron chloride etc.With respect to the reflection film composition, preferred low resistance agent is 0.2～15 mass parts.Water-soluble cellulose derivative is the non-ionized surfactant, compares with other surfactant, even a small amount of the interpolation; The ability of dispersed metal nano particle is also high; In addition, through the interpolation of water-soluble cellulose derivative, also can improve the reflectivity of the reflectance coating of formation.As water-soluble cellulose derivative, can enumerate hydroxypropyl cellulose, HPMC etc.With respect to reflection film composition 100 mass parts, preferred water-soluble cellulose derivative is 0.2～5 mass parts.
In the scope of not damaging the object of the invention, and then as required, the reflection film composition can cooperate oxidation inhibitor, levelling agent, thixotropic agent, filler, Stress Release agent, other additive etc.
[reinforcement film composition]
The reinforcement film composition (below be called strengthen film composition) that is used for light-emitting component for be used for possessing luminescent layer successively, the reinforcement film composition of the light-emitting component of reflection of light film that light-transmitting substrate, reflection are sent by luminescent layer and strengthening membrane, strengthen film composition and contain adhesive.Strengthen film composition and can form strengthening membrane; When this external reflectance coating has emptying aperture; Be penetrated into reflectance coating, contain adhesive, can improve the intensity or the reflectance coating of reflectance coating itself and increase the dhering strength of reflective transparent film at the emptying aperture and/or the reflectance coating of reflectance coating and the interface that increases the reflective transparent film.
Adhesive preferably contain through ultraviolet irradiation, heating or after ultraviolet irradiation heating and the organic system of cured polymer type adhesive or inorganic be base material, perhaps non-polymeric adhesive inorganic is any side or the both sides in the base material.The organic system base material of polymer type adhesive preferably contains one or more in the polymer that is selected from acrylic compounds, epoxies, polyurethanes, acroleic acid polyurethane class, propylene oxide acids, cellulose family and type siloxane.
As acrylic adhesives, can use and in acrylic monomer, add Photoepolymerizationinitiater initiater, to this mixture irradiation ultraviolet radiation (UV), carry out photopolymerization and the acrylic polymer that obtains.As acrylic monomer; Can enumerate and be selected from 1; 6-hexanediyl ester, trimethylolpropane triacrylate, neopentylglycol diacrylate, tetramethylol methane tetraacrylate, two (trimethylolpropane) tetraacrylate, 1, the single monomer or the mix monomer of one or more in 9-nonanediol diacrylate, tri (propylene glycol) diacrylate, epoxidation cyamelide triacrylate and the tetramethylol methane tetraacrylate.In these monomers, preferably add MIBK (methyl iso-butyl ketone (MIBK)), PGME (1-methoxyl group-2-propyl alcohol), PGMEA (propylene glycol methyl ether acetate) equal solvent.Wherein, If can dissolve the common organic solvents of above-mentioned monomer, then can use ethanol, methyl alcohol, benzene,toluene,xylene, NMP (N-methyl pyrrolidone), acrylonitrile, acetonitrile, THF (oxolane), ethyl acetate, MEK (MEK), DEGMBE, butyl carbitol acetate, butyl cellosolve, butyl cellosolve acetate, carbitol, diethylene glycol monoethyl ether acetate, IPA (isopropyl alcohol), acetone, DMF (dimethyl formamide), DMSO (dimethyl sulfoxide (DMSO)), piperidines, phenol etc.In addition; As Photoepolymerizationinitiater initiater, can enumerate 1-hydroxyl-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-1 propane-1-ketone, 2-hydroxyl-1-[4-[4-(2-hydroxy-2-methyl-propiono)-benzyl]-phenyl]-2-methyl-propane-1-ketone, 1-[4-(2-hydroxyl-oxethyl)-phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone etc.Acrylic monomer can be with above-mentioned solvent dilution arbitrarily, be adjusted into the viscosity that is prone to coating and use.With respect to acrylic monomer 100 mass parts, add the Photoepolymerizationinitiater initiater of 0.1～30 mass parts.This be because, with respect to acrylic monomer 100 mass parts, the addition of Photoepolymerizationinitiater initiater solidifies during less than 0.1 mass parts and becomes insufficient, if surpass 30 mass parts then cured film (strengthening membrane) variable color or residual stress and cause that driving fit is bad.So, in acrylic monomer, add solvent and Photoepolymerizationinitiater initiater, stir, the mixture that obtains is as the substrate liquid of strengthening film composition.And, in acrylic monomer, add solvent and Photoepolymerizationinitiater initiater, stir, under the uneven situation of the mixed liquor that obtains, can also heat to about 40 ℃.
As epoxy adhesive, can use in epoxylite and to add solvent and stir, in this mixed liquor, add thermal curing agents, stir and obtain mixed liquor, resulting mixed liquor is heated and the epoxide polymer that obtains.As epoxylite, can enumerate biphenyl type epoxy resin, cresol novolak epoxy, bisphenol A type epoxy resin, bisphenol f type epoxy resin, naphthalene type epoxy resin etc.In addition, as solvent, can enumerate BCA (butyl carbitol acetate), ECA (diethylene glycol monoethyl ether acetate), BC (DEGMBE) etc.Wherein, If can dissolve above-mentioned epoxylite common organic solvents, then can use ethanol, methyl alcohol, benzene,toluene,xylene, PGME (1-methoxyl group-2-propyl alcohol), PGMEA (propylene glycol methyl ether acetate), NMP (N-methyl pyrrolidone), MIBK (methyl iso-butyl ketone (MIBK)), acrylonitrile, acetonitrile, THF (oxolane), ethyl acetate, MEK (MEK), DEGMBE, butyl carbitol acetate, butyl cellosolve, butyl cellosolve acetate, carbitol, diethylene glycol monoethyl ether acetate, IPA (isopropyl alcohol), acetone, DMF (dimethyl formamide), DMSO (dimethyl sulfoxide (DMSO)), piperidines, phenol etc.Further; As thermal curing agents; Can enumerate 2-ethyl-4-methylimidazole, boron fluoride MEA, DICY (dicyandiamide), diethylamino propyl group amine, IPD, diaminodiphenyl-methane, piperidines, 2,4,6-three-(dimethylaminomethyl) phenol, glyoxal ethyline, hexahydrophthalic anhydride, 7; 11-18 carbon diene-1,18-two carbohydrazides etc.Epoxylite can be with above-mentioned solvent dilution arbitrarily, be adjusted into the viscosity that is prone to coating and use.With respect to epoxylite 100 mass parts, add thermal curing agents 0.5～20 mass parts.This be because, with respect to epoxylite 100 mass parts, the addition of thermal curing agents is during less than 0.5 mass parts, solidifies to become insufficient, if surpass 20 mass parts, then solidfied material (strengthening membrane) produced big internal stress, causes that adaptation is bad.So, in epoxylite, add solvent and thermal curing agents, stir, the mixture that obtains is as the substrate liquid of strengthening film composition.And, in epoxylite, add solvent, stir, under the uneven situation of the mixed liquor that obtains, can also heat to about 40 ℃.
The cellulose family adhesive can stir through in cellulosic polymer, adding solvent, in this mixed liquor, adds gelatin, stirs and obtains mixed liquor, and resulting mixed liquor is heated and obtains.As cellulosic polymer, can enumerate hydroxypropyl cellulose as water-soluble cellulose derivative, HPMC, methylcellulose, HEMC etc.In addition, as solvent, can enumerate IPA (isopropyl alcohol), ethanol, methyl alcohol, PGME (propylene glycol monomethyl ether), PGMEA (propylene glycol methyl ether acetate), MIBK (methyl iso-butyl ketone (MIBK)), acetone etc.Cellulosic polymer can be with above-mentioned solvent dilution arbitrarily, be adjusted into the viscosity that is prone to coating and use.With respect to cellulosic polymer 100 mass parts, add gelatin 0.1～20 mass parts.This be because, with respect to cellulosic polymer 100 mass parts, if the addition of gelatin less than 0.1 mass parts or surpass 20 mass parts, then can not get being fit to the viscosity of coating.So, in cellulosic resin, add solvent and gelatin, stir, the mixture that obtains is as the substrate liquid of strengthening film composition.And, in cellulosic polymer, add solvent and gelatin, heat to about 30 ℃ and stir, even thereby mixed liquor becomes.
Use has the polyurethane binding of Thermocurable polyurethane resin to be prepared as follows.At first; Making with polyol compounds such as trimethylolpropane or neopentyl glycols is the polyol component of representative and the excessive polyisocyanate compounds reaction that is representative with toluene di-isocyanate(TDI) (TDI), diphenyl-methane isocyanates (MDI) etc., thereby obtains the polyurethane prepolymer that end contains the active isocyanate base.Then, make this end contain the polyurethane prepolymer of active isocyanate base with the methylphenol be representative phenols, with β-butyrolactam be representative lactams, or be block agent such as the oximes reaction of representative with the methyl ethyl ketoxime.As solvent, can use ketone, alkyl benzene, cellosolve class, ester class, alcohols etc.As the concrete example of ketone, can enumerate acetone, MEK etc., as the concrete example of alkyl benzene, can enumerate benzene, toluene etc.In addition,, can enumerate methyl cellosolve, butyl cellosolve etc.,, can enumerate butyl cellosolve acetate, butyl acetate etc.,, can enumerate isopropyl alcohol, butanols etc. as the concrete example of alcohols as the concrete example of ester class as the concrete example of cellosolve.On the other hand, as thermal curing agents (reactant), can use polyamine.Concrete example as polyamine; Can enumerate N-octyl group-N-aminopropyl-N '-aminopropyl propane diamine, N-lauryl-N-aminopropyl-N '-aminopropyl propane diamine, N-myristyl-N-aminopropyl-N '-aminopropyl propane diamine, N-octyl group-N-aminopropyl-N ', N '-two (aminopropyl) propane diamine etc.The polyurethane prepolymer that makes the end that obtains of above-mentioned polyol component and isocyanate compound reaction contain the active isocyanate base is implemented the blockization of utilizing the block agent to carry out, thereby make block polyisocyanate.The amino that polyamine has is preferably (0.7～1.1 scope) about 1 with respect to the equivalent proportion of the NCO that this block polyisocyanate has.This be because; If the equivalent proportion of the NCO that the amino that has of polyamine has with respect to block polyisocyanate is less than 0.7 or surpass 1.1; Then the side in block polyisocyanate and the polyamine increases, and reaction becomes insufficient, and therefore becoming, it is insufficient to solidify.Polyether polyols with reduced unsaturation can be with above-mentioned solvent dilution arbitrarily, be adjusted into the viscosity that is prone to coating and use.
As acroleic acid polyurethane class adhesive; Contain the urethane acrylate quasi-oligomer, can enumerate solidify through the irradiation of ultraviolet ray (UV), purple light UV-3310B or purple light UV-6100B (the synthetic society of Japan system), EBECRYL4820 or EBECRYL284 (ダ ィ セ Le サ ィ テ ッ Network society system), U-4HA or UA-32P acroleic acid polyurethane base polymers such as (Xin Zhong village chemical industry society systems).And, add the Photoepolymerizationinitiater initiater (for example 1-hydroxyl-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone etc.) that uses in the esters of acrylic acid as required, thereby can improve curable.In addition, as solvent, can use ketone, alkyl benzene, cellosolve class, ester class, alcohols etc.As the concrete example of ketone, can enumerate acetone, MEK etc., as the concrete example of alkyl benzene, can enumerate benzene, toluene etc.As the concrete example of cellosolve class, can enumerate methyl cellosolve, butyl cellosolve etc., as the concrete example of ester class, can enumerate butyl cellosolve acetate, butyl acetate etc., as the concrete example of alcohols, can enumerate isopropyl alcohol, butanols etc.With respect to acroleic acid polyurethane base polymer 100 mass parts, in the scope of 0.1～30 mass parts, add Photoepolymerizationinitiater initiater as required.This be because, the addition of Photoepolymerizationinitiater initiater is during less than 0.1 mass parts, solidifies to become insufficient, if surpass 30 mass parts, then the internal stress of backplate strengthening membrane increases, the adaptation that becomes is bad.In addition, acroleic acid polyurethane class monomer can be used above-mentioned solvent dilution arbitrarily, is adjusted into the viscosity that is prone to coating and uses.
As propylene oxide acids adhesive, can use the epoxy acrylic base polymer.As the epoxy acrylic base polymer; Can enumerate bisphenol-a epoxy acrylate (the for example NK ォ リ go EA-1020 of Xin Zhong village chemical industry society system), 1,6-hexylene glycol diglycidyl ether diacrylate (the for example NK ォ リ go EA-5521 of Xin Zhong village chemical industry society system) etc.In addition, can also use ネ ォ Port one Le 8318, ネ ォ Port one Le 8355 etc. of Japanese ュ ピ カ society system.As solvent, can use ketone, alkyl benzene, cellosolve class, ester class, alcohols etc.As the concrete example of ketone, can enumerate acetone, MEK etc., as the concrete example of alkyl benzene, can enumerate benzene, toluene etc.As the concrete example of cellosolve class, can enumerate methyl cellosolve, butyl cellosolve etc., as the concrete example of ester class, can enumerate butyl cellosolve acetate, butyl acetate etc., as the concrete example of alcohols, can enumerate isopropyl alcohol, butanols etc.As required, can in the epoxy acrylic esters polymer, add thermal curing agents, Photoepolymerizationinitiater initiater.So, through thermal curing agents, Photoepolymerizationinitiater initiater, be heating and curing or UV curing, perhaps, UV is heating and curing after solidifying.In addition, the epoxy acrylic esters polymer can be with above-mentioned solvent dilution arbitrarily, be adjusted into the viscosity that is prone to coating and use.
As the type siloxane adhesive, can use the type siloxane polymer.As the type siloxane polymer, can enumerate dimethyl silicone polymer, gather hydrogenated methyl siloxanes, PSI etc.In addition, as the type siloxane polymer shown in here, can use pure silicon oil (Straight silicone oil) and modified silicon oil the two.As modified silicon oil, can and then use the part of the side chain of polysiloxanes import organic group silicone oil (side chain type), import the silicone oil (single tip type) of organic group and at the part of the side chain of polysiloxanes and the silicone oil (side chain two tip type) of two terminal importing organic groups etc. two terminal any sides that import in the silicone oil (two tip type) of organic groups, two ends of polysiloxanes at polysiloxanes.Responding property silicone oil and non-reactive silicone oil in the modified silicon oil can be used these both sides.And; Reactive silicone oil is represented amino-modified silicone oil, epoxy radicals modified silicon oil, carboxy-modified silicone oil, methyl alcohol modified silicon oil, sulfhydryl modified silicone oil or xenogenesis functional group modification (epoxy radicals, amino, polyether-based) silicone oil, and non-reactive silicone oil is represented polyether modified silicon oil, methyl styrene base modified silicon oil, alkyl modified silicon oil, high-grade aliphatic ester modified silicon oil, fluorine modified silicon oil or hydrophilic special modified silicon oil.In addition, as solvent, can use ketone, alkyl benzene, cellosolve class, ester class, alcohols etc.As the concrete example of ketone, can enumerate acetone, MEK etc.As the concrete example of alkyl benzene, can enumerate benzene, toluene etc.In addition, as the concrete example of cellosolve class, can enumerate methyl cellosolve, butyl cellosolve etc.As the concrete example of ester class, can enumerate butyl cellosolve acetate, butyl acetate etc.As the concrete example of alcohols, can enumerate isopropyl alcohol, butanols etc.As required, can in the type siloxane polymer, add thermal curing agents, Photoepolymerizationinitiater initiater, yet, need not thermal curing agents even do not add under the situation that the thermal curing agents film also solidifies.In addition, the type siloxane polymer can be with above-mentioned solvent dilution arbitrarily, be adjusted into the viscosity that is prone to coating and use.
The inorganic of polymer type adhesive is that base material preferably contains one or more in the hydrolysate that is selected from metallic soap, metal complex, metal alkoxide and metal alkoxide.The inorganic of these polymer type adhesives is that base material is that being changed to inorganic through heating from organic system is the material of base material.That is, can form that to have inorganic be the film of base material character through burning till.And the metal that contains in the hydrolysate of above-mentioned metallic soap, metal complex, metal alkoxide or metal alkoxide is preferably and is selected from aluminium, silicon, titanium, zirconium and the tin one or more.As above-mentioned metallic soap, can enumerate chromium acetate, formic acid manganese, ironic citrate, cobaltous formate, nickel acetate, silver citrate, copper acetate, copper citrate, tin acetate, zinc acetate, zinc oxalate, acetate molybdenum etc.As metal complex, can enumerate acetylacetone,2,4-pentanedione Zn complex, acetylacetone,2,4-pentanedione chromic compound, acetylacetone,2,4-pentanedione nickel complex etc.As metal alkoxide, can enumerate isopropyl titanate, methyl silicate, isocyanic acid propyl trimethoxy silicane, aminopropyltriethoxywerene werene etc.
On the other hand, be base material as the inorganic of non-polymeric adhesive, can enumerate SiO
2Bond.This SiO
2Bond can be made as an example as follows.At first, in the time of stirring HCl is dissolved in the pure water preparation HCl aqueous solution.Then, tetraethoxysilane is mixed with ethanol, behind the above-mentioned HCl aqueous solution of adding, heating is reacted in this mixed liquor.Thus, make SiO
2Bond.In addition, the non-polymeric adhesive preferably contains one or more in hydrolysate, halogenated silanes class, 2-alkoxyethanol, beta-diketon and the alkyl acetates that is selected from metallic soap, metal complex, metal alkoxide, metal alkoxide.Contain collosol and gel in the hydrolysate of this metal alkoxide.And the metal that contains in the hydrolysate of above-mentioned metallic soap, metal complex, metal alkoxide or metal alkoxide is preferably and is selected from aluminium, silicon, titanium, zirconium and the tin one or more.As metallic soap; Can enumerate chromium acetate, formic acid manganese, ironic citrate, cobaltous formate, nickel acetate, silver citrate, copper acetate, copper citrate, tin acetate, zinc acetate, zinc oxalate, acetate molybdenum etc.; As metal complex; Acetylacetone,2,4-pentanedione Zn complex, acetylacetone,2,4-pentanedione chromic compound, acetylacetone,2,4-pentanedione nickel complex etc. can be enumerated,, isopropyl titanate, methyl silicate, isocyanic acid propyl trimethoxy silicane, aminopropyltriethoxywerene werene etc. can be enumerated as metal alkoxide.As the halogenated silanes class, can enumerate chlorosilane, bromo-silicane, silicon fluoride etc.As the 2-alkoxyethanol, can enumerate 2-methyl cellosolve, cellosolvo, butoxy ethanol etc.As beta-diketon, can enumerate 2,4-pentanedione, 1,3-diphenyl-1,3-propanedione etc.As alkyl acetates, can enumerate ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate etc.
In addition, strengthening film composition can contain and be selected from silane coupler, aluminum coupling agent and the titanium coupling agent one or more.Strengthen film composition through containing silane coupler, aluminum coupling agent etc., can further improve the adaptation of strengthening membrane reflectance coating.Therefore, after forming a plurality of luminescent layers on 1 light-transmitting substrate, form slot segmentation from the reflectance coating side at light-transmitting substrate, use when being divided into the operation of each light-emitting component, can suppress strengthening membrane and peel off from reflectance coating through cutting.
In addition, strengthen film composition and can contain one or more particulate or the flat particle that is selected from silicon dioxide granule, silicate particles, metallic or the metal oxide particle.For example, strengthen film composition and can contain one or more particulate or the flat particle that is selected from cataloid, aerosil particle, silicon dioxide granule, mica particle and the montmorillonite particle.Cataloid is SiO
2Or the colloid of its hydrate, average grain diameter is 1～100nm, is preferably 5～50nm, does not have certain structure.The aerosil particle is with silicon chloride gasification, oxidized and generate under gas phase state in the flame of high temperature, and average grain diameter is 1～50nm, is preferably 5～30nm.Silicon dioxide granule is that average grain diameter is the particle of 1～100nm, preferred 5～50nm.Mica particle is that the average grain diameter for preparing through synthetic method is the particle of 10～50000nm, and preferred average diameter is that 1～20 μ m and average thickness are the flat particle of 10～100nm.The montmorillonite particle is to have a kind of with the ion exchangeable laminar silicic acid salt compound of the overlapping abreast crystalline texture of weak each other bonding force of the face that constitutes through ionic bond etc.; Be that average grain diameter is the particle of 10～100000nm, preferred average diameter is that 1～20 μ m and average thickness are the flat particle of 10～100nm.Strengthen film composition through containing cataloid, aerosil particle etc., can further increase the hardness of strengthening membrane.Therefore, form separating tank through cutting after, promptly use air knife etc. to remove overlap (バ リ) or the sediment that remains on this separating tank because the mar proof and the resistance to impact of strengthening membrane are good, can not lack the edge part in the separating tank of strengthening membrane.With respect to strengthening film composition 100 mass parts, their addition is preferably 0.1～30 mass parts, more preferably 0.2～20 mass parts.Be difficult to obtain effect during less than 0.1 mass parts, on the other hand, if surpass 30 mass parts, then adaptation is prone to reduce.And in the present invention, the average grain diameter of each particle and each particulate is measured as follows.(the hole field makes made, model: LA-950) measure the 50% average grain diameter (D that the particle diameter benchmark calculates with the number form with laser diffraction/diffuse transmission type particle size distribution device
50).Utilize the value of the number benchmark average grain diameter that this laser diffraction/diffuse transmission type particle size distribution device obtains, roughly consistent with the average grain diameter during to 50 particles actual measurement particle diameters arbitrarily in the image of observing through scanning electron microscope (the Ha ィ テ of Hitachi Network ノ ロ ジ one ズ system, model: S-4300SE and S-900).In addition, the average diameter of above-mentioned flat particle and average thickness, after state each flat particulate average diameter and average thickness also likewise measure with above-mentioned.
And, the scope that the average grain diameter of cataloid is defined as 1～100nm be because, colloid is unstable and be prone to cohesion during less than 1nm, then particle diameter not be greatly, can form dispersion liquid if surpass 100nm.In addition; With the size of aerosil particle, silicon dioxide granule, mica particle, montmorillonite particle be defined as above-mentioned scope be because; These sizes are the particle sizes that can access, perhaps in order to make them can be greater than the size range of the thickness of the film (reflectance coating) of lower floor.
Further; Strengthen film composition and can contain particulate or flat particulate, this particulate or flat particulate contain one or more metal or the oxide of these metals that is selected from gold, platinum, palladium, ruthenium, nickel, copper, tin, indium, zinc, iron, chromium, manganese and the aluminium.The average grain diameter of these particulates is set at the scope of 1～50000nm, preferred 100～5000nm.The average diameter of flat particulate is preferably 1～50000nm, and the average thickness of flat particulate is preferably 100～20000nm.Strengthen film composition through containing the particulate or the flat particulate of gold, platinum etc., can further give flexibility strengthening membrane.Therefore, during cutting, even strengthening membrane is produced stress, ductility and the malleability of utilizing strengthening membrane to have can discharge stress.Wherein, it is because the size of resulting particulate is defined that the size of the particulate of metal is defined as above-mentioned scope, and it is owing to form the size range that can not surpass reflectance coating thickness that the size of the flat particulate of metal is defined as above-mentioned scope.The addition of these particulates or flat particulate is preferably 0.1～30 mass parts, more preferably 0.2～20 mass parts.This be because, be difficult to obtain effect during less than 0.1 mass parts, on the other hand,, then be prone to reduce adaptation if surpass 30 mass parts.In addition, the content in the particulate of metal or metal oxide or the flat particulate is defined as that 70 quality % are above, the scope of preferred 80～100 quality %.This be because, during less than 70 quality %, the processability of strengthening membrane reduces.
In the scope of not damaging the object of the invention, and then as required, strengthen film composition and can cooperate oxidation inhibitor, levelling agent, thixotropic agent, Stress Release agent, other additive etc.
[light-emitting component]
Light-emitting component of the present invention possesses luminescent layer, light-transmitting substrate and reflection successively by the reflection of light film that luminescent layer sends, and it is characterized in that reflectance coating contains metal nanoparticle.
Fig. 1 representes the sectional view of an example of light-emitting component.Light-emitting component 1 possesses reflectance coating 10, light-transmitting substrate 20, luminescent layer 30 successively.Usually, reflectance coating 10 utilizes adhesive linkage 50 to engage with supporting substrate 60, after luminescent layer 30 forms the wiring of expectation, is sealed material 40 sealings.
Fig. 2 representes the sectional view of a preferred example of light-emitting component.Light-emitting component 2 is if possess strengthening membrane 12, reflectance coating 11, substrate 21, luminescent layer 31 successively; Then through strengthening membrane 12; Can improve thermal endurance, the corrosion resistance of reflectance coating 11; And then can improve light-transmitting substrate and reflectance coating adaptation, suppress reflectance coating 11 in the cutting action from the peeling off of substrate 21, therefore preferred.And strengthening membrane 12 be if containing adhesive can pass through the manufacturing of wet type rubbing method, so more preferably, yet even also can improve thermal endurance, the corrosion resistance of reflectance coating 11 through manufacturings such as vacuum film formation methods.In formation shown in Figure 2, strengthening membrane 12 engages with supporting substrate 61 through adhesive linkage 51, after luminescent layer 31 forms the wiring of expectation, with 41 sealings of sealing material.
< reflectance coating >
The reflectance coating reflection is through the light of the luminescent layer of matrix.Reflectance coating contains metal nanoparticle, and then preferably contains additive.Metal nanoparticle, additive are as stated.
With respect to nesa coating 100 mass parts, additive contain proportional 0.1～25 mass parts that is preferably, more preferably 0.2～10 mass parts.If more than 0.1 mass parts, then the bonding force with nesa coating is good, if the film of 25 mass parts during with next difficult generation film forming is uneven.
Consider that from the viewpoint of reflectivity, conductivity the thickness of reflectance coating is preferably 0.05～1.0 μ m, more preferably 0.1～0.5 μ m.
If be present in the average diameter of pore of face of the light-transmitting substrate side of reflectance coating and be below the 100nm, mean depth is below the 100nm, number density is 30/μ m
2, then in the scope of wavelength 380～780nm, can reach the high diffuse reflectance more than 80% of theoretical reflectivity, so preferred.Usually reflectance spectrum shows the high project of reflectivity, shows the low project of reflectivity at short wavelength side at long wavelength side.If the average diameter of pore surpasses 100nm, then, can not obtain good reflectivity, so preferred average diameter is below the 100nm because the flex point that reflectivity begins to reduce moves to longer wavelength side.In addition, if the mean depth of pore surpasses 100nm, then, can not get good reflectivity, so the mean depth of pore is preferably below the 100nm because the slope (gradient) of reflectance spectrum increases.If the number density of pore surpasses 30/μ m
2, then, can not get good reflectivity, so the number density of pore is preferably 30/μ m because the reflectivity of long wavelength side reduces
2Below.
< strengthening membrane >
Strengthening membrane improves the thermal endurance and the corrosion resistance of reflectance coating, is suppressed at peeling off of reflectance coating when using cutting in the manufacturing process of light-emitting component.Strengthening membrane contains adhesive, and adhesive as stated.
For example; When containing the adhesive of polymer class, can also contain and be selected from acrylic polymer, epoxide polymer, polyurethane polymer, acroleic acid polyurethane base polymer, epoxy acrylic base polymer, cellulosic polymer and the type siloxane polymer one or more.In addition, can also contain the inorganic of polymer class adhesive is that base material or the inorganic of non-polymer class adhesive are base material.
In addition, as to strengthening shown in the film composition explanation, can also contain being selected from one or more particulate or the flat particle in silica-based particle, silicate particles, metallic or the metal oxide particle.
Consider that from the viewpoint of thermal endurance, corrosion resistance the thickness of strengthening membrane is preferably 0.01～0.5 μ m, more preferably 0.01～0.2 μ m.
[manufacturing approach of light-emitting component]
The manufacturing approach of light-emitting component of the present invention is characterised in that; After containing the reflection film composition of metal nanoparticle and additive through wet type rubbing method coating on the light-transmitting substrate; Reflectance coating is burnt till or solidify to form in utilization, forms luminescent layer at the opposing face of the reflectance coating of light-transmitting substrate.
At first, on light-transmitting substrate, contain metal nanoparticle, preferably contain the reflection film composition of additive through wet type rubbing method coating.The coating here is 0.05～1.0 μ m with the thickness after burning till preferably, and more preferably the mode of 0.1～0.5 μ m is carried out.Then, this is filmed under 120～350 ℃ of temperature, preferred 150～250 ℃ dry 5～60 minutes, preferred 15～40 minutes.So form reflectance coating.
Light-transmitting substrate is still considered from the viewpoint of light transmission, exothermicity if can form luminescent layer does not then limit especially, is preferably sapphire substrate.
The reflection film composition can pass through the composition that coating blender, ball mill, sand mill, centrifugal grinding mills, triple-roller mill (three ロ one Le) etc. mix to be expected according to common method, and dispersion light transmission adhesive, according to circumstances disperses the transparent conductivity particle to wait to make.Certainly, also can make through common stirring operation.And, if after mixing the composition except metal nanoparticle, mixes with the decentralized medium that contains the metal nanoparticle that disperses in advance in addition, then consider preferably from the viewpoint of the reflection film composition of the homogeneous that is easy to get.
The wet type rubbing method is preferably any one in spraying process, point gum machine rubbing method (デ ィ ス ペ Application サ one コ one テ ィ Application グ method), spin-coating method, knife coating, slot coated method, ink-jet application method, screen painting method, hectographic printing method or the mold rubbing method; But be not limited to this, all methods capable of using.
Spraying process is the reflection film composition to be nebulized and coat on the light-transmitting substrate or dispersion itself pressurizeed through compressed air to nebulize and coat the method on the light-transmitting substrate; The point gum machine rubbing method is for example to be injected in the syringe and the piston of pushing this syringe to coat the method on the light-transmitting substrate from the minute nozzle of the syringe front end dispersion that spues through reflecting film composition.Spin-coating method is the reflection film composition that on the light-transmitting substrate of rotation, drips; Use method for compositions through its centrifugal force to this reflectance coating that drips of light-transmitting substrate circumferential expansion; Knife coating is that the light-transmitting substrate that separates predetermined gap with the front end of scraper is set in the horizontal direction movably; To supplying with the reflection film composition, the method that light-transmitting substrate is moved horizontally towards the downstream on more near the light-transmitting substrate of upstream side than this scraper.The slot coated method is to make the reflection film composition flow out and coat the method on the light-transmitting substrate from narrow slit; The ink-jet application method is that the reflection film composition is filled in the print cartridge of commercially available ink-jet printer, on light-transmitting substrate, carries out the method for ink jet printing.The screen painting method is to utilize yarn to indicate material as pattern, will reflect method that film composition be transferred to light-transmitting substrate through the domain picture that makes above that.The hectographic printing method is not make the reflection film composition that invests on the version directly be attached to light-transmitting substrate; But carry out once transfer printing, and transfer to the printing process of the water proofing property of the utilization reflection film composition on the light-transmitting substrate again from film from version to film.The mold rubbing method is to distribute through manifold to be supplied to the reflection film composition in the mould, is extruded on the film method that the surface of the light-transmitting substrate of advancing is coated with through slit.The mold rubbing method has slotted coating method or slidingtype coating method, curtain formula coating method.
At last, the light-transmitting substrate that will have a reflective coating film is in atmosphere or in the inert gas atmospheres such as nitrogen or argon gas, preferably 130～250 ℃, more preferably under 180～220 ℃ temperature, keep 5～60 minutes, preferably keep burning till in 15～40 minutes.And adhesive can be in more low temperature curing down during through reaction such as hydrolysis.
Make the firing temperature with the light-transmitting substrate of filming be 130～250 ℃ scope be because, when being lower than 130 ℃, in reflectance coating, producing and solidify inadequate bad problem.In addition, if surpass 250 ℃, then can not produce advantage in the production of so-called low temperature process, promptly cause manufacturing cost to increase, productivity ratio descends.And, be that To Be Protected from Heat because luminescent layer compares, because of the firing process luminous efficiency descends.
Make the firing time with the light-transmitting substrate of filming be 5～60 minutes scope be because, when firing time is lower than lower limit, in reflectance coating, produces adhesive and burn till inadequate bad problem.Surpass higher limit as if firing time, then manufacturing cost increases to necessary above and productivity ratio decline, and, the bad problem that the luminous efficiency of generation luminescent layer descends.
The method that opposing face at the reflectance coating of light-transmitting substrate is formed luminescent layer does not limit especially, can be known Metalorganic chemical vapor deposition method (MOCVD), hydride gas phase epitaxial growth method (HVPE), molecular beam epitaxial growth method methods such as (MBE).
Thus; Manufacturing approach of the present invention is through using the wet type rubbing method; Owing to can get rid of vacuum vapour deposition, sputtering method equal vacuum technology as much as possible, therefore can make reflectance coating more at an easy rate, can be easily make thermal endurance of the present invention, light-emitting component that corrosion resistance is high with low cost.And when light-emitting component and other part bonding, if directly through high-temperature solder Au-Sn solder bonds reflectance coating, then reflectance coating might be corroded by the Au-Sn scolder, so not preferred.
In addition; If after forming reflectance coating, form luminescent layer before; And then after containing the reinforcement film composition of adhesive through wet type rubbing method coating on the reflectance coating, utilize and burn till or solidify to form strengthening membrane, then owing to can further improve thermal endurance, the corrosion resistance of light-emitting component; And then be suppressed at peeling off of reflectance coating when using cutting in the manufacturing process of light-emitting component, so preferred.
The adhesive of strengthening membrane as stated; Manufacturing approach, the wet type rubbing method of strengthening film composition are identical with the reflection film composition; Just under the situation of strengthening film composition, be preferably 0.01～0.5 μ m with the thickness after burning till, more preferably the mode of 0.01～0.2 μ m is carried out.And, can also suitably select the heating means or the ultraviolet irradiation method that are used to solidify according to the kind of the adhesive of strengthening film composition.
And; Additive as the particle that in the substrate liquid of strengthening film composition, adds above-mentioned necessity, particulate, flat particulate etc.; Thereby make these additives be dispersed in the method in the substrate liquid, can enumerate to disperse to stir and wait the shearing of dispersion, planet stirring or the triple-roller mill etc. that utilize wing stirring to carry out to disperse, comprise the dispersion that utilizes pearl of ball mill or coating blender etc.In addition, can also adopt and to utilize the said method dispersion liquid that dispersing additive forms in the solvent composition in substrate liquid in advance to carry out method of mixing.Further, additive itself has become under the situation of the dispersion liquid that disperses through appropriate solvent, except said method, can use the liquid mixing method of utilizing ultrasonic homogenizer or ultrasonic vibration to carry out.
As stated,, nesa coating be can make more at an easy rate, can be easily thermal endurance, light-emitting component that corrosion resistance is higher be made with low cost through using the wet type rubbing method.
[embodiment]
Below through embodiment the present invention is specified, but the present invention not limit by them.
[embodiment 1]
At first make the reflection film composition.Below represent production order.
< making of reflection film composition >
Silver nitrate is dissolved in the deionized water preparation aqueous metal salt.In addition, natrium citricum is dissolved in the deionized water, preparation concentration is the sodium citrate aqueous solution of 26 quality %.In remaining 35 ℃ stream of nitrogen gas, in this sodium citrate aqueous solution, directly add granular ferrous sulfate and make its dissolving, preparation contains the reducing agent aqueous solution of citrate ions and ferrous ion with 3: 2 mol ratio.
Then, when above-mentioned stream of nitrogen gas is remained on 35 ℃, in the reducing agent aqueous solution, add the stirrer of magnetic stirring apparatus, when stirring with the rotating speed 100rpm of stirrer, the above-mentioned aqueous metal salt that in this reducing agent aqueous solution, drips mixes.At this, the concentration of each solution is adjusted so that aqueous metal salt is below 1/10 of amount of the reducing agent aqueous solution to the addition of the reducing agent aqueous solution, thus, even the aqueous metal salt of the room temperature of dripping also can remain on 40 ℃ with reaction temperature.In addition, the mixing ratio of the reducing agent aqueous solution and aqueous metal salt is adjusted so that the mol ratio of the citrate ions of the reducing agent aqueous solution and ferrous ion all is 3 times of moles with respect to the total atom valence mumber of the metal ion in the aqueous metal salt.Aqueous metal salt and then continued to mix liquid 15 minutes after dripping of the reducing agent aqueous solution finished, thus, at the inner Nano silver grain that produces of mixed liquor, obtain being dispersed with the Nano silver grain dispersion liquid of Nano silver grain thus.The pH of Nano silver grain dispersion liquid is 5.5, and the stoichiometry growing amount of the Nano silver grain in the dispersion liquid is the 5g/ liter.
The Nano silver grain dispersion liquid that obtains is at room temperature placed, and makes the Nano silver grain sedimentation in the dispersion liquid thus, through decant to sedimentation the condensation product of Nano silver grain separate.In the nano grain of silver subcondensation that has separated, add deionized water and form dispersion, carry out desalting processing through ultrafiltration after, nano grain of silver subcondensation and then carry out displacement washing with methyl alcohol, the content that makes metal (silver) is 50 quality %.Then, use centrifugal separator, adjust the centrifugal force of this centrifugal separator, the bigger silver particles that particle diameter is surpassed 100nm is separated, and thus, the content of the Nano silver grain in primary particle size 10～50nm scope is adjusted into according to number on average counts 71%.That is, will be adjusted into 71% with respect to whole Nano silver grain 100% shared ratios, obtain the Nano silver grain dispersion liquid according to the Nano silver grain in the average meter of number primary particle size 10～50nm scope.The Nano silver grain that obtains is carried out chemical modification by the protective agent of natrium citricum.
Then, this metal nanoparticle is disperseed, make the reflection film composition through the metal nanoparticle that obtains 10 mass parts being added be mixed into.And the metal nanoparticle that constitutes the reflection film composition contains the above metal nanoparticle of 75 quality %.
For the reflection film composition, on glass substrate, form reflective coating film through spin-coating method, in nitrogen atmosphere, burnt till under 200 ℃ 20 minutes, obtain the reflectance coating of thickness 200nm thus.At this, the mensuration of thickness is measured through the cross-section of utilizing the Ha ィ テ of Hitachi Network ノ ロ ジ one ズ system scanning electron microscope (SEM, device name: S-4300, SU-8000) to carry out.In other embodiment, comparative example, likewise measure thickness.
[embodiment 2]
After likewise making the Nano silver grain dispersion liquid with embodiment 1; Through the metal nanoparticle that obtains 10 mass parts being added be mixed into this metal nanoparticle is disperseed; In this dispersion liquid, add polyvinylpyrrolidone (PVP, molecular weight 360000), tin acetate, thereby make the reflection film composition with the ratio that forms metal nanoparticle 96 mass parts, PVP 4 mass parts.And the metal nanoparticle that constitutes the reflection film composition contains the above metal nanoparticle of 75 quality %.Then, likewise carry out, obtain the reflectance coating of thickness 100nm with embodiment 1.
[embodiment 3]
After likewise making the Nano silver grain dispersion liquid with embodiment 1; Through the metal nanoparticle that obtains 10 mass parts being added be mixed into this metal nanoparticle is disperseed; In this dispersion liquid, add zinc acetate, thereby make the reflection film composition with the ratio that forms metal nanoparticle 95 mass parts, zinc acetate 5 mass parts.Then, likewise carry out, obtain the reflectance coating of thickness 200nm with embodiment 1.
Then, make the reinforcement film composition.Below represent production order.
< strengthening the making of film composition >
With neopentylglycol diacrylate as starting monomer, at PGME 100cm
3Middle dissolving 10g adds 1-hydroxyl-cyclohexyl-phenyl-ketone 0.5g, remains on 50 ℃, keeps 1 hour the synthesizing propylene acid resin in the time of vigorous stirring.Using this acrylic resin of ethanol dilution is 1 quality % to form solid component concentration, strengthens film composition thereby make.
On reflectance coating, make reinforcement film composition film forming with spin coater.Further, under 150 ℃, burnt till 10 minutes, film is strengthened.
[embodiment 4]
After likewise making the Nano silver grain dispersion liquid with embodiment 1; Through the metal nanoparticle that obtains 10 mass parts being added be mixed into this metal nanoparticle is disperseed; In this dispersion liquid, add copper acetate, thereby make the reflection film composition with the ratio that forms metal nanoparticle 95 mass parts, copper acetate 5 mass parts.Then, likewise carry out, obtain the reflectance coating of thickness 150nm with embodiment 1.
Then, as the SiO that strengthens film composition
2Bond is prepared as follows.Use 500cm
3Glass four neck flasks; The tetraethoxysilane and the ethanol of 140g that add 140g, in the time of stirring with 60% nitric acid dissolve also disposable adding in the pure water of 120g of 1.7g, then; 50 ℃ were reacted 3 hours down, and preparation is as the SiO that strengthens film composition thus
2Bond.
On reflectance coating, make electrically conducting transparent film composition film forming, under 160 ℃, burnt till 30 minutes, thereby obtain the nesa coating of thickness 100nm with spin-coating method.
[embodiment 5～6,17]
Except the composition that forms table 1 record, thickness, likewise carry out with embodiment 4, make embodiment 5～6,17.And, the SiO that uses among the embodiment 5
2Bond uses the SiO that uses among the embodiment 4
2Bond.
[embodiment 7～16,18～20]
Except the composition that forms table 1 record, thickness, likewise carry out with embodiment 3, make embodiment 7～16,18～20.At this, use neopentylglycol diacrylate in the acrylic compounds of strengthening using in the film composition, use bisphenol A type epoxy resin in the epoxies, use methylcellulose in the cellulose family, use diphenylmethane isocyanate and methylphenol in the polyurethanes.
[embodiment 21]
Except the composition that forms table 1 record, thickness, likewise carry out with embodiment 2, make embodiment 21.And, the SiO that uses in the present embodiment
2Bond uses the SiO that uses among the embodiment 4
2Bond.
[comparative example 1]
On glass substrate, form the silver-colored film of thickness 100nm through the sputtering method of vacuum film formation method.
[comparative example 2]
On glass substrate, form the silver-colored film of thickness 100nm through sputtering method, and then pass through the titanium film that sputtering method forms thickness 30nm.
[mensuration of reflectivity]
For the evaluation of the reflectivity of embodiment 1～21, comparative example 1～2,, measure the diffuse reflectance of the reflectance coating under the wavelength 450nm through the combination of ultraviolet-uisible spectrophotometer and integrating sphere.In addition, 200 ℃, 1000 hours condition is heat-treated test, under hydrogen sulfide 10ppm, 25 ℃ of temperature, relative humidity 75%RH, 504 hours condition, carries out the sulfuration test as corrosion resistance test, measures the reflectivity after each test.Their result of table 1 expression.
[adaptation evaluation]
For the adaptation evaluation; Through method according to tape test (JIS K-5600), to measuring embodiment 2, the embodiment 5 behind the reflectivity, with the adhesive tape driving fit to film and when peeling off; Peel off or the degree of crimped configuration according to the film that forms, estimate with excellent, three levels of passing, fail.To not paste film in the adhesive tape side forms thing, only situation that jointing tape is stripped from is arranged as excellent; The situation of the state that the photoelectric conversion layer of peeling off and form base material that will mix has jointing tape exposes will be failed owing to the situation conduct that peeling off of jointing tape exposed the whole surface of the opto-electronic conversion laminar surface that forms base material as qualifying.Embodiment 2 is for passing, and embodiment 5 is excellent.
[table 1]
Can be known that by table 1 among embodiment 1, the embodiment 2, the reflectivity after initial stage, the heat treatment is high, the reflectivity after the sulfuration test also is about 30%.Therewith relatively, though the reflectivity at 1 initial stage of comparative example of making through sputtering method is high, the deterioration after the heat treatment is big, and the reflectivity after the sulfuration test significantly reduces, is 14%.Can know that in addition among the embodiment 3～21, the reflectivity after initial stage, the heat treatment, after the sulfuration test is all very high, thermal endurance and corrosion resistance are very high, and the temperature rising that the luminescent layer owing to high-output power is caused also is the few light-emitting component of deterioration.Therewith relatively, through the comparative example 2 that sputtering method is made, the reflectivity after the sulfuration test is low, be 65%.
Light-emitting component of the present invention possesses the reflectance coating that contains metal nanoparticle between light-transmitting substrate and luminescent layer; Even be the light-emitting component of high-output power thus; Also can improve thermal endurance, corrosion resistance, can suppress because the deterioration of the reflectance coating that heat that is produced by luminescent layer or environment bring.This reflectance coating can utilize the wet type rubbing method to make, and therefore can make manufacturing process easy, and cost is low.In addition, between luminescent layer and reflectance coating and then possess the nesa coating that contains the light transmission adhesive, therefore can further improve thermal endurance, light resistance, be very useful.
Claims (15)
1. a reflection film composition that is used for light-emitting component is characterized in that, is used for possessing successively the light-emitting component of the reflection of light film that luminescent layer, light-transmitting substrate and reflection sent by luminescent layer, and the reflection film composition contains metal nanoparticle.
2. the reflection film composition that is used for light-emitting component according to claim 1, and then contain additive.
3. the reflection film composition that is used for light-emitting component according to claim 1 and 2, and then contain decentralized medium.
4. reinforcement film composition that is used for light-emitting component, the reflection of light film that be used for possessing luminescent layer successively, light-transmitting substrate, reflection is sent by luminescent layer and the light-emitting component of strengthening membrane are strengthened film composition and are contained adhesive.
5. the reinforcement film composition that is used for light-emitting component according to claim 4 is characterized in that, contains one or more particulate or the flat particle that is selected from silica-based particle, silicate particles, metallic or the metal oxide particle.
6. a light-emitting component is characterized in that, possesses the reflection of light film that luminescent layer, light-transmitting substrate and reflection are sent by luminescent layer successively, and reflectance coating contains metal nanoparticle.
7. light-emitting component according to claim 6, reflectance coating and then contain additive.
8. according to claim 6 or 7 described light-emitting components, and then have strengthening membrane, possess said luminescent layer, said light-transmitting substrate, said reflectance coating and said strengthening membrane successively, said strengthening membrane contains adhesive.
9. light-emitting component according to claim 8 is characterized in that, said strengthening membrane and then contain is selected from one or more particulate or the flat particle in silica-based particle, silicate particles, metallic or the metal oxide particle.
10. according to claim 6 or 7 described light-emitting components, said reflectance coating is made through the wet type rubbing method.
11. light-emitting component according to claim 8, said reflectance coating and/or strengthening membrane are made through the wet type rubbing method.
12. according to claim 6 or 7 described light-emitting components, the thickness of reflectance coating is 0.05～1.0 μ m.
13. light-emitting component according to claim 8, the thickness of reflectance coating are 0.05～1.0 μ m.
14. the manufacturing approach of a light-emitting component; It is characterized in that; After utilizing wet type rubbing method coating to contain the reflection film composition of metal nanoparticle and additive on the light-transmitting substrate, through burning till or solidify to form reflectance coating, at the opposing face formation luminescent layer of the reflectance coating of light-transmitting substrate.
15. the manufacturing approach of light-emitting component according to claim 14; After forming reflectance coating, form before the luminescent layer; And then after utilizing the coating of wet type rubbing method to contain the reinforcement film composition of adhesive on the reflectance coating, through burning till or solidify to form strengthening membrane.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011037725A JP5741810B2 (en) | 2011-02-23 | 2011-02-23 | REFLECTIVE FILM COMPOSITION FOR LIGHT EMITTING ELEMENT, LIGHT EMITTING ELEMENT, AND METHOD FOR PRODUCING LIGHT EMITTING ELEMENT |
| JP2011-037725 | 2011-02-23 |
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| Publication Number | Publication Date |
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| CN102651441A true CN102651441A (en) | 2012-08-29 |
| CN102651441B CN102651441B (en) | 2016-09-21 |
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| CN201210041065.1A Expired - Fee Related CN102651441B (en) | 2011-02-23 | 2012-02-21 | Composition for reflective film, light-emitting component and manufacture method thereof for light-emitting component |
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| Country | Link |
|---|---|
| JP (1) | JP5741810B2 (en) |
| KR (1) | KR101739149B1 (en) |
| CN (1) | CN102651441B (en) |
| TW (1) | TWI537346B (en) |
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| CN106756714A (en) * | 2016-11-30 | 2017-05-31 | 佛山市高明区诚睿基科技有限公司 | A kind of preparation method of the stainless steel material with surface insulation layer |
| CN107407479A (en) * | 2015-03-31 | 2017-11-28 | 优志旺电机株式会社 | Fluorescence light source device |
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| JP5169389B2 (en) * | 2007-04-19 | 2013-03-27 | 三菱マテリアル株式会社 | Method for manufacturing conductive reflective film |
| JP2010123605A (en) * | 2008-11-17 | 2010-06-03 | Seiko Instruments Inc | Light-emitting device and method of manufacturing the same |
| WO2011010659A1 (en) * | 2009-07-21 | 2011-01-27 | 日亜化学工業株式会社 | Method for producing conductive material, conductive material obtained by the same method, electronic device containing the conductive material, and light-emitting device |
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- 2012-02-20 KR KR1020120017069A patent/KR101739149B1/en active IP Right Grant
- 2012-02-21 CN CN201210041065.1A patent/CN102651441B/en not_active Expired - Fee Related
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| JP2008191592A (en) * | 2007-02-07 | 2008-08-21 | Hitachi Ltd | Optical member |
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| CN107407479A (en) * | 2015-03-31 | 2017-11-28 | 优志旺电机株式会社 | Fluorescence light source device |
| CN107407479B (en) * | 2015-03-31 | 2018-09-28 | 优志旺电机株式会社 | Fluorescent light source device |
| CN106756714A (en) * | 2016-11-30 | 2017-05-31 | 佛山市高明区诚睿基科技有限公司 | A kind of preparation method of the stainless steel material with surface insulation layer |
| CN106756714B (en) * | 2016-11-30 | 2018-12-28 | 佛山市高明区诚睿基科技有限公司 | A kind of preparation method of the stainless steel material with surface insulation layer |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI537346B (en) | 2016-06-11 |
| KR101739149B1 (en) | 2017-06-08 |
| KR20120096891A (en) | 2012-08-31 |
| CN102651441B (en) | 2016-09-21 |
| TW201247792A (en) | 2012-12-01 |
| JP2012175007A (en) | 2012-09-10 |
| JP5741810B2 (en) | 2015-07-01 |
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