WO2011125452A1 - 表面処理蛍光体及び表面処理蛍光体の製造方法 - Google Patents
表面処理蛍光体及び表面処理蛍光体の製造方法 Download PDFInfo
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- WO2011125452A1 WO2011125452A1 PCT/JP2011/056409 JP2011056409W WO2011125452A1 WO 2011125452 A1 WO2011125452 A1 WO 2011125452A1 JP 2011056409 W JP2011056409 W JP 2011056409W WO 2011125452 A1 WO2011125452 A1 WO 2011125452A1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/77342—Silicates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F13/00—Illuminated signs; Luminous advertising
- G09F13/04—Signs, boards or panels, illuminated from behind the insignia
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/15—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components having potential barriers, specially adapted for light emission
-
- 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
- H01L33/48—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 semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
-
- 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
- H01L2933/0033—Processes relating to semiconductor body packages
- H01L2933/0041—Processes relating to semiconductor body packages relating to wavelength conversion elements
Definitions
- the present invention relates to a surface-treated phosphor with significantly improved moisture resistance and a method for producing the surface-treated phosphor.
- white LEDs semiconductor light-emitting elements that emit white light have attracted attention as next-generation light sources because they have advantages such as low power consumption, high efficiency, environmental friendliness, and long life.
- a method for producing white light in a white LED a method of combining a blue or ultraviolet LED and a phosphor (red, yellow, green phosphor, etc.) that can be excited by the light is generally used.
- silicate (also called silicate) phosphors having alkaline earth metal elements are attracting attention because they have characteristics such as easy emission of a wide range of emission wavelengths by composition adjustment and high emission efficiency.
- silicate fluorescence having a structure such as (Sr, Ba, Ca) 2 SiO 4 : Eu 2+ described in Patent Document 1 and (Sr, Ba, Ca) 3 SiO 5 : Eu 2+ described in Patent Document 2.
- the body is a typical example.
- the emission wavelength can be tuned by adjusting the relative amount of Sr and Ba or Ca.
- the silicate phosphor having such an alkaline earth metal element has a problem that its surface is easily decomposed and deteriorated by water vapor or moisture in the air. For this reason, when used for a long time in the atmosphere, the emission intensity and the color tone are liable to decrease, the characteristics as a phosphor are lowered, and there is a serious problem in durability.
- a method of improving the moisture resistance of the phosphor there is a method of coating the surface of the phosphor particles with an oxide or the like using a gas phase method (dry method), a liquid phase method (wet method) or the like. It is being considered.
- a method using a vapor phase method aluminum oxide is formed on the surface of sulfide phosphor particles by a method using chemical vapor deposition (CVD) (Patent Document 3) or a method using a plasma method (Patent Document 4).
- CVD chemical vapor deposition
- Patent Document 4 A method for coating a membrane is disclosed.
- liquid phase method examples include a sol-gel reaction method and a neutralization precipitation method.
- Patent Document 5 discloses an alkoxide such as Si and Ti and / or a derivative thereof at a reaction temperature of 0 to 20 ° C.
- a surface treatment method for phosphor particles by hydrolysis and dehydration polymerization in the presence of a large amount of ammonia water is disclosed.
- Patent Document 6 discloses a phosphor having a particulate or layered Si-containing compound placed on its surface.
- Patent Document 7 discloses a method for coating a zirconia film using a sol-gel method.
- Patent Document 8 discloses a method in which an ion-containing acidic solution such as aluminum is added to an alkaline solution in which a phosphor is dispersed, and a metal hydroxide is precipitated on the surface of the phosphor particles by a neutralization reaction. Yes.
- the sol-gel method which is a liquid phase method
- the degree of freedom in selecting the type of coating is large, but the metal alkoxide as a starting material is usually highly reactive, and the phosphor It was very difficult to control the reaction conditions for causing the hydrolysis reaction only on the surface of the particles.
- the film obtained by the sol-gel method usually contains an organic component such as an alkoxyl group left behind due to incomplete hydrolysis or alcohol released by the hydrolysis reaction, and thus it is usually difficult to obtain a dense film. It was.
- An object of the present invention is to provide a surface-treated phosphor that can greatly improve moisture resistance without deteriorating fluorescence properties and has high dispersibility, and a method for producing the surface-treated phosphor. To do.
- the present invention provides a surface-treated phosphor having a surface treatment layer containing at least one specific element selected from Group 3 to 6 elements of the periodic table and fluorine on the surface of the phosphor,
- a surface treatment layer containing at least one specific element selected from Group 3 to 6 elements of the periodic table and fluorine on the surface of the phosphor
- the inventors of the present invention formed a surface treatment layer containing a specific element and fluorine on the surface of the phosphor, and the peak position measured by energy dispersive X-ray elemental analysis was predetermined.
- the peak position measured by energy dispersive X-ray elemental analysis was predetermined.
- the surface-treated phosphor of the present invention has a surface treatment layer containing at least one specific element selected from Group 3 to 6 elements of the periodic table and fluorine on the surface of the phosphor.
- the surface treatment layer contains the specific element and fluorine.
- the surface treatment layer contains fluorine, it is possible to prevent the phosphor from being deteriorated by water in the coating treatment step.
- the coating treatment can be performed in an aqueous solution by forming the surface treatment layer. This eliminates problems such as waste liquid treatment in the case of using an organic solvent.
- the moisture resistance at the time of use of a surface treatment fluorescent substance can be improved because the surface treatment layer containing a fluorine is formed. Since the surface treatment layer has higher stability to water than the silicate phosphor, it contributes to improvement of moisture resistance during use.
- the said surface treatment layer contains a specific element. This is considered due to the fact that the oxide of the specific element is stable.
- the chemical bond of fluoride is basically an ionic bond, and the dissociation tendency is larger than that of the covalently bonded oxide. Therefore, in an atmosphere where moisture or moisture exists. If used for a long time, the hydrolysis reaction of the alkaline earth metal in the fluoride may proceed gradually, which is insufficient to ensure long-term stability.
- the specific element by forming a more stable oxide layer with respect to water, it is possible to impart excellent moisture resistance during long-term use. it can.
- the specific element is at least one selected from elements of Groups 3 to 6 of the periodic table, and among them, elements of Groups 4 and 5 of the periodic table are preferable. Specifically, zirconium, titanium, hafnium, niobium, vanadium, and tantalum are preferable. Further, these elements may be used in combination.
- the specific element is preferably present in an oxide state.
- the oxide of the specific element include zirconium oxide, titanium oxide, hafnium oxide, niobium oxide, vanadium oxide, and tantalum oxide. Of these, zirconium oxide and titanium oxide are particularly preferable.
- the minimum with preferable content of the specific element in the said surface treatment layer is 5.0 weight%, and a preferable upper limit is 85 weight%. If the content of the specific element is less than 5.0% by weight, the long-term stability of moisture resistance may be insufficient, and if it exceeds 85% by weight, the phosphor characteristics of the surface-treated phosphor deteriorate. Sometimes.
- the fluorine is preferably present in the form of an alkaline earth metal fluoride formed from an alkaline earth metal and fluorine ions.
- alkaline earth metal fluoride include a layer made of strontium fluoride, barium fluoride, calcium fluoride, and magnesium fluoride. Of these, strontium fluoride and calcium fluoride are particularly preferable.
- the preferable lower limit of the fluorine content in the surface treatment layer is 1.0% by weight, and the preferable upper limit is 60% by weight. If the fluorine content is less than 1.0% by weight, it may not be possible to completely suppress degradation and degradation of the phosphor due to water during the coating process, and if it exceeds 60% by weight, long-term stability of moisture resistance. May be insufficient.
- the thickness of the surface treatment layer is preferably 0.5 to 5000 nm.
- the thickness is more preferably 1.0 to 3000 nm, still more preferably 5.0 to 1000 nm, and particularly preferably 10 to 500 nm. If the thickness of the surface treatment layer is too thin, the moisture resistance may be insufficient, and if it is too thick, the fluorescent properties of the surface treatment phosphor may deteriorate.
- the maximum peak of the content of the specific element is It is characterized by being located on the surface side of the maximum peak of the content of.
- the “electron microscope and the energy dispersive X-ray elemental analysis attached thereto” are, for example, SEM-EDS (Scanning Electron Microscopy / Energy Dispersive Spectroscopy), or TEM-EDS (Transmission Electroscopy Microscopy). A method using an apparatus is used.
- “maximum peak of content of specific element” or “maximum peak of content of fluorine” is “content of fluorine”. It is assumed that the condition of being located on the surface side of “the maximum peak of” is satisfied.
- the “maximum peak of the content of the specific element” and the “maximum peak of the content of fluorine” satisfy the above-described conditions, thereby suppressing degradation and degradation of the phosphor due to water during the coating process.
- excellent moisture resistance can be imparted to the surface-treated phosphor after coating treatment.
- the surface treatment layer is a single layer and that fluorine is detected at the maximum peak position of the specific element in the element distribution in the cross-sectional thickness direction of the surface treatment layer.
- the affinity of the phosphor after the coating treatment with the sealing resin is improved, and the dispersibility in the sealing resin is improved.
- the minimum with preferable fluorine content in the maximum peak position of a specific element is 0.01 weight%, and a preferable upper limit is 30 weight%.
- the preferable lower limit of the content of the specific element at the maximum peak position is 1.0% by weight, and the preferable upper limit is 75% by weight. By setting it within the above range, a phosphor with little deterioration can be obtained even when used for a long time.
- a preferable lower limit of the content of the fluorine at the maximum peak position is 0.1% by weight, and a preferable upper limit is 50% by weight. By setting it within the above range, degradation and deterioration of the phosphor during the coating treatment process can be suppressed as compared with water, and at the same time, it contributes to improvement of moisture resistance of the surface treatment phosphor.
- the surface treatment layer is preferably a single layer. This is because, for example, in the energy dispersive X-ray elemental analysis, the curve of the content of the specific element and fluorine gradually increases or decreases continuously except at the peak portion, and abrupt changes in content caused by the interlayer interface It can be confirmed by the absence. Such a structure greatly contributes to the adhesion of the surface treatment layer, and the problem of delamination is less likely to occur compared to a structure laminated by a physical method.
- the surface treatment layer may be formed by sequentially forming a fluoride layer and an oxide layer containing an oxide of a specific element in order toward the outermost surface.
- a fluoride layer when processing a phosphor having poor moisture resistance, there is a tendency to avoid the use of an aqueous solution.
- the coating treatment can be performed in an aqueous solution. This eliminates the problem of waste liquid treatment and the like.
- the moisture resistance during use can be improved.
- the fluoride layer is preferably made of an alkaline earth metal fluoride formed from an alkaline earth metal and fluorine ions.
- Specific examples include a layer made of strontium fluoride, barium fluoride, calcium fluoride, and magnesium fluoride. Of these, strontium fluoride and calcium fluoride are preferred.
- a preferable lower limit of the content of fluoride in the fluoride layer is 5% by weight, and a preferable upper limit is 95% by weight.
- a preferable upper limit is 95% by weight.
- the thickness of the fluoride layer is not particularly limited, and is usually preferably 0.5 to 5000 nm. More preferably, it is 1 to 2000 nm, and still more preferably 5 to 1000 nm. If the thickness of the fluoride layer is too thin, the above-described effect of preventing deterioration due to water becomes insufficient, and if it is too thick, the fluorescent properties of the phosphor may be adversely affected.
- the oxide layer preferably contains, for example, zirconium oxide, titanium oxide, hafnium oxide, niobium oxide, vanadium oxide, tantalum oxide, or a composite thereof. Of these, zirconium oxide and titanium oxide are preferable.
- the preferable lower limit of the oxide content in the oxide layer is 10% by weight, and the preferable upper limit is 95% by weight. If the content of the oxide is less than 10% by weight or exceeds 95% by weight, the long-term stability of moisture resistance becomes insufficient.
- the thickness of the oxide layer is not particularly limited, and is usually preferably 0.5 to 5000 nm. More preferably, it is 1.0 to 3000 nm, and still more preferably 5.0 to 1000 nm. If the thickness of the oxide layer is too thin, the effect of preventing deterioration is insufficient, and if it is too thick, the fluorescent properties of the phosphor may be adversely affected.
- a phosphor containing an alkaline earth metal element is preferable.
- Phosphors having such an alkaline earth metal include, for example, sulfide phosphors, aluminate phosphors, nitride phosphors, oxynitride phosphors, phosphate phosphors, and halon phosphates. Examples thereof include salt-based phosphors and silicate-based phosphors.
- a silicate phosphor having an alkaline earth metal element is preferable.
- silicate phosphor having the alkaline earth metal element for example, as a host crystal structure, a structure substantially the same as the crystal structure of M 3 SiO 5 or M 2 SiO 4 (where M is Mg, Ca, Sr and Represents at least one selected from the group consisting of Ba), and Fe, Mn, Cr, Bi, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Examples include phosphors containing at least one selected from the group consisting of Tm and Yb.
- the phosphor having the alkaline earth metal element may contain an appropriate amount of a metal element other than the alkaline earth metal (for example, Zn, Ga, Al, Y, Gd, Tb).
- the phosphor having the alkaline earth metal element may contain a small amount of a halogen element (for example, F, Cl, Br), sulfur (S) or phosphorus (P).
- Examples of the phosphor include an orange phosphor having a composition represented by the following general formula (1), an orange phosphor having a composition represented by the following general formula (2), and the like.
- M is at least one metal selected from the group consisting of Ba, Ca, Mg, and Zn, 0 ⁇ x ⁇ 1.0, and 2.6 ⁇ y ⁇ 3.3.
- M is at least one metal selected from the group consisting of Ba, Ca, Mg and Zn
- D is a halogen anion selected from the group consisting of F, Cl and Br, and 0 ⁇ x ⁇ 1.0 and 2.6 ⁇ y ⁇ 3.3.
- the phosphor include, for example, Sr 3 SiO 5 : Eu 2+ , (Sr 0.9 Mg 0.025 Ba 0.075 ) 3 SiO 5 : Eu 2+ , (Sr 0.9 Mg 0.05 Ba 0.05 ) 2.7 SiO 5 : Eu 2+ , (Sr 0.9 Mg 0.025 Ba 0.075 ) 3 SiO 5 : Eu 2+ , (Sr 0.9 Ba 0.1 ) 3 SiO 5 : Eu 2+ , Sr 0.97 SiO 5 : Eu 2+ F, (Sr 0.9 Mg 0.1 ) 2.9 SiO 5 : Eu 2+ F, (Sr 0.9 Ca 0.1 ) 3.0 SiO 5 : Eu 2+ Orange phosphors having the same composition of F, (Sr 0.4 Ba 0.6 ) 2 SiO 4 : Eu 2+ , (Sr 0.3 Ba 0.7 ) 2 SiO 4 : Eu 2+ , (Sr 0.2 Ba 0.8 ) 2 SiO 4 : Eu 2+
- the particle diameter of the phosphor is not particularly limited, but the median particle diameter (D 50 ) is usually preferably in the range of 0.1 to 100 ⁇ m, more preferably 1.0 to 50 ⁇ m, and still more preferably 5.0. ⁇ 30 ⁇ m.
- D 50 median particle diameter
- the D 50 is too small, not only the luminance decreases, base phosphor itself becomes agglutination reagent, uniform coating processing becomes difficult. Further, when D 50 is too large, dispersibility becomes poor in the resin, which may adversely affect the characteristics of the light emitting device.
- the surface-treated phosphor of the present invention preferably has a water conductivity of 100 mS / m or less when 0.1 part by weight of the phosphor is immersed in 100 parts by weight of pure water for 10 minutes.
- the water conductivity is 100 mS / m or less, the phosphor is less degraded and degraded by water, and exhibits excellent moisture resistance.
- the electrical conductivity of the water can be measured by, for example, a conductivity meter.
- the elution amount of silicon is 50 ppm or less when 0.1 part by weight of the phosphor is immersed in 100 parts by weight of pure water for 10 minutes.
- the elution amount of the silicon is 50 ppm or less, the phosphor is less decomposed and deteriorated by water and exhibits excellent moisture resistance.
- the surface-treated phosphor of the present invention preferably has an elution amount of strontium of 200 ppm or less when 0.1 part by weight of the phosphor is immersed in 100 parts by weight of pure water for 10 minutes.
- the elution amount of the strontium is 200 ppm or less, the phosphor is less decomposed and deteriorated by water and exhibits excellent moisture resistance.
- the elution amount of silicon and strontium can be measured by, for example, inductively coupled plasma emission spectrometry (ICP, apparatus: ICPS-8000, manufactured by Shimadzu Corporation).
- the surface-treated phosphor of the present invention uses, for example, a method having a step of forming a surface-treated layer by dispersing the phosphor in a solution containing a complex ion containing a specific element and fluorine ions and bringing them into contact with each other. Can be manufactured.
- a method for producing such a surface-treated phosphor is also one aspect of the present invention.
- the complex ion containing the specific element and fluorine ion include, for example, a complex ion having a structure of AF 6 2- (A: at least one specific element selected from elements of Groups 3 to 6 of the periodic table) ) And the like.
- a fluorine-containing solution in which a complex ion having a structure of AO 2 F 4 2 ⁇ or an oxide of a specific element is dissolved may be used.
- the phosphor is AF 6 2- complex ion (A: at least one specific element selected from Group 3 to 6 elements of the periodic table). It can form by performing the process of forming a surface treatment layer by disperse
- AF 6 2- complex ions generate free fluorine ions by the following hydrolysis reaction formula (3) in an aqueous solution.
- the concentration of AF 6 2- complex ions is preferably 0.0005 to 2.0M, more preferably 0.001 to 1.5M, and still more preferably 0.005 to 1.0M. If the AF 6 2- complex ion concentration is too low, the free fluorine ion concentration is low, and the rate of the fluoride formation reaction is slow. If the rate of the fluoride formation reaction is too slow, the phosphor may be degraded by hydrolysis during the treatment process. On the other hand, if the AF 6 2-complex ion concentration is too high, or the solution itself becomes unstable, the reaction is too fast, it may be difficult quality film can be obtained.
- the MF 6 2- complex ion gradually undergoes a hydrolysis reaction as shown in the above formula (3) in an aqueous solution, and finally, AO 2 is formed as shown in the following formula (4).
- the reaction of the following formula (4) proceeds slowly even when no phosphor is present in the solution, and oxide particles are formed.
- the AO 2 oxide is preferentially deposited on the surface of the phosphor.
- the hydrolysis reaction is promoted by the presence of a compound (hydrolysis accelerator) capable of forming a more stable complex with fluorine ions.
- the hydrolysis accelerator used in the present invention can be selected from compounds containing boron (B) or aluminum (Al).
- the compound containing boron and the compound containing aluminum may be used alone or in combination of two or more.
- Examples of the boron-containing compound include boron oxide, sodium tetraborate, boric acid (H 3 BO 3 ), and the like. Of these, boric acid is preferred.
- Examples of the aluminum-containing compound include AlCl 3 , AlBr 3 , aluminum hydroxide (Al (OH) 3 ), and the like.
- the amount of the hydrolysis accelerator with respect to the AF 6 2- complex ion is not particularly limited, but usually the amount of the hydrolysis accelerator with respect to 1 mol of AF 6 2- complex ion is 5 times or less, more preferably 4 times. It is as follows.
- the reaction time may be appropriately adjusted according to the reaction conditions such as the thickness of the target oxide layer, the concentration of the reaction solution, and the temperature, and is usually about 5 minutes to 20 hours, preferably about 10 minutes to 10 hours. is there. In general, if the amount of the prepared phosphor is constant, the film thickness increases as the reaction time increases. If the reaction time is too short, the formation of the surface treatment layer is incomplete. On the other hand, if the reaction time is too long, it is uneconomical.
- the reaction temperature may be appropriately adjusted according to the thickness of the target oxide layer, and is usually about 0 to 90 ° C., preferably about 5 to 70 ° C., more preferably about 10 to 50 ° C. .
- the dispersion conditions during the reaction are not particularly limited as long as the phosphor can be dispersed.
- magnetic stirrer stirring mechanical stirring with a motor, gas barbbling, liquid circulation, ultrasonic dispersion, rotational dispersion such as a ball mill or a rotary mixer, or a combination of the above methods can be used.
- the phosphor is recovered through filtration, washing, and drying steps. Drying may be atmospheric drying or reduced pressure drying.
- the drying temperature is suitably room temperature to 150 ° C.
- the dried phosphor may be further heat-treated at a temperature of 200 to 600 ° C.
- the fluoride is formed. Is preferentially formed. As the fluoride is formed, the fluorine ion concentration in the solution decreases, and the reaction of the above general formula (3) or (4) proceeds to the right. As a result, oxide (AO 2 ) starts to precipitate.
- the surface-treated phosphor of the present invention can be used as a phosphor-containing resin composition by being added to an epoxy resin and / or a silicone resin.
- the said fluorescent substance containing resin composition is used with a well-known form, for example, it may be filled with a dispenser as a paste, or may be processed and laminated
- epoxy resin known ones may be used.
- a hydroxyl, carboxyl or amine-containing compound may be used in the presence of a basic catalyst such as a metal hydroxide (such as sodium hydroxide).
- a metal hydroxide such as sodium hydroxide
- the thing etc. which can be manufactured by making it react with chlorohydrin are mentioned.
- an epoxy resin produced by a reaction between a compound having one or more, preferably two or more carbon-carbon double bonds, and a peroxide (peracid, etc.) is also included.
- the epoxy resin examples include aliphatic epoxy resins, alicyclic epoxy resins, bisphenol-A epoxy resins, bisphenol-F epoxy resins, phenol novolac epoxy resins, cresol-novolak epoxy resins, biphenyl epoxy resins, 4,4 ′. -Biphenyl epoxy resins, polyfunctional epoxy resins, divinylbenzene dioxide and 2-glycidylphenyl glycidyl ether. Of these, alicyclic epoxy resins and aliphatic epoxy resins are preferred. These epoxy resins may be used alone or in combination of two or more. Examples of the aliphatic epoxy resin include compounds having one or more aliphatic groups and one or more epoxy groups.
- Examples include butadiene dioxide, dimethylpentane dioxide, diglycidyl ether, 1,4-butane.
- Examples include diol diglycidyl ether, diethylene glycol diglycidyl ether, and dipentene dioxide.
- Examples of the alicyclic epoxy resin include compounds having one or more alicyclic groups and one or more oxirane groups. Specific examples include 2- (3,4-epoxy) cyclohexyl-5,5-spiro. -(3,4-epoxy) cyclohexane-m-dioxane, 3,4-epoxycyclohexylalkyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6 -Methylcyclohexanecarboxylate, vinylcyclohexane dioxide, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, exo-exo bis (2,3-epoxycyclopentyl) ) Ether, endo-exo bis (2,3- Poxycyclopentyl)
- silicone resin known materials may be used, and examples thereof include a material having a (—SiR 1 R 2 —O—) n polysiloxane skeleton.
- R 1 R 2 preferably has 2 to 10 carbon atoms, particularly 2 to 6 carbon atoms, and includes alkenyl groups such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, acryloxy group, methacryloxy group and the like. Can be mentioned.
- R 2 is preferably one having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group or a cyclohexyl group, an aryl group such as a phenyl group or a tolyl group, Representative examples include an aralkyl group such as a benzyl group.
- the surface-treated phosphor of the present invention is dispersed in at least one resin selected from the group consisting of polyvinyl acetate, polyvinyl butyral, polyethylene, polypropylene, polymethyl methacrylate, polycarbonate, and cyclic olefin copolymer, It can be used as a wavelength conversion complex.
- the wavelength conversion composite is used as an illumination system, a wavelength conversion member for a solar cell, or the like.
- the surface treatment fluorescent substance of this invention may be made into the well-known surface treatment matched with corresponding resin. Further, it may be dispersed in the resin by a known kneading dispersion method.
- the wavelength conversion composite can be used as a wavelength conversion sheet by forming it into a sheet.
- a known method can be used as the method for forming the sheet. Specifically, for example, a master batch composed of the surface-treated phosphor of the present invention and a resin is prepared, and a film is formed by an extruder, and the resin and the surface-treated phosphor of the present invention are dispersed in a solvent for dissolving the resin. The method of casting etc. are mentioned.
- an efficient photoelectric conversion device By using the wavelength conversion composite or the wavelength conversion sheet of the present invention, an efficient photoelectric conversion device can be obtained.
- a photoelectric conversion device is also one aspect of the present invention.
- the wavelength of received light may not necessarily be an efficient wavelength of the element itself.
- the conversion efficiency of the photoelectric conversion device is improved by converting the wavelength of received light into a wavelength that is efficient for the device.
- the conventional phosphor has low moisture resistance and could not be used suitably.
- the surface-treated phosphor of the present invention is dispersed in the encapsulant resin and used on the surface of the solar cell. A battery is obtained.
- a semiconductor light emitting device can be manufactured by forming a phosphor layer using the surface-treated phosphor of the present invention. Such a semiconductor light emitting device is also one aspect of the present invention.
- the phosphor layer is sealed with the surface-treated phosphor of the present invention. By setting it as the structure containing a stop resin, it can be set as the LED light-emitting device excellent in moisture resistance.
- Such an LED light-emitting device is also one aspect of the present invention.
- the LED light-emitting device of the present invention has a luminous intensity retention of 80% or more after being energized for 1000 hours under conditions of a temperature of 60 ° C., a relative humidity of 90%, and a current of 20 mA.
- the luminous intensity retention is less than 80%, the light emission intensity tends to decrease with time during actual use, and the durability may be insufficient.
- the luminous intensity retention is preferably 90% or more.
- the luminous intensity retention ratio represents the ratio of luminous intensity before and after energization under the above-mentioned conditions [(luminous intensity after energization / luminance before energization) ⁇ 100], and the luminous intensity is, for example, OL770 manufactured by Optronic Laboratories. It can be measured using a measurement system or the like.
- the LED light emitting device of the present invention preferably has a luminous intensity retention rate of 50% or more after being held for 72 hours in an environment of a temperature of 121 ° C. and a relative humidity of 100%.
- the application of the LED light-emitting device of the present invention is not particularly limited, and can be used in various fields where a normal LED light-emitting device is used. Moreover, you may use individually or in combination. Specifically, for example, it can be used for a liquid crystal display element backlight, an image display device, a lighting device, and the like.
- the liquid crystal display element backlight a known structure can be used. For example, it may be arranged on the frame of the display element and emit light toward the light guide plate, or may be arranged on the back side of the liquid crystal cell with a diffusion plate interposed therebetween.
- An example of the image display device is a liquid crystal display element having at least a liquid crystal cell and the liquid crystal display element backlight.
- Another example includes an LED display that forms an image by regularly emitting light by arranging a plurality of LEDs regularly in two dimensions.
- the lighting device is not particularly limited, and can be applied to a known LED light emitting device. Since the lighting device has high moisture resistance, for example, indicator lights used for transportation and transportation of vehicles and the like, illumination lights, indoor and outdoor lighting used for residences and buildings, mobile phones, mobile communication, etc. It can be used for lighting used for terminals and the like.
- a surface-treated phosphor can be obtained.
- an expensive reaction apparatus is not required, and the coating treatment can be performed in an aqueous solution in a short time. Can be manufactured economically.
- FIG. 2 is a cross-sectional photograph of a cross section of the surface-treated phosphor obtained in Example 1.
- FIG. 3 is element distribution data in a cross-sectional direction of the surface-treated phosphor obtained in Example 1.
- FIG. 4 is a cross-sectional photograph obtained by photographing a cross section of the surface-treated phosphor obtained in Example 2.
- FIG. 3 is element distribution data in a cross-sectional direction of the surface-treated phosphor obtained in Example 2.
- FIG. 4 is a cross-sectional photograph obtained by photographing a cross section of the surface-treated phosphor obtained in Example 3.
- FIG. 3 is element distribution data in a cross-sectional direction of the surface-treated phosphor obtained in Example 3.
- FIG. 4 is a cross-sectional photograph obtained by photographing a cross section of the surface-treated phosphor obtained in Example 4.
- FIG. 4 is element distribution data in the cross-sectional direction of the surface-treated phosphor obtained in Example 4.
- FIG. 6 is a cross-sectional photograph obtained by photographing a cross section of the surface-treated phosphor obtained in Example 5.
- FIG. 6 is element distribution data in the cross-sectional direction of the surface-treated phosphor obtained in Example 5.
- FIG. 6 is a cross-sectional photograph obtained by photographing a cross section of the surface-treated phosphor obtained in Example 6.
- FIG. 7 is a cross-sectional photograph obtained by photographing a cross section of the surface-treated phosphor obtained in Example 7.
- FIG. 7 is element distribution data in a cross-sectional direction of the surface-treated phosphor obtained in Example 7.
- FIG. 2 is a cross-sectional photograph obtained by photographing a cross section of the surface-treated phosphor obtained in Comparative Example 1.
- FIG. 3 is element distribution data in a cross-sectional direction of the surface-treated phosphor obtained in Comparative Example 1.
- 6 is a cross-sectional photograph obtained by photographing a cross section of the surface-treated phosphor obtained in Comparative Example 2. It is element distribution data of the cross-sectional direction of the surface treatment fluorescent substance obtained in the comparative example 2.
- FIG. 6 is a cross-sectional photograph obtained by photographing a cross section of the surface-treated phosphor obtained in Comparative Example 3.
- Example 1 An orange silicate phosphor (Sr 3 SiO) having a median particle diameter (D 50 ) of about 17 ⁇ m was added to 250 ml of a 0.1 mol / L ammonium fluoride titanate ((NH 4 ) 2 TiF 6 ) and 0.1 mol / L boric acid-containing aqueous solution. 5 : Eu 2+ ) 7.5 g was added. While the mixed solution to which the phosphor was added was dispersed by stirring, the mixture was reacted at 35 ° C. for 2 hours. After the reaction, the phosphor recovered through filtration and washing steps was vacuum-dried at 120 ° C. for 1 hour.
- Sr 3 SiO an orange silicate phosphor having a median particle diameter (D 50 ) of about 17 ⁇ m was added to 250 ml of a 0.1 mol / L ammonium fluoride titanate ((NH 4 ) 2 TiF 6 ) and 0.1 mol / L boric acid-containing aqueous
- the obtained surface-treated phosphor was subjected to “measurement of coating layer thickness and elemental composition analysis in the cross-sectional direction” by the following method, and a surface-treated layer having a thickness of about 180 nm was formed on the surface of the phosphor. I understood.
- the elemental composition curve obtained by the elemental composition analysis in the cross-sectional direction a curve indicating the titanium content and a curve indicating the fluorine content are obtained, and the maximum peak of the titanium content is the fluorine content. It was confirmed that it is located on the surface side of the maximum peak of. In addition, about content of specific elements other than titanium, it was below the detection limit.
- the fluorine content at the maximum peak position of the titanium content was 1.0% by weight.
- An FE-TEM cross-sectional photograph of the obtained surface-treated phosphor is shown in FIG. 1, and elemental analysis results in the cross-sectional direction are shown in FIG.
- ⁇ Measurement of coating layer thickness, cross-sectional elemental composition analysis> The obtained surface-treated phosphor is cut in the cross-sectional direction using a Focused Beam (FIB), and the cut surface is observed with a transmission electron microscope (FE-TEM, JEM-2010FEF). The thickness was measured. In addition, thickness measured 5 points
- the elemental composition of the surface treatment layer is analyzed and identified using energy dispersive X-rays (EDX) attached to the FE-TEM, so that specific elements in the thickness direction (period table 3 to 3) are identified. A curve of the content of the group 6 element) and fluorine was obtained.
- EDX energy dispersive X-rays
- Example 2 An orange silicate phosphor having a median particle size (D 50 ) of about 17 ⁇ m (main component: main component: 250 ml of 0.1 mol / L ammonium fluoride titanate ((NH 4 ) 2 TiF 6 ) and 0.1 mol / L boric acid-containing mixed aqueous solution. Sr 3 SiO 5 : Eu 2+ ) 7.5 g was added. While the mixed solution to which the phosphor was added was dispersed by stirring, the mixture was reacted at 35 ° C. for 4 hours. After the reaction, the phosphor recovered through filtration and washing steps was vacuum-dried at 120 ° C. for 1 hour.
- Example 3 An orange silicate phosphor (main component: Sr 3 SiO 5 : Eu 2+ ) having a median particle diameter (D 50 ) of about 17 ⁇ m was added to 250 ml of an aqueous solution containing 0.75 mol / L ammonium fluorinated titanate ((NH 4 ) 2 TiF 6 ). 7.5 g was added. While the mixed solution to which the phosphor was added was dispersed by stirring, the mixture was reacted at 35 ° C. for 30 minutes. After the reaction, the phosphor recovered through filtration and washing steps was vacuum-dried at 120 ° C. for 1 hour.
- D 50 median particle diameter
- Example 4 An orange silicate phosphor (main component: Sr 3 SiO 5 : Eu 2+ Cl) having a median particle diameter (D 50 ) of about 17 ⁇ m was added to 250 ml of an aqueous solution containing 1.0 mol / L ammonium fluorotitanate ((NH 4 ) 2 TiF 6 ). ) 7.5 g was added. While the mixed solution to which the phosphor was added was dispersed by stirring, the mixture was reacted at 35 ° C. for 30 minutes. After the reaction, the phosphor recovered through filtration and washing steps was vacuum-dried at 120 ° C. for 1 hour.
- D 50 median particle diameter
- the obtained surface-treated phosphor was subjected to “measurement of the thickness of the coating layer and elemental composition analysis in the cross-sectional direction” in the same manner as in Example 1. As a result, a coating layer having a thickness of about 300 nm was formed on the surface of the phosphor. I found out.
- the elemental composition curve obtained by the elemental composition analysis in the cross-sectional direction a curve indicating the titanium content and a curve indicating the fluorine content are obtained, and the maximum peak of the titanium content is the fluorine content. It was confirmed that it is located on the surface side of the maximum peak of. In addition, about content of specific elements other than titanium, it was below the detection limit. The fluorine content at the maximum peak position of the titanium content was 6.0% by weight.
- An FE-TEM cross-sectional photograph of the obtained surface-treated phosphor is shown in FIG. 7, and elemental analysis results in the cross-sectional direction are shown in FIG.
- Example 5 0.02 mol / L ammonium fluorinated titanate ((NH 4 ) 2 TiF 6 ) and 0.02 mol / L boric acid-containing mixed aqueous solution 250 ml, an orange silicate phosphor having a median particle size (D 50 ) of about 17 ⁇ m (main component: Sr 3 SiO 5 : Eu 2+ ) 7.5 g was added. While the mixed solution to which the phosphor was added was dispersed by stirring, the mixture was reacted at 35 ° C. for 2 hours. After the reaction, the phosphor recovered through filtration and washing steps was vacuum-dried at 120 ° C. for 1 hour.
- D 50 median particle size
- Example 6 An orange silicate phosphor having a median particle diameter (D 50 ) of about 17 ⁇ m (main component: main component: 250 ml of 0.1 mol / L ammonium fluorotitanate ((NH 4 ) 2 TiF 6 ) and 0.2 mol / L boric acid-containing mixed aqueous solution. 1.5 g of Sr 3 SiO 5 : Eu 2+ ) was added. While the mixed solution to which the phosphor was added was dispersed by stirring, the mixture was reacted at 35 ° C. for 2 hours. After the reaction, the phosphor recovered through filtration and washing steps was vacuum-dried at 120 ° C. for 1 hour.
- Example 7 An orange silicate phosphor having a median particle diameter (D 50 ) of about 17 ⁇ m (principal component: main component: 250 ml of 0.1 mol / L ammonium fluoride zirconate ((NH 4 ) 2 ZrF 6 ) and 0.1 mol / L boric acid-containing mixed aqueous solution Sr 3 SiO 5 : Eu 2+ ) 7.5 g was added. While the mixed solution to which the phosphor was added was dispersed by stirring, the mixture was reacted at 35 ° C. for 2 hours. After the reaction, the phosphor recovered through filtration and washing steps was vacuum-dried at 120 ° C. for 1 hour.
- D 50 median particle diameter
- the obtained surface-treated phosphor was subjected to “measurement of coating layer thickness and elemental composition analysis in the cross-sectional direction” in the same manner as in Example 1. As a result, a coating layer having a thickness of about 170 nm was formed on the surface of the phosphor. I found out.
- the elemental composition curve obtained by elemental composition analysis in the cross-sectional direction a curve indicating the zirconium content and a curve indicating the fluorine content are obtained, and the maximum peak of the zirconium content is the fluorine content. It was confirmed that it is located on the surface side of the maximum peak of. The content of specific elements other than zirconium was below the detection limit.
- the fluorine content at the maximum peak position of the zirconium content was 0.6% by weight.
- An FE-TEM cross-sectional photograph of the obtained surface-treated phosphor is shown in FIG. 12, and an elemental analysis result in the cross-sectional direction is shown in FIG.
- Example 8 To 250 ml of hydrofluoric acid aqueous solution in which 0.05 mol / L of vanadium oxide is dissolved, 7.5 g of an orange silicate phosphor (main component: Sr 3 SiO 5 : Eu 2+ ) having a median particle size (D 50 ) of about 17 ⁇ m is added. did. While the mixed solution to which the phosphor was added was dispersed by stirring, the mixture was reacted at 35 ° C. for 30 hours. After the reaction, the phosphor recovered through filtration and washing steps was vacuum-dried at 120 ° C. for 1 hour.
- an orange silicate phosphor main component: Sr 3 SiO 5 : Eu 2+
- Example 9 An orange silicate phosphor (main component: Sr 3 SiO 5 : Eu) having a median particle size (D 50 ) of about 17 ⁇ m was added to 250 ml of an aqueous 0.1 mol / L ammonium fluormolybdate ((NH 4 ) 2 MoO 2 F 4 ) solution. 2+ ) 7.5 g was added. While the mixed solution to which the phosphor was added was dispersed by stirring, the mixture was reacted at 35 ° C. for 30 hours. After the reaction, the phosphor recovered through filtration and washing steps was vacuum-dried at 120 ° C. for 1 hour.
- the obtained surface-treated phosphor was subjected to “measurement of coating layer thickness and elemental composition analysis in the cross-sectional direction” by the following method, and it was found that a coating layer having a thickness of about 50 nm was formed on the surface of the phosphor. It was.
- the elemental composition curve obtained by the elemental composition analysis in the cross-sectional direction a curve indicating the molybdenum content and a curve indicating the fluorine content are obtained, and the maximum peak of the molybdenum content is the fluorine content. It was confirmed that it is located on the surface side of the maximum peak of. The content of specific elements other than molybdenum was below the detection limit. Further, the fluorine content at the maximum peak position of the molybdenum content was 1.5% by weight.
- the phosphor particles subjected to the coating treatment were subjected to “measurement of the thickness of the coating layer and elemental composition analysis in the cross-sectional direction” in the same manner as in Example 1.
- a coating layer having a thickness of about 34 nm was formed on the surface.
- the elemental composition curve obtained by the elemental composition analysis in the cross-sectional direction only a curve indicating the titanium content was obtained.
- the fluorine content was below the detection limit.
- the content of the titanium maximum peak in the surface treatment layer was 20% by weight.
- An FE-TEM cross-sectional photograph of the obtained surface-treated phosphor is shown in FIG. 18, and an elemental analysis result in the cross-sectional direction is shown in FIG.
- the phosphor particles subjected to the coating treatment were subjected to “measurement of the thickness of the coating layer and elemental composition analysis in the cross-sectional direction” in the same manner as in Example 1. As a result, a coating layer having a thickness of about 55 nm was formed on the surface. I understood.
- the obtained LED light emitting device was subjected to a moisture resistance test in a sealed pressure resistant device having a temperature of 121 ° C. and a relative humidity of 100% (Pressure Cooker Test (PCT test)).
- the moisture resistance of the phosphor was evaluated from the amount of change in luminous intensity by measuring the light emission characteristics of the LED chips before and after the PCT test.
- relative humidity resistance between samples was evaluated based on the luminous intensity retention rate after 72 hours of the PCT test (PCT72h luminous intensity retention rate) with respect to the luminous intensity before the PCT test.
- PCT72h luminous intensity retention rate (%) (luminance after PCT 72 hours treatment / luminance before treatment) ⁇ 100
- an OL770 measuring system manufactured by Optronic Laboratories was used as the measuring apparatus. The results are shown in Table 1.
- ⁇ Moisture resistance evaluation 2 of phosphor (electric current test)> First, an LED light-emitting device was fabricated in the same manner as in “Moisture resistance evaluation of phosphor 1 (PCT test)”. Next, the obtained LED light-emitting device was energized for 1000 hours under a constant current condition of 20 mA in a constant temperature and humidity chamber at a temperature of 60 ° C. and a relative humidity of 90%. The light emission characteristics of the LED chips before and after the energization test were measured, and the moisture resistance was evaluated from the amount of change in luminous intensity.
- Luminance retention rate (%) after energization for 1000 hours (luminosity after energization for 1000 hours / luminosity before energization) ⁇ 100
- OL770 measuring system manufactured by Optronic Laboratories was used as the measuring apparatus. The results are shown in Table 1.
- ⁇ Moisture resistance evaluation 3 of phosphor (conductivity measurement after immersion in water)> 1 g of the surface-treated phosphor or phosphor obtained in Examples and Comparative Examples was added to 1000 g of pure water (temperature: 35 ° C.) with stirring, and the conductivity of the dispersion at the time when 10 minutes had elapsed after the addition was measured. It was measured using a rate meter (ES-51, manufactured by Horiba, Ltd.).
- ⁇ Moisture resistance evaluation 4 of phosphor (measurement of dissolved Si and Sr concentration during immersion in water)> 1 g of the surface-treated phosphor or phosphor obtained in Examples and Comparative Examples was added to 1000 g of pure water (temperature: 35 ° C.) with stirring, and the dispersion liquid was filtered when 10 minutes had passed after the addition.
- concentrations of Si and Sr in the liquid were measured using inductively coupled plasma emission spectrometry (ICP, apparatus: ICPS-8000, manufactured by Shimadzu Corporation).
- the dispersibility of the phosphor in the resin was evaluated using a centrifugal sedimentation / light transmission type dispersion stability analyzer (LUMiSizer 612, manufactured by LUM). Specifically, about 1 ml of the phosphor-silicone resin composition in which the surface-treated phosphors or phosphors obtained in Examples and Comparative Examples are dispersed in an amount of 8% by weight with respect to the silicone resin is used as a glass analysis cell. Then, the supernatant was irradiated with light, and the integrated value of the amount of change in the amount of light transmitted per hour was determined to evaluate the dispersibility.
- LUMiSizer 612 centrifugal sedimentation / light transmission type dispersion stability analyzer
- a surface-treated phosphor that can greatly improve moisture resistance without deteriorating fluorescence characteristics and has high dispersibility, and a method for producing the surface-treated phosphor. it can.
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Abstract
Description
白色LEDにおいて、白色光を作り出す方法としては、青色や紫外光のLEDとそれらの光によって励起されうる蛍光体(赤、黄、緑色蛍光体等)とを組み合わせる方法が一般的用いられている。
これに対して、蛍光体の耐湿性を改善する方法として、気相法(乾式法)、液相法(湿式法)等を用いて、蛍光体粒子の表面を酸化物等で被覆する方法が検討されている。
例えば、気相法による方法としては、化学的気相成長法(CVD)を用いる方法(特許文献3)や、プラズマ法を用いる方法(特許文献4)によって硫化物蛍光体粒子の表面に酸化アルミニウム膜をコーティングする方法が開示されている。
更に、特許文献7には、ゾルーゲル法を用いたジルコニア膜の被覆方法が開示されている。特許文献8には、アルミニウム等のイオン含有酸性溶液を、蛍光体を分散させたアルカリ性溶液中に添加し、中和反応によって蛍光体粒子の表面に金属水酸化物を析出する方法が開示されている。
更に、特許文献5に開示された被覆方法は、加水分解反応が多量のアンモニア水の存在下で行うため、殆どの原料が蛍光体粒子表面以外の溶液中に反応、消費され、反応効率とコストにも問題点があった。加えて、多量のアンモニア水が含まれるので、処理過程中に蛍光体が加水分解によって劣化する恐れもあった。
特許文献6に開示された方法では、被覆物であるSi含有化合物が粒子状又は層状で蛍光体粒子の表面に載置されるとしているが、実際には、耐湿性の改善は殆ど見られなかった。また、特許文献6の実施例に記載された反応条件では、蛍光体粒子の表面に被覆反応が殆ど起こらず、一部被覆ができたとしても、粒子状被覆の場合には水蒸気を効率的に遮断するのは困難であるという問題点があった。
特許文献7に開示された方法は、長時間の反応と精密な温度及びプロセスの制御が必要であり、効率とコストの点に問題があった。
一方、特許文献8に開示された中和沈殿法では、被覆物を蛍光体粒子の表面に連続膜として析出することは事実上困難であった。
以下、本発明を詳述する。
上記表面処理層は、上記特定元素とフッ素とを含有することを特徴とする。
また、フッ素を含有する表面処理層が形成されていることで、表面処理蛍光体の使用時の耐湿性についても向上されることができる。上記表面処理層はシリケート蛍光体に比べ、水に対する安定性が高いので、使用時の耐湿性改善にも寄与する。
更に、上記表面処理層がフッ素のみを含有する場合は、フッ化物の化学結合は基本的にイオン性結合であり、解離傾向が共有結合の酸化物より大きいため、湿気又は水分が存在する雰囲気に長時間使用すると、フッ化物中のアルカリ土類金属の加水分解反応が徐々に進行する恐れがあり、長期的な安定性の確保に不充分となる。
これに対して、上記フッ素に加えて、上記特定元素を添加することで、水に対してより安定な酸化物層を形成することにより、長期間使用時における優れた耐湿性を付与することができる。
上記アルカリ土類金属のフッ化物としては、例えば、フッ化ストロンチウム、フッ化バリウム、フッ化カルシウム、フッ化マグネシウムからなる層が挙げられる。これらのなかでは、フッ化ストロンチウム、フッ化カルシウムが特に好ましい。
ここで、「電子顕微鏡及びそれに付属するエネルギー分散型X線元素分析」とは、例えば、SEM-EDS(Scanning Electron Microscopy/Energy Dispersive Spectroscopy)、又は、TEM-EDS(Transmision Electron Microscopy/Energy Dispersive Spectroscopy)装置を用いた方法等が用いられる。
なお、本発明では、「特定元素の含有量の最大ピーク」又は「フッ素の含有量の最大ピーク」が複数存在する場合でも、「特定元素の含有量の最大ピーク」が、「フッ素の含有量の最大ピーク」よりも表面側に位置するという条件を満たすこととする。
また、特定元素の最大ピーク位置での、フッ素の含有量の好ましい下限は0.01重量%、好ましい上限は30重量%である。
また、上記表面処理層の断面厚み方向の元素分布において、上記フッ素の最大ピーク位置における含有量の好ましい下限は0.1重量%、好ましい上限は50重量%である。上記範囲内とすることで、被覆処理過程中における蛍光体の水より分解劣化が抑えられると同時に、表面処理蛍光体の耐湿性の向上にも寄与する。
一般的に、耐湿性に劣る蛍光体を処理する場合には、水溶液の使用を避ける傾向にあるが、上記フッ化物層を形成することで、被覆処理を水溶液中で行うことができ、有機溶媒を使用する場合における廃液処理等の問題がなくなる。また、使用時の耐湿性についても向上することができる。また、上記酸化物層が形成されていることで、耐湿性の更なる向上と長期安定性が実現される。
従って、上記フッ化物層の上に、水に対してより安定な酸化物層を被覆することにより、長期間使用時における優れた耐湿性を付与することができる。
具体的には例えば、フッ化ストロンチウム、フッ化バリウム、フッ化カルシウム、フッ化マグネシウムからなる層が挙げられる。これらのなかでは、フッ化ストロンチウムとフッ化カルシウムが好ましい。
上記蛍光体としては、なかでも、アルカリ土類金属元素を有するシリケート蛍光体が好ましい。
上記アルカリ土類金属元素を有する蛍光体は、アルカリ土類金属以外の金属元素(例えば、Zn、Ga、Al、Y、Gd、Tb)を適量含有してもよい。
また、上記アルカリ土類金属元素を有する蛍光体は、少量のハロゲン元素(例えば、F,Cl,Br)、硫黄(S)またはリン(P)を適量含有してもよい。
式中、MはBa、Ca、Mg及びZnからなる群より選択される少なくとも1種の金属であり、0≦x<1.0であり、2.6≦y≦3.3である。
式中、MはBa、Ca、Mg及びZnからなる群より選択される少なくとも1種の金属であり、DはF、Cl及びBrからなる群より選択されるハロゲンアニオンであり、0≦x<1.0であり、2.6≦y≦3.3である。
なかでも、上記蛍光体は、M3SiO5の結晶構造を有する橙色(オレンジ)蛍光体が特に好適である。
上記水の導電率が100mS/m以下であることで、蛍光体が水による分解劣化が少なく、優れた耐湿性を示すこととなる。
なお、上記水の導電率は、例えば、導電率計等によって測定することができる。
上記ケイ素の溶出量が50ppm以下であることで、蛍光体が水による分解劣化が少なく、優れた耐湿性を示すこととなる。
上記ストロンチウムの溶出量が200ppm以下であることで、蛍光体が水による分解劣化が少なく、優れた耐湿性を示すこととなる。
なお、上記ケイ素及びストロンチウムの溶出量は、例えば、誘導結合プラズマ発光分析(ICP、装置:ICPS-8000、島津製作所社製)によって測定することができる。
上記特定元素とフッ素イオンとを含有する錯体イオンとしては、例えば、AF6 2-の構造を有する錯体イオン(A:周期律表第3~6族の元素から選択される少なくとも1種の特定元素)等が挙げられる。
他に、AO2F4 2-の構造を有する錯体イオンや、特定元素の酸化物を溶解したフッ素含有溶液を用いてもよい。
AF6 2-+nH2O → [AF6-n(OH)n]2- + nH+ + nF- (3)
上記加水分解反応は、下記式(5)に示すように、フッ素イオンとより安定な錯体を作りうる化合物(加水分解促進剤)の存在によって促進される。本発明に使用する加水分解促進剤は、ホウ素(B)又はアルミニウム(Al)を含有する化合物から選ぶことができる。ホウ素を含有する化合物及びアルミニウムを含有する化合物は、単独で使用してもよく、2種以上を混合して使用してもよい。
AF6 2- + 2H2O → AO2 + 4H+ + 6F- (4)
BO3 3- + 6H+ + 4F- → BF4- + 3H2O (5)
上記アルミニウムを含有する化合物としては、例えば、AlCl3、AlBr3、水酸化アルミニウム(Al(OH)3)等が挙げられる。
一般には、仕込みの蛍光体の量が一定であれば、反応時間が長くなるほど膜厚が厚くなる。反応時間が短すぎると表面処理層の形成が不完全となる。一方、反応時間が長すぎると非経済的である。
反応温度は、目的とする酸化物層の厚みに応じて適宜調整すればよく、通常、0~90℃程度、好ましくは5~70℃程度、より好ましくは、10~50℃程度とすればよい。
反応時の分散条件は特に限定されず、蛍光体を分散させることができる条件であればよい。例えば、磁気スターラー攪拌、モーター付きの機械的な攪拌、ガスバーブリング、液循環、超音波分散、ボールミルやロータリーミキサーのような回転分散、又は上記方法を併用することによって行うことができる。
また、本発明の表面処理蛍光体の製造方法では、上記乾燥した蛍光体を200~600℃の温度で更に熱処理してもよい。
上述の条件では、フッ化物の形成と特定元素の酸化物の形成が実質的に同じ溶液中に進行するが、蛍光体をAF6 2-錯体イオン含有水溶液に分散、接触させた時に、フッ化物が優先的に形成すると推測される。フッ化物の形成に伴い、溶液中のフッ素イオン濃度が低下し、上記一般式(3)又は(4)の反応が右方向へ進む。その結果、酸化物(AO2)が析出し始める。
なお、上記蛍光体含有樹脂組成物は公知の形態で使用され、例えば、ペーストとしてディスペンサーで充填されたり、テープ、シート状に加工され積層されたりしても良い。
また、1以上、好ましくは2以上の炭素-炭素二重結合を有する化合物と過酸化物(過酸等)との反応で製造されるエポキシ樹脂等も挙げられる。
上記脂肪族エポキシ樹脂としては、1以上の脂肪族基と1以上のエポキシ基を有する化合物が挙げられ、具体例としては、ブタジエンジオキシド、ジメチルペンタンジオキシド、ジグリシジルエーテル、1,4-ブタンジオールジグリシジルエーテル、ジエチレングリコールジグリシジルエーテル及びジペンテンジオキシド等が挙げられる。
上記波長変換複合体は、照明システム、太陽電池用の波長変換部材等として使用される。
上記波長変換複合体の製造方法は特に限定されないが、本発明の表面処理蛍光体は、対応する樹脂に合わせた公知の表面処理がなされていてもよい。また、公知の混練分散方法により樹脂中に分散されていてもよい。
太陽電池に代表される光電変換装置では、受光する光の波長が必ずしも素子自体の効率の良い波長ではないことがある。その際に、受光する光の波長を素子にとって効率のよい波長に変換することにより、光電変換装置の変換効率が向上する。
一方で、従来の蛍光体は、耐湿性が低く好適に使用できなかったが、封止材樹脂に本発明の表面処理蛍光体を分散させ、太陽電池の表面に使用することで効率の良い太陽電池が得られる。
また、LEDチップと、前記LEDチップを囲繞する樹脂フレームと、樹脂フレームが形成する凹部に充填される蛍光体層を備えるLED発光装置において、前記蛍光体層を本発明の表面処理蛍光体と封止樹脂とを含有する構成とすることで、耐湿性に優れたLED発光装置とすることができる。このようなLED発光装置もまた本発明の1つである。
なお、上記光度保持率とは、上述した条件で通電前後の光度の比率[(通電後の光度/通電前の光度)×100]を表し、上記光度は、例えば、オプトロニックラボラトリーズ社製のOL770測定システム等を用いて測定することができる。
また、上記画像表示装置としては、例えば、少なくとも液晶セルと上記液晶表示素子バックライトと有する液晶表示素子がその1例である。他の例としては、複数のLEDを2次元的に規則的に配列して選択的に発光させることにより画像を形成するLEDディスプレイ等が挙げられる。
更に、上記照明装置としては、特に限定されず、既知のLED発光装置への適用が可能である。上記照明装置は、耐湿性が高いことから、例えば、車両等の交通、運輸に用いられる表示灯、照明灯や、住居、建築物等に用いられる屋内外の照明や、携帯電話、移動体通信端末等に用いられる照明等に使用することができる。
0.1mol/Lフッ化チタン酸アンモニウム((NH4)2TiF6)と0.1mol/Lほう酸含有混合水溶液250mlに、中央粒径(D50)約17μmの橙色シリケート蛍光体(Sr3SiO5:Eu2+)7.5gを添加した。上記蛍光体を添加した混合液を攪拌によって分散しながら、35℃で2時間を反応させた。反応後に、ろ過、洗浄工程を経て回収した蛍光体を120℃で1時間真空乾燥した。
得られた表面処理蛍光体について、以下の方法で「被覆層の厚み測定、断面方向の元素組成分析」を行ったところ、蛍光体の表面に厚み約180nmの表面処理層が形成されていることが分かった。
また、断面方向の元素組成分析によって得られた元素組成曲線では、チタンの含有量を示す曲線と、フッ素の含有量を示す曲線が得られ、チタンの含有量の最大ピークが、フッ素の含有量の最大ピークよりも表面側に位置することが確認できた。なお、チタン以外の特定元素の含有量については検出限界以下であった。
また、チタンの含有量の最大ピーク位置におけるフッ素の含有量は1.0重量%であった。なお、得られた表面処理蛍光体のFE-TEM断面写真を図1に、その断面方向の元素分析結果を図2に示す。
得られた表面処理蛍光体について、Focused ion Beam(FIB)を用いて、断面方向に切断し、その切断面を透過電子顕微鏡(FE-TEM、JEM-2010FEF)で観察することによって表面処理層の厚みを測定した。なお、厚みは5点を測定し、その平均値を用いた。
また、表面処理層の元素組成は、上記FE-TEMに付属されているエネルギー分散型X線(EDX)を用いて分析し、同定することにより、厚み方向における特定元素(周期律表第3~6族の元素)及びフッ素の含有量の曲線を得た。
0.1mol/Lフッ化チタン酸アンモニウム((NH4)2TiF6)と0.1mol/Lほう酸含有混合水溶液250mlに、中央粒径(D50)約17μmの橙色シリケート蛍光体(主成分:Sr3SiO5:Eu2+)7.5gを添加した。上記蛍光体を添加した混合液を攪拌によって分散しながら、35℃で4時間を反応させた。反応後に、ろ過、洗浄工程を経て回収した蛍光体を120℃で1時間真空乾燥した。
得られた表面処理蛍光体について、実施例1と同様の方法で「被覆層の厚み測定、断面方向の元素組成分析」を行ったところ、蛍光体の表面に厚み約210nmの表面処理層が形成されていることが分かった。
また、断面方向の元素組成分析によって得られた元素組成曲線では、チタンの含有量を示す曲線と、フッ素の含有量を示す曲線が得られ、チタンの含有量の最大ピークが、フッ素の含有量の最大ピークよりも表面側に位置することが確認できた。なお、チタン以外の特定元素の含有量については検出限界以下であった。
また、チタンの含有量の最大ピーク位置におけるフッ素の含有量は1.8重量%であった。
なお、得られた表面処理蛍光体のFE-TEM断面写真を図3に、その断面方向の元素分析結果を図4に示す。
0.75mol/Lフッ化チタン酸アンモニウム((NH4)2TiF6)含有水溶液250mlに、中央粒径(D50)約17μmの橙色シリケート蛍光体(主成分:Sr3SiO5:Eu2+)7.5gを添加した。上記蛍光体を添加した混合液を攪拌によって分散しながら、35℃で30分を反応させた。反応後に、ろ過、洗浄工程を経て回収した蛍光体を120℃で1時間真空乾燥した。
得られた表面処理蛍光体について、実施例1と同様の方法で「被覆層の厚み測定、断面方向の元素組成分析」を行ったところ、蛍光体の表面に厚み約250nmの被覆層が形成されていることが分かった。
また、断面方向の元素組成分析によって得られた元素組成曲線では、チタンの含有量を示す曲線と、フッ素の含有量を示す曲線が得られ、チタンの含有量の最大ピークが、フッ素の含有量の最大ピークよりも表面側に位置することが確認できた。なお、チタン以外の特定元素の含有量については検出限界以下であった。
また、チタンの含有量の最大ピーク位置におけるフッ素の含有量は4.8重量%であった。
なお、得られた表面処理蛍光体のFE-TEM断面写真を図5に、その断面方向の元素分析結果を図6に示す。
1.0mol/Lフッ化チタン酸アンモニウム((NH4)2TiF6)含有水溶液250mlに、中央粒径(D50)約17μmの橙色シリケート蛍光体(主成分:Sr3SiO5:Eu2+Cl)7.5gを添加した。上記蛍光体を添加した混合液を攪拌によって分散しながら、35℃で30分を反応させた。反応後に、ろ過、洗浄工程を経て回収した蛍光体を120℃で1時間真空乾燥した。
得られた表面処理蛍光体について、実施例1と同様の方法で「被覆層の厚み測定、断面方向の元素組成分析」を行ったところ、蛍光体の表面に厚み約300nmの被覆層が形成されていることが分かった。
また、断面方向の元素組成分析によって得られた元素組成曲線では、チタンの含有量を示す曲線と、フッ素の含有量を示す曲線が得られ、チタンの含有量の最大ピークが、フッ素の含有量の最大ピークよりも表面側に位置することが確認できた。なお、チタン以外の特定元素の含有量については検出限界以下であった。
また、チタンの含有量の最大ピーク位置におけるフッ素の含有量は6.0重量%であった。
なお、得られた表面処理蛍光体のFE-TEM断面写真を図7に、その断面方向の元素分析結果を図8に示す。
0.02mol/Lフッ化チタン酸アンモニウム((NH4)2TiF6)と0.02mol/Lほう酸含有混合水溶液250mlに、中央粒径(D50)約17μmの橙色シリケート蛍光体(主成分:Sr3SiO5:Eu2+)7.5gを添加した。上記蛍光体を添加した混合液を攪拌によって分散しながら、35℃で2時間を反応させた。反応後に、ろ過、洗浄工程を経て回収した蛍光体を120℃で1時間真空乾燥した。
得られた表面処理蛍光体について、実施例1と同様の方法で「被覆層の厚み測定、断面方向の元素組成分析」を行ったところ、蛍光体の表面に厚み約110nmの被覆層が形成されていることが分かった。
また、断面方向の元素組成分析によって得られた元素組成曲線では、チタンの含有量を示す曲線と、フッ素の含有量を示す曲線が得られ、チタンの含有量の最大ピークが、フッ素の含有量の最大ピークよりも表面側に位置することが確認できた。なお、チタン以外の特定元素の含有量については検出限界以下であった。
また、チタンの含有量の最大ピーク位置におけるフッ素の含有量は0.15重量%であった。なお、得られた表面処理蛍光体のFE-TEM断面写真を図9に、その断面方向の元素分析結果を図10に示す。
0.1mol/Lフッ化チタン酸アンモニウム((NH4)2TiF6)と0.2mol/Lほう酸含有混合水溶液250mlに、中央粒径(D50)約17μmの橙色シリケート蛍光体(主成分:Sr3SiO5:Eu2+)1.5gを添加した。上記蛍光体を添加した混合液を攪拌によって分散しながら、35℃で2時間を反応させた。反応後に、ろ過、洗浄工程を経て回収した蛍光体を120℃で1時間真空乾燥した。
得られた表面処理蛍光体について、実施例1と同様の方法で「被覆層の厚み測定、断面方向の元素組成分析」を行ったところ、蛍光体の表面に厚み約200nmの被覆層が形成されていることが分かった。
また、断面方向の元素組成分析によって得られた元素組成曲線では、チタンの含有量を示す曲線と、フッ素の含有量を示す曲線が得られ、チタンの含有量の最大ピークが、フッ素の含有量の最大ピークよりも表面側に位置することが確認できた。なお、チタン以外の特定元素の含有量については検出限界以下であった。
また、チタンの含有量の最大ピーク位置におけるフッ素の含有量は2.5重量%であった。
なお、得られた表面処理蛍光体のFE-TEM断面写真を図11に示す。
0.1mol/Lフッ化ジルコン酸アンモニウム((NH4)2ZrF6)と0.1mol/Lほう酸含有混合水溶液250mlに、中央粒径(D50)約17μmの橙色シリケート蛍光体(主成分:Sr3SiO5:Eu2+)7.5gを添加した。上記蛍光体を添加した混合液を攪拌によって分散しながら、35℃で2時間を反応させた。反応後に、ろ過、洗浄工程を経て回収した蛍光体を120℃で1時間真空乾燥した。
得られた表面処理蛍光体について、実施例1と同様の方法で「被覆層の厚み測定、断面方向の元素組成分析」を行ったところ、蛍光体の表面に厚み約170nmの被覆層が形成されていることが分かった。
また、断面方向の元素組成分析によって得られた元素組成曲線では、ジルコニウムの含有量を示す曲線と、フッ素の含有量を示す曲線が得られ、ジルコニウムの含有量の最大ピークが、フッ素の含有量の最大ピークよりも表面側に位置することが確認できた。なお、ジルコニウム以外の特定元素の含有量については検出限界以下であった。
また、ジルコニウムの含有量の最大ピーク位置におけるフッ素の含有量は0.6重量%であった。
なお、得られた表面処理蛍光体のFE-TEM断面写真を図12に、その断面方向の元素分析結果を図13に示す。
0.05mol/Lの酸化バナジウムを溶解したフッ化水素酸水溶液250mlに、中央粒径(D50)約17μmの橙色シリケート蛍光体(主成分:Sr3SiO5:Eu2+)7.5gを添加した。上記蛍光体を添加した混合液を攪拌によって分散しながら、35℃で30時間を反応させた。反応後に、ろ過、洗浄工程を経て回収した蛍光体を120℃で1時間真空乾燥した。
得られた表面処理蛍光体について、実施例1と同様の方法で「被覆層の厚み測定、断面方向の元素組成分析」を行ったところ、蛍光体の表面に厚み約100nmの被覆層が形成されていることが分かった。
また、断面方向の元素組成分析によって得られた元素組成曲線では、バナジウムの含有量を示す曲線と、フッ素の含有量を示す曲線が得られ、バナジウムの含有量の最大ピークが、フッ素の含有量の最大ピークよりも表面側に位置することが確認できた。なお、バナジウム以外の特定元素の含有量については検出限界以下であった。
また、バナジウムの含有量の最大ピーク位置におけるフッ素の含有量は3.6重量%であった。
0.1mol/Lのフッ化モリブデン酸アンモニウム((NH4)2MoO2F4)水溶液250mlに、中央粒径(D50)約17μmの橙色シリケート蛍光体(主成分:Sr3SiO5:Eu2+)7.5gを添加した。上記蛍光体を添加した混合液を攪拌によって分散しながら、35℃で30時間を反応させた。反応後に、ろ過、洗浄工程を経て回収した蛍光体を120℃で1時間真空乾燥した。
得られた表面処理蛍光体について以下の方法で「被覆層の厚み測定、断面方向の元素組成分析」を行ったところ、蛍光体の表面に厚み約50nmの被覆層が形成されていることが分かった。
また、断面方向の元素組成分析によって得られた元素組成曲線では、モリブデンの含有量を示す曲線と、フッ素の含有量を示す曲線が得られ、モリブデンの含有量の最大ピークが、フッ素の含有量の最大ピークよりも表面側に位置することが確認できた。なお、モリブデン以外の特定元素の含有量については検出限界以下であった。
また、モリブデンの含有量の最大ピーク位置におけるフッ素の含有量は1.5重量%であった。
表面未処理の中央粒径(D50)約17μmの橙色シリケート蛍光体(主成分:Sr3SiO5:Eu2+)を用い、この蛍光体について、実施例1と同様の方法で「被覆層の厚み測定、断面方向の元素組成分析」を行ったところ、蛍光体の表面に表面被覆層は形成されておらず、特定元素の含有量を示す曲線も、フッ素の含有量を示す曲線も得られなかった。
なお、得られた蛍光体のFE-TEM断面写真と断面方向の元素分析結果をそれぞれ図14と図15に示す。
主成分Sr3SiO5:Eu2+の橙色シリケート蛍光体粒子1.0gを、濃度2.0%のトリフルオロプロピルトリメトキシシランを溶かしたエタノールと0.01%の酢酸水の混合水溶液(エタノール:水=5:1)に添加し、1時間反応させた。その後、エタノールを除去し、更に110℃で1時間真空乾燥することによって蛍光体粒子を回収した。
上記処理した蛍光体粒子について、実施例1と同様の方法で「被覆層の厚み測定、断面方向の元素組成分析」を行ったところ、表面に厚み約47nmの被覆層が形成されていたことが分かった。
また、断面方向の元素組成分析によって得られた元素組成曲線では、フッ素の含有量を示す曲線のみが得られた。なお、特定元素の含有量については検出限界以下であった。
更に、表面処理層における、フッ素最大値ピークの含有量は9.5重量%であった。
なお、得られた表面処理蛍光体のFE-TEM断面写真を図16に、その断面方向の元素分析結果を図17に示す。
主成分Sr3SiO5:Eu2+の橙色シリケート蛍光体粒子12.0gを分散した無水エタノール溶液(400ml)にチタンイソプロポキシド(関東化学社製)8.4gを添加し溶解した。次に、4.2gの水(アンモニア水でpH9.0まで調製)を含有する120mlエタノール液を0.5ml/分の速度で上記分散液に滴下した。滴下終了後にも更に1時間攪拌した。その後、ろ過、洗浄工程を経て、回収した蛍光体粒子を120℃で1時間真空乾燥した。
上記被覆処理した蛍光体粒子について、実施例1と同様の方法で「被覆層の厚み測定、断面方向の元素組成分析」を行ったところ、表面に厚み約34nmの被覆層が形成されていたことが分かった。
また、断面方向の元素組成分析によって得られた元素組成曲線では、チタンの含有量を示す曲線のみが得られた。なお、フッ素の含有量については検出限界以下であった。
更に、表面処理層におけるチタン最大ピークの含有量は20重量%であった。
なお、得られた表面処理蛍光体のFE-TEM断面写真を図18に、その断面方向の元素分析結果を図19に示す。
主成分Sr3SiO5:Eu2+の橙色シリケート蛍光体粒子12.0gを分散した無水エタノール溶液(400ml)にチタンイソプロポキシド(関東化学社製)8.4gを添加し溶解した。次に、4.2gの水(アンモニア水でpH9.0まで調製)を含有する120mlエタノール液を0.5ml/分の速度で上記分散液に滴下した。滴下終了後にも更に1時間攪拌した。その後、ろ過、洗浄工程を経て、回収した蛍光体粒子を120℃で1時間真空乾燥した。
上記乾燥した蛍光体粒子を、濃度2.0%のトリフルオロプロピルトリメトキシシランを溶かしたエタノールと0.01%の酢酸水の混合水溶液(エタノール:水=5:1)に添加し、1時間反応させた。その後、エタノールを除去し、更に110℃で1時間真空乾燥することによって蛍光体粒子を回収した。
上記被覆処理した蛍光体粒子について、実施例1と同様の方法で「被覆層の厚み測定、断面方向の元素組成分析」を行ったところ、表面に厚み約55nmの被覆層が形成されていたことが分かった。
また、断面方向の元素組成分析によって得られた元素組成曲線では、チタンの含有量を示す曲線と、フッ素の含有量を示す曲線が得られ、チタンの含有量の最大ピークが、フッ素の含有量の最大ピークよりも蛍光体側に位置することが確認できた。なお、チタン以外の特定元素の含有量については検出限界以下であった。
なお、得られた表面処理蛍光体のFE-TEM断面写真を図20に、その断面方向の元素分析結果を図21に示す。
<蛍光体の耐湿性評価1(PCT試験)>
実施例及び比較例で得られた表面処理蛍光体又は蛍光体をシリコーン樹脂(ダウ・コーニング社製、OE6630)100重量部に対して8重量部混合分散し、更に脱泡することにより蛍光体含有樹脂組成物を調製した。次に、調製した蛍光体含有樹脂組成物を、基板に実装したLEDパッケージ(発光ピーク波長460nm)の上に注入、充填し、更に150℃で2時間加熱することにより、樹脂組成物を硬化させた。上記工程により、LED発光装置を作製した。
得られたLED発光装置を温度121℃、相対湿度100%の密閉耐圧装置において耐湿性試験を行った(Pressure Cooker Test(PCT試験))。
蛍光体の耐湿性は、PCT試験前後のLEDチップの発光特性を測定し、光度の変化量から評価した。具体的には、PCT試験前の光度に対し、PCT試験72時間後の光度の保持率(PCT72h光度保持率)でサンプル間の相対耐湿性を評価した。
PCT72h光度保持率(%)=(PCT72時間処理後の光度/処理前の光度)×100
なお、測定装置には、オプトロニックラボラトリーズ社製のOL770測定システムを用いた。結果を表1に示した。
「蛍光体の耐湿性評価1(PCT試験)」と同様の方法でLED発光装置をまず作製した。
次に、得られたLED発光装置を温度60℃、相対湿度90%の恒温恒湿器において、20mAの定電流条件で1000時間を通電した。通電試験前後のLEDチップの発光特性を測定し、光度の変化量から耐湿性を評価した。具体的には、通電試験前の光度(初期光度)に対し、1000時間通電後の光度の保持率でサンプル間の相対耐湿性を評価した。
1000時間通電後の光度保持率(%)=(1000時間通電後の光度/通電前の光度)×100
なお、測定装置には、オプトロニックラボラトリーズ社製のOL770測定システムを用いた。結果を表1に示した。
実施例及び比較例で得られた表面処理蛍光体又は蛍光体1gを、攪拌しながら純水(温度:35℃)1000gに添加し、添加後10分経過した時点における分散液の導電率を導電率計(ES-51、堀場製作所社製)を用いて測定した。
実施例及び比較例で得られた表面処理蛍光体又は蛍光体1gを、攪拌しながら純水(温度:35℃)1000gに添加し、添加後10分経過した時点で分散液をろ過し、ろ液中のSi及びSrの濃度を誘導結合プラズマ発光分析(ICP、装置:ICPS-8000、島津製作所社製)を用いて測定した。
蛍光体の樹脂における分散性は遠心沈降・光透過方式の分散安定性分析装置(LUMiSizer612、L.U.M社製)を用いて評価した。具体的には、シリコーン樹脂に対して、実施例及び比較例で得られた表面処理蛍光体又は蛍光体を8重量%の割合で分散した蛍光体-シリコーン樹脂組成物約1mlをガラス製分析セルに入れ、その上澄み液に光を照射し、1時間あたりの透過する光量の変化量の積分値を求め、分散性を評価した。
なお、表1には、比較例1の蛍光体を用いた蛍光体-樹脂組成物の透過光量の変化量を1.00とし、比較例1の蛍光体を用いた蛍光体-樹脂組成物に対する比率を記載した。
Claims (24)
- 周期律表第3~6族の元素から選択される少なくとも1種の特定元素と、フッ素とを含有する表面処理層を蛍光体の表面に有する表面処理蛍光体であって、
表面処理層の断面厚み方向の元素分布を、電子顕微鏡及びそれに付属するエネルギー分散型X線元素分析により測定した場合、特定元素の含有量の最大ピークが、フッ素の含有量の最大ピークよりも表面側に位置する
ことを特徴とする表面処理蛍光体。 - 表面処理層が単層であり、かつ、表面処理層の断面厚み方向の元素分布において、特定元素の最大ピーク位置で、フッ素が検出されることを特徴とする請求項1記載の表面処理蛍光体。
- 表面処理層は、最表面に向かって順に、フッ化物層、及び、特定元素の酸化物を含有する酸化物層が存在することを特徴とする請求項1記載の表面処理蛍光体。
- 蛍光体は、アルカリ土類金属を含有することを特徴とする請求項1、2又は3記載の表面処理蛍光体。
- 蛍光体は、アルカリ土類金属を含有するシリケート系蛍光体からなることを特徴とする請求項1、2、3又は4記載の表面処理蛍光体。
- 蛍光体は、下記一般式(1)で示されるシリケート系蛍光体からなることを特徴とする請求項1、2、3、4又は5記載の表面処理蛍光体。
(Sr1-xMx)ySiO5:Eu2+ (1)
式中、MはBa、Ca、Mg及びZnからなる群より選択される少なくとも1種の金属であり、0≦x<1.0であり、2.6≦y≦3.3である。 - 蛍光体は、下記一般式(2)で示されるシリケート系蛍光体からなることを特徴とする請求項1、2、3、4又は5記載の表面処理蛍光体。
(Sr1-xMx)ySiO5:Eu2+D (2)
式中、MはBa、Ca、Mg及びZnからなる群より選択される少なくとも1種の金属であり、DはF、Cl及びBrからなる群より選択されるハロゲンアニオンであり、0≦x<1.0であり、2.6≦y≦3.3である。 - 純水100重量部中に、蛍光体0.1重量部を10分間浸漬した場合における、水の導電率が100mS/m以下であることを特徴とする請求項1、2、3、4、5、6又は7記載の表面処理蛍光体。
- 純水100重量部中に、蛍光体0.1重量部を10分間浸漬した場合における、ケイ素の溶出量が50ppm以下であることを特徴とする請求項5、6又は7記載の表面処理蛍光体。
- 純水100重量部中に、蛍光体0.1重量部を10分間浸漬した場合における、ストロンチウムの溶出量が200ppm以下であることを特徴とする請求項6又は7記載の表面処理蛍光体。
- 請求項1、2、3、4、5、6、7、8、9又は10記載の表面処理蛍光体と、エポキシ樹脂及び/又はシリコーン樹脂を含有することを特徴とする蛍光体含有樹脂組成物。
- 請求項1、2、3、4、5、6、7、8、9又は10記載の表面処理蛍光体が、ポリ酢酸ビニル、ポリビニルブチラール、ポリエチレン、ポリプロピレン、ポリメチルメタクリレート及びポリカーボネート及び環状オレフィン共重合体からなる群より選択される少なくとも1種の樹脂に分散されてなることを特徴とする波長変換複合体。
- 請求項12記載の波長変換樹脂複合体をシート状にしてなることを特徴とする波長変換シート。
- 請求項12記載の波長変換複合体、又は、請求項13記載の波長変換シートを構成部材として用いることを特徴とする光電変換装置。
- 請求項1、2、3、4、5、6、7、8、9又は10記載の表面処理蛍光体を用いてなることを特徴とする半導体発光素子。
- LEDチップと、前記LEDチップを囲繞する樹脂フレームと、樹脂フレームが形成する凹部に充填される蛍光体層を備えるLED発光装置であって、前記蛍光体層が請求項1、2、3、4、5、6、7、8、9又は10記載の表面処理蛍光体と封止樹脂とを含有することを特徴とするLED発光装置。
- 温度60℃、相対湿度90%、電流20mAの条件で1000時間通電した後の光度保持率が80%以上であることを特徴とする請求項16記載のLED発光装置。
- 温度121℃、相対湿度100%環境下で72時間保持した後の光度保持率が50%以上であることを特徴とする請求項16記載のLED発光装置。
- 請求項16、17又は18記載のLED発光装置を構成部材として用いることを特徴とする液晶表示素子バックライト。
- 請求項16、17又は18記載のLED発光装置を構成部材として用いることを特徴とする画像表示装置。
- 請求項16、17又は18記載のLED発光装置を構成部材として用いることを特徴とする照明装置。
- 請求項1、2、3、4、5、6、7、8、9又は10記載の表面処理蛍光体を製造する方法であって、
蛍光体を特定元素とフッ素とを含有する錯体イオンを含む溶液に分散し、接触させることにより表面処理層を形成する工程を有することを特徴とする表面処理蛍光体の製造方法。 - 特定元素とフッ素とを含有する錯体イオンが、AF6 2-(A:周期律表第3~6族の元素から選択される少なくとも1種の特定元素)であることを特徴とする請求項22記載の表面処理蛍光体の製造方法。
- 表面処理層を形成する工程において、更にホウ酸を添加することを特徴とする請求項22又は23記載の表面処理蛍光体の製造方法。
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CN110093154B (zh) * | 2019-05-23 | 2020-03-24 | 东北大学 | Mg2+/Si4+取代Ga3+的掺Cr3+镓酸锌基近红外长余辉材料及制备方法 |
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Also Published As
Publication number | Publication date |
---|---|
EP2554628B1 (en) | 2016-07-13 |
KR20130009779A (ko) | 2013-01-23 |
CN102822313A (zh) | 2012-12-12 |
CN102822313B (zh) | 2014-11-26 |
EP2554628A1 (en) | 2013-02-06 |
JPWO2011125452A1 (ja) | 2013-07-08 |
US20130094186A1 (en) | 2013-04-18 |
TWI495709B (zh) | 2015-08-11 |
EP2554628A4 (en) | 2014-03-05 |
TW201139618A (en) | 2011-11-16 |
JP4846066B2 (ja) | 2011-12-28 |
JP2012031425A (ja) | 2012-02-16 |
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