WO2005073342A1 - 金属酸化物系蛍光体微粒子及びその製造方法、それを利用した分散液、蛍光変換膜、金属酸化物系蛍光体微粒子の分離方法、蛍光性液体、蛍光性ペースト、蛍光体及びその製造方法並びに蛍光変換体 - Google Patents
金属酸化物系蛍光体微粒子及びその製造方法、それを利用した分散液、蛍光変換膜、金属酸化物系蛍光体微粒子の分離方法、蛍光性液体、蛍光性ペースト、蛍光体及びその製造方法並びに蛍光変換体 Download PDFInfo
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- WO2005073342A1 WO2005073342A1 PCT/JP2005/000976 JP2005000976W WO2005073342A1 WO 2005073342 A1 WO2005073342 A1 WO 2005073342A1 JP 2005000976 W JP2005000976 W JP 2005000976W WO 2005073342 A1 WO2005073342 A1 WO 2005073342A1
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- 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
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7774—Aluminates
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- 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
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- 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
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- 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
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/30—Devices specially adapted for multicolour light emission
- H10K59/38—Devices specially adapted for multicolour light emission comprising colour filters or colour changing media [CCM]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/778—Nanostructure within specified host or matrix material, e.g. nanocomposite films
- Y10S977/783—Organic host/matrix, e.g. lipid
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/778—Nanostructure within specified host or matrix material, e.g. nanocomposite films
- Y10S977/786—Fluidic host/matrix containing nanomaterials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/256—Heavy metal or aluminum or compound thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
Definitions
- the present invention relates to metal oxide-based phosphor fine particles, and particularly to a metal oxide-based phosphor fine particle having a small particle size and a high affinity for a light-transmitting resin and a high dispersibility and not scattering light emitted from a light source.
- Fluorescence conversion films that use a fluorescent material to convert the wavelength of light emitted from a light source are used in various fields including the field of electronic displays.
- an organic electroluminescent material portion that emits blue light or blue-green light and a fluorescent material portion that absorbs the light emitted from the light emitting layer and emits at least one color visible light from blue green to red are provided. (See, for example, Patent Document 1)
- a red fluorescence conversion film comprising a rhodamine-based fluorescent pigment and a fluorescent pigment having absorption in the blue region and inducing energy transfer or re-absorption to the rhodamine-based fluorescent pigment dispersed in a light-transmitting medium.
- a fluorescence conversion film an organic fluorescent dye having a cycloalkyl group and a Z or heterocyclo ring as a steric hindrance group, for example, as disclosed in Patent Document 3 is used.
- a reaction curable resin such as a photocurable resin or a thermosetting resin is mainly used for reasons such as improvement in heat resistance and productivity of the film.
- the reaction components in the resin react with the organic fluorescent dye, the dye is decomposed or the structure is changed, and the fluorescent property is further reduced.
- FIG. 16 is a diagram showing the relationship between the absorbance and the fluorescence quantum yield when the concentration of the dye in the fluorescence conversion film is changed.
- circles indicate a fluorescence conversion film in which rhodamine 6G is dispersed as an organic fluorescent dye in a benzoguanamine resin
- open triangles indicate a fluorescence conversion film in which coumarin 6 is dispersed as an organic fluorescent dye in the resin
- black triangles indicate The fluorescence conversion film in which coumarin 6 is dispersed in a photocurable resin is shown.
- the fluorescence quantum yield is less than 50% in a region where the absorbance to excitation light exceeds 1. .
- the fluorescence quantum yield is as low as about 30%.
- Patent Document 4 as an inorganic phosphor, yttrium 'aluminum garnet phosphor (commonly known as YAG: Ce phosphor) activated with cerium is used, and a sheet obtained by dispersing the phosphor in a thermoplastic resin sheet is subjected to fluorescence conversion. It has a membrane.
- fine particles are produced by pulverizing the fired YAG: Ce compact, so that the particle size of the fine particles is on the order of micrometer size. Therefore, in order to absorb the excitation light sufficiently without scattering it, the thickness of the resin sheet should be large, for example, 120 xm, and fine particles should be separated at a low concentration.
- Patent Document 5 as a method for producing a metal oxide phosphor, carbonates, nitrates, hydroxides, sulfates, phosphates, borates, and the like of a metal element constituting a base of the phosphor and an activator are disclosed.
- a metal complex obtained by reacting at least one compound selected from silicates, aluminates, carboxylates, halides and alkoxides with an oxycarboxylic acid or a polyamino chelating agent is dissolved in a solvent.
- a production method is disclosed in which a complex polymer is formed by a polymerization reaction with a polyol, and the complex polymer is calcined.
- the calcination is performed at a high temperature of 800 ° C or higher, so that the organic components contained in the product are thermally decomposed.
- the particles caused secondary aggregation, and the particle size was about 100 nm, which was still insufficient. Further, for the same reason, there is a problem that the dispersibility in an organic solvent or a resin is poor.
- Non-Patent Document 1 fine particles obtained by a sol-gel method are fired at a high temperature of 800 ° C. or higher to obtain a YAG: Ge phosphor of about 35 nm.
- Patent Document 5 there is a problem that fine particles do not contain an organic component, and thus dispersibility in organic solvents and resins is poor.
- Patent Document 6 a film in which nanocrystals of a II-VI semiconductor such as cadmium selenide (CdSe) are dispersed in a resin is used as a fluorescence conversion film.
- a II-VI semiconductor such as cadmium selenide (CdSe)
- metal chalcogenide rugs are inferior in durability such as water resistance, chemical resistance and heat resistance.
- Patent Document 1 JP-A-3-152897
- Patent Document 2 JP-A-8-286033
- Patent Document 3 JP-A-2000-44824
- Patent Document 4 JP-A-11-199781
- Patent Document 5 JP-A-11-181419
- Patent Document 6 U.S. Patent No. 6608439
- Non-patent document 1 APPLIED PHYSICS LETTERS, VOLUME 80, NUMBER 19, p.3608-3610 (2002)
- the present invention has been made to solve the above-mentioned problems, and does not scatter light emitted from a light source having a high affinity and a high dispersibility with a light-transmitting medium having a small particle size, and Metal oxide-based phosphor fine particles having excellent water resistance, chemical resistance, and heat resistance, a method for producing the same, a metal oxide-based phosphor fine particle dispersion liquid, a fluorescence conversion film, and a metal oxide-based phosphor fine particle using the same.
- An object of the present invention is to provide a separation method, a fluorescent liquid, a fluorescent paste, a phosphor, a method for producing the same, and a fluorescence converter.
- the inventors of the present invention have conducted intensive studies in order to achieve the above object, and as a result, a metal oxide in which a metal element serving as a luminescent center is doped in a host crystal made of a metal oxide as a fluorescent material. It has been found that the above object can be achieved by using organic phosphor fine particles having an organic group coordinated on the surface thereof, thereby completing the present invention.
- the present invention provides metal oxide-based phosphor fine particles in which a metal element serving as a luminescence center is doped in a host crystal composed of a metal oxide, and the organic fine particles are provided on the surface of the phosphor fine particles.
- a dispersion medium containing an organic compound having at least one functional group at a terminal or a side chain containing an organic compound having at least one functional group at a terminal or a side chain
- a metal oxide in which a metal element serving as a luminescence center is doped in a host crystal composed of a metal oxide a metal oxide-based phosphor fine particle in which at least one functional group is dissociated from the organic compound on the surface of the phosphor fine particle; Body fine particle dispersion,
- a solution prepared by dissolving or dispersing a matrix composed of a metal oxide and a compound of a metal element serving as a luminescence center in a dispersion medium containing an organic compound having at least one functional group at a terminal or side chain is placed in a pressure vessel.
- a method for producing metal oxide-based phosphor fine particles which are sealed and heated at a temperature not lower than the boiling point of the organic compound,
- a mixture of a metal oxide-based phosphor fine particle and a solvent is subjected to classification treatment by single or combination of centrifugation, filter treatment, or natural sedimentation, and a transparent metal oxide containing a solvent Method for separating metal oxide-based phosphor fine particles to be separated as fine-particle-based phosphor fine particles, wherein the solvent contains 10% by weight or more of the metal-oxide-based fluorescent fine particles, and is caused by the metal oxide in the metal-oxide-based fluorescent fine particles.
- a transparent fluorescent liquid that transmits 50% or more of light having an emission wavelength
- the solvent contains the metal oxide-based phosphor fine particles in an amount of 50% by weight or more, and transmits at least 50% of light having an emission wavelength due to the metal oxide in the metal oxide-based phosphor fine particles in terms of an optical path length of 150 xm.
- Transparent fluorescent paste
- a method for producing a phosphor wherein the phosphor liquid or the paste is calcined at a temperature of 500 ° C. or lower,
- the metal oxide-based phosphor fine particles of the present invention are excellent in water resistance, chemical resistance, and heat resistance, which have a small particle size, a high affinity for a light transmitting resin, and a high dispersibility. For this reason, the fluorescence conversion film, the fluorescent liquid, the fluorescent paste, the phosphor, and the fluorescent converter using the metal oxide-based phosphor fine particles of the present invention do not scatter the light emitted from the light source, and are placed on the light source. It is very practical and useful as it is arranged to convert the wavelength of the excitation light emitted from the light source into light having a longer wavelength and emit fluorescence.
- FIG. 1 is a diagram illustrating the structure of a metal oxide-based phosphor fine particle of the present invention.
- FIG. 2 is a diagram illustrating a surface state of metal oxide-based phosphor fine particles of the present invention.
- FIG. 3 is a diagram illustrating a metal oxide-based phosphor fine particle dispersion of the present invention.
- FIG. 4 is a diagram illustrating functions of the fluorescence conversion film of the present invention.
- FIG. 5 is a diagram illustrating a method for producing metal oxide-based phosphor fine particles of the present invention.
- FIG. 6 is another drawing explaining the method for producing metal oxide-based phosphor fine particles of the present invention.
- Figure 7 X-ray diffraction pattern (upper row) of powder of Example 1 and JCPDS force corresponding to YAlO
- FIG. 1 A first figure.
- FIG. 8 shows an excitation spectrum and a fluorescence spectrum of the powder of Example 1.
- FIG. 9 is a diagram showing an emission spectrum of the organic EL device and an emission spectrum obtained through a fluorescence conversion film in Example 6.
- FIG. 1 A first figure.
- FIG. 11 is a schematic diagram of a thin film sample in Example 9.
- FIG. 12 is a photograph of a thin film sample in Example 9 viewed from above.
- FIG. 13 is a view showing a transmission spectrum of a paste of Example 9.
- FIG. 14 shows an excitation spectrum and a fluorescence spectrum of the paste of Example 9.
- FIG. 15 is a view showing the relationship between the film thickness and the fluorescence intensity in the pastes of Example 16 and Comparative Example 3.
- FIG. 16 is a diagram showing the relationship between the absorbance and the fluorescence quantum yield when the dye concentration in a conventional fluorescence conversion film is changed.
- the metal oxide-based phosphor fine particles of the present invention as shown in FIG. 1, have metal oxide-based phosphor fine particles in which a metal element serving as an emission center is doped in a base crystal made of a metal oxide. Wherein an organic group is coordinated on the surface of the phosphor fine particles.
- the organic group is at least one functional group dissociated from an organic compound having at least one functional group at a terminal or a side chain, and the organic group is a metal atom in a metal oxide of a host crystal.
- the functional group X is dissociated from the organic compound (X-R), and Organic group R is coordinated.
- Me is a metal atom
- O is an oxygen atom.
- the host crystal is composed of at least one kind of metal oxide, for example, B ⁇ , BO, BaAl ⁇ , BaAl ⁇ , BaBOBr, BaMgAlO, BaM
- LaOBr La ⁇ Cl, Mg As O, MgB O, MgSiO, Mg SiO, Mg TiO, ScBO
- Y A1 O, (Y Gd) Al O, Y (Al G x 1-x 2 4 3 5 12 x 1-x 3 5 12 3 xa) O, Y ⁇ , (Y Gd) ⁇ are preferred.
- (Y) means that (1-x) at% is replaced by gadolinium (Gd).
- the metal element serving as the emission center is added as an impurity in the form of a metal atom or ion as an impurity in the base metal oxide crystal, and exists as a solid solution in the base crystal. This metal element absorbs light emitted from the excitation light source and becomes an excited state, and emits light when the excited state is deactivated and returns to the ground state.
- the metal element serving as the emission center can be listed as the following elements as a series.
- Manganese ions (Mn + , Mn 4+ ), chromium ions (Cr 3+ )
- rare earth metal element ions are preferred because of their high luminous efficiency, europium (Eu), terbium (Tb), praseodymium (Pr), cerium (Ce), samarium (Sm), thulium ( Tm), dysprosium (Dy) and lutetium (Lu).
- a metal element in the metal oxide of the host crystal and a metal element which is a luminescence center As a preferable combination with, for example, the metal element force in the metal oxide of the host crystal, yttrium (Y), aluminum (A1), gadolinium (Gd), lanthanum (La), gallium (Ga) and barium (Ba)
- the metal element that is the emission center is at least one selected from europium (Eu), cerium (Ce), and terbium (Tb).
- the compound obtained in combination include an example in which europium (Eu) is used as an emission center, BaAl O: Eu BaMgAl O: Eu BaMgAl O: Eu 2+ , Y ⁇ : Eu 2+ , Ba
- GdNbO Eu 3+
- BaMgAl O Eu 3+
- BaMg Al O Eu
- GdBO Eu ⁇ LuBO
- the organic group is obtained by dissociating at least one of the functional groups from an organic compound having one or more functional groups at a terminal or a side chain.
- Examples of the organic group include a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, Substituted or unsubstituted cycloalkyl group having 1 to 50 carbon atoms, substituted or unsubstituted aryl group having 650 carbon atoms, substituted or unsubstituted heteroaryl group having 5 to 50 carbon atoms, substituted or unsubstituted Examples thereof include an aralkyl group having 750 carbon atoms and a substituted or unsubstituted aryloxy group having 5 to 50 carbon atoms.
- Examples of the substituted or unsubstituted alkyl group include a methynole group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s_butyl group, an isobutyl group, a t_butyl group and an n-pentyl group , N-hexyl group, n-heptyl group, n-octyl group, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 2-hydroxyisobutyl group, 1,2-dihydroxy Ethyl group, 1,3-dihydroxyisopropyl group, 2,3-dihydroxy-t-butyl group, 1,2,3-trihydroxypropyl group, chloromethyl group, 1-chloroethyl group, 2-chloroethyl group , 2_ isobutyl, 1,2-dichloroethyl, 1,3-dichlor
- Examples of the substituted or unsubstituted alkenyl group include bier group, aryl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1,3-butanenyl group, 1-methylvinyl group, styryl group, 2 1,2-divinyl vinyl group, 1,2-divinyl vinyl group, 1-methylaryl group, 1,1-dimethylaryl group, 2-methylaryl group, 1-phenylaryl group, 2-phenylaryl group, 3-phenylaryl group, 3, Examples thereof include 3-diphenylaryl group, 1,2-dimethylaryl group, 11-phenyl-1-buturyl group, 3-phenyl-1-buturyl group, and the like, preferably styryl group and 2,2-diphenylvinyl. And 1,2-diphenylvinyl group.
- the substituted or unsubstituted alkoxy group is a group represented by _OY.
- Examples of ⁇ include the specific examples exempl
- Examples of a substituted or unsubstituted cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 4-methylcyclohexyl group, a 1-adamantyl group, a 2-adamantyl group, and a 1-norbornyl group. , 2_ norbornyl group and the like.
- substituted or unsubstituted aryl group examples include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, and 2-phenanthryl.
- substituted or unsubstituted heteroaryl groups include 1_pyrrolyl, 2_pyrrolyl, 3-pyrrolyl, virazinyl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 1-indolyl , 2—indolyl, 3—indolyl, 4—indolyl, 5—indolyl, 6—indolyl, 7—indolyl, 1—isoindolyl, 2—isoindolyl, 3—isoindolyl, 4—isoindolyl Group, 5-isoindolyl group, 6-isoindolyl group, 7-isoindolyl group, 2-furinole group, 3-furinole group, 2-benzofuranyl group, 3-benzofuranyl group, 4-benzofuranyl group, 5-benzofuranyl group , 6-benzofuranyl, 7-benzofuranyl, 1-
- substituted or unsubstituted aralkyl groups include benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, 2_phenylisopropyl, phenyl-1-butyl, and Naphthylmethyl group, 1-hyphenaphthylethyl group, 2_hyphthnaphthylethyl group, 1-hyphthnaphthylisopropyl group, 2-hyphthnaphthylisopropyl group,; 3-naphthylmethyl group, 11-naphthylethyl group, 2- 1-naphthylethyl group, 1_ ⁇ 1-naphthylisopropyl group, 2--1-naphthylisopropyl group, 1-pyrrolylmethyl group, 2- (1-pyrrolyl) ethyl group, p-methylbenzyl group, benz
- the substituted or unsubstituted aryloxy group is a group represented by —OY ′, and examples of Y ′ include the specific examples exemplified for the aryl group.
- each of the above groups is a monovalent group, but may be a divalent or higher valent group in which hydrogen has been dissociated, or may be a group in which hydrogen is substituted with the following functional group.
- the average particle diameter of the metal oxide-based phosphor fine particles of the present invention is preferably as small as 110 nm, and is preferably 160 nm.
- the functional group include a ZH group having at least one proton (where Z is
- n is an integer of 1 or more) and the like; OH group, NH group, SH group
- An OH group which is preferably an NHR 'group (R' is an alkyl group), is more preferable.
- Examples of the organic compound having one or more functional groups at the terminal or side chain include isopinole alcohol, 1,4-butanediol, 1,5_pentanediol, 1,6-hexanediol, glycerone, ethylene Glyconore, trimethylene glycolone, 1,3-propanediol, 1,4-hydroxybenzene, 1,3-hydroxybenzene, 1,2-hydroxybenzene, 2-hydroxyethyl mercaptan, 2-hydroxyethyl And 4-butanediol, glycerol and ethylene glycol are preferred.
- TG-DTA differential thermal-thermogravimetric analysis
- Whether or not OH is coordinated on the surface of the fine particles can be determined based on whether or not the weight loss continues to be observed even when the temperature rises above the boiling point of 1,4-butanediol above 229 ° C. . If the temperature continues to rise, the organic groups coordinated on the surface are thermally decomposed and the weight loss continues.
- the metal oxide-based phosphor fine particle dispersion liquid of the present invention comprises: (a) a dispersion medium containing an organic compound having at least one functional group at a terminal or a side chain; In a metal oxide phosphor fine particle in which a metal element serving as an emission center is doped in a host crystal made of a metal oxide, at least one functional group is dissociated from the organic compound on the surface of the phosphor fine particle. Metal oxide-based phosphor fine particles to which an organic group is coordinated. As described above, the metal oxide-based phosphor fine particle dispersion of the present invention uses the above-described metal oxide-based phosphor fine particles of the present invention as the component (b) and uses the component (b) as the component (a).
- the dispersion medium of the component (a) may contain other known components in addition to the organic compound.
- ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone
- Cellosolves such as methyl-solve, ethyl-solve, butyl-solve, and cellosolve acetate, ratatones such as ⁇ -butyrolataton, polyethylene glycol And the like.
- the metal oxide-based phosphor fine particle dispersion of the present invention may further contain (c) a resin component.
- the resin component examples include a non-curable resin, a thermosetting resin, and a photocurable resin.
- oligomer or polymer melamine resin phenol resin, alkyd resin, epoxy resin, polyurethane resin, Maleic acid resin, polyamide resin, or polymethylenmethacrylate, polyarylate, polycarbonate, polyvinyl alcohol, polyvinylinolepyrrolidone, hydroxyethylcellulose, carboxymethylcellulose, etc. Coalescence.
- a photocurable resin component is used.
- the photocurable resin include photopolymerizable acrylic acid, methacrylic acid-based, methacrylic acid ester-methacrylic acid copolymers having a reactive butyl group containing a photosensitizer, and photocrosslinkable resins such as polycaeic acid butyl.
- a mold is used.
- a monomer and / or oligomer having a photopolymerizable ethylenically unsaturated group, a photopolymerization initiator or a sensitizer can be added.
- the monomer and oligomer components include 2-hydroxyethyl (meth) atalylate, 2-hydroxypropyl (meth) atalylate, and 2-hydroxyhexyl (meth) atalylate as monomers having a hydroxyl group.
- (meth) acrylates such as ethylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylate.
- photopolymerization initiator or sensitizer for example, acetophenones, benzophenones, benzoin ethers, thio compounds, anthraquinones, organic peroxides, and thiols are preferably used.
- the resin component (c) is a light-transmitting resin.
- the light-transmitting resin refers to a resin having a transmittance of 30% or more with respect to light emitted from an excitation light source and light emitted from a phosphor, and includes the same examples as the resin components.
- the metal oxide-based phosphor fine particle dispersion liquid of the present invention may have, if necessary, Additives such as chemicals, thermal polymerization inhibitors, plasticizers, defoamers and leveling agents can be added.
- Examples of the curing accelerator include perbenzoic acid derivatives, peracetic acid, and benzophenones.
- the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, and phenothiazine.
- Examples of the agent include dibutyl phthalate, octyl phthalate, tricresyl and the like.
- the fluorescence conversion film of the present invention is obtained by dispersing the metal oxide-based phosphor fine particles of the present invention in a light transmitting resin.
- the light transmitting resin is the same as described above.
- the production of the fluorescence conversion film is not particularly limited, and a dispersion in which the metal oxide-based phosphor fine particles of the present invention, a dispersion medium and a light-transmitting resin are mixed is formed by a known film forming method, for example, a spin coating method, The film is formed on the supporting substrate by a method such as a screen printing method, a dipping method, and an inkjet method. After the film is formed, the dispersion medium is evaporated from the film by appropriately heating according to the boiling point, vapor pressure, and film thickness of the dispersion medium, and the dispersed fluorescence of the metal oxide-based phosphor fine particles in the light-transmitting resin. Obtain a conversion membrane.
- the thickness of the fluorescence conversion film is usually 0.1 / im-1 mm, preferably 1 / im-100 / im.
- the amount of the metal oxide-based phosphor fine particles in the fluorescence conversion film is usually 0.1 to 90% by mass, and preferably 1 to 70% by mass. When the amount of the fine particles is 0.1% by mass or more, light emitted from the excitation light source can be sufficiently absorbed, and the resulting fluorescence intensity is high. When the amount of the fine particles is 90% by mass or less, it is preferable because the smoothness of the film is good and the mechanical strength is high.
- the fluorescent conversion film, the fluorescent liquid, the fluorescent paste, the fluorescent substance, and the fluorescent converter of the present invention are arranged on an excitation light source as shown in FIG.
- the excitation light source include an organic electroluminescent device, an inorganic electroluminescent device, a light emitting diode, a cold cathode tube, a fluorescent tube, a laser, and the like, and are particularly suitable for the organic electroluminescent device and the light emitting diode.
- a compound of a metal element forming a base composed of a metal oxide and a compound of a metal element which is a luminescent center are terminated or A raw material solution dissolved or dispersed in a dispersion medium containing an organic compound having at least one functional group in a side chain is sealed in a pressure vessel, and heated at a temperature equal to or higher than the boiling point of the organic compound.
- the specific production method can be roughly divided into (1) selection of raw materials (base metal oxide source, metal element source of luminescence center, the organic compound and dispersion medium), “preparation” preparation, (2) heating, (3) ) It consists of three steps of purification. Hereinafter, description will be made in order.
- the metal element forming the base metal oxide constituting the metal oxide-based phosphor fine particles of the present invention and the supply source of the metal element serving as the luminescent center include the metal oxide serving as the base and the metal serving as the luminescent center.
- Elemental compounds such as carbonates, acetates, nitrates, hydroxides, sulfates, phosphates, borates, silicates, aluminates, carboxylates, halides, alkoxides and the like Japanese products can be mentioned. These are prepared by a conventional method at a compounding ratio at which a target compound can be obtained, and dissolved or dispersed in the dispersion medium to obtain a raw material solution.
- the prepared raw material solution is sealed in a pressure vessel typified by an autoclave.
- the dispersion medium containing an organic compound having one or more functional groups in the terminal or side chain is described in the metal oxide phosphor fine particle dispersion. It is the same as what was done.
- the volume ratio (volume ratio) of the raw material solution to the internal volume of the pressure vessel is preferably as large as possible because heating time described later can be reduced. Specifically, it is preferably 40% or more. More preferably, it is 60% or more.
- the reaction In order to advance the reaction of the raw material solution, heat is supplied from a heating source installed outside the pressure vessel.
- a heating source installed outside the pressure vessel.
- the reaction it is usually necessary to fire at a high temperature of 800 ° C. or higher.
- the reaction can be performed at a low temperature of, for example, 200 ° C. to 500 ° C., Fine particles smaller than the particle size normally obtained can be obtained. That is, it is necessary to increase the pressure in the pressure vessel, and the heating is performed at a temperature not lower than the boiling point of the dispersion medium to be used.
- the pressure during the reaction is usually 0.5 lOMPa, and preferably 18 MPa.
- the heating time can be appropriately selected because the ultimate pressure varies depending on the type of the target metal oxide phosphor fine particles, the raw material compound, and the type of the dispersion medium, and is usually in the range of 1 hour to 10 hours. . If the time is shorter than 1 hour, the crystallinity of the fine particles does not increase, and the required fluorescence intensity cannot be obtained. If the time is longer than 10 hours, impurities are likely to be mixed due to carbonization of the dispersion medium, and secondary aggregation of fine particles is liable to occur.
- the mixture After completion of the reaction, the mixture is cooled to room temperature. If necessary, centrifuge the product, add organic solvent to the remaining precipitate, and centrifuge again.
- known production methods such as the coprecipitation method and the sol-gel method, it was necessary to bake at a high temperature of 1000 ° C. or more after completion of the reaction in order to increase crystallinity. Then, secondary aggregation proceeded, and as a result, only large particles of 100 nm or more could be obtained. According to the production method of the present invention, it is not necessary to perform calcination after the reaction, so that fine particles having a small particle diameter can be obtained. Furthermore, if purification is necessary, an organic solvent may be added and centrifugation may be repeated several times.
- the mixture of the metal oxide-based phosphor fine particles and a solvent is classified by centrifugation, filter treatment, or natural sedimentation alone or in combination. , Separated as transparent metal oxide-based phosphor particles containing solvent To do.
- the mixture is subjected to classification treatment by centrifugation, filter treatment, or natural sedimentation alone or in combination, It is preferable to separate them as transparent metal oxide-based phosphor fine particles containing a solvent.
- a solvent or water used for synthesizing the following metal oxide-based phosphor fine particles can be suitably used, and has a function of changing the dispersion state of the fine particles.
- a solvent used for phosphor synthesis eg, 1,4-butanediol
- the ratio of the dispersed fine particles to the solvent changes, the adsorption equilibrium changes, and the dispersibility changes.
- an organic solvent such as acetone
- dispersion of fine particles becomes unstable, and sedimentation is accelerated.
- Typical solvents include linear or branched alcohols, monohydric alcohols, polyhydric alcohols, alkanes, ketones, ethers, esters, aromatic solvents, water and the like.
- the amount of the solvent to be added should be set to an optimum value while observing the condition.
- the fluorescent liquid of the present invention contains the metal oxide-based phosphor fine particles of the present invention in a solvent in an amount of 10% by weight or more, and emits light having an emission wavelength caused by the metal oxide in the metal oxide-based phosphor fine particles. It is a transparent fluorescent liquid that transmits 50% or more in terms of lcm.
- the fluorescent liquid mentioned here generally means a liquid having a viscosity of 50, OOOcp or less, and in a narrow sense, a liquid having a viscosity of 1 or less, OOOcp.
- the fluorescent paste of the present invention contains the metal oxide-based phosphor fine particles of the present invention in a solvent in an amount of 50% by weight or more, and emits light having an emission wavelength due to the metal oxide in the metal oxide-based phosphor fine particles.
- Transparent fluorescent paste that transmits 50% or more when converted to an optical path length of 150 / m.
- the fluorescent paste mentioned here generally refers to a paste having a viscosity of 1, OOOcp or more, and in a narrow sense, a paste having a viscosity of 50, OOOcp or more.
- solvent in the fluorescent liquid and the fluorescent paste in addition to 1,4-butanediol, linear or branched alcohols, monohydric alcohols, polyhydric alcohols, alkanes, ketones, ethers, esters, aromatic solvents, water, etc. Is mentioned.
- a fluorescent substance that is a transparent solid By firing the fluorescent liquid and the fluorescent paste at a temperature of 500 ° C. or less, a fluorescent substance that is a transparent solid can be obtained.
- the firing atmosphere is in the air, It can be appropriately selected such as in an inert gas.
- the fluorescence converter of the present invention is a force obtained by solidifying the phosphor of the present invention alone or by adding a resin and / or a solvent to the phosphor, or the phosphor of the present invention. Is dispersed in a resin and / or a solvent.
- the resin used for the fluorescent converter of the present invention is not particularly limited, and any known resin may be used, and examples thereof include the same examples as the resin component (c).
- the solvent used for the fluorescence converter of the present invention is not particularly limited, and a known solvent may be used.
- any route to the separated object may be passed according to the direction of the arrow.
- the mixture is cooled to room temperature. From this product, a mixture of a metal oxide-based phosphor fine particle and an organic group and a solvent coordinated to the surface of the metal oxide-based phosphor fine particle Take out the phosphor. At this time, if the conditions are appropriately selected, the phosphor can be separated as a transparent phosphor.
- the separation procedure first, one or more kinds of the above-mentioned solvents for changing the dispersion state are added in order to assist the separation in the post-treatment.
- the amount of the solvent added is 1 / 20-2 / 1, preferably 1Z5-1-1 based on the volume of the product.
- the mixing may be promoted by an ultrasonic homogenizer or a mechanical homogenizer. Further, if the post-treatment can be easily separated depending on the state of the product, the solvent may not be added.
- coarse particles are removed by the first standing, the first filter filtration, or the first centrifugation (classification operation), and the removal range is usually 1 micron or more, preferably 0.1 micron. Remove coarse particles of at least ⁇ m, more preferably at least 0.01 xm.
- the classified fine particles are separated by a second standing, a second filter, or a second centrifugation.
- the first and second settling times at this time are preferably about one day to one month, and are appropriately selected depending on the production condition of the fine particles.
- the first and second filters can be any filters as long as they can be separated by filtration.
- the centrifugal force is usually 100 g to 100,000 g, preferably 1000 g to 5000 g, and the processing time is usually 10 minutes to 3 hours, preferably 30 minutes to 60 minutes.
- the precipitate after centrifugation is separated by decantation. At this time, a transparent phosphor dispersion liquid having a low solid content is generated near the solid-liquid interface.
- the separated phosphor is in a paste state. Further, when this paste is fired, for example, at a temperature of usually 500 ° C or lower, preferably 400 ° C or lower, more preferably 250 to 300 ° C under a nitrogen stream, a transparent phosphor (solid) is obtained.
- the firing time depends on the total amount of the paste to be processed, but is preferably about 10 minutes to 1 hour.
- a sample obtained by fixing the obtained product powder to a glass substrate was used as a sample, and the relationship between the X-ray diffraction angle and the diffraction intensity was determined using an X-ray diffraction measurement device (Rint2200, manufactured by Rigaku Corporation).
- the powder was identified by comparison with a powder X-ray diffraction database compiled by jCPDS (Joint Committee on Powder Diffraction Standards) of the JCPDS card (ICDD Ontemational Center for Diffraction Data).
- the powder was filled in a quartz cell, and the peak wavelength of the excitation spectrum was determined using a fluorescence spectrophotometer (FP-6500, manufactured by JASCO Corporation). Next, the fluorescence when ⁇ is the excitation wavelength
- the peak wavelength ⁇ and peak intensity I of the spectrum were determined.
- the thin film sample is placed in place of the quartz cell, and a magnesium oxide plate with high diffuse reflectance is placed on the back of the thin film sample to enable efficient measurement of the backward fluorescence. did.
- the excitation light was incident on the thin film at an angle of 45 °, the fluorescence in the 45 ° direction was measured, and the peak intensity was measured.
- the transmittance of the phosphor sample was measured using an ultraviolet-visible light spectrophotometer (Shimadzu Corporation UV3 100). The transmittance of the thin-film sample, which was perpendicularly incident on the substrate and transmitted through the thin-film folder, was measured. The solution sample was measured in a 1 cm square solution cell.
- Example 1 Metal oxide-based phosphor fine particles Y AI O: Ce
- Table 1 shows these raw materials and production conditions.
- Figure 7 shows the obtained X-ray diffraction pattern (upper) and the JCPDS card corresponding to YAlO (lower). As can be seen from Figure 7
- the average particle size of the powder measured by the method (3) was 46 nm.
- Figure 8 shows the excitation state obtained by the measurement.
- 2 shows a fluorescence spectrum and a fluorescence spectrum.
- Example 2 Metal oxide-based phosphor fine particles Y AI O: Ce
- Table 1 shows these raw materials and production conditions.
- the average particle size of the powder measured by the method (3) was 52 nm.
- Example 3 Metal oxide-based phosphor fine particles Y AI O: Ce Lu
- Table 1 shows these raw materials and production conditions.
- the obtained powder was subjected to the above-described methods (1) and (4), and the results of the measurements are shown below.
- Example 4 Metal oxide phosphor fine particles Y AI O: Ce
- Table 1 shows these raw materials and production conditions.
- the obtained powder was subjected to the above-described methods (1) and (4), and the results of the measurements are shown below.
- the average particle size of the powder measured by the method (3) was 82 nm.
- Example 5 Metal oxide-based phosphor fine particles Y AI O: Ce
- EG (10.8 ml) was added to the gap between the inner glass cylinder and the pressure vessel.
- the inner volume of the pressure vessel was 120 ml
- the charged volume of the raw material was 63.6 ml
- the charged volume ratio of the raw material solution to the inner volume of the pressure vessel was 53.0%.
- Table 1 shows these raw materials and production conditions.
- the average particle diameter of the powder measured by the method (3) was 51 nm.
- Example 6 Metal oxide-based phosphor fine particles Y AI O: Ce
- the charged volume ratio of the raw material solution to the internal volume of the pressure vessel was 53.0%.
- Table 1 shows these raw materials and production conditions.
- the measurement results of the obtained powder by the methods (1) and (4) are shown below.
- the average particle size of the powder measured by the method (3) was 52 nm.
- Example 7 Metal oxide-based phosphor fine particles Y AI O: Ce
- Table 1 shows these raw materials and production conditions.
- the obtained powder was subjected to the above-described methods (1) and (4), and the results of the measurements are shown below.
- the mass% of Ce in the powder was measured by the method of the above (2), it was 0.55 mass%.
- the power was confirmed to be S-doped.
- the average particle size of the powder measured by the method (3) was 104 nm.
- Table 1 shows these raw materials and production conditions.
- FIG. 10 shows the obtained X-ray diffraction pattern and the JCPDS card corresponding to YA1 ⁇ .
- the obtained X-ray diffraction pattern is compatible with the JCPDS card corresponding to YAIO.
- the wavelengths ⁇ and ⁇ and the peak intensity I were measured by the method (4), but significant fluorescence was measured.
- the fluorescence peak wavelength at this time was 520 nm. From the measurement of the absorption spectrum in (5), the transmittance at a wavelength of 520 nm was 88%. From the weight loss when this transparent dispersion was heated to 300 ° C, the solvent contained in the dispersion was 85% by weight. That is, the solid concentration was 15%.
- the phosphor obtained from the precipitated portion was a yellow transparent paste.
- the solvent contained in the paste was about 20% by weight due to the weight loss when the paste was heated to 300 ° C in nitrogen. That is, the solid content concentration was 80% by weight.
- the phosphor after heating became a transparent mass.
- FIGS. 11 and 12 show a schematic diagram and a photograph viewed from above.
- FIG. 13 shows the transmission spectrum obtained from this thin film sample
- FIG. 14 shows the fluorescence spectrum and the excitation spectrum.
- the peak wavelength of the fluorescence spectrum was 520 nm.
- the transmittance at a wavelength of 520 nm was 89%.
- the characters through the thin film of the paste were clearly read, and the high transparency was confirmed.
- Example 2 The powder obtained in Example 1 and polyethylene glycol (molecular weight: 600) were mixed at a weight ratio of 75:25 to prepare a yellow-white turbid paste. A gap of 150 / m was formed between the two glass plates with a spacer, and the paste was sandwiched therebetween and sealed with a sealant to obtain a transparent thin film sample.
- the peak wavelength of the fluorescence spectrum was 525 nm when measured by the method (4), and the transmittance at a wavelength of 525 nm was 45 according to the absorption spectrum measurement of (5). /. Met
- the phosphor obtained from the precipitate was a yellow transparent paste.
- the weight loss when the paste was heated to 300 ° C in nitrogen indicated that the solvent contained in the paste was about 30% by weight. That is, the solid concentration was 70% by weight.
- the phosphor after heating decreased in volume and became a transparent mass. The solvent was removed from the paste to obtain a transparent solid.
- the phosphor obtained from the precipitated portion was a yellow transparent paste.
- the weight loss when the paste was heated to 300 ° C in nitrogen indicated that the solvent contained in the paste was about 25% by weight. That is, the solid concentration was 75% by weight.
- the phosphor after heating decreased in volume and became a transparent mass. The solvent was removed from the paste to obtain a transparent solid.
- the phosphor obtained from the precipitate was a yellow transparent paste.
- the weight loss when the paste was heated to 300 ° C in nitrogen indicated that the solvent contained in the paste was about 45% by weight. That is, the solid concentration was 55% by weight.
- the phosphor after heating decreased in volume and became a transparent mass. The solvent was removed from the paste to obtain a transparent solid.
- the phosphor obtained from the precipitate was a yellow transparent paste.
- the weight loss when the paste was heated to 300 ° C in nitrogen indicated that the solvent contained in the paste was about 45% by weight. That is, the solid concentration was 55% by weight.
- the phosphor after heating decreased in volume and became a transparent mass. The solvent was removed from the paste to obtain a transparent solid.
- Example 15 The yellow transparent paste obtained in Example 12 was heated to 300 ° C. in an oven purged with nitrogen and held for 30 minutes. After cooling, it was taken out to obtain a transparent solid. When this solid material was exposed to ultraviolet light with a wavelength of 365 nm, it glowed green, confirming that it was a fluorescent converter.
- Example 15
- Example 12 The yellow transparent paste obtained in Example 12 and PEG (average molecular weight: 2,000) were weighed into a beaker so that the weight ratio became 1:10, and the mixture obtained by mixing at about 150 ° C. on a hot plate was mixed with a glass substrate. Spreading on top gave a yellow film. The same mixture was poured into a heat-resistant box (made of stainless steel) in a heated state to obtain a resin substrate having a thickness of 2 mm. Both the thin film and the resin substrate glowed green when exposed to ultraviolet light with a wavelength of 365 nm, confirming that it was a fluorescent converter.
- Example 9 (viii) when the obtained yellow transparent paste was sandwiched between two glass plates, the gap (film thickness) was changed to 100 am, 200 ⁇ m, and 300 ⁇ m, and the resulting fluorescent paste was changed. The peak intensity dependence of petal was measured.
- FIG. 15 shows the results obtained by plotting the film thickness on the horizontal axis and the fluorescence intensity on the vertical axis as the peak intensity. As shown in the figure, the film thickness and the fluorescence intensity were almost directly proportional, and it was found that the paste was transparent and the fluorescence could be efficiently extracted.
- FIG. 15 shows the results obtained by plotting the film thickness on the horizontal axis and the fluorescence intensity on the vertical axis as the peak intensity. As shown in the figure, the relationship between the film thickness and the fluorescence intensity was found to be less dependent, and it was found that the fluorescence could not be efficiently extracted even when the film thickness was increased because the paste was opaque.
- Example 9 The yellow transparent paste obtained in Example 9 was mixed with polyethylene glycol (molecular weight: 6000) at a weight ratio of 75:25 while increasing the temperature to 150 ° C. The mixture was poured into a stainless steel vat and cooled to room temperature to obtain a substrate having a thickness of 2 mm. When illuminated with 365 nm light, it glowed green, confirming that it was a fluorescence conversion plate that functions as a fluorescence conversion body.
- polyethylene glycol molecular weight: 6000
- Example 9 The yellow transparent paste obtained in Example 9 was mixed with polyethylene glycol (molecular weight: 6000) at a weight ratio of 75:25 while increasing the temperature to 150 ° C.
- Blue light emitting diode (Nichia) Resin (NSPE520S, manufactured by Nippon Kabushiki Kaisha) was carefully removed, and the mixture was added dropwise to the removed light-emitting portion, followed by cooling. When the light emitting diode is turned on, yellow-green-white light is emitted.
- Example 8 In (i) of Example 8, except that the yellow transparent paste obtained in Example 9 was used in place of the powder, (i) one (m) operation was performed, and the same procedure was performed in Gii). The emission spectrum when excited by the light source was measured. As a result, green light with CIE chromaticity coordinates (0.25, 0.44) and luminosity of 130 nit was obtained.
- the metal oxide-based phosphor fine particles of the present invention have a high affinity for a light-transmitting resin having a small particle size, a high dispersibility, and are resistant to water, chemicals, and heat. Excellent in nature. For this reason, the fluorescence conversion film, the fluorescent liquid, the fluorescent paste, the phosphor, and the fluorescent converter using the metal oxide-based phosphor fine particles of the present invention do not scatter the light emitted from the light source, and are not scattered on the light source. It is extremely practical and useful as an arrangement that converts the wavelength of the excitation light emitted from the light source into light having a longer wavelength and emits fluorescence.
- the light source include an organic electroluminescent device, an inorganic electroluminescent device, a light emitting diode, a cold cathode tube, a fluorescent tube, and a laser.
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Abstract
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EP05704113A EP1715022A4 (en) | 2004-01-29 | 2005-01-26 | METAL OXIDE LIQUID MICROPARTICLES AND METHOD FOR THE PRODUCTION THEREOF, DISPERSION LIQUID THEREOF, FLUORESCENCE REVERSE TEMPERATURES, METHOD FOR SEPARATING METAL OXIDE LIGHT MATERIAL MICROPARTICLES, FLUORESCENT LIQUID, FLUORESCENT PASTE, FLUORESCENT AND METHOD FOR PRODUCING THEM; AS WELL AS FLUORESCENCE |
US10/587,631 US20070166543A1 (en) | 2004-01-29 | 2005-01-26 | Metal oxide phosphor microparticle and process for producing the same; utilizing the same, dispersion liquid, fluorescence conversion membrane, method of separating metal oxide phosphor microparticle, fluorescent liquid, fluorescent paste, phosphor and process for producing the same; and fluorescence converter |
JP2005517448A JP4989891B2 (ja) | 2004-01-29 | 2005-01-26 | 金属酸化物系蛍光体微粒子を利用した蛍光体及びその製造方法並びに蛍光変換体 |
US12/546,162 US7883641B2 (en) | 2004-01-29 | 2009-08-24 | Metal oxide phosphor microparticle and process for producing the same; utilizing the same, dispersion liquid, fluorescence conversion membrane, method of separating metal oxide phosphor microparticle, fluorescent liquid, fluorescent paste, phosphor and process for producing the same; and fluorescence converter |
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US10/587,631 A-371-Of-International US20070166543A1 (en) | 2004-01-29 | 2005-01-26 | Metal oxide phosphor microparticle and process for producing the same; utilizing the same, dispersion liquid, fluorescence conversion membrane, method of separating metal oxide phosphor microparticle, fluorescent liquid, fluorescent paste, phosphor and process for producing the same; and fluorescence converter |
US12/546,162 Division US7883641B2 (en) | 2004-01-29 | 2009-08-24 | Metal oxide phosphor microparticle and process for producing the same; utilizing the same, dispersion liquid, fluorescence conversion membrane, method of separating metal oxide phosphor microparticle, fluorescent liquid, fluorescent paste, phosphor and process for producing the same; and fluorescence converter |
US12/546,162 Continuation US7883641B2 (en) | 2004-01-29 | 2009-08-24 | Metal oxide phosphor microparticle and process for producing the same; utilizing the same, dispersion liquid, fluorescence conversion membrane, method of separating metal oxide phosphor microparticle, fluorescent liquid, fluorescent paste, phosphor and process for producing the same; and fluorescence converter |
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US (2) | US20070166543A1 (ja) |
EP (1) | EP1715022A4 (ja) |
JP (1) | JP4989891B2 (ja) |
KR (1) | KR20060123537A (ja) |
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US7393618B2 (en) * | 2006-09-15 | 2008-07-01 | Idemitsu Kosan Co., Ltd. | Composition for color converting member and production method of color conversion substrate using the same |
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2005
- 2005-01-26 KR KR1020067016260A patent/KR20060123537A/ko not_active Application Discontinuation
- 2005-01-26 WO PCT/JP2005/000976 patent/WO2005073342A1/ja active Application Filing
- 2005-01-26 JP JP2005517448A patent/JP4989891B2/ja not_active Expired - Fee Related
- 2005-01-26 US US10/587,631 patent/US20070166543A1/en not_active Abandoned
- 2005-01-26 CN CNA2005800087377A patent/CN1934217A/zh active Pending
- 2005-01-26 EP EP05704113A patent/EP1715022A4/en not_active Withdrawn
- 2005-01-28 TW TW094102787A patent/TW200528538A/zh unknown
-
2009
- 2009-08-24 US US12/546,162 patent/US7883641B2/en not_active Expired - Fee Related
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2006222403A (ja) * | 2005-02-14 | 2006-08-24 | Kri Inc | 光増幅素器 |
JP2007214579A (ja) * | 2006-01-16 | 2007-08-23 | Philips Lumileds Lightng Co Llc | 蛍光体変換発光デバイス |
JP2009526379A (ja) * | 2006-02-06 | 2009-07-16 | セミョーノヴィチ アブラモフ、ウラジミール | 窒化ガリウム系半導体ヘテロ構造体の成長方法 |
US8174042B2 (en) | 2006-02-06 | 2012-05-08 | Seoul Semiconductor Co., Ltd. | Method of growing semiconductor heterostructures based on gallium nitride |
US8546830B2 (en) | 2006-02-06 | 2013-10-01 | Seoul Semiconductor Co., Ltd. | Method of growing semiconductor heterostructures based on gallium nitride |
JP2022141807A (ja) * | 2013-03-21 | 2022-09-29 | ボード オブ トラスティーズ オブ ミシガン ステート ユニバーシティ | 透明エネルギー取り込み装置 |
JP7498509B2 (ja) | 2013-03-21 | 2024-06-12 | ボード オブ トラスティーズ オブ ミシガン ステート ユニバーシティ | 透明エネルギー取り込み装置 |
KR20200129289A (ko) * | 2019-05-08 | 2020-11-18 | 신동현 | 벌브형 레이저 발광램프 |
KR102318332B1 (ko) * | 2019-05-08 | 2021-10-28 | 신동현 | 벌브형 레이저 발광램프 |
Also Published As
Publication number | Publication date |
---|---|
TW200528538A (en) | 2005-09-01 |
EP1715022A1 (en) | 2006-10-25 |
US20100047561A1 (en) | 2010-02-25 |
JPWO2005073342A1 (ja) | 2007-09-13 |
CN1934217A (zh) | 2007-03-21 |
US20070166543A1 (en) | 2007-07-19 |
EP1715022A4 (en) | 2009-04-15 |
JP4989891B2 (ja) | 2012-08-01 |
KR20060123537A (ko) | 2006-12-01 |
US7883641B2 (en) | 2011-02-08 |
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