CN102203896B - Light-emitting laminate - Google Patents

Light-emitting laminate Download PDF

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Publication number
CN102203896B
CN102203896B CN200980143745.0A CN200980143745A CN102203896B CN 102203896 B CN102203896 B CN 102203896B CN 200980143745 A CN200980143745 A CN 200980143745A CN 102203896 B CN102203896 B CN 102203896B
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powder
light
magnesia
emitting
fluorophor
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CN102203896A (en
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植木明
加藤裕三
稻垣彻
山内正人
野口诚司
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Ube Chemical Industries Co Ltd
Ube Material Industries Ltd
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Ube Chemical Industries Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J1/00Details of electrodes, of magnetic control means, of screens, or of the mounting or spacing thereof, common to two or more basic types of discharge tubes or lamps
    • H01J1/54Screens on or from which an image or pattern is formed, picked-up, converted, or stored; Luminescent coatings on vessels
    • H01J1/62Luminescent screens; Selection of materials for luminescent coatings on vessels
    • H01J1/68Luminescent screens; Selection of materials for luminescent coatings on vessels with superimposed luminescent layers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J11/00Gas-filled discharge tubes with alternating current induction of the discharge, e.g. alternating current plasma display panels [AC-PDP]; Gas-filled discharge tubes without any main electrode inside the vessel; Gas-filled discharge tubes with at least one main electrode outside the vessel
    • H01J11/20Constructional details
    • H01J11/34Vessels, containers or parts thereof, e.g. substrates
    • H01J11/42Fluorescent layers
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    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
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    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/55Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing beryllium, magnesium, alkali metals or alkaline earth metals
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/57Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing manganese or rhenium
    • C09K11/572Chalcogenides
    • C09K11/574Chalcogenides with zinc or cadmium
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    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/61Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
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    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/778Borates
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J1/00Details of electrodes, of magnetic control means, of screens, or of the mounting or spacing thereof, common to two or more basic types of discharge tubes or lamps
    • H01J1/54Screens on or from which an image or pattern is formed, picked-up, converted, or stored; Luminescent coatings on vessels
    • H01J1/62Luminescent screens; Selection of materials for luminescent coatings on vessels
    • H01J1/63Luminescent screens; Selection of materials for luminescent coatings on vessels characterised by the luminescent material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J11/00Gas-filled discharge tubes with alternating current induction of the discharge, e.g. alternating current plasma display panels [AC-PDP]; Gas-filled discharge tubes without any main electrode inside the vessel; Gas-filled discharge tubes with at least one main electrode outside the vessel
    • H01J11/10AC-PDPs with at least one main electrode being out of contact with the plasma
    • H01J11/12AC-PDPs with at least one main electrode being out of contact with the plasma with main electrodes provided on both sides of the discharge space
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J11/00Gas-filled discharge tubes with alternating current induction of the discharge, e.g. alternating current plasma display panels [AC-PDP]; Gas-filled discharge tubes without any main electrode inside the vessel; Gas-filled discharge tubes with at least one main electrode outside the vessel
    • H01J11/20Constructional details
    • H01J11/34Vessels, containers or parts thereof, e.g. substrates
    • H01J11/40Layers for protecting or enhancing the electron emission, e.g. MgO layers

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  • Materials Engineering (AREA)
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  • Plasma & Fusion (AREA)
  • Luminescent Compositions (AREA)
  • Gas-Filled Discharge Tubes (AREA)

Abstract

A light-emitting laminate wherein a phosphor layer composed of a phosphor which emits visible light when excited by ultraviolet light having a wavelength within the range of 230-260 nm is formed on a base. The light-emitting laminate is characterized in that (1) a wavelength conversion layer composed of a sintered magnesium oxide powder which emits ultraviolet light having a peak within the wavelength range of 230-260 nm when excited by ultraviolet light produced by Xe gas discharge is formed under the phosphor layer; (2) a sintered magnesium oxide powder which emits ultraviolet light having a peak within the wavelength range of 230-260 nm when excited by ultraviolet light produced by Xe gas discharge is added into the phosphor layer; or (3) a phosphor protective layer composed of a sintered magnesium oxide powder which emits ultraviolet light having a peak within the wavelength range of 230-260 nm when excited by ultraviolet light produced by Xe gas discharge is formed on the phosphor layer.

Description

Light-emitting laminate
Technical field
The present invention relates to be formed with the light-emitting laminate of luminescent coating on matrix, described luminescent coating comprises by Xe gas and discharges and and the ultraviolet light that produces is excited, send the fluorophor of visible ray.
Background technology
As being combined in the light-emitting laminate that is formed with luminescent coating (described luminescent coating comprise by Xe gas discharge and sent the fluorophor of visible ray and the ultraviolet light that produces excites) on matrix and the discharge gas that comprises Xe gas, and the ultraviolet light producing by being discharged by Xe gas comes excited fluophor to send the visible ray light-emitting device of visible ray, known AC plasma display panel (below also referred to as AC type PDP), Xe lamp.By Xe gas, discharged and the resonance line (wavelength 146nm) and the Xe that comprise Xe in the ultraviolet light that produces 2molecular ray (wavelength 172nm).
AC type PDP is filled with the discharge space of the discharge gas that comprises Xe gas by the front panel as picture display face and clamping and the backplate of subtend configuration forms.In AC type PDP, backplate is normally formed with the light-emitting laminate of luminescent coating in the dielectric layer surface of matrix and bulkhead sides, wherein using the laminated body of the dielectric layer of the addressing electrode that comprises substrate (being generally glass plate), form on substrate (address electrode), coated addressing electrode and the dividing plate that forms on dielectric layer as matrix.With regard to the luminescent coating of backplate, utilize the luminescent coating of three looks of baffle for separating au bleu light-emitting fluophor layer, green emitting luminescent coating and red light-emitting phosphor layer, by blueness, green, the red visible light that excites the fluorophor of luminescent coating of all kinds to send, combine to show image.
Xe lamp conventionally like this forms: using tubular glass or glass framework processed as matrix, side is formed with in the light-emitting component of luminescent coating within it, is filled with discharge gas.In Xe lamp, light-emitting component is light-emitting laminate.The luminescent coating of light-emitting component is formed by the phosphor blends that blue-light-emitting fluorescent material, green emitting fluorophor and red light-emitting phosphor are mixed conventionally.
As light-emitting laminate used in AC type PDP or Xe lamp, the laminated body of known following formation.
Following content is disclosed in patent documentation 1: under the luminescent coating of the light-emitting laminate of using at AC type PDP, formation comprises fluorine-containing magnesian layer, for this fluorine-containing magnesium oxide, the magnesium oxide purity that the scope of 0.01~10 quality % of take contains fluorine more than 99.8 quality % and BET specific area at 0.1~30m 2in the scope of/g.According to this patent documentation 1, think for fluorine-containing magnesium oxide, by Xe gas, discharged and produced ultraviolet excitation time, be emitted in the ultraviolet light in the wave-length coverage of 220~270nm with peak, the ultraviolet light that has passed through luminescent coating is transformed to the ultraviolet light of the wave-length coverage of 220~270nm, again irradiate luminescent coating, thus the fluorophor of excited fluophor layer and improve the luminosity of luminescent coating.
Following content is disclosed in patent documentation 2: to adding in the luminescent coating of AC type PDP, excited and while being emitted in the magnesium oxide crystalline solid of the ultraviolet light in the wave-length coverage of 230~250nm with peak by the ultraviolet light that is discharged by Xe gas and produce, the ultraviolet light that utilization is discharged by magnesium oxide crystalline solid, also the fluorophor in can excited fluophor layer, thereby brightness improves.
In patent documentation 3, disclose and on the luminescent coating of AC type PDP, formed the fluorophor protective layer that comprises magnesium oxide powder.In this patent documentation 3, there is following record: fluorophor protective layer is owing to preventing because ion collides the deteriorated of the fluorophor cause, thereby there is the effect that extends phosphor lifetime.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2008-10403 communique
Patent documentation 2: TOHKEMY 2008-171670 communique
Patent documentation 3: TOHKEMY 2003-297250 communique
Summary of the invention
The problem that invention will solve
The object of the present invention is to provide the hair photosensitiveness laminated body that luminosity is high, this light-emitting laminate can be advantageously used in utilize by Xe gas discharge and the ultraviolet light that produces so that the visible ray light-emitting device that visible ray sends.
Solve the means of problem
The invention reside in light-emitting laminate, it is on matrix, via wavelength conversion layer, to be formed with the light-emitting laminate of luminescent coating,
Described wavelength conversion layer contain by Xe gas discharge and the ultraviolet light that produces is excited, be emitted in the wave-length coverage of 230~260nm, have peak ultraviolet light, be selected from least one magnesia roast powder in following (1)~(4),
Described luminescent coating contains by being in the ultraviolet excitation in the wave-length coverage of 230~260nm and demonstrates the luminous fluorophor of visible ray.
(1) the chloride magnesia roast powder that contains chlorine with the scope of 0.005~10 quality %.
(2) magnesia roast powder containing zinc that contains zinc with the scope of 0.1~30 quality %.
(3) mixture of powders of γ type alumina powder and magnesium oxide source powder is burnt till and aluminium content at the magnesia roast powder containing aluminium of the scope of 2~38 quality %.
(4) with respect to 100 moles, magnesium, amount with the scope of 0.01~24 mole contains fluorine, and with respect to 100 moles, magnesium, the magnesia roast powder that contains fluorine and assistant metal that contains at least one assistant metal in alkaline-earth metal, rare earth metal, aluminium, zinc and the tin being selected from beyond alkali metal, demagging with the amount of the scope of 0.01~30 mole.
The present invention is also fluorophor powder composition, and this fluorophor powder composition comprises:
By Xe gas discharge and the ultraviolet light that produces is excited, be emitted in the wave-length coverage of 230~260nm, have peak ultraviolet light, be selected from least one magnesia roast powder in following (1)~(5); With
By being in the ultraviolet excitation in the wave-length coverage of 230~260nm and demonstrate the luminous fluorophor powder of visible ray,
The content ratio of described magnesia roast powder and described fluorophor powder is: with respect to fluorophor powder 1 mass parts, the amount of magnesia roast powder is the scope of 0.001~0.080 mass parts.
(1) the fluorine-containing magnesia roast powder that contains fluorine with the scope of 0.01~10 quality %.
(2) the chloride magnesia roast powder that contains chlorine with the scope of 0.005~10 quality %.
(3) magnesia roast powder containing zinc that contains zinc with the scope of 0.1~30 quality %.
(4) mixture of powders of γ type alumina powder and magnesium oxide source powder is burnt till and aluminium content at the magnesia roast powder containing aluminium of the scope of 2~38 quality %.
(5) with respect to 100 moles, magnesium, amount with the scope of 0.01~24 mole contains fluorine, and with respect to 100 moles, magnesium, the magnesia roast powder that contains fluorine and assistant metal that contains at least one assistant metal in alkaline-earth metal, rare earth metal, aluminium, zinc and the tin being selected from beyond alkali metal, demagging with the amount of the scope of 0.01~30 mole.
The present invention is also light-emitting laminate, and it is the light-emitting laminate that is formed with the luminescent coating that comprises fluorophor powder composition on matrix,
Described fluorophor powder composition comprises:
By Xe gas discharge and the ultraviolet light that produces is excited, be emitted in the wave-length coverage of 230~260nm, have peak ultraviolet light, be selected from least one magnesia roast powder in following (1)~(5); With
By being in the ultraviolet excitation in the wave-length coverage of 230~260nm and demonstrate the luminous fluorophor powder of visible ray,
The content ratio of described magnesia roast powder and described fluorophor powder is: with respect to fluorophor powder 1 mass parts, the amount of magnesia roast powder is the scope of 0.001~0.080 mass parts.
(1) the fluorine-containing magnesia roast powder that contains fluorine with the scope of 0.01~10 quality %.
(2) the chloride magnesia roast powder that contains chlorine with the scope of 0.005~10 quality %.
(3) magnesia roast powder containing zinc that contains zinc with the scope of 0.1~30 quality %.
(4) mixture of powders of γ type alumina powder and magnesium oxide source powder is burnt till and aluminium content at the magnesia roast powder containing aluminium of the scope of 2~38 quality %.
(5) with respect to 100 moles, magnesium, amount with the scope of 0.01~24 mole contains fluorine, and with respect to 100 moles, magnesium, the magnesia roast powder that contains fluorine and assistant metal that contains at least one assistant metal in alkaline-earth metal, rare earth metal, aluminium, zinc and the tin being selected from beyond alkali metal, demagging with the amount of the scope of 0.01~30 mole.
The present invention is also light-emitting laminate, the fluorophor protective layer that this light-emitting laminate comprises the luminescent coating on matrix, this matrix and forms on this luminescent coating,
Described luminescent coating comprises by being in the ultraviolet excitation in the wave-length coverage of 230~260nm and demonstrates the luminous fluorophor of visible ray,
Described fluorophor protective layer comprise by Xe gas discharge and the ultraviolet light that produces is excited, be emitted in the wave-length coverage of 230~260nm, have peak ultraviolet light, be selected from least one magnesia roast powder in following (1)~(5).
(1) the fluorine-containing magnesia roast powder that contains fluorine with the scope of 0.01~10 quality %.
(2) the chloride magnesia roast powder that contains chlorine with the scope of 0.005~10 quality %.
(3) magnesia roast powder containing zinc that contains zinc with the scope of 0.1~30 quality %.
(4) mixture of powders of γ type alumina powder and magnesium oxide source powder is burnt till and aluminium content at the magnesia roast powder containing aluminium of the scope of 2~38 quality %.
(5) with respect to 100 moles, magnesium, amount with the scope of 0.01~24 mole contains fluorine, and with respect to 100 moles, magnesium, the magnesia roast powder that contains fluorine and assistant metal that contains at least one assistant metal in alkaline-earth metal, rare earth metal, aluminium, zinc and the tin being selected from beyond alkali metal, demagging with the amount of the scope of 0.01~30 mole.
Invention effect
From the data shown in aftermentioned embodiment, compare with the laminated body that is only formed with luminescent coating on matrix, for the light-emitting laminate that is provided with luminescent coating via wavelength conversion layer of the present invention, by ultraviolet light (resonance line that is equivalent to Xe) and the ultraviolet light of wavelength 172nm of wavelength 146nm, (be equivalent to Xe 2molecular ray) cause excite and the luminosity of the visible ray that sends significantly improves.Therefore, described light-emitting laminate can be advantageously used for the backplate of AC type PDP and the light-emitting component of Xe lamp.
From the data shown in aftermentioned embodiment, compare with fluorophor powder monomer, with regard to the fluorophor powder composition that comprises fluorophor powder and magnesia roast powder of the present invention, by ultraviolet light (resonance line that is equivalent to Xe) and the ultraviolet light of wavelength 172nm of wavelength 146nm, (be equivalent to Xe 2molecular ray) cause excite and the luminosity of the visible ray that sends significantly improves.Therefore the light-emitting laminate that is formed with the luminescent coating that comprises fluorophor powder composition, can be advantageously used for the backplate of AC type PDP and the light-emitting component of Xe lamp.
From the data shown in aftermentioned embodiment; with fluorophor protective layer by not shown that by the ultraviolet excitation that is discharged by Xe gas and produce the light-emitting laminate in the past that luminous magnesium oxide powder forms compares; with regard to the light-emitting laminate that is formed with fluorophor protective layer on luminescent coating of the present invention, the luminosity of luminescent coating can maintain high level for a long time.Therefore, described light-emitting laminate can be advantageously used for the backplate of AC type PDP and the light-emitting component of Xe lamp.
Embodiment
[magnesia roast powder]
In light-emitting laminate of the present invention, can use at least one magnesia roast powder being selected from following (1)~(5).
(1) the fluorine-containing magnesia roast powder that contains fluorine with the scope of 0.01~10 quality %.
The fluorine content of above-mentioned fluorine-containing magnesia roast powder is preferably in the scope of 0.03~5 quality %, in the scope particularly preferably in 0.03~3 quality %.
Can, under the existence in fluorine source or under fluoro-gas atmosphere, by burning till magnesium oxide source powder, manufacture fluorine-containing magnesia roast powder.
As magnesium oxide source powder, can use magnesium oxide powder and by heating, generate the magnesium compound powder (still, except magnesium chloride powder) of magnesium oxide powder.As the example of magnesium compound powder, can enumerate magnesium hydroxide powder, basic carbonate magnesium dust, magnesium nitrate powder and magnesium acetate powder.Magnesium oxide source powder preferential oxidation magnesium dust.Particularly preferably purity is that 99.95 quality % are above to magnesium oxide powder, BET specific area is at 5~150m 2the scope of/g is (particularly preferably in 7~50m 2the scope of/g), the magnesium oxide powder that utilizes gas phase synthesis method to make.Gas phase synthesis method refers to, magnesium metal steam is contacted in gas phase with oxygen-containing gas, makes magnesium metal vapor-phase oxidation manufacture the method for magnesium oxide powder.
As fluorine source, can use magnesium fluoride powder and ammonium fluoride powder.The preferred purity in fluorine source is more than 99 quality %.Under the existence in fluorine source, while carrying out the burning till of raw materials of magnesium oxide powder, preferably before burning till, raw materials of magnesium oxide powder and fluorine source are mixed equably.
As fluoro-gas, can use hydrogen fluoride gas, by ammonium fluoride, fluorinated organic compound (CF 4, C 2f 6, C 3f 8deng) or magnesium fluoride powder heating be vaporized the gas forming.
The firing temperature of the magnesium oxide source powder under fluorine source exists and under fluoro-gas atmosphere is preferably more than 850 ℃, more preferably 900~1500 ℃, be particularly preferably the scope of 1000~1500 ℃.Firing time is preferably more than 10 minutes, more preferably 10 minutes~2 hours, is particularly preferably 20 minutes~scope of 2 hours.For example burning till of magnesium oxide source powder can be carried out in the following way: under normal pressure, under the condition of 100~500 ℃/h of programming rates, be warming up to above-mentioned firing temperature, then, burn till after above-mentioned firing time, under the condition of 100~500 ℃/h of cooling rates, be cooled to room temperature.
(2) the chloride magnesia roast powder that contains chlorine with the scope of 0.005~10 quality %.
The chlorinity of above-mentioned chloride magnesia roast powder is preferably in the scope of 0.01~10 quality %, particularly preferably in the scope of 0.1~10 quality %.
Can, under the existence in chlorine source or under chlorine-containing gas atmosphere, by burning till magnesium oxide source powder, manufacture chloride magnesia roast powder.
As magnesium oxide source powder, can use magnesium oxide powder and by heating, generate the magnesium compound powder (still, except magnesium chloride powder) of magnesium oxide powder.As the example of magnesium compound powder, can enumerate magnesium hydroxide powder, basic carbonate magnesium dust, magnesium nitrate powder and magnesium acetate powder.Magnesium oxide source powder preferential oxidation magnesium dust.Particularly preferably purity is that 99.95 quality % are above to magnesium oxide powder, BET specific area is at 5~150m 2the scope of/g is (particularly preferably in 7~50m 2the scope of/g), the magnesium oxide powder that utilizes gas phase synthesis method to make.
As chlorine source, can use magnesium chloride powder and ammonium chloride powder.The preferred purity in chlorine source is more than 99.0 quality %.Under the existence in chlorine source, while carrying out the burning till of raw materials of magnesium oxide powder, preferably before burning till, raw materials of magnesium oxide powder and chlorine source are mixed equably.
As chlorine-containing gas, can use hydrogen chloride gas or by ammonium chloride powder, magnesium chloride powder or chlorine-containing organic compounds (CHCl 3, CCl 4deng) heating is vaporized the gas forming.
The firing temperature of the magnesium oxide source powder under chlorine source exists and under chlorine-containing gas atmosphere is preferably more than 850 ℃, more preferably 900~1500 ℃, be particularly preferably the scope of 1000~1500 ℃.Firing time is preferably more than 10 minutes, more preferably 10 minutes~2 hours, is particularly preferably 20 minutes~scope of 2 hours.
(3) magnesia roast powder containing zinc that contains zinc with the scope of 0.1~30 quality %.
The zinc content of the above-mentioned magnesia roast powder containing zinc is particularly preferably in the scope of 0.5~7 quality %.
Can, by magnesium oxide source powder and zinc oxide source powder are obtained by mixing to mixture of powders, then burn till gained mixture of powders and manufacture the magnesia roast powder containing zinc.
As magnesium oxide source powder, can use magnesium oxide powder or by heating the magnesium compound powder that generates magnesium oxide powder.Magnesium oxide source powder preferential oxidation magnesium dust.Particularly preferably purity is that 99.95 quality % are above to magnesium oxide powder, BET specific area is at 5~150m 2the scope of/g is (particularly preferably in 7~50m 2the scope of/g), the magnesium oxide powder that utilizes gas phase synthesis method to make.
As zinc oxide source powder, can use Zinc oxide powder and by heating the zinc compound powder that generates Zinc oxide powder.As the example of zinc compound powder, can enumerate zinc hydroxide powder, zinc carbonate powder, zinc nitrate powder, zinc acetate powder and zinc oxalate powder.Zinc oxide source powder preferential oxidation zinc powder.More than the purity of zinc oxide source powder is preferably 99.0 quality %.
The firing temperature of the mixture of powders of magnesium oxide source powder and zinc oxide source powder is preferably more than 850 ℃, more preferably 900~1500 ℃, be particularly preferably the scope of 1000~1500 ℃.Firing time is preferably more than 10 minutes, more preferably 10 minutes~2 hours, is particularly preferably 20 minutes~scope of 2 hours.
(4) mixture of powders of γ type alumina powder and magnesium oxide source powder is burnt till and aluminium content at the magnesia roast powder that contains aluminium of the scope of 2~38 quality %.
The aluminium content of the above-mentioned magnesia roast powder containing aluminium is preferably in the scope of 5~35 quality %.
Can, by γ type alumina powder and magnesium oxide source powder are obtained by mixing to mixture of powders, then burn till gained mixture of powders and manufacture the magnesia roast powder containing aluminium.
As magnesium oxide source powder, can use magnesium oxide powder or by heating the magnesium compound powder that generates magnesium oxide powder.Magnesium oxide source powder preferential oxidation magnesium dust.Particularly preferably purity is that 99.95 quality % are above to magnesium oxide powder, BET specific area is at 5~150m 2the scope of/g is (particularly preferably in 7~50m 2the scope of/g), the magnesium oxide powder that utilizes gas phase synthesis method to make.
More than the purity of γ type alumina powder is preferably 99.0 quality %.
The firing temperature of the mixture of powders of γ type alumina powder and magnesium oxide source powder is preferably more than 850 ℃, more preferably 900~1500 ℃, be particularly preferably the scope of 1000~1500 ℃.Firing time is preferably more than 10 minutes, more preferably 10 minutes~2 hours, is particularly preferably 20 minutes~scope of 2 hours.
(5) with respect to 100 moles, magnesium, amount with the scope of 0.01~24 mole contains fluorine, and with respect to 100 moles, magnesium, the magnesia roast powder that contains fluorine and assistant metal that contains at least one assistant metal in alkaline-earth metal, rare earth metal, aluminium, zinc and the tin being selected from beyond alkali metal, demagging with the amount of the scope of 0.01~30 mole.
In the above-mentioned magnesia roast powder that contains fluorine and assistant metal, with respect to 100 moles, magnesium, fluorine content is preferably the scope of 0.02~12 mole, particularly preferably in the scope of 0.02~5 mole.With respect to 100 moles, magnesium, the content of assistant metal is preferably the scope of 0.025~25 mole, particularly preferably in the scope of 0.1~5 mole.In addition,, with respect to 1 mole, fluorine, the content of assistant metal is preferably the scope of 0.25~50 mole, particularly preferably in the scope of 0.4~30 mole.
As the alkali-metal example as assistant metal, can enumerate lithium, sodium and potassium.As the example of alkaline-earth metal, can enumerate calcium and barium.As the example of rare earth metal, can enumerate yttrium, cerium and gadolinium.Assistant metal can be used, or two or more may be used separately.
The magnesia roast powder that contains fluorine and assistant metal can be manufactured by the following method: the fluoride powder of magnesium oxide source powder and assistant metal is mixed, obtain with 100 moles, the magnesium with respect in magnesium oxide source powder, the amount of fluoride is that the scope of 0.05~30 mole (is preferably the scope of 0.1~25 mole, be particularly preferably the scope of 0.2~15 mole) the amount mixture of powders that contains fluoride, then burn till the mixture of powders of gained.
Can use the oxide powder of assistant metal or by heating the compound powder (except fluoride powder) of the assistant metal that is converted into metal oxide and being selected from magnesium fluoride powder and at least one fluoride powder of ammonium fluoride powder replaces the fluoride powder of assistant metal., the magnesia roast powder that contains fluorine and assistant metal can be manufactured by the following method: by magnesium oxide source powder, the oxide powder of assistant metal or by heating the compound powder beyond the fluoride of the assistant metal that generates metal oxide, mix with at least one the fluoride powder that is selected from magnesium fluoride powder and ammonium fluoride powder, obtain the mixture of powders that comprises assistant metal and fluoride, wherein with respect to 100 moles, the magnesium in mixed-powder, the amount of assistant metal is the scope of 0.05~30 mole, and, with respect to 1 mole of assistant metal, the amount of the fluoride in fluoride powder is the amount of the scope of 0.1~10 mole, then burn till the mixture of powders of gained.
As magnesium oxide source powder, can use magnesium oxide powder or by heating the magnesium compound powder that generates magnesium oxide powder.Magnesium oxide source powder preferential oxidation magnesium dust.Particularly preferably purity is that 99.95 quality % are above to magnesium oxide powder, BET specific area is at 5~150m 2the scope of/g is (particularly preferably in 7~50m 2the scope of/g), the magnesium oxide powder that utilizes gas phase synthesis method to make.
The fluoride powder of the assistant metal mixing with magnesium oxide source powder, the oxide powder of assistant metal, by heating compound powder and the preferred purity of fluoride powder of the oxide powder that generates assistant metal, be more than 99.0 quality %.As by heating the example of the compound powder of the oxide powder that generates assistant metal, can enumerate hydroxide powder, carbonate powder, bicarbonate powder, nitrate powder, acetate powder, the oxalates powder of assistant metal.
The mixture of powders of the fluoride powder of magnesium oxide source powder and assistant metal; And, the oxide powder of magnesium oxide source powder, assistant metal or by heat the firing temperature of the compound powder of the oxide powder that generates assistant metal and the mixture of powders of fluoride powder be preferably 850 ℃ above, more preferably 900~1500 ℃, be particularly preferably the scope of 1000~1500 ℃.Firing time is preferably more than 10 minutes, more preferably 10 minutes~2 hours, is particularly preferably 20 minutes~scope of 2 hours.
The preferred BET specific area of magnesia roast powder is at 0.1~30m 2the scope of/g, particularly preferably in 0.2~12m 2the scope of/g.
[fluorophor powder]
In light-emitting laminate of the present invention, fluorophor powder used comprises the luminous fluorophor that is demonstrated visible ray by the ultraviolet excitation of the wave-length coverage at 230~260nm.As fluorophor, can use blue-light-emitting fluorescent material, green emitting fluorophor and red light-emitting phosphor.
As the example of blue-light-emitting fluorescent material, can enumerate basic composition formula by CaMgSi 2o 6: Eu 2+, (Ca, Sr) MgSi 2o 6: Eu 2+, Sr 3mgSi 2o 8: Eu 2+, and BaMgAl 10o 17: Eu 2+the blue-light-emitting fluorescent material representing.As the example of green emitting fluorophor, can enumerate basic composition formula by Zn 2siO 4: Mn 2+, (Ba, Sr, Mg) O α Al 2o 3: Mn 2+, YBO 3: Tb 3+, (Y, Gd) BO 3: Tb 3+, BaAl 12o 19: Mn 2+and BaMgAl 10o 17: Eu 2+, Mn 2+the fluorophor representing.As the example of red light-emitting phosphor, can enumerate basic composition formula by YBO 3: Eu 3+, (Y, Gd) BO 3: Eu 3+, Y 2o 3: Eu 3+(Y, Gd) 2o 3: Eu 3+the fluorophor representing.Fluorophor powder can be used, or two or more may be used separately.
[via wavelength conversion layer, being provided with the light-emitting laminate of luminescent coating]
The thickness of wavelength conversion layer preferably in the scope of 0.5~10 μ m, more preferably in the scope of 1.0~10 μ m.Wavelength conversion layer can form in the following way: utilize silk screen print method or used the rubbing method of the various coating machines such as various coating machines such as reverse coating machine, curtain formula coating machine, chill coating machine, slit coating machine (slot coater), the pastel that is dispersed with magnesia roast powder is applied on matrix to drying coating film.
The thickness of luminescent coating preferably in the scope of 0.1~30 μ m, more preferably in the scope of 1.0~30 μ m.Luminescent coating can form in the following way: utilize silk screen print method or used the rubbing method of various coating machines such as reverse coating machine, curtain formula coating machine, chill coating machine, slit coating machine etc., the pastel that is dispersed with fluorophor powder is applied on wavelength conversion layer to drying coating film.
As matrix, can use glass tube, glass substrate etc. to be used as the material of the matrix of the backplate of AC type PDP and the light-emitting component of Xe lamp.
The light-emitting laminate using as the backplate of AC type PDP can form as follows: will comprise the dielectric layer of substrate (being generally glass plate), the addressing electrode forming, coated addressing electrode on substrate, the laminated body of the dividing plate that forms on dielectric layer, as matrix, forms in order wavelength conversion layer and luminescent coating in dielectric layer surface and bulkhead sides; Or, make the dielectric layer of matrix disperse magnesia roast powder and become wavelength conversion layer, in wavelength conversion layer surface and bulkhead sides, form in order wavelength conversion layer and luminescent coating.The backplate with the wavelength conversion layer of said structure has been that above-mentioned patent documentation 1 (TOHKEMY 2008-10403 communique) is disclosed.
In the backplate of AC type PDP, luminescent coating is conventionally by the tri-color phosphor layer of baffle for separating au bleu light-emitting fluophor layer, green emitting luminescent coating and red light-emitting phosphor layer.Wavelength conversion layer can be formed uniformly respectively under these tri-color phosphor layers, also can be for the equilibrium phase of the luminosity of each color is coordinated, and only under one or two luminescent coating in tri-color phosphor layer, arrange.
[being formed with the light-emitting laminate of the luminescent coating that comprises fluorophor powder composition (this fluorophor powder composition contains fluorophor powder and magnesia roast powder)]
The thickness of luminescent coating preferably in the scope of 0.1~40 μ m, more preferably in the scope of 1.0~40 μ m.
The magnesia roast powder of fluorophor powder composition and the mixing ratio of fluorophor powder that form luminescent coating are following ratio: with respect to fluorophor powder 1 mass parts, the amount of magnesia roast powder is the scope of 0.001~0.080 mass parts, is preferably the scope of 0.05~0.080 mass parts.
Fluorophor powder composition can be by manufacturing according to aforementioned proportion mixed oxidization magnesium roast powder and fluorophor powder.Magnesia roast powder carried out according to wet method with mixing preferably of fluorophor powder.
Luminescent coating can form in the following way: utilize silk screen print method or used the rubbing method of the various coating machines such as reverse coating machine, curtain formula coating machine, chill coating machine, slit coating machine, the pastel that is dispersed with fluorophor powder composition is applied on matrix to drying coating film.
[on luminescent coating, being formed with the light-emitting laminate of fluorophor protective layer]
The thickness of luminescent coating preferably in the scope of 0.1~30 μ m, more preferably in the scope of 1.0~30 μ m.Luminescent coating can form in the following way: utilize silk screen print method or used the rubbing method of the various coating machines such as reverse coating machine, curtain formula coating machine, chill coating machine, slit coating machine, the pastel that is dispersed with fluorophor powder is applied on matrix to drying coating film.
The thickness of fluorophor protective layer preferably in the scope of 0.5~10 μ m, more preferably in the scope of 1.0~10 μ m.Fluorophor protective layer can form in the following way: utilize silk screen print method or used the rubbing method of the various coating machines such as reverse coating machine, curtain formula coating machine, chill coating machine, slit coating machine; the pastel that is dispersed with magnesia roast powder is applied on luminescent coating to drying coating film.
The light-emitting laminate that is used as the backplate of AC type PDP can form as follows: using the laminated body of the dividing plate that comprises the dielectric layer of substrate (being generally glass plate), the addressing electrode forming, coated addressing electrode and form on dielectric layer on substrate as matrix, form in order luminescent coating and fluorophor protective layer in dielectric layer surface and bulkhead sides.In the backplate of AC type PDP, luminescent coating is conventionally by the tri-color phosphor layer of baffle for separating au bleu light-emitting fluophor layer, green emitting luminescent coating and red light-emitting phosphor layer.Fluorophor protective layer can be formed uniformly respectively on these tri-color phosphor layers, also can only be arranged on by being easy to cause on formed one or two luminescent coating of fluorophor that luminosity reduces.
Light-emitting laminate as the light-emitting component of Xe lamp can form as follows: using glass tube or glass framework processed as matrix, form in order luminescent coating and fluorophor protective layer inside this matrix.
Embodiment
Magnesia roast powder (the MgCl that [synthesis example 1] is chloride 2synthesizing MgO)
By the magnesium oxide powder that utilizes gas phase synthesis method to make (2000A, the マ テ リ ア Le ズ of space portion (strain) system, purity: 99.98 quality %, BET specific area: 8.7m 2/ g) 250g and magnesium chloride powder (purity: 99%) 500g mixes, and obtains mixture of powders.Gained mixture of powders put in alumina crucible and added a cover, put it in electric furnace, with the programming rates of 240 ℃/h, being warming up to 1300 ℃, then at this temperature, burning till 30 minutes.Then, with the cooling rate of 240 ℃/h, temperature in stove is cooled to room temperature.Gained burned material is that BET specific area is 0.57m 2/ g, chlorinity are the chloride magnesia roast powder of 0.8 quality %.Can confirm after the ultraviolet light of the chloride magnesia roast powder illumination wavelength 146nm of gained and wavelength 172nm, be emitted in the ultraviolet light in the wave-length coverage of 230~260nm with peak.
[synthesis example 2] is synthetic containing the magnesia roast powder (ZnOMgO) of zinc
By the magnesium oxide powder that utilizes gas phase synthesis method to make (2000A, the マ テ リ ア Le ズ of space portion (strain) system) 500g and Zinc oxide powder (purity: 99.9%) 20g mixes, and obtains mixture of powders.Gained mixture of powders put in alumina crucible and added a cover, put it in electric furnace, with the programming rates of 240 ℃/h, being warming up to 1300 ℃, then at this temperature, burning till 30 minutes.Then, with the cooling rate of 240 ℃/h, temperature in stove is cooled to room temperature.Gained burned material is that BET specific area is 5.73m 2/ g, zinc content are the magnesia roast powder containing zinc of 3.09 quality %.Can confirm to gained during containing the magnesia roast powder illumination wavelength 146nm of zinc and the ultraviolet light of wavelength 172nm, be emitted in the ultraviolet light in the wave-length coverage of 230~260nm with peak.
[synthesis example 3] is containing the magnesia roast powder (γ-Al of aluminium 2o 3synthesizing MgO)
By the magnesium oxide powder (2000A that utilizes gas phase synthesis method to make, the マ テ リ ア Le ズ of space portion (strain) system) 500g and γ type acidifying aluminium powder (Sumitomo Chemical (strain) system, high-purity alpha-alumina AKP-G015) 26.38g mixes, and obtains mixture of powders.Gained mixture of powders put in alumina crucible and added a cover, put it in electric furnace, with the programming rates of 240 ℃/h, being warming up to 1300 ℃, then at this temperature, burning till 30 minutes.Then, with the cooling rate of 240 ℃/h, temperature in stove is cooled to room temperature.Gained burned material is that BET specific area is 6.07m 2/ g, aluminium content are the magnesia roast powder containing aluminium of 2.48 quality %.Can confirm to gained during containing the magnesia roast powder illumination wavelength 146nm of aluminium and the ultraviolet light of wavelength 172nm, be emitted in the ultraviolet light in the wave-length coverage of 230~260nm with peak.
[synthesis example 4] is synthetic containing the magnesia roast powder (LiFMgO) of lithium, fluorine
By the magnesium oxide powder that utilizes gas phase synthesis method to make (2000A, the マ テ リ ア Le ズ of space portion (strain) system) 6.0g and lithium fluoride powder (purity: 99.9 quality %) 0.0386g mixes, and obtains mixture of powders.Gained mixture of powders put in alumina crucible and added a cover, put it in electric furnace, with the programming rates of 240 ℃/h, being warming up to 1200 ℃, then at this temperature, burning till 30 minutes.Then, with the cooling rate of 240 ℃/h, temperature in stove is cooled to room temperature.Gained burned material is: BET specific area is 0.26m 2/ g; With respect to 100 moles, magnesium, lithium content is 0.2 mole; With respect to 100 moles, magnesium, fluorine content is the magnesia roast powder containing lithium, fluorine of 0.09 mole.Can confirm to gained when lithium, the magnesia roast powder illumination wavelength 146nm of fluorine and the ultraviolet light of wavelength 172nm, be emitted in the ultraviolet light in the wave-length coverage of 230~260nm with peak.
[synthesis example 5] is synthetic containing the magnesia roast powder (NaFMgO) of sodium, fluorine
By the magnesium oxide powder that utilizes gas phase synthesis method to make (2000A, the マ テ リ ア Le ズ of space portion (strain) system) 6.0g and sodium fluoride powder (purity: 99.9 quality %) 0.0625g mixes, and obtains mixture of powders.Gained mixture of powders put in alumina crucible and added a cover, put it in electric furnace, with the programming rates of 240 ℃/h, being warming up to 1200 ℃, then at this temperature, burning till 30 minutes.Then, with the cooling rate of 240 ℃/h, temperature in stove is cooled to room temperature.Gained burned material is: BET specific area is 0.21m 2/ g; With respect to 100 moles, magnesium, sodium content is 0.2 mole; With respect to 100 moles, magnesium, fluorine content is the magnesia roast powder containing sodium, fluorine of 0.10 mole.Can confirm to gained when sodium, the magnesia roast powder illumination wavelength 146nm of fluorine and the ultraviolet light of wavelength 172nm, be emitted in the ultraviolet light in the wave-length coverage of 230~260nm with peak.
[synthesis example 6] is synthetic containing the magnesia roast powder (KFMgO) of potassium, fluorine
By the magnesium oxide powder that utilizes gas phase synthesis method to make (2000A, the マ テ リ ア Le ズ of space portion (strain) system) 6.0g and potassium fluoride powder (purity: 99.9 quality %) 0.432g mixes, and obtains mixture of powders.Gained mixture of powders put in alumina crucible and added a cover, put it in electric furnace, with the programming rates of 240 ℃/h, being warming up to 1200 ℃, then at this temperature, burning till 30 minutes.Then, with the cooling rate of 240 ℃/h, temperature in stove is cooled to room temperature.Gained burned material is: BET specific area is 0.60m 2/ g; With respect to 100 moles, magnesium, potassium content is 0.1 mole; With respect to 100 moles, magnesium, fluorine content is the magnesia roast powder containing potassium, fluorine of 0.07 mole.Can confirm to gained when potassium, the magnesia roast powder illumination wavelength 146nm of fluorine and the ultraviolet light of wavelength 172nm, be emitted in the ultraviolet light in the wave-length coverage of 230~260nm with peak.
Magnesia roast powder (the CaF of [synthesis example 7] calcic, fluorine 2synthesizing MgO)
By the magnesium oxide powder that utilizes gas phase synthesis method to make (2000A, the マ テ リ ア Le ズ of space portion (strain) system) 6.0g and calcirm-fluoride powder (purity: 99.9 quality %) 0.0581g mixes, and obtains mixture of powders.Gained mixture of powders put in alumina crucible and added a cover, put it in electric furnace, with the programming rates of 240 ℃/h, being warming up to 1200 ℃, then at this temperature, burning till 30 minutes.Then, with the cooling rate of 240 ℃/h, temperature in stove is cooled to room temperature.Gained burned material is: BET specific area is 1.36m 2/ g; With respect to 100 moles, magnesium, calcium content is 0.5 mole; With respect to 100 moles, magnesium, fluorine content is the calcic of 0.82 mole, the magnesia roast powder of fluorine.In the time of can confirming to the magnesia roast powder illumination wavelength 146nm of gained calcic, fluorine and the ultraviolet light of wavelength 172nm, be emitted in the ultraviolet light in the wave-length coverage of 230~260nm with peak.
Magnesia roast powder (the BaF of [synthesis example 8] baric, fluorine 2synthesizing MgO)
By the magnesium oxide powder that utilizes gas phase synthesis method to make (2000A, the マ テ リ ア Le ズ of space portion (strain) system) 6.0g and barium fluoride powder (purity: 99.9 quality %) 0.2610g mixes, and obtains mixture of powders.Gained mixture of powders put in alumina crucible and added a cover, put it in electric furnace, with the programming rates of 240 ℃/h, being warming up to 1200 ℃, then at this temperature, burning till 30 minutes.Then, with the cooling rate of 240 ℃/h, temperature in stove is cooled to room temperature.Gained burned material is: BET specific area is 1.49m 2/ g; With respect to 100 moles, magnesium, barium content is 1.0 moles; With respect to 100 moles, magnesium, fluorine content is the baric of 1.91 moles, the magnesia roast powder of fluorine.In the time of can confirming to the magnesia roast powder illumination wavelength 146nm of gained baric, fluorine and the ultraviolet light of wavelength 172nm, be emitted in the ultraviolet light in the wave-length coverage of 230~260nm with peak.
[synthesis example 9] is containing the magnesia roast powder (AlF of aluminium, fluorine 3synthesizing MgO)
By the magnesium oxide powder that utilizes gas phase synthesis method to make (2000A, the マ テ リ ア Le ズ of space portion (strain) system) 6.0g and aluminum fluoride powder (purity: 99.9 quality %) 0.1250g mixes, and obtains mixture of powders.Gained mixture of powders put in alumina crucible and added a cover, put it in electric furnace, with the programming rates of 240 ℃/h, being warming up to 1300 ℃, then at this temperature, burning till 30 minutes.Then, with the cooling rate of 240 ℃/h, temperature in stove is cooled to room temperature.Gained burned material is: BET specific area is 0.96m 2/ g; With respect to 100 moles, magnesium, aluminium content is 1.0 moles; With respect to 100 moles, magnesium, fluorine content is the magnesia roast powder containing aluminium, fluorine of 0.47 mole.Can confirm to gained when aluminium, the magnesia roast powder illumination wavelength 146nm of fluorine and the ultraviolet light of wavelength 172nm, be emitted in the ultraviolet light in the wave-length coverage of 230~260nm with peak.
[synthesis example 10] is containing the magnesia roast powder (ZnF of zinc, fluorine 2synthesizing MgO)
By the magnesium oxide powder that utilizes gas phase synthesis method to make (2000A, the マ テ リ ア Le ズ of space portion (strain) system) 6.0g and zinc fluoride-tetrahydrate powder (purity: 99.9 quality %) 0.1306g mixes, and obtains mixture of powders.Gained mixture of powders put in alumina crucible and added a cover, put it in electric furnace, with the programming rates of 240 ℃/h, being warming up to 1300 ℃, then at this temperature, burning till 30 minutes.Then, with the cooling rate of 240 ℃/h, temperature in stove is cooled to room temperature.Gained burned material is: BET specific area is 1.29m 2/ g; With respect to 100 moles, magnesium, zinc content is 0.5 mole; With respect to 100 moles, magnesium, fluorine content is the magnesia roast powder containing zinc, fluorine of 0.03 mole.Can confirm to gained when zinc, the magnesia roast powder illumination wavelength 146nm of fluorine and the ultraviolet light of wavelength 172nm, be emitted in the ultraviolet light in the wave-length coverage of 230~260nm with peak.
[synthesis example 11] is stanniferous, the magnesia roast powder (SnF of fluorine 2synthesizing MgO)
By the magnesium oxide powder that utilizes gas phase synthesis method to make (2000A, the マ テ リ ア Le ズ of space portion (strain) system) 6.0g and tin fluoride powder (purity: 99.9 quality %) 0.2334g mixes, and obtains mixture of powders.Gained mixture of powders put in alumina crucible and added a cover, put it in electric furnace, with the programming rates of 240 ℃/h, being warming up to 1300 ℃, then at this temperature, burning till 30 minutes.Then, with the cooling rate of 240 ℃/h, temperature in stove is cooled to room temperature.Gained burned material is: BET specific area is 0.80m 2/ g; With respect to 100 moles, magnesium, tin content is 1.0 moles; With respect to 100 moles, magnesium, fluorine content is the magnesia roast powder of stanniferous, the fluorine of 0.07 mole.In the time of can confirming, the magnesia roast powder illumination wavelength 146nm of fluorine stanniferous to gained and the ultraviolet light of wavelength 172nm, be emitted in the ultraviolet light in the wave-length coverage of 230~260nm with peak.
[synthesis example 12] is containing the magnesia roast powder (CeF of cerium, fluorine 3synthesizing MgO)
By the magnesium oxide powder that utilizes gas phase synthesis method to make (2000A, the マ テ リ ア Le ズ of space portion (strain) system) 6.0g and cerium fluoride powder (purity: 99.9 quality %) 0.1460g mixes, and obtains mixture of powders.Gained mixture of powders put in alumina crucible and added a cover, put it in electric furnace, with the programming rates of 240 ℃/h, being warming up to 1300 ℃, then at this temperature, burning till 30 minutes.Then, with the cooling rate of 240 ℃/h, temperature in stove is cooled to room temperature.Gained burned material is: BET specific area is 0.99m 2/ g; With respect to 100 moles, magnesium, cerium content is 1.0 moles; With respect to 100 moles, magnesium, fluorine content is the magnesia roast powder containing cerium, fluorine of 0.26 mole.Can confirm to gained when cerium, the magnesia roast powder illumination wavelength 146nm of fluorine and the ultraviolet light of wavelength 172nm, be emitted in the ultraviolet light in the wave-length coverage of 230~260nm with peak.
[synthesis example 13] is containing the magnesia roast powder (YF of yttrium, fluorine 3synthesizing MgO)
By the magnesium oxide powder that utilizes gas phase synthesis method to make (2000A, the マ テ リ ア Le ズ of space portion (strain) system) 6.0g and yttrium fluoride powder (purity: 99.9 quality %) 0.2180g mixes, and obtains mixture of powders.Gained mixture of powders put in alumina crucible and added a cover, put it in electric furnace, with the programming rates of 240 ℃/h, being warming up to 1300 ℃, then at this temperature, burning till 30 minutes.Then, with the cooling rate of 240 ℃/h, temperature in stove is cooled to room temperature.Gained burned material is: BET specific area is 0.97m 2/ g; With respect to 100 moles, magnesium, yttrium content is 1.0 moles; With respect to 100 moles, magnesium, fluorine content is the magnesia roast powder containing yttrium, fluorine of 1.52 moles.Can confirm to gained when yttrium, the magnesia roast powder illumination wavelength 146nm of fluorine and the ultraviolet light of wavelength 172nm, be emitted in the ultraviolet light in the wave-length coverage of 230~260nm with peak.
[synthesis example 14] is containing the magnesia roast powder (GdF of gadolinium, fluorine 3synthesizing MgO)
By the magnesium oxide powder that utilizes gas phase synthesis method to make (2000A, the マ テ リ ア Le ズ of space portion (strain) system) 6.0g and gadolinium fluoride powder (purity: 99.9 quality %) 0.0796g mixes, and obtains mixture of powders.Gained mixture of powders put in alumina crucible and added a cover, put it in electric furnace, with the programming rates of 240 ℃/h, being warming up to 1300 ℃, then at this temperature, burning till 30 minutes.Then, with the cooling rate of 240 ℃/h, temperature in stove is cooled to room temperature.Gained burned material is: BET specific area is 1.10m 2/ g; With respect to 100 moles, magnesium, gadolinium concentrations is 0.5 mole; With respect to 100 moles, magnesium, fluorine content is the magnesia roast powder containing gadolinium, fluorine of 0.59 mole.Can confirm to gained containing gadolinium, the magnesia roast powder illumination wavelength 146nm of fluorine and the vacuum ultraviolet (VUV) light time of wavelength 172nm, be emitted in the ultraviolet light in the wave-length coverage of 230~260nm with peak.
Magnesia roast powder (the MgF that [synthesis example 15] is fluorine-containing 2synthesizing MgO)
By the magnesium oxide powder that utilizes gas phase synthesis method to make (2000A, the マ テ リ ア Le ズ of space portion (strain) system) 5g and magnesium fluoride powder (purity: 99.1%) 0.05g mixes, and obtains mixture of powders.Gained mixture of powders put in alumina crucible and added a cover, put it in electric furnace, with the programming rates of 240 ℃/h, being warming up to 1200 ℃, then at this temperature, burning till 30 minutes.Then, with the cooling rate of 240 ℃/h, temperature in stove is cooled to room temperature.Gained burned material is that BET specific area is 1.81m 2/ g, fluorine content are the fluorine-containing magnesia roast powder of 0.0496 quality %.In the time of can confirming the ultraviolet light to the fluorine-containing magnesia roast powder illumination wavelength 146nm of gained and wavelength 172nm, be emitted in the ultraviolet light in the wave-length coverage of 230~260nm with peak.
[embodiment 1]
In isopropyl alcohol 300mL, add ethylmethylcellulose 21g, use magnetic stirrer 15 minutes, prepare pasty state base material.In described pasty state base material, add the chloride magnesia roast powder (MgCl being synthesized by synthesis example 1 2mgO) 2.5g, is used defoamer to mix 7 minutes, prepares chloride magnesia roast powder pastel.In addition, in the pasty state base material of same preparation, add CaMgSi 2o 6: Eu 2+blue irradiance fluorophor powder 2.5g, is used defoamer to mix 7 minutes, preparation CaMgSi 2o 6: Eu 2+blue irradiance fluorophor powder pastel.
Use screen process press that the chloride magnesia roast powder pastel of above-mentioned preparation is applied on the quartz base plate of diameter 19.8mm, thickness 2.0mm, after dry at the temperature of 70 ℃, at the temperature of 600 ℃, anneal 1 hour, form the chloride magnesia roast layer of thickness 3 μ m.Then, use screen process press by the CaMgSi of above-mentioned preparation 2o 6: Eu 2+blue irradiance fluorophor powder pastel is applied on chloride magnesia roast layer, after being dried, anneals 1 hour at the temperature of 600 ℃ at the temperature of 70 ℃, forms the CaMgSi of thickness 7 μ m 2o 6: Eu 2+blue-light-emitting fluorescent material layer, is formed with CaMgSi to be manufactured on quartz base plate via the wavelength conversion layer that comprises chloride magnesia roast powder 2o 6: Eu 2+the light-emitting laminate of blue-light-emitting fluorescent material layer.
[embodiment 2~14]
Except using the magnesia roast powder being made by synthesis example 2~14 to replace chloride magnesia roast powder, operate to be manufactured on the CaMgSi that is formed with thickness 7 μ m on quartz base plate via the wavelength conversion layer that comprises magnesia roast powder of thickness 3 μ m equally 2o 6: Eu 2+the light-emitting laminate of blue-light-emitting fluorescent material layer.
[comparative example 1]
Except not forming on quartz base plate wavelength conversion layer, operation similarly to Example 1, to be manufactured on the CaMgSi that is formed with thickness 7 μ m on quartz base plate 2o 6: Eu 2+the light-emitting laminate of blue-light-emitting fluorescent material layer.
[evaluation of light-emitting laminate]
From the luminescent coating top illumination wavelength 146nm of the light-emitting laminate that made by embodiment 1~14 and comparative example 1 and the ultraviolet light of wavelength 172nm, measure the luminescent spectrum of the visible ray of emitting from laminated body.The peak-peak of gained luminescent spectrum is shown in to table 1 as maximum luminousing brightness.
Table 1 (luminescent coating: CaMgSi 2o 6: Eu 2+blue-light-emitting fluorescent material layer)
Figure BPA00001358431500171
Note) maximum luminousing brightness is the value of comparative example 1 to be made as to 100 relative value.
[embodiment 15~28]
Except using Ca 0.5sr 0.5mgSi 2o 6: Eu 2+blue irradiance fluorophor powder replaces CaMgSi 2o 6: Eu 2+outside blue irradiance fluorophor powder, operate equally with embodiment 1~14, be manufactured on the Ca that is formed with thickness 7 μ m on quartz base plate via the wavelength conversion layer of thickness 3 μ m 0.5sr 0.5mgSi 2o 6: Eu 2+the light-emitting laminate of blue-light-emitting fluorescent material layer.
[comparative example 2]
Except not forming on quartz base plate wavelength conversion layer, operate equally with embodiment 15~28, be manufactured on the Ca that is formed with thickness 7 μ m on quartz base plate 0.5sr 0.5mgSi 2o 6: Eu 2+the light-emitting laminate of blue-light-emitting fluorescent material layer.
[evaluation of light-emitting laminate]
From the luminescent coating top illumination wavelength 146nm of the light-emitting laminate that made by embodiment 15~28 and comparative example 2 and the ultraviolet light of wavelength 172nm, measure the luminescent spectrum of the visible ray of emitting from laminated body.The peak-peak of gained luminescent spectrum is shown in to table 2 as maximum luminousing brightness.
Table 2 (luminescent coating: Ca 0.5sr 0.5mgSi 2o 6: Eu 2+blue-light-emitting fluorescent material layer)
Figure BPA00001358431500181
Note) maximum luminousing brightness is the value of comparative example 2 to be made as to 100 relative value.
[embodiment 29~42]
Except using BaMgAl 10o 17: Eu 2+blue irradiance fluorophor powder replaces CaMgSi 2o 6: Eu 2+outside blue irradiance fluorophor powder, operate equally with embodiment 1~14, be manufactured on the BaMgAl that is formed with thickness 7 μ m on quartz base plate via the wavelength conversion layer of thickness 3 μ m 10o 17: Eu 2+the light-emitting laminate of blue-light-emitting fluorescent material layer.
[comparative example 3]
Except not forming on quartz base plate wavelength conversion layer, operate equally with embodiment 29~42, be manufactured on the BaMgAl that is formed with thickness 7 μ m on quartz base plate 10o 17: Eu 2+the light-emitting laminate of blue-light-emitting fluorescent material layer.
[evaluation of light-emitting laminate]
From the luminescent coating top illumination wavelength 146nm of the light-emitting laminate that made by embodiment 29~42 and comparative example 3 and the ultraviolet light of wavelength 172nm, measure the luminescent spectrum of the visible ray of emitting from laminated body.The peak-peak of gained luminescent spectrum is shown in to table 3 as maximum luminousing brightness.
Table 3 (luminescent coating: BaMgAl 10o 17: Eu 2+blue-light-emitting fluorescent material layer)
Figure BPA00001358431500191
Note) maximum luminousing brightness is the value of comparative example 3 to be made as to 100 relative value.
[embodiment 43~56]
Except using Zn 2siO 4: Mn 2+green emitting fluorophor powder replaces CaMgSi 2o 6: Eu 2+outside blue irradiance fluorophor powder, operate equally with embodiment 1~14, be manufactured on the Zn that is formed with thickness 7 μ m on quartz base plate via the wavelength conversion layer of thickness 3 μ m 2siO 4: Mn 2+the light-emitting laminate of green emitting luminescent coating.
[comparative example 4]
Except not forming on quartz base plate wavelength conversion layer, operate equally with embodiment 43~56, be manufactured on the Zn that is formed with thickness 7 μ m on quartz base plate 2siO 4: Mn 2+the light-emitting laminate of green emitting luminescent coating.
[evaluation of light-emitting laminate]
From the luminescent coating top illumination wavelength 146nm of the light-emitting laminate that made by embodiment 43~56 and comparative example 4 and the ultraviolet light of wavelength 172nm, measure the luminescent spectrum of the visible ray of emitting from laminated body.The peak-peak of gained luminescent spectrum is shown in to table 4 as maximum luminousing brightness.
Table 4 (luminescent coating: Zn 2siO 4: Mn 2+green emitting luminescent coating)
Figure BPA00001358431500201
Note) maximum luminousing brightness is the value of comparative example 4 to be made as to 100 relative value.
[embodiment 57~70]
Except using (Y, Gd) BO 3: Eu 3+red light-emitting phosphor powder replaces CaMgSi 2o 6: Eu 2+outside blue irradiance fluorophor powder, operate equally with embodiment 1~14, be manufactured on (Y, the Gd) BO that is formed with thickness 7 μ m on quartz base plate via the wavelength conversion layer of thickness 3 μ m 3: Eu 3+the light-emitting laminate of red light-emitting phosphor layer.
[comparative example 5]
Except not forming on quartz base plate wavelength conversion layer, operate equally with embodiment 57~70, be manufactured on (Y, the Gd) BO that is formed with thickness 7 μ m on quartz base plate 3: Eu 3+the light-emitting laminate of red light-emitting phosphor layer.
[evaluation of light-emitting laminate]
From the luminescent coating top illumination wavelength 146nm of the light-emitting laminate that made by embodiment 57~70 and comparative example 5 and the ultraviolet light of wavelength 172nm, measure the luminescent spectrum of the visible ray of emitting from laminated body.The peak-peak of gained luminescent spectrum is shown in to table 5 as maximum luminousing brightness.
Table 5 (luminescent coating: (Y, Gd) BO 3: Eu 3+red light-emitting phosphor layer)
Figure BPA00001358431500211
Note) maximum luminousing brightness is the value of comparative example 5 to be made as to 100 relative value.
[embodiment 71~84]
Except using Sr 3mgSi 2o 8: Eu 2+blue-light-emitting fluorescent material replaces CaMgSi 2o 6: Eu 2+outside blue irradiance fluorophor powder, operate equally with embodiment 1~14, be manufactured on the Sr that is formed with thickness 7 μ m on quartz base plate via the wavelength conversion layer of thickness 3 μ m 3mgSi 2o 8: Eu 2+the light-emitting laminate of blue-light-emitting fluorescent material layer.
[comparative example 6]
Except not forming on quartz base plate wavelength conversion layer, operate equally with embodiment 71~84, be manufactured on the Sr that is formed with thickness 7 μ m on quartz base plate 3mgSi 2o 8: Eu 2+the light-emitting laminate of blue-light-emitting fluorescent material layer.
[evaluation of light-emitting laminate]
From the luminescent coating top illumination wavelength 146nm of the light-emitting laminate that made by embodiment 71~84 and comparative example 6 and the ultraviolet light of wavelength 172nm, measure the luminescent spectrum of the visible ray of emitting from laminated body.The peak-peak of gained luminescent spectrum is shown in to table 6 as maximum luminousing brightness.
Table 6 (luminescent coating: Sr 3mgSi 2o 8: Eu 2+blue-light-emitting fluorescent material layer)
Figure BPA00001358431500221
Note) maximum luminousing brightness is the value of comparative example 6 to be made as to 100 relative value.
From the result shown in above-mentioned table 1~6, can find out, compare with the light-emitting laminate that is only formed with luminescent coating, with regard to the light-emitting laminate that is formed with luminescent coating via wavelength conversion layer according to the present invention, luminosity significantly improves.
[embodiment 85]
By CaMgSi 2o 6: Eu 2+blue emitting phophor powder 1.00g and the fluorine-containing magnesia roast powder (MgF being synthesized by synthesis example 15 2mgO) 0.01g puts in isopropyl alcohol 30mL, carries out ultrasonic wave and disperses to prepare mixture of powders dispersion liquid.With the mixture of powders dispersion liquid of magnetic stirrer gained 1 hour, then put in evaporator evaporative removal isopropyl alcohol and obtain powder hybrid dry matter.Under air atmosphere, at the temperature of 600 ℃, the powder hybrid dry matter of heating gained 1 hour, manufactures fluorophor powder composition further.
[embodiment 86~114 and comparative example 7~21]
With the amount that becomes in following table 7 content of recording to CaMgSi 2o 6: Eu 2+in blue irradiance fluorophor powder 1.00g, mix by the synthetic magnesia roast powder of synthesis example 1~15, in addition, manufacture fluorophor powder composition with the same operation of embodiment 85.
[evaluation of the luminosity of fluorophor powder]
To the fluorophor powder composition being made by embodiment 85~114 and comparative example 7~21 and CaMgSi used in the manufacture of 22 fluorophor powder composition as a comparative example 2o 6: Eu 2+blue irradiance fluorophor powder, the ultraviolet light of difference illumination wavelength 146nm and wavelength 172nm, the luminescent spectrum of the visible ray that mensuration is emitted from fluorophor powder.The peak-peak of gained luminescent spectrum is shown in to table 7 as maximum luminousing brightness.
Table 7 (fluorophor powder: CaMgSi 2o 6: Eu 2+blue irradiance fluorophor powder)
Figure BPA00001358431500231
Note) maximum luminousing brightness is the value of comparative example 22 to be made as to 100 relative value.
[embodiment 115~144 and comparative example 23~37]
Use Ca 0.5sr 0.5mgSi 2o 6: Eu 2+blue irradiance fluorophor powder 1.00g replaces CaMgSi 2o 6: Eu 2+blue irradiance fluorophor powder, mixes by the synthetic magnesia roast powder of synthesis example 1~15 to become the amount of the content of recording in following table 8, in addition, manufactures fluorophor powder composition with the same operation of embodiment 85.
[evaluation of the luminosity of fluorophor powder]
To the fluorophor powder composition being made by embodiment 115~144 and comparative example 23~37 and Ca used in the manufacture of 38 fluorophor powder composition as a comparative example 0.5sr 0.5mgSi 2o 6: Eu 2+blue irradiance fluorophor powder, the ultraviolet light of difference illumination wavelength 146nm and wavelength 172nm, the luminescent spectrum of the visible ray that mensuration is emitted from fluorophor powder.The peak-peak of gained luminescent spectrum is shown in to table 8 as maximum luminousing brightness.
Table 8 (fluorophor powder: Ca 0.5sr 0.5mgSi 2o 6: Eu 2+blue irradiance fluorophor powder)
Figure BPA00001358431500251
Note) maximum luminousing brightness is the value of comparative example 38 to be made as to 100 relative value.
[embodiment 145~174 and comparative example 39~53]
Use BaMgAl 10o 17: Eu 2+blue irradiance fluorophor powder 1.00g replaces CaMgSi 2o 6: Eu 2+blue irradiance fluorophor powder, mixes by the synthetic magnesia roast powder of synthesis example 1~15 to become the amount of the content of recording in following table 9, in addition, manufactures fluorophor powder composition with the same operation of embodiment 85.
[evaluation of the luminosity of fluorophor powder]
To the fluorophor powder composition being made by embodiment 145~174 and comparative example 39~53 and BaMgAl used in the manufacture of 54 fluorophor powder composition as a comparative example 10o 17: Eu 2+blue irradiance fluorophor powder, the ultraviolet light of difference illumination wavelength 146nm and wavelength 172nm, the luminescent spectrum of the visible ray that mensuration is emitted from fluorophor powder.The peak-peak of gained luminescent spectrum is shown in to table 9 as maximum luminousing brightness.
Table 9 (fluorophor powder: BaMgAl 10o 17: Eu 2+blue irradiance fluorophor powder)
Note) maximum luminousing brightness is the value of comparative example 54 to be made as to 100 relative value.
[embodiment 175~204 and comparative example 55~69]
Use Zn 2siO 4: Mn 2+green emitting fluorophor powder 1.00g replaces CaMgSi 2o 6: Eu 2+blue irradiance fluorophor powder, mixes by the synthetic magnesia roast powder of synthesis example 1~15 to become the amount of the content of recording in following table 10, in addition, manufactures fluorophor powder composition with the same operation of embodiment 85.
[evaluation of the luminosity of fluorophor powder]
To the fluorophor powder composition being made by embodiment 175~204 and comparative example 55~69 and Zn used in the manufacture of 70 fluorophor powder composition as a comparative example 2siO 4: Mn 2+green emitting fluorophor powder, the ultraviolet light of difference illumination wavelength 146nm and wavelength 172nm, the luminescent spectrum of the visible ray that mensuration is emitted from fluorophor powder.The peak-peak of gained luminescent spectrum is shown in to table 10 as maximum luminousing brightness.
Table 10 (fluorophor powder: Zn 2siO 4: Mn 2+green emitting fluorophor powder)
Figure BPA00001358431500291
Note) maximum luminousing brightness is the value of comparative example 70 to be made as to 100 relative value.
[embodiment 205~234 and comparative example 71~85]
Use (Y, Gd) BO 3: Eu 3+red light-emitting phosphor powder 1.00g replaces CaMgSi 2o 6: Eu 2+blue irradiance fluorophor powder, mixes by the synthetic magnesia roast powder of synthesis example 1~15 to become the amount of the content of recording in following table 11, in addition, manufactures fluorophor powder composition with the same operation of embodiment 85.
[evaluation of the luminosity of fluorophor powder]
To the fluorophor powder composition being made by embodiment 205~234 and comparative example 71~85 and (Y, Gd) BO used in the manufacture of 86 fluorophor powder composition as a comparative example 3: Eu 3+red light-emitting phosphor powder, the ultraviolet light of difference illumination wavelength 146nm and wavelength 172nm, the luminescent spectrum of the visible ray that mensuration is emitted from fluorophor powder.The peak-peak of gained luminescent spectrum is shown in to table 11 as maximum luminousing brightness.
Table 11 (fluorophor powder: (Y, Gd) BO 3: Eu 3+red light-emitting phosphor powder)
Figure BPA00001358431500311
Note) maximum luminousing brightness is the value of comparative example 86 to be made as to 100 relative value.
[embodiment 235~264 and comparative example 87~101]
Use Sr 3mgSi 2o 8: Eu 2+blue irradiance fluorophor powder 1.00g replaces CaMgSi 2o 6: Eu 2+blue irradiance fluorophor powder, mixes by the synthetic magnesia roast powder of synthesis example 1~15 to become the amount of the content of recording in following table 12, in addition, manufactures fluorophor powder composition with the same operation of embodiment 85.
[evaluation of the luminosity of fluorophor powder]
To the fluorophor powder composition being made by embodiment 235~264 and comparative example 87~101 and Sr used in the manufacture of 102 fluorophor powder composition as a comparative example 3mgSi 2o 8: Eu 2+blue irradiance fluorophor powder, the ultraviolet light of difference illumination wavelength 146nm and wavelength 172nm, the luminescent spectrum of the visible ray that mensuration is emitted from fluorophor powder.The peak-peak of gained luminescent spectrum is shown in to table 12 as maximum luminousing brightness.
Table 12 (fluorophor powder: Sr 3mgSi 2o 8: Eu 2+blue irradiance fluorophor powder)
Note) maximum luminousing brightness is the value of comparative example 102 to be made as to 100 relative value.
From the result shown in above-mentioned table 7~12, can find out, compare with independent fluorophor powder, with regard to the fluorophor powder composition that comprises fluorophor powder and magnesia roast powder within the scope of the invention, the wavelength 146nm producing for being discharged by Xe gas and the ultraviolet light of wavelength 172nm, be especially equivalent to Xe 2the luminosity of ultraviolet light of wavelength 172nm of molecular ray high.
[embodiment 265]
In isopropyl alcohol 300mL, add ethylmethylcellulose 21g, use magnetic stirrer 15 minutes, prepare pasty state base material.In described pasty state base material, add the fluorine-containing magnesia roast powder (MgF being synthesized by synthesis example 15 2mgO) 2.5g, is used defoamer to mix 7 minutes, prepares fluorine-containing magnesia roast powder pastel.In addition, in the pasty state base material of same preparation, add CaMgSi 2o 6: Eu 2+blue irradiance fluorophor powder 2.5g, is used defoamer to mix 7 minutes, preparation CaMgSi 2o 6: Eu 2+blue irradiance fluorophor powder pastel.
Use screen process press by the CaMgSi of above-mentioned preparation 2o 6: Eu 2+blue irradiance fluorophor powder pastel is applied on the quartz base plate of diameter 19.8mm, thickness 2.0mm, dry at the temperature of 70 ℃, then at the temperature of 600 ℃, anneals 1 hour, forms the CaMgSi of thickness 7 μ m 2o 6: Eu 2+blue-light-emitting fluorescence coating.Then, use screen process press that the fluorine-containing magnesia roast powder pastel of above-mentioned preparation is applied to CaMgSi 2o 6: Eu 2+on blue-light-emitting fluorescence coating, dry at the temperature of 70 ℃, then at the temperature of 600 ℃, anneal 1 hour, form the fluorine-containing magnesia roast layer of thickness 3 μ m, be manufactured on and on quartz base plate, be formed with in order CaMgSi 2o 6: Eu 2+blue-light-emitting fluorescent material layer and comprise the light-emitting laminate of the fluorophor protective layer of fluorine-containing magnesia roast powder.
[embodiment 266~279]
Except using the magnesia roast powder being made by synthesis example 1~14 to replace fluorine-containing magnesia roast powder, operate equally with embodiment 265, be manufactured on the CaMgSi that is formed with in order thickness 7 μ m on quartz base plate 2o 6: Eu 2+the light-emitting laminate of the fluorophor protective layer that comprises magnesia roast powder of blue-light-emitting fluorescent material layer and thickness 3 μ m.
[comparative example 103]
Except not forming on luminescent coating fluorophor protective layer, operate equally with embodiment 265, be manufactured on the CaMgSi that is formed with thickness 7 μ m on quartz base plate 2o 6: Eu 2+the light-emitting laminate of blue-light-emitting fluorescent material layer.
[comparative example 104]
Except using the irradiation of the ultraviolet light by wavelength 146nm and wavelength 172nm and not showing that luminous magnesium oxide powder replaces fluorine-containing magnesia roast powder, operate equally with embodiment 265, be manufactured on the CaMgSi that is formed with in order thickness 7 μ m on quartz base plate 2o 6: Eu 2+the light-emitting laminate of the fluorophor protective layer that comprises magnesium oxide powder of blue-light-emitting fluorescent material layer and thickness 3 μ m.
[evaluation of light-emitting laminate]
From the fluorophor protective layer top of the light-emitting laminate that made by embodiment 265~279 and comparative example 104 and the luminescent coating top of the light-emitting laminate being made by comparative example 103, the ultraviolet light 15 minutes of illumination wavelength 146nm and wavelength 172nm respectively.Mensuration moment and from irradiating the luminescent spectrum that starts the visible ray that the light-emitting laminate after 15 hours emits from the irradiation of ultraviolet light starts.Obtain irradiate the luminescent spectrum start rear moment peak-peak as initial stage maximum luminousing brightness, obtain the peak-peak that irradiation is started to the luminescent spectrum of rear moment and be made as the relative value of peak-peak that 100% irradiation starts the luminescent spectrum after 15 hours as brightness sustainment rate, its result is as shown in table 13.
Table 13 (luminescent coating: CaMgSi 2o 6: Eu 2+blue-light-emitting fluorescent material layer)
Figure BPA00001358431500351
Note) initial stage maximum luminousing brightness is the value of comparative example 103 to be made as to 100 relative value.
[embodiment 280~294]
Except using Ca 0.5sr 0.5mgSi 2o 6: Eu 2+blue irradiance fluorophor powder replaces CaMgSi 2o 6: Eu 2+outside blue irradiance fluorophor powder, operate equally with embodiment 265~279, be manufactured on the Ca that is formed with in order thickness 7 μ m on quartz base plate 0.5sr 0.5mgSi 2o 6: Eu 2+the light-emitting laminate of the fluorophor protective layer that comprises magnesia roast powder of blue-light-emitting fluorescent material layer and thickness 3 μ m.
[comparative example 105]
Except not forming on luminescent coating fluorophor protective layer, operate equally with embodiment 280~294, be manufactured on the Ca that is formed with thickness 7 μ m on quartz base plate 0.5sr 0.5mgSi 2o 6: Eu 2+the light-emitting laminate of blue-light-emitting fluorescent material layer.
[comparative example 106]
Except using the irradiation of the ultraviolet light by wavelength 146nm and wavelength 172nm and not showing that luminous magnesium oxide powder replaces magnesia roast powder, operate equally with embodiment 280~294, be manufactured on the Ca that is formed with in order thickness 7 μ m on quartz base plate 0.5sr 0.5mgSi 2o 6: Eu 2+the light-emitting laminate of the fluorophor protective layer that comprises magnesium oxide powder of blue-light-emitting fluorescent material layer and thickness 3 μ m.
[evaluation of light-emitting laminate]
Obtain equally initial stage maximum luminousing brightness and the brightness sustainment rate of the fluorophor protective layer of the light-emitting laminate being made by embodiment 280~294 and comparative example 105,106 with above-described embodiment 265~279 and comparative example 103,104.The results are shown in table 14.
Table 14 (luminescent coating: Ca 0.5sr 0.5mgSi 2o 6: Eu 2+blue-light-emitting fluorescent material layer)
Note) maximum luminousing brightness is the value of comparative example 105 to be made as to 100 relative value.
[embodiment 295~309]
Except using BaMgAl 10o 17: Eu 2+blue irradiance fluorophor powder replaces CaMgSi 2o 6: Eu 2+outside blue irradiance fluorophor powder, operate equally with embodiment 265~279, be manufactured on the BaMgAl that is formed with in order thickness 7 μ m on quartz base plate 10o 17: Eu 2+the light-emitting laminate of the fluorophor protective layer that comprises magnesia roast powder of blue-light-emitting fluorescent material layer and thickness 3 μ m.
[comparative example 107]
Except not forming on luminescent coating fluorophor protective layer, operate equally with embodiment 295~309, be manufactured on the BaMgAl that is formed with thickness 7 μ m on quartz base plate 10o 17: Eu 2+the light-emitting laminate of blue-light-emitting fluorescent material layer.
[comparative example 108]
Except using the irradiation of the ultraviolet light by wavelength 146nm and wavelength 172nm and not showing that luminous magnesium oxide powder replaces magnesia roast powder, operate equally with embodiment 295~309, be manufactured on the BaMgAl that is formed with in order thickness 7 μ m on quartz base plate 10o 17: Eu 2+the light-emitting laminate of the fluorophor protective layer that comprises magnesium oxide powder of blue-light-emitting fluorescent material layer and thickness 3 μ m.
[evaluation of light-emitting laminate]
Obtain equally initial stage maximum luminousing brightness and the brightness sustainment rate of the fluorophor protective layer of the light-emitting laminate being made by embodiment 295~309 and comparative example 107,108 with above-described embodiment 265~279 and comparative example 103,104.The results are shown in table 15.
Table 15 (luminescent coating: BaMgAl 10o 17: Eu 2+blue-light-emitting fluorescent material layer)
Figure BPA00001358431500381
Note) initial stage maximum luminousing brightness is the value of comparative example 107 to be made as to 100 relative value.
[embodiment 310~324]
Except using Zn 2siO 4: Mn 2+green emitting fluorophor powder replaces CaMgSi 2o 6: Eu 2+outside blue irradiance fluorophor powder, operate equally with embodiment 265~279, be manufactured on the Zn that is formed with in order thickness 7 μ m on quartz base plate 2siO 4: Mn 2+the light-emitting laminate of the fluorophor protective layer that comprises magnesia roast powder of green emitting luminescent coating and thickness 3 μ m.
[comparative example 109]
Except not forming on luminescent coating fluorophor protective layer, operate equally with embodiment 310~324, be manufactured on the Zn that is formed with thickness 7 μ m on quartz base plate 2siO 4: Mn 2+the light-emitting laminate of green emitting luminescent coating.
[comparative example 110]
Except using the irradiation of the ultraviolet light by wavelength 146nm and wavelength 172nm and not showing that luminous magnesium oxide powder replaces magnesia roast powder, operate equally with embodiment 310~324, be manufactured on the Zn that is formed with in order thickness 7 μ m on quartz base plate 2siO 4: Mn 2+the light-emitting laminate of the fluorophor protective layer that comprises magnesium oxide powder of green emitting luminescent coating and thickness 3 μ m.
[evaluation of light-emitting laminate]
Obtain equally initial stage maximum luminousing brightness and the brightness sustainment rate of the fluorophor protective layer of the light-emitting laminate being made by embodiment 310~324 and comparative example 109,110 with above-described embodiment 265~279 and comparative example 103,104.The results are shown in table 16.
Table 16 (luminescent coating: Zn 2siO 4: Mn 2+green emitting luminescent coating)
Figure BPA00001358431500391
Note) initial stage maximum luminousing brightness is the value of comparative example 109 to be made as to 100 relative value.
[embodiment 325~339]
Except using (Y, Gd) BO 3: Eu 3+red light-emitting phosphor powder replaces CaMgSi 2o 6: Eu 2+outside blue irradiance fluorophor powder, operate equally with embodiment 265~279, be manufactured on (Y, the Gd) BO that is formed with in order thickness 7 μ m on quartz base plate 3: Eu 3+the light-emitting laminate of the fluorophor protective layer that comprises magnesia roast powder of red light-emitting phosphor layer and thickness 3 μ m.
[comparative example 111]
Except not forming on luminescent coating fluorophor protective layer, operate equally with embodiment 325~339, be manufactured on (Y, the Gd) BO that is formed with thickness 7 μ m on quartz base plate 3: Eu 3+the light-emitting laminate of red light-emitting phosphor layer.
[comparative example 112]
Except using the irradiation of the ultraviolet light by wavelength 146nm and wavelength 172nm and not showing that luminous magnesium oxide powder replaces magnesia roast powder, operate equally with embodiment 325~339, be manufactured on (Y, the Gd) BO that is formed with in order thickness 7 μ m on quartz base plate 3: Eu 3+the light-emitting laminate of the fluorophor protective layer that comprises magnesium oxide powder of red light-emitting phosphor layer and thickness 3 μ m.
[evaluation of light-emitting laminate]
Obtain equally initial stage maximum luminousing brightness and the brightness sustainment rate of the fluorophor protective layer of the light-emitting laminate being made by embodiment 325~339 and comparative example 111,112 with above-described embodiment 265~279 and comparative example 103,104.The results are shown in table 17.
Table 17 (luminescent coating: (Y, Gd) BO 3: Eu 3+red light-emitting phosphor layer)
Figure BPA00001358431500401
Note) initial stage maximum luminousing brightness is the value of comparative example 111 to be made as to 100 relative value.
[embodiment 340~354]
Except using Sr 3mgSi 2o 8: Eu 2+blue irradiance fluorophor powder replaces CaMgSi 2o 6: Eu 2+outside blue irradiance fluorophor powder, operate equally with embodiment 265~279, be manufactured on the Sr that is formed with in order thickness 7 μ m on quartz base plate 3mgSi 2o 8: Eu 2+the light-emitting laminate of the fluorophor protective layer that comprises magnesia roast powder of blue-light-emitting fluorescent material layer and thickness 3 μ m.
[comparative example 113]
Except not forming on luminescent coating fluorophor protective layer, operate equally with embodiment 340~354, be manufactured on the Sr that is formed with thickness 7 μ m on quartz base plate 3mgSi 2o 8: Eu 2+the light-emitting laminate of blue-light-emitting fluorescent material layer.
[comparative example 114]
Except using the irradiation of the ultraviolet light by wavelength 146nm and wavelength 172nm and not showing that luminous magnesium oxide powder replaces magnesia roast powder, operate equally with embodiment 340~354, be manufactured on the Sr that is formed with in order thickness 7 μ m on quartz base plate 3mgSi 2o 8: Eu 2+the light-emitting laminate of the fluorophor protective layer that comprises magnesium oxide powder of blue-light-emitting fluorescent material layer and thickness 3 μ m.
[evaluation of light-emitting laminate]
Obtain equally initial stage maximum luminousing brightness and the brightness sustainment rate of the fluorophor protective layer of the light-emitting laminate being made by embodiment 340~354 and comparative example 113,114 with above-described embodiment 265~279 and comparative example 103,104.The results are shown in table 18.
Table 18 (luminescent coating: Sr 3mgSi 2o 8: Eu 2+blue-light-emitting fluorescent material layer)
Figure BPA00001358431500411
Note) initial stage maximum luminousing brightness is the value of comparative example 113 to be made as to 100 relative value.
From the result shown in table 13~18, can find out; comprise not by the ultraviolet excitation of wavelength 146nm and wavelength 172nm and do not show that the light-emitting laminate of the fluorophor protective layer of luminous magnesium oxide powder compares with being formed with; with regard to light-emitting laminate according to the present invention, the luminosity at initial stage is high.In addition, compare with the light-emitting laminate that is not formed with fluorophor protective layer, with regard to light-emitting laminate according to the present invention, the change of the brightness sustainment rate being caused by the difference of luminescent coating is little.

Claims (1)

1. light-emitting laminate, it is on matrix, via wavelength conversion layer, to be formed with the light-emitting laminate of luminescent coating,
Described wavelength conversion layer comprise by Xe gas discharge and the ultraviolet light that produces is excited, be emitted in the wave-length coverage of 230 ~ 260nm, have peak ultraviolet light, be selected from least one magnesia roast powder in following (1) ~ (4),
Described luminescent coating comprises by being in the ultraviolet excitation in the wave-length coverage of 230 ~ 260nm and demonstrates the luminous fluorophor of visible ray,
(1) the chloride magnesia roast powder that contains chlorine with the scope of 0.005 ~ 10 quality %;
(2) magnesia roast powder containing zinc that contains zinc with the scope of 0.1 ~ 30 quality %;
(3) mixture of powders of γ type alumina powder and magnesium oxide source powder is burnt till and aluminium content at the magnesia roast powder containing aluminium of the scope of 2 ~ 38 quality %;
(4) with respect to 100 moles, magnesium, amount with the scope of 0.01 ~ 24 mole contains fluorine, and with respect to 100 moles, magnesium, the magnesia roast powder that contains fluorine and assistant metal that contains at least one assistant metal in alkaline-earth metal, rare earth metal, aluminium, zinc and the tin being selected from beyond alkali metal, demagging with the amount of the scope of 0.01 ~ 30 mole.
2. light-emitting laminate according to claim 1, wherein, the thickness of wavelength conversion layer is in the scope of 0.5 ~ 10 μ m, and the thickness of luminescent coating is in the scope of 0.1 ~ 30 μ m.
3. light-emitting laminate according to claim 1, wherein, luminescent coating is: contain by being selected from CaMgSi 2o 6: Eu 2+, (Ca, Sr) MgSi 2o 6: Eu 2+, Sr 3mgSi 2o 8: Eu 2+and BaMgAl 10o 17: Eu 2+in the blue-light-emitting fluorescent material layer of the blue-light-emitting fluorescent material that represents of at least one basic composition formula; Contain by Zn 2siO 4: Mn 2+the green emitting luminescent coating of the green emitting fluorophor that represents of basic composition formula; Or contain the BO by (Y, Gd) 3: Eu 3+the red light-emitting phosphor layer of the red light-emitting phosphor that represents of basic composition formula.
4. light-emitting laminate according to claim 1, this light-emitting laminate is the backplate of AC plasma display panel or the light-emitting component of Xe lamp.
5. light-emitting laminate, it is the light-emitting laminate that is formed with the luminescent coating that comprises fluorophor powder composition on matrix,
Described fluorophor powder composition comprises:
By Xe gas discharge and the ultraviolet light that produces is excited, be emitted in the wave-length coverage of 230 ~ 260nm, have peak ultraviolet light, be selected from least one magnesia roast powder in following (1) ~ (3); With
By being in the ultraviolet excitation in the wave-length coverage of 230 ~ 260nm and demonstrate the luminous fluorophor powder of visible ray,
The content ratio of described magnesia roast powder and described fluorophor powder is: with respect to fluorophor powder 1 mass parts, the amount of magnesia roast powder is the scope of 0.001 ~ 0.080 mass parts,
(1) the chloride magnesia roast powder that contains chlorine with the scope of 0.005 ~ 10 quality %;
(2) magnesia roast powder containing zinc that contains zinc with the scope of 0.1 ~ 30 quality %;
(3) mixture of powders of γ type alumina powder and magnesium oxide source powder is burnt till and aluminium content at the magnesia roast powder containing aluminium of the scope of 2 ~ 38 quality %.
6. light-emitting laminate according to claim 5, wherein, the thickness of luminescent coating is in the scope of 0.1 ~ 40 μ m.
7. light-emitting laminate according to claim 5, wherein, fluorophor powder is: contain by being selected from CaMgSi 2o 6: Eu 2+, (Ca, Sr) MgSi 2o 6: Eu 2+, Sr 3mgSi 2o 8: Eu 2+and BaMgAl 10o 17: Eu 2+in the powder of the blue-light-emitting fluorescent material that represents of at least one basic composition formula; Contain by Zn 2siO 4: Mn 2+the powder of the green emitting fluorophor that represents of basic composition formula; Or contain the BO by (Y, Gd) 3: Eu 3+the powder of the red light-emitting phosphor that represents of basic composition formula.
8. light-emitting laminate according to claim 5, this light-emitting laminate is the backplate of AC plasma display panel or the light-emitting component of Xe lamp.
9. light-emitting laminate, the fluorophor protective layer that this light-emitting laminate comprises the luminescent coating on matrix, this matrix and forms on this luminescent coating,
Described luminescent coating comprises by being in the ultraviolet excitation in the wave-length coverage of 230 ~ 260nm and demonstrates the luminous fluorophor of visible ray,
Described fluorophor protective layer comprise by Xe gas discharge and the ultraviolet light that produces is excited, be emitted in the wave-length coverage of 230 ~ 260nm, have peak ultraviolet light, be selected from least one magnesia roast powder in following (1) ~ (3),
(1) the chloride magnesia roast powder that contains chlorine with the scope of 0.005 ~ 10 quality %;
(2) magnesia roast powder containing zinc that contains zinc with the scope of 0.1 ~ 30 quality %;
(3) mixture of powders of γ type alumina powder and magnesium oxide source powder is burnt till and aluminium content at the magnesia roast powder containing aluminium of the scope of 2 ~ 38 quality %.
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TWI548722B (en) * 2011-12-01 2016-09-11 蕭一修 Photo-luminance coating, glass and applications thereof
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WO2017078015A1 (en) * 2015-11-06 2017-05-11 宇部興産株式会社 Coated silicate fluorescent body and method for producing same, and white led device
JP7102748B2 (en) * 2018-01-26 2022-07-20 堺化学工業株式会社 Manufacturing method of blue-green phosphor
JP6962569B2 (en) * 2018-06-04 2021-11-05 国立研究開発法人物質・材料研究機構 A phosphor and a phosphor-containing composition using the same, and a light emitting device, a lighting device, and an image display device using these.

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JPH08212929A (en) * 1995-02-09 1996-08-20 Dainippon Printing Co Ltd Ac type plasma display panel and manufacture thereof
JP3623406B2 (en) * 1999-09-07 2005-02-23 松下電器産業株式会社 Gas discharge panel and manufacturing method thereof
JP2002348571A (en) * 2001-05-28 2002-12-04 Toshiba Corp Vacuum ultraviolet-excited fluorescent substance and light-emitting device using the same
JP4100187B2 (en) * 2003-02-07 2008-06-11 松下電器産業株式会社 Plasma display panel
JP4873680B2 (en) * 2004-07-22 2012-02-08 独立行政法人物質・材料研究機構 Method for producing cubic magnesia powder
JP5108218B2 (en) * 2005-09-28 2012-12-26 日本化学工業株式会社 Magnesium oxide powder, precursor for magnesium oxide molded body, manufacturing method thereof, magnesium oxide molded body, and magnesium oxide sintered body pellet
JP4562742B2 (en) * 2006-02-21 2010-10-13 宇部マテリアルズ株式会社 Fluorine-containing magnesium oxide powder
JP4818200B2 (en) * 2006-05-29 2011-11-16 宇部マテリアルズ株式会社 Back plate for AC type plasma display panel
JP2008050523A (en) * 2006-08-28 2008-03-06 Hitachi Ltd Plasma display device and light-emitting device
JP4110234B2 (en) * 2006-09-08 2008-07-02 パイオニア株式会社 Plasma display panel and driving method thereof
CN101362946B (en) * 2007-08-10 2013-02-06 宇部材料工业株式会社 Magnesia roast powder

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