JP2010080440A - Luminescent laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel luminescent laminate useful as a visible light emitting device for emitting visible light by utilizing ultraviolet rays generated by the discharge of Xe gas. <P>SOLUTION: The luminescent laminate includes a phosphor layer formed on a substrate via a wavelength conversion layer containing specified magnesium oxide sintered material power which is excited by ultraviolet rays generated by the discharge of Xe gas to emit ultraviolet rays having peaks in a wavelength range of 230-260 nm, the phosphor layer containing phosphor which is excited by the ultraviolet rays in the wavelength range of 230-260 nm to show visible light emission. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a luminescent laminate in which a phosphor layer made of a phosphor that emits visible light when excited by ultraviolet light generated by discharge of Xe gas is formed on a substrate.

A combination of a light-emitting laminate in which a phosphor layer including a phosphor that emits visible light when excited by ultraviolet light generated by discharge of Xe gas is formed on a substrate and a discharge gas containing Xe gas As a visible light emitting device that emits visible light by exciting a phosphor with ultraviolet light generated by the discharge of Xe gas, an AC type plasma display panel (hereinafter also referred to as AC type PDP) and an Xe lamp are known. Yes. The ultraviolet light generated by the discharge of Xe gas includes Xe resonance line (wavelength 146 nm) and Xe ₂ molecular beam (wavelength 172 nm).

  The AC type PDP is composed of a front plate serving as an image display surface and a back plate disposed opposite to each other across a discharge space filled with a discharge gas containing Xe gas. In the AC type PDP, a back plate is generally formed on a substrate (usually a glass plate), an address electrode formed on the substrate, a dielectric layer covering the address electrode, and the dielectric layer. A light emitting laminate in which a phosphor layer is formed on the dielectric layer surface of the substrate and the side walls of the laminate using the laminate comprising the barrier ribs as a substrate. The phosphor layer of the back plate is divided into three color phosphor layers, a blue light-emitting phosphor layer, a green light-emitting phosphor layer, and a red light-emitting phosphor layer, by partition walls, and excites the phosphor of each color phosphor layer. The image is displayed by a combination of blue, green, and red visible light emitted.

  In general, the Xe lamp has a configuration in which a discharge gas is filled in a light emitting element having a tubular glass or a glass casing as a base and a phosphor layer formed inside thereof. In the Xe lamp, the light emitting element is a light emitting laminate. The phosphor layer of the light emitting element is usually formed from a phosphor mixture in which a blue light emitting phosphor, a green light emitting phosphor and a red light emitting phosphor are mixed.

  As a method for improving the visible light emission efficiency of the light-emitting laminate, a wavelength conversion layer that emits ultraviolet light that can be excited by ultraviolet light generated by the discharge of Xe gas and excite the phosphor of the phosphor layer can be converted to fluorescent light. A method of providing under a body layer is known. That is, it is a method in which ultraviolet light having passed through the phosphor layer is converted into ultraviolet light having another wavelength by the wavelength conversion layer, and the phosphor layer is irradiated to excite the phosphor in the phosphor layer.

Patent Document 1 discloses that the purity of magnesium oxide containing fluorine in the range of 0.01 to 10% by mass is 99.8% by mass or more under the phosphor layer of the light-emitting laminate for AC type PDP, and It is disclosed to form a layer made of fluorine-containing magnesium oxide having a BET specific surface area in the range of 0.1 to 30 m ² / g. According to this Patent Document 1, fluorine-containing magnesium oxide emits ultraviolet light having a peak in the wavelength range of 220 to 270 nm when excited by ultraviolet light generated by discharge of Xe gas, and passes through the phosphor layer. The light is converted into ultraviolet light having a wavelength range of 220 to 270 nm and irradiated to the phosphor layer again, whereby the phosphor of the phosphor layer is excited and the emission luminance of the phosphor layer is increased.

JP 2008-10403 A

  An object of the present invention is to provide a novel light-emitting laminate that is useful for a visible light emitting device that emits visible light using ultraviolet light generated by discharge of Xe gas.

The present invention is a group consisting of the following (1) to (4) that emits ultraviolet light having a peak in a wavelength range of 230 to 260 nm when excited by ultraviolet light generated by discharge of Xe gas on a substrate. A phosphor layer containing a phosphor that emits visible light when excited by ultraviolet light in the wavelength range of 230 to 260 nm is formed through a wavelength conversion layer containing at least one magnesium oxide fired powder selected from the above. It is in the light emitting laminate.
(1) Chlorine-containing magnesium oxide fired powder containing chlorine in a range of 0.005 to 10% by mass.
(2) Zinc-containing magnesium oxide fired powder containing zinc in a range of 0.1 to 30% by mass.
(3) An aluminum-containing magnesium oxide fired powder obtained by firing a powder mixture of a γ-type aluminum oxide powder and a magnesium oxide source powder and having an aluminum content in the range of 2 to 38% by mass.
(4) Fluorine is contained in an amount in the range of 0.01 to 24 mol with respect to 100 mol of magnesium, and selected from the group consisting of alkali metals, alkaline earth metals other than magnesium, rare earth metals, aluminum, zinc and tin. Magnesium oxide calcined powder containing fluorine and an auxiliary metal containing at least one auxiliary metal in an amount in the range of 0.01 to 30 mol with respect to 100 mol of magnesium.

Preferred embodiments of the luminescent laminate of the present invention are as follows.
(1) The thickness of the wavelength conversion layer is in the range of 0.5 to 10 μm.
(2) The thickness of the phosphor layer is in the range of 0.1 to 30 μm.
(3) The phosphor layer has CaMgSi ₂ O ₆ : Eu ²⁺ , (Ca, Sr) MgSi ₂ O ₆ : Eu ²⁺ , Sr ₃ MgSi ₂ O ₈ : Eu ²⁺ , and BaMgAl ₁₀ O ₁₇ : Eu ² A blue light-emitting phosphor layer containing a blue light-emitting phosphor represented by at least one basic composition formula selected from the group consisting of ⁺ .
(4) The phosphor layer is a green light-emitting phosphor layer including a green light-emitting phosphor represented by a basic composition formula of Zn ₂ SiO ₄ : Mn ²⁺ .
(5) The phosphor layer is a red light-emitting phosphor layer including a red light-emitting phosphor represented by a basic composition formula of (Y, Gd) BO ₃ : Eu ³⁺ .
(6) A back plate of an AC type plasma display panel.
(7) A light emitting element of a Xe lamp.

The light-emitting laminate in which the wavelength conversion layer is provided under the phosphor layer of the present invention is more clear than the laminate in which only the phosphor layer is formed on the substrate, as is apparent from the data shown in the examples below. In addition, the emission luminance of visible light emitted by excitation with ultraviolet light having a wavelength of 146 nm (corresponding to the Xe resonance line) and ultraviolet light having a wavelength of 172 nm (corresponding to the molecular beam of Xe ₂ ) is remarkably increased. Therefore, the light emitting laminate of the present invention can be advantageously used as a back plate of an AC type PDP or a light emitting element of an Xe lamp.

  The luminescent laminate of the present invention comprises a substrate, a wavelength conversion layer formed on the substrate, and a phosphor layer formed on the wavelength conversion layer.

  In the light emitting laminate of the present invention, the wavelength conversion layer emits ultraviolet light having a peak in the wavelength range of 230 to 260 nm when excited by ultraviolet light generated by discharge of Xe gas. 4) formed of at least one magnesium oxide fired powder selected from the group consisting of:

(1) Chlorine-containing magnesium oxide fired powder containing chlorine in a range of 0.005 to 10% by mass.
It is preferable that the chlorine content of the said chlorine containing magnesium oxide baked material powder exists in the range of 0.01-10 mass%, and it is especially preferable that it exists in the range of 0.1-10 mass%.

  The chlorine-containing magnesium oxide fired powder can be produced by firing the magnesium oxide source powder in the presence of a chlorine source or in an atmosphere of a chlorine-containing gas.

As the magnesium oxide source powder, magnesium oxide powder and magnesium compound powder (except for magnesium chloride powder) that generates magnesium oxide powder by heating can be used. Examples of the magnesium compound powder include magnesium hydroxide powder, basic magnesium carbonate powder, magnesium nitrate powder, and magnesium acetate powder. The magnesium oxide source powder is preferably magnesium oxide powder. The magnesium oxide powder preferably has a purity of 99.95% by mass or more and a BET specific surface area of 5 to 150 m ² / g, particularly 7 to 50 m ² / g, and is produced by a gas phase synthesis method. Particularly preferred is magnesium oxide powder. The vapor phase synthesis method is a method for producing magnesium oxide powder by bringing a metal magnesium vapor and an oxygen-containing gas into contact with each other in the gas phase and oxidizing the metal magnesium vapor.

  As the chlorine source, magnesium chloride powder and ammonium chloride powder can be used. The chlorine source preferably has a purity of 99.0% by mass or more. When the magnesium oxide raw material powder is fired in the presence of a chlorine source, it is preferable to uniformly mix the magnesium oxide raw material powder and the chlorine source before firing.

As the chlorine-containing gas, hydrogen chloride gas, or gas obtained by heating and vaporizing ammonium chloride powder, magnesium chloride powder, or a chlorine-containing organic compound (CHCl ₃ , CCl _4, etc.) can be used.

  The firing temperature of the magnesium oxide source powder in the presence of a chlorine source and in a chlorine-containing gas atmosphere is preferably 850 ° C. or higher, more preferably 900 to 1500 ° C., and particularly preferably 1000 to 1500 ° C. The firing time is preferably 10 minutes or more, more preferably 10 minutes to 2 hours, and particularly preferably 20 minutes to 2 hours. The firing of the magnesium oxide source powder is performed, for example, by raising the temperature to the above-mentioned firing temperature under normal pressure and a temperature rise rate of 100 to 500 ° C./hour, and then firing the above firing time, followed by a temperature drop rate of 100 to 500 It can carry out by cooling to room temperature on the conditions of (degreeC / hour).

(2) Zinc-containing magnesium oxide fired powder containing zinc in a range of 0.1 to 30% by mass.
The zinc content in the zinc-containing magnesium oxide fired powder is particularly preferably in the range of 0.5 to 7% by mass.

  The zinc-containing magnesium oxide fired powder can be produced by mixing a magnesium oxide source powder and a zinc oxide source powder to obtain a powder mixture, and then firing the obtained powder mixture.

As the magnesium oxide source powder, magnesium oxide powder or magnesium compound powder that forms magnesium oxide powder by heating can be used. The magnesium oxide source powder is preferably magnesium oxide powder. The magnesium oxide powder preferably has a purity of 99.95% by mass or more and a BET specific surface area of 5 to 150 m ² / g, particularly 7 to 50 m ² / g, and is produced by a gas phase synthesis method. Particularly preferred is magnesium oxide powder.

  As the zinc oxide source powder, zinc oxide powder and zinc compound powder that generates zinc oxide powder by heating can be used. Examples of the zinc compound powder include zinc hydroxide powder, zinc carbonate powder, zinc nitrate powder, zinc acetate powder and zinc oxalate powder. The zinc oxide source powder is preferably zinc oxide powder. The purity of the zinc oxide source powder is preferably 99.0% by mass or more.

  The firing temperature of the powder mixture of the magnesium oxide source powder and the zinc oxide source powder is preferably 850 ° C. or higher, more preferably 900 to 1500 ° C., and particularly preferably 1000 to 1500 ° C. The firing time is preferably 10 minutes or more, more preferably 10 minutes to 2 hours, and particularly preferably 20 minutes to 2 hours.

(3) An aluminum-containing magnesium oxide fired powder obtained by firing a powder mixture of a γ-type aluminum oxide powder and a magnesium oxide source powder and having an aluminum content in the range of 2 to 38% by mass.
The aluminum content of the aluminum-containing fired magnesium oxide powder is preferably in the range of 5 to 35% by mass.

  The aluminum-containing fired magnesium oxide powder can be produced by mixing a γ-type aluminum oxide powder and a magnesium oxide source powder to obtain a powder mixture, and then firing the obtained powder mixture.

As the magnesium oxide source powder, magnesium oxide powder or magnesium compound powder that forms magnesium oxide powder by heating can be used. The magnesium oxide source powder is preferably magnesium oxide powder. The magnesium oxide powder preferably has a purity of 99.95% by mass or more and a BET specific surface area of 5 to 150 m ² / g, particularly 7 to 50 m ² / g, and is produced by a gas phase synthesis method. Particularly preferred is magnesium oxide powder.

  The purity of the γ-type aluminum oxide powder is preferably 99.0% by mass or more.

  The firing temperature of the powder mixture of the γ-type aluminum oxide powder and the magnesium oxide source powder is preferably 850 ° C. or higher, more preferably 900 to 1500 ° C., and particularly preferably 1000 to 1500 ° C. The firing time is preferably 10 minutes or more, more preferably 10 minutes to 2 hours, and particularly preferably 20 minutes to 2 hours.

(4) Fluorine is contained in an amount in the range of 0.01 to 24 mol with respect to 100 mol of magnesium, and selected from the group consisting of alkali metals, alkaline earth metals other than magnesium, rare earth metals, aluminum, zinc and tin. Magnesium oxide calcined powder containing fluorine and an auxiliary metal containing at least one auxiliary metal in an amount in the range of 0.01 to 30 mol with respect to 100 mol of magnesium.
The magnesium oxide fired powder containing the fluorine and the auxiliary metal preferably has a fluorine content in the range of 0.02 to 12 moles relative to 100 moles of magnesium, and in the range of 0.02 to 5 moles. It is particularly preferred. The content of the auxiliary metal is preferably in the range of 0.025 to 25 mol, particularly preferably in the range of 0.1 to 5 mol, with respect to 100 mol of magnesium. Moreover, it is preferable that content of an auxiliary metal exists in the range of 0.25-50 mol with respect to 1 mol of fluorine, and it is especially preferable that it exists in the range of 0.4-30 mol.

  Examples of the alkali metal used as the auxiliary metal include lithium, sodium and potassium. Examples of alkaline earth metals include calcium and barium. Examples of rare earth metals include yttrium, cerium and gadolinium. An auxiliary metal may be used individually by 1 type, and may use 2 or more types together.

  Magnesium oxide calcined powder containing fluorine and auxiliary metal is prepared by mixing magnesium oxide source powder and auxiliary metal fluoride powder so that the fluoride is 0 with respect to 100 mol of magnesium in the magnesium oxide source powder. Obtaining a powder mixture containing in an amount ranging from 0.05 to 30 mol, preferably 0.1 to 25 mol, particularly preferably 0.2 to 15 mol, and then firing the obtained powder mixture Can be manufactured.

  Instead of auxiliary metal fluoride powder, it consists of auxiliary metal oxide powder or auxiliary metal compound powder (except fluoride powder) that is converted to metal oxide by heating, magnesium fluoride powder and ammonium fluoride powder. At least one fluoride powder selected from the group can be used. That is, the calcined magnesium oxide powder containing fluorine and an auxiliary metal includes a magnesium oxide source powder, an auxiliary metal oxide powder, or a powder of a compound other than the auxiliary metal fluoride that generates a metal oxide by heating. , Mixed with at least one fluoride powder selected from the group consisting of magnesium fluoride powder and ammonium fluoride powder, and the auxiliary metal is in the range of 0.05 to 30 mol with respect to 100 mol of magnesium in the powder mixture. By obtaining a powder mixture comprising the amount of fluoride in the fluoride powder in an amount ranging from 0.1 to 10 moles per mole of auxiliary metal, and then firing the resulting powder mixture It can also be manufactured.

As the magnesium oxide source powder, magnesium oxide powder or magnesium compound powder that forms magnesium oxide powder by heating can be used. The magnesium oxide source powder is preferably magnesium oxide powder. The magnesium oxide powder preferably has a purity of 99.95% by mass or more and a BET specific surface area of 5 to 150 m ² / g, particularly 7 to 50 m ² / g, and is produced by a gas phase synthesis method. Particularly preferred is magnesium oxide powder.

  The auxiliary metal fluoride powder mixed with the magnesium oxide source powder, the auxiliary metal oxide powder, the compound powder that generates the auxiliary metal oxide powder by heating, and the fluoride powder have a purity of 99.0% by mass or more. Preferably there is. Examples of compound powders that produce auxiliary metal oxide powders upon heating include auxiliary metal hydroxide powders, carbonate powders, bicarbonate powders, nitrate powders, acetate powders, and oxalate powders. it can.

  Powder mixture of magnesium oxide source powder and auxiliary metal fluoride powder, and powder mixture of magnesium oxide source powder and auxiliary metal oxide powder or compound powder and fluoride powder that produce auxiliary metal oxide powder by heating The firing temperature is preferably 850 ° C. or higher, more preferably 900 to 1500 ° C., and particularly preferably 1000 to 1500 ° C. The firing time is preferably 10 minutes or more, more preferably 10 minutes to 2 hours, and particularly preferably 20 minutes to 2 hours.

Magnesium oxide calcined product to form a wavelength converting layer powder is in the range BET specific surface area of 0.1~30m ² / g, it is particularly preferably from 0.2~12m ² / g.

  The thickness of the wavelength conversion layer is preferably in the range of 0.5 to 10 μm, and more preferably in the range of 1.0 to 10 μm.

  The wavelength conversion layer is applied by applying a paste in which the magnesium oxide fired powder is dispersed on the substrate by a screen printing method or a coating method using various coaters such as a reverse coater, curtain coater, die coater, and slot coater. It can be formed by drying the membrane.

  In the light emitting laminate of the present invention, the phosphor layer is formed of a phosphor that emits visible light when excited by ultraviolet light in the wavelength range of 230 to 260 nm. As the phosphor, a blue light emitting phosphor, a green light emitting phosphor and a red light emitting phosphor are usually used.

As an example of a blue light emitting phosphor, the basic composition formula is CaMgSi ₂ O ₆ : Eu ²⁺ , (Ca, Sr) MgSi ₂ O ₆ : Eu ²⁺ , Sr ₃ MgSi ₂ O ₈ : Eu ²⁺ , and BaMgAl ₁₀ A blue light emitting phosphor represented by O ₁₇ : Eu ²⁺ can be given. As an example of the green light emitting phosphor, the basic composition formula is Zn ₂ SiO ₄ : Mn ²⁺ , (Ba, Sr, Mg) O.αAl ₂ O ₃ : Mn ²⁺ , YBO ₃ : Tb ³⁺ , (Y, Examples include phosphors represented by Gd) BO ₃ : Tb ³⁺ , BaAl ₁₂ O ₁₉ : Mn ²⁺ and BaMgAl ₁₀ O ₁₇ : Eu ²⁺ , Mn ²⁺ . As an example of a red light emitting phosphor, the basic composition formula is YBO ₃ : Eu ³⁺ , (Y, Gd) BO ₃ : Eu ³⁺ , Y ₂ O ₃ : Eu ³⁺ and (Y, Gd) ₂ O ₃ : A phosphor represented by Eu ³⁺ can be given. The phosphor powder may be used alone or in combination of two or more.

  The thickness of the phosphor layer is preferably in the range of 0.1 to 30 μm, and more preferably in the range of 1.0 to 30 μm.

  For the phosphor layer, a paste in which the phosphor powder is dispersed is applied onto the substrate by a screen printing method or a coating method using various coaters such as a reverse coater, curtain coater, die coater, slot coater, and a coating film is formed. It can be formed by drying.

  The light emitting laminate of the present invention can be used as a back plate of an AC type PDP or a light emitting element of an Xe lamp.

  The light emitting laminate used as the back plate of the AC type PDP is a substrate (usually a glass plate), an address electrode formed on the substrate, a dielectric layer covering the address electrode, and a dielectric layer on the dielectric layer. A structure in which a multilayer body formed of barrier ribs formed on a substrate is used as a substrate and a wavelength conversion layer and a phosphor layer are formed in this order on the surface of the dielectric layer and the side surfaces of the barrier ribs. The fired powder may be dispersed to form a wavelength conversion layer, and the wavelength conversion layer and the phosphor layer may be formed in this order on the surface of the wavelength conversion layer and the side wall of the partition wall. A back plate having a wavelength conversion layer having such a configuration is disclosed in Japanese Unexamined Patent Application Publication No. 2008-10403.

  In the back plate of the AC type PDP, the phosphor layer is generally divided into three color phosphor layers, a blue light emitting phosphor layer, a green light emitting phosphor layer, and a red light emitting phosphor layer, by partition walls. The wavelength conversion layer may be formed uniformly under each of the three color phosphor layers, or one or two of the three color phosphor layers may be used to balance the emission luminance of each color. You may provide only under a fluorescent substance layer.

  The light emitting laminate used as the light emitting element of the Xe lamp can have a structure in which a glass tube or a glass housing is used as a base, and a wavelength conversion layer and a phosphor layer are formed in this order inside the base.

[Example 1]
Magnesium oxide powder (2000A, manufactured by Ube Materials Co., Ltd., purity: 99.98% by mass, BET specific surface area: 8.7 m ² / g) manufactured by the vapor phase synthesis method, and magnesium chloride powder (purity: 99%) and 500 g were mixed to obtain a powder mixture. The obtained powder mixture was put into an alumina crucible, covered, put into an electric furnace, raised to 1300 ° C. at a heating rate of 240 ° C./hour, and then baked at that temperature for 30 minutes. Thereafter, the furnace temperature was cooled to room temperature at a temperature lowering rate of 240 ° C./hour. The obtained fired product was a chlorine-containing fired magnesium oxide powder having a BET specific surface area of 0.57 m ² / g and a chlorine content of 0.8% by mass. When the obtained chlorine-containing magnesium oxide fired powder was irradiated with ultraviolet light having a wavelength of 146 nm and a wavelength of 172 nm, it was confirmed that ultraviolet light having a peak in the wavelength range of 230 to 260 nm was emitted.

21 g of ethyl methylcellulose was added to 300 mL of isopropyl alcohol and stirred for 15 hours with a magnetic stirrer to prepare a paste base material. To this paste base material, 2.5 g of the chlorine-containing magnesium oxide fired powder produced above was added and mixed for 7 minutes using a defoaming machine to prepare a chlorine-containing magnesium oxide fired powder paste. Further, 2.5 g of CaMgSi ₂ O ₆ : Eu ²⁺ blue light-emitting phosphor powder is added to the paste base material prepared in the same manner, and mixed for 7 minutes using a defoamer, and CaMgSi ₂ O ₆ : Eu. ^{A 2+} blue light emitting phosphor powder paste was prepared.

The chlorine-containing magnesium oxide fired powder paste prepared above is applied to a quartz substrate having a diameter of 19.8 mm and a thickness of 2.0 mm using a screen printer, dried at a temperature of 70 ° C., and then a temperature of 600 ° C. Was annealed for 1 hour to form a 3 μm thick layer of fired chlorine-containing magnesium oxide. Next, the CaMgSi ₂ O ₆ : Eu ²⁺ blue light emitting phosphor powder paste prepared above was applied on a chlorine-containing magnesium oxide fired product layer with a screen printer and dried at a temperature of 70 ° C. Annealing is performed at a temperature of 600 ° C. for 1 hour to form a CaMgSi ₂ O ₆ : Eu ²⁺ blue light emitting phosphor layer having a thickness of 7 μm, and a chlorine-containing magnesium oxide fired powder (MgCl _2. A light-emitting laminate in which a CaMgSi ₂ O ₆ : Eu ²⁺ blue light-emitting phosphor layer was formed through a wavelength conversion layer made of MgO) was produced.

[Example 2]
500 g of magnesium oxide powder (2000A, manufactured by Ube Materials Co., Ltd.) manufactured by a gas phase synthesis method and 20 g of zinc oxide powder (purity: 99.9%) were mixed to obtain a powder mixture. The obtained powder mixture was put into an alumina crucible, covered, put into an electric furnace, raised to 1300 ° C. at a heating rate of 240 ° C./hour, and then baked at that temperature for 30 minutes. Thereafter, the furnace temperature was cooled to room temperature at a temperature lowering rate of 240 ° C./hour. The obtained fired product was a zinc-containing fired magnesium oxide powder having a BET specific surface area of 5.73 m ² / g and a zinc content of 3.09% by mass. When the obtained zinc-containing magnesium oxide fired powder was irradiated with ultraviolet light having a wavelength of 146 nm and a wavelength of 172 nm, it was confirmed that ultraviolet light having a peak in the wavelength range of 230 to 260 nm was emitted.

  The zinc-containing magnesium oxide fired powder (on the quartz substrate) was used in the same manner as in Example 1 except that the zinc-containing magnesium oxide fired powder produced above was used instead of the chlorine-containing magnesium oxide fired powder. A light-emitting laminate in which a phosphor layer was formed via a wavelength conversion layer made of ZnO · MgO was manufactured.

[Example 3]
500 g of magnesium oxide powder (2000A, manufactured by Ube Materials Co., Ltd.) manufactured by a gas phase synthesis method and 26.38 g of γ-type aluminum oxide powder (manufactured by Sumitomo Chemical Co., Ltd., high-purity alumina AKP-G015) Mixed to obtain a powder mixture. The obtained powder mixture was put into an alumina crucible, covered, put into an electric furnace, raised to 1300 ° C. at a heating rate of 240 ° C./hour, and then baked at that temperature for 30 minutes. Thereafter, the furnace temperature was cooled to room temperature at a temperature lowering rate of 240 ° C./hour. The obtained fired product was an aluminum-containing fired magnesium oxide powder having a BET specific surface area of 6.07 m ² / g and an aluminum content of 2.48% by mass. When the obtained aluminum-containing magnesium oxide fired powder was irradiated with ultraviolet light having a wavelength of 146 nm and a wavelength of 172 nm, it was confirmed to emit ultraviolet light having a peak in the wavelength range of 230 to 260 nm.

In the same manner as in Example 1 except that the aluminum-containing magnesium oxide calcined powder produced above was used instead of the chlorine-containing magnesium oxide calcined powder, the aluminum-containing magnesium oxide calcined powder ( A light-emitting laminate having a phosphor layer formed through a wavelength conversion layer made of (γ-Al ₂ O ₃ .MgO) was manufactured.

[Example 4]
A powder obtained by mixing 6.0 g of magnesium oxide powder (2000A, manufactured by Ube Materials Co., Ltd.) and 0.0386 g of lithium fluoride powder (purity: 99.9% by mass) manufactured by a gas phase synthesis method. A mixture was obtained. The obtained powder mixture was put into an alumina crucible, covered, put into an electric furnace, raised to 1200 ° C. at a temperature rising rate of 240 ° C./hour, and then baked at that temperature for 30 minutes. Thereafter, the furnace temperature was cooled to room temperature at a temperature lowering rate of 240 ° C./hour. The obtained fired product has a BET specific surface area of 0.26 m ² / g, a lithium content of 0.2 mol per 100 mol of magnesium, and a fluorine content of 0.09 mol per 100 mol of magnesium. -It was a fluorine-containing magnesium oxide fired powder. When the obtained lithium / fluorine-containing fired magnesium oxide powder was irradiated with ultraviolet light having a wavelength of 146 nm and a wavelength of 172 nm, it was confirmed that ultraviolet light having a peak in the wavelength range of 230 to 260 nm was emitted.

  A lithium / fluorine-containing magnesium oxide was formed on a quartz substrate in the same manner as in Example 1 except that the lithium / fluorine-containing magnesium oxide fired powder produced above was used instead of the chlorine-containing magnesium oxide fired powder. The light emitting laminated body in which the fluorescent substance layer was formed through the wavelength conversion layer which consists of baked material powder (LiF * MgO) was manufactured.

[Example 5]
A powder obtained by mixing 6.0 g of magnesium oxide powder (2000A, manufactured by Ube Materials Co., Ltd.) produced by a gas phase synthesis method and 0.0625 g of sodium fluoride powder (purity: 99.9% by mass). A mixture was obtained. The obtained powder mixture was put into an alumina crucible, covered, put into an electric furnace, raised to 1200 ° C. at a temperature rising rate of 240 ° C./hour, and then baked at that temperature for 30 minutes. Thereafter, the furnace temperature was cooled to room temperature at a temperature lowering rate of 240 ° C./hour. The obtained fired product has a BET specific surface area of 0.21 m ² / g, a sodium content of 0.2 mol with respect to 100 mol of magnesium, and a fluorine content of 0.10 mol with respect to 100 mol of magnesium. -It was a fluorine-containing magnesium oxide fired powder. When the obtained sodium / fluorine-containing magnesium oxide fired powder was irradiated with ultraviolet light having a wavelength of 146 nm and a wavelength of 172 nm, it was confirmed to emit ultraviolet light having a peak in the wavelength range of 230 to 260 nm.

  A sodium / fluorine-containing magnesium oxide was formed on a quartz substrate in the same manner as in Example 1, except that the sodium / fluorine-containing magnesium oxide fired powder produced above was used instead of the chlorine-containing magnesium oxide fired powder. A light-emitting laminate having a phosphor layer formed through a wavelength conversion layer made of a fired powder (NaF · MgO) was produced.

[Example 6]
6.0 g of magnesium oxide powder (2000A, manufactured by Ube Materials Co., Ltd.) produced by a gas phase synthesis method and 0.432 g of potassium fluoride powder (purity: 99.9% by mass) are mixed to obtain a powder. A mixture was obtained. The obtained powder mixture was put into an alumina crucible, covered, put into an electric furnace, raised to 1200 ° C. at a temperature rising rate of 240 ° C./hour, and then baked at that temperature for 30 minutes. Thereafter, the furnace temperature was cooled to room temperature at a temperature lowering rate of 240 ° C./hour. The obtained fired product has a BET specific surface area of 0.60 m ² / g, a potassium content of 0.1 mol per 100 mol of magnesium, and a fluorine content of 0.07 mol per 100 mol of magnesium. -It was a fluorine-containing magnesium oxide fired powder. When the obtained potassium / fluorine-containing magnesium oxide fired powder was irradiated with ultraviolet light having a wavelength of 146 nm and a wavelength of 172 nm, it was confirmed to emit ultraviolet light having a peak in the wavelength range of 230 to 260 nm.

  A potassium / fluorine-containing magnesium oxide was formed on a quartz substrate in the same manner as in Example 1 except that the potassium / fluorine-containing magnesium oxide fired powder produced above was used instead of the chlorine-containing magnesium oxide fired powder. A light-emitting laminate having a phosphor layer formed through a wavelength conversion layer made of fired powder (KF · MgO) was produced.

[Example 7]
6.0 g of magnesium oxide powder (2000A, manufactured by Ube Materials Co., Ltd.) manufactured by a gas phase synthesis method and 0.0581 g of calcium fluoride powder (purity: 99.9 mass%) are mixed to obtain a powder. A mixture was obtained. The obtained powder mixture was put into an alumina crucible, covered, put into an electric furnace, raised to 1200 ° C. at a temperature rising rate of 240 ° C./hour, and then baked at that temperature for 30 minutes. Thereafter, the furnace temperature was cooled to room temperature at a temperature lowering rate of 240 ° C./hour. The obtained calcined product has a BET specific surface area of 1.36 m ² / g, a calcium content of 0.5 mol with respect to 100 mol of magnesium, and a fluorine content of 0.82 mol with respect to 100 mol of magnesium. -It was a fluorine-containing magnesium oxide fired powder. When the obtained calcium / fluorine-containing magnesium oxide fired powder was irradiated with ultraviolet light having a wavelength of 146 nm and a wavelength of 172 nm, it was confirmed that ultraviolet light having a peak in the wavelength range of 230 to 260 nm was emitted.

A calcium / fluorine-containing magnesium oxide was formed on a quartz substrate in the same manner as in Example 1 except that the calcium / fluorine-containing magnesium oxide fired powder produced above was used instead of the chlorine-containing magnesium oxide fired powder. calcined powder was produced luminescent laminate phosphor layer via a wavelength conversion layer consisting of (CaF ₂ · MgO) is formed.

[Example 8]
A powder obtained by mixing 6.0 g of magnesium oxide powder (2000A, manufactured by Ube Materials Co., Ltd.) produced by a gas phase synthesis method and 0.2610 g of barium fluoride powder (purity: 99.9% by mass). A mixture was obtained. The obtained powder mixture was put into an alumina crucible, covered, put into an electric furnace, raised to 1200 ° C. at a temperature rising rate of 240 ° C./hour, and then baked at that temperature for 30 minutes. Thereafter, the furnace temperature was cooled to room temperature at a temperature lowering rate of 240 ° C./hour. The obtained fired product has a BET specific surface area of 1.49 m ² / g, a barium content of 1.0 mol per 100 mol of magnesium and a fluorine content of 1.91 mol per 100 mol of magnesium. -It was a fluorine-containing magnesium oxide fired powder. When the obtained barium / fluorine-containing calcined magnesium oxide powder was irradiated with ultraviolet light having a wavelength of 146 nm and a wavelength of 172 nm, it was confirmed to emit ultraviolet light having a peak in the wavelength range of 230 to 260 nm.

A barium / fluorine-containing magnesium oxide was formed on a quartz substrate in the same manner as in Example 1 except that the barium / fluorine-containing magnesium oxide fired powder produced above was used instead of the chlorine-containing magnesium oxide fired powder. A light-emitting laminate having a phosphor layer formed through a wavelength conversion layer made of a fired powder (BaF ₂ .MgO) was produced.

[Example 9]
A powder obtained by mixing 6.0 g of magnesium oxide powder (2000A, manufactured by Ube Materials Co., Ltd.) produced by a gas phase synthesis method and 0.1250 g of aluminum fluoride powder (purity: 99.9% by mass). A mixture was obtained. The obtained powder mixture was put into an alumina crucible, covered, put into an electric furnace, raised to 1300 ° C. at a heating rate of 240 ° C./hour, and then baked at that temperature for 30 minutes. Thereafter, the furnace temperature was cooled to room temperature at a temperature lowering rate of 240 ° C./hour. The obtained fired product has a BET specific surface area of 0.96 m ² / g, an aluminum content of 1.0 mol with respect to 100 mol of magnesium, and a fluorine content of 0.47 mol with respect to 100 mol of magnesium. -It was a fluorine-containing magnesium oxide fired powder. When the obtained aluminum / fluorine-containing magnesium oxide fired powder was irradiated with ultraviolet light having a wavelength of 146 nm and a wavelength of 172 nm, it was confirmed to emit ultraviolet light having a peak in the wavelength range of 230 to 260 nm.

An aluminum / fluorine-containing magnesium oxide was formed on a quartz substrate in the same manner as in Example 1 except that the aluminum / fluorine-containing magnesium oxide fired powder produced above was used instead of the chlorine-containing magnesium oxide fired powder. A light-emitting laminate having a phosphor layer formed through a wavelength conversion layer made of fired powder (AlF ₃ .MgO) was produced.

[Example 10]
6.0 g of magnesium oxide powder (2000A, manufactured by Ube Materials Co., Ltd.) produced by a gas phase synthesis method and 0.1306 g of zinc fluoride tetrahydrate powder (purity: 99.9% by mass) Mixed to obtain a powder mixture. The obtained powder mixture was put into an alumina crucible, covered, put into an electric furnace, raised to 1300 ° C. at a heating rate of 240 ° C./hour, and then baked at that temperature for 30 minutes. Thereafter, the furnace temperature was cooled to room temperature at a temperature lowering rate of 240 ° C./hour. The obtained fired product has a BET specific surface area of 1.29 m ² / g, a zinc content of 0.5 mol with respect to 100 mol of magnesium, and a fluorine content of 0.03 mol with respect to 100 mol of magnesium. -It was a fluorine-containing magnesium oxide fired powder. When the obtained zinc / fluorine-containing magnesium oxide fired powder was irradiated with ultraviolet light having a wavelength of 146 nm and a wavelength of 172 nm, it was confirmed to emit ultraviolet light having a peak in the wavelength range of 230 to 260 nm.

A zinc / fluorine-containing magnesium oxide was formed on a quartz substrate in the same manner as in Example 1 except that the zinc / fluorine-containing magnesium oxide fired powder produced above was used instead of the chlorine-containing magnesium oxide fired powder. A light-emitting laminate having a phosphor layer formed through a wavelength conversion layer made of a fired powder (ZnF ₂ .MgO) was produced.

[Example 11]
A powder obtained by mixing 6.0 g of magnesium oxide powder (2000A, manufactured by Ube Materials Co., Ltd.) produced by a gas phase synthesis method and 0.2334 g of tin fluoride powder (purity: 99.9% by mass). A mixture was obtained. The obtained powder mixture was put into an alumina crucible, covered, put into an electric furnace, raised to 1300 ° C. at a heating rate of 240 ° C./hour, and then baked at that temperature for 30 minutes. Thereafter, the furnace temperature was cooled to room temperature at a temperature lowering rate of 240 ° C./hour. The obtained fired product has a BET specific surface area of 0.80 m ² / g, a tin content of 1.0 mol with respect to 100 mol of magnesium, and a fluorine content of 0.07 mol with respect to 100 mol of magnesium. -It was a fluorine-containing magnesium oxide fired powder. When the obtained tin / fluorine-containing fired magnesium oxide powder was irradiated with ultraviolet light having a wavelength of 146 nm and a wavelength of 172 nm, it was confirmed to emit ultraviolet light having a peak in the wavelength range of 230 to 260 nm.

A tin / fluorine-containing magnesium oxide was formed on a quartz substrate in the same manner as in Example 1 except that the tin / fluorine-containing magnesium oxide fired powder produced above was used instead of the chlorine-containing magnesium oxide fired powder. calcined powders were prepared (SnF ₂ · MgO) through the wavelength conversion layer consisting of luminescent laminate phosphor layer is formed.

[Example 12]
A powder obtained by mixing 6.0 g of magnesium oxide powder (2000A, manufactured by Ube Materials Co., Ltd.) produced by a gas phase synthesis method and 0.1460 g of cerium fluoride powder (purity: 99.9% by mass). A mixture was obtained. The obtained powder mixture was put into an alumina crucible, covered, put into an electric furnace, raised to 1300 ° C. at a heating rate of 240 ° C./hour, and then baked at that temperature for 30 minutes. Thereafter, the furnace temperature was cooled to room temperature at a temperature lowering rate of 240 ° C./hour. The obtained fired product has a BET specific surface area of 0.99 m ² / g, a cerium content of 1.0 mol per 100 mol of magnesium, and a fluorine content of 0.26 mol per 100 mol of magnesium. -It was a fluorine-containing magnesium oxide fired powder. When the obtained cerium / fluorine-containing fired magnesium oxide powder was irradiated with ultraviolet light having a wavelength of 146 nm and a wavelength of 172 nm, it was confirmed that ultraviolet light having a peak in the wavelength range of 230 to 260 nm was emitted.

A cerium / fluorine-containing magnesium oxide was formed on a quartz substrate in the same manner as in Example 1 except that the cerium / fluorine-containing magnesium oxide fired powder produced above was used instead of the chlorine-containing magnesium oxide fired powder. A light-emitting laminate having a phosphor layer formed through a wavelength conversion layer made of a fired powder (CeF ₃ .MgO) was produced.

[Example 13]
A powder obtained by mixing 6.0 g of magnesium oxide powder (2000A, manufactured by Ube Materials Co., Ltd.) and 0.2180 g of yttrium fluoride powder (purity: 99.9% by mass) manufactured by a gas phase synthesis method. A mixture was obtained. The obtained powder mixture was put into an alumina crucible, covered, put into an electric furnace, raised to 1300 ° C. at a heating rate of 240 ° C./hour, and then baked at that temperature for 30 minutes. Thereafter, the furnace temperature was cooled to room temperature at a temperature lowering rate of 240 ° C./hour. The obtained fired product has a BET specific surface area of 0.97 m ² / g, an yttrium content of 1.0 mol with respect to 100 mol of magnesium, and a fluorine content of 1.52 mol with respect to 100 mol of magnesium. -It was a fluorine-containing magnesium oxide fired powder. When the obtained yttrium / fluorine-containing magnesium oxide fired powder was irradiated with ultraviolet light having a wavelength of 146 nm and a wavelength of 172 nm, it was confirmed to emit ultraviolet light having a peak in the wavelength range of 230 to 260 nm.

A yttrium / fluorine-containing magnesium oxide was formed on a quartz substrate in the same manner as in Example 1, except that the yttrium / fluorine-containing magnesium oxide fired powder produced above was used instead of the chlorine-containing magnesium oxide fired powder. A light-emitting laminate having a phosphor layer formed through a wavelength conversion layer made of a fired powder (YF ₃ .MgO) was produced.

[Example 14]
A powder obtained by mixing 6.0 g of magnesium oxide powder (2000A, manufactured by Ube Materials Co., Ltd.) produced by a gas phase synthesis method and 0.0796 g of gadolinium fluoride powder (purity: 99.9% by mass). A mixture was obtained. The obtained powder mixture was put into an alumina crucible, covered, put into an electric furnace, raised to 1300 ° C. at a heating rate of 240 ° C./hour, and then baked at that temperature for 30 minutes. Thereafter, the furnace temperature was cooled to room temperature at a temperature lowering rate of 240 ° C./hour. The obtained fired product has a BET specific surface area of 1.10 m ² / g, a gadolinium content of 0.5 mol per 100 mol of magnesium, and a fluorine content of 0.59 mol per 100 mol of magnesium. -It was a fluorine-containing magnesium oxide fired powder. When the obtained powder of fired gadolinium / fluorine-containing magnesium oxide was irradiated with vacuum ultraviolet light having a wavelength of 146 nm and a wavelength of 172 nm, it was confirmed to emit ultraviolet light having a peak in the wavelength range of 230 to 260 nm.

The gadolinium / fluorine-containing magnesium oxide was formed on the quartz substrate in the same manner as in Example 1 except that the gadolinium / fluorine-containing magnesium oxide fired powder produced above was used instead of the chlorine-containing magnesium oxide fired powder. A light-emitting laminate having a phosphor layer formed through a wavelength conversion layer made of a fired powder (GdF ₃ .MgO) was produced.

[Comparative Example 1]
A CaMgSi ₂ O ₆ : Eu ² having a thickness of 7 μm is formed on the quartz substrate in the same manner as in Example 1 except that the wavelength conversion layer made of the baked chlorine-containing magnesium oxide is not formed on the quartz substrate. ⁺ A light emitting laminate having a blue light emitting phosphor layer formed thereon was produced.

[Evaluation of luminous laminate]
From the phosphor layer of the light emitting laminate manufactured in Examples 1 to 14 and Comparative Example 1, ultraviolet light having a wavelength of 146 nm and a wavelength of 172 nm is irradiated, and an emission spectrum of visible light emitted from the laminate is obtained. It was measured. The maximum peak value of the obtained emission spectrum is shown in Table 1 as the maximum emission luminance.

Table 1 (phosphor layer: CaMgSi ₂ O ₆ : Eu ²⁺ blue light emitting phosphor layer)
────────────────────────────────────────
Maximum luminance
──────────────────
Material of wavelength conversion layer Wavelength 146nm Wavelength 172nm
────────────────────────────────────────
Example 1 MgCl ₂ .MgO 198 247
Example 2 ZnO.MgO 205 238
Example 3 γ-Al ₂ O ₃ .MgO 202 229
Example 4 LiF · MgO 224 253
Example 5 NaF · MgO 225 249
Example 6 KF · MgO 218 243
Example 7 CaF ₂ .MgO 222 245
Example 8 BaF ₂ .MgO 219 243
Example 9 AlF ₃ .MgO 230 261
Example 10 ZnF ₂ .MgO 195 234
Example 11 SnF ₂ .MgO 201 233
Example 12 CeF ₃ .MgO 207 237
Example 13 YF ₃ .MgO 212 242
Example 14 GdF ₃ .MgO 224 252
────────────────────────────────────────
Comparative Example 1 None 100 100
──────────────────────────────────────── Note) Maximum emission brightness is Comparative Example 1. The relative value with the value of 100 as 100.

[Example 15]
A quartz substrate in the same manner as in Example 1 except that Ca _0.5 Sr _0.5 MgSi ₂ O ₆ : Eu ²⁺ blue light-emitting phosphor powder was used instead of CaMgSi ₂ O ₆ : Eu ²⁺ blue light-emitting phosphor powder. 7 μm thick Ca _0.5 Sr _0.5 MgSi ₂ O ₆ : Eu ²⁺ blue light emitting phosphor through a 3 μm thick wavelength conversion layer made of baked chlorine-containing magnesium oxide powder (MgCl ₂ · MgO) A luminescent laminate having a layer formed thereon was produced.

[Example 16]
A zinc-containing magnesium oxide fired product is formed on a quartz substrate in the same manner as in Example 15 except that the zinc-containing magnesium oxide fired powder produced in Example 2 is used instead of the chlorine-containing magnesium oxide fired powder. A light-emitting laminate having a phosphor layer formed through a wavelength conversion layer made of powder (ZnO.MgO) was produced.

[Example 17]
An aluminum-containing magnesium oxide fired product is formed on a quartz substrate in the same manner as in Example 15 except that the aluminum-containing magnesium oxide fired material powder produced in Example 3 is used instead of the chlorine-containing magnesium oxide fired powder. A light-emitting laminate having a phosphor layer formed through a wavelength conversion layer made of powder (γ-Al ₂ O ₃ .MgO) was produced.

[Example 18]
A lithium / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 15 except that the lithium / fluorine-containing magnesium oxide fired material powder produced in Example 4 was used instead of the chlorine-containing magnesium oxide powder. The light emitting laminated body in which the fluorescent substance layer was formed through the wavelength conversion layer which consists of a magnesium oxide baked material powder (LiF * MgO) was manufactured.

[Example 19]
Instead of the chlorine-containing magnesium oxide calcined powder, the sodium / fluorine-containing magnesium oxide calcined powder produced in Example 5 was used in the same manner as in Example 15 on the quartz substrate. The light emitting laminated body in which the fluorescent substance layer was formed through the wavelength conversion layer which consists of a magnesium oxide baked material powder (NaF * MgO) was manufactured.

[Example 20]
A potassium / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 15 except that the potassium / fluorine-containing magnesium oxide fired powder produced in Example 6 was used instead of the chlorine-containing magnesium oxide powder. A light-emitting laminate having a phosphor layer formed through a wavelength conversion layer made of magnesium oxide fired powder (KF · MgO) was produced.

[Example 21]
A calcium / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 15 except that the calcium / fluorine-containing magnesium oxide fired powder produced in Example 7 was used instead of the chlorine-containing magnesium oxide fired powder. was prepared phosphor layer is formed through the wavelength conversion layer made of magnesium calcined powder oxide (CaF ₂ · MgO) luminescent laminate.

[Example 22]
A barium / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 15 except that the barium / fluorine-containing magnesium oxide fired material powder produced in Example 8 was used instead of the chlorine-containing magnesium oxide fired material powder. was prepared phosphor layer is formed through the wavelength conversion layer made of magnesium calcined powder oxide (BaF ₂ · MgO) luminescent laminate.

[Example 23]
Instead of the chlorine-containing magnesium oxide fired powder, the aluminum / fluorine-containing magnesium oxide fired powder produced in Example 9 was used in the same manner as in Example 15 on the quartz substrate. was prepared phosphor layer is formed through the wavelength conversion layer made of magnesium calcined powder oxide (AlF ₃ · MgO) luminescent laminate.

[Example 24]
A zinc / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 15 except that the zinc / fluorine-containing magnesium oxide fired powder produced in Example 10 was used instead of the chlorine-containing magnesium oxide fired powder. A light-emitting laminate having a phosphor layer formed through a wavelength conversion layer made of a magnesium oxide fired powder (ZnF ₂ .MgO) was produced.

[Example 25]
A tin / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 15 except that the tin / fluorine-containing magnesium oxide fired powder produced in Example 11 was used instead of the chlorine-containing magnesium oxide fired powder. was prepared phosphor layer is formed through the wavelength conversion layer made of magnesium calcined powder oxide (SnF ₂ · MgO) luminescent laminate.

[Example 26]
A cerium / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 15 except that the cerium / fluorine-containing magnesium oxide fired powder produced in Example 12 was used instead of the chlorine-containing magnesium oxide fired material powder. was prepared phosphor layer is formed through the wavelength conversion layer made of magnesium calcined powder oxide (CeF ₃ · MgO) luminescent laminate.

[Example 27]
A yttrium / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 15 except that the yttrium / fluorine-containing magnesium oxide powder produced in Example 13 was used instead of the chlorine-containing magnesium oxide powder. A light-emitting laminate in which a phosphor layer was formed through a wavelength conversion layer made of magnesium oxide fired powder (YF ₃ .MgO) was produced.

[Example 28]
A gadolinium / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 15 except that the gadolinium / fluorine-containing magnesium oxide fired powder produced in Example 14 was used instead of the chlorine-containing magnesium oxide fired powder. A light-emitting laminate having a phosphor layer formed through a wavelength conversion layer made of magnesium oxide fired powder (GdF ₃ .MgO) was produced.

[Comparative Example 2]
A Ca _0.5 Sr _0.5 MgSi ₂ having a thickness of 7 μm was formed on the quartz substrate in the same manner as in Example 15 except that the wavelength conversion layer made of the chlorine-containing fired magnesium oxide powder was not formed on the quartz substrate. A light emitting laminate in which an O ₆ : Eu ²⁺ blue light emitting phosphor layer was formed was manufactured.

[Evaluation of luminous laminate]
From the phosphor layer of the light emitting laminate manufactured in Examples 15 to 28 and Comparative Example 2, ultraviolet light having a wavelength of 146 nm and a wavelength of 172 nm is irradiated to obtain an emission spectrum of visible light emitted from the laminate. It was measured. Table 2 shows the maximum peak value of the obtained emission spectrum as the maximum emission luminance.

Table 2 (phosphor layer: Ca _0.5 Sr _0.5 MgSi ₂ O ₆ : Eu ²⁺ blue light emitting phosphor layer) ───────────────────────── ───────────────
Maximum luminance
──────────────────
Material of wavelength conversion layer Wavelength 146nm Wavelength 172nm
────────────────────────────────────────
Example 15 MgCl ₂ .MgO 206 259
Example 16 ZnO.MgO 220 250
Example 17 γ-Al ₂ O ₃ .MgO 218 237
Example 18 LiF · MgO 229 244
Example 19 NaF · MgO 224 245
Example 20 KF · MgO 206 236
Example 21 CaF ₂ .MgO 227 241
Example 22 BaF ₂ .MgO 226 241
Example 23 AlF ₃ .MgO 228 259
Example 24 ZnF ₂ .MgO 204 245
Example 25 SnF ₂ .MgO 196 232
Example 26 CeF ₃ .MgO 214 240
Example 27 YF ₃ .MgO 218 233
Example 28 GdF ₃ .MgO 230 245
────────────────────────────────────────
Comparative Example 2 None 100 100
──────────────────────────────────────── Note) The maximum emission brightness is the value of Comparative Example 2 The relative value with the value of 100 as 100.

[Example 29]
In the same manner as in Example 1 except that BaMgAl ₁₀ O ₁₇ : Eu ²⁺ blue light-emitting phosphor powder was used instead of CaMgSi ₂ O ₆ : Eu ²⁺ blue light-emitting phosphor powder, A light-emitting laminate in which a BaMgAl ₁₀ O ₁₇ : Eu ²⁺ blue light-emitting phosphor layer having a thickness of 7 μm is formed through a wavelength conversion layer having a thickness of 3 μm, which is made of a calcined magnesium oxide powder (MgCl ₂ · MgO) The body was manufactured.

[Example 30]
A zinc-containing magnesium oxide fired product is formed on a quartz substrate in the same manner as in Example 29 except that the zinc-containing magnesium oxide fired powder produced in Example 2 is used instead of the chlorine-containing magnesium oxide fired powder. A light-emitting laminate having a phosphor layer formed through a wavelength conversion layer made of powder (ZnO.MgO) was produced.

[Example 31]
An aluminum-containing magnesium oxide fired product is formed on a quartz substrate in the same manner as in Example 29 except that the aluminum-containing magnesium oxide fired powder produced in Example 3 is used instead of the chlorine-containing magnesium oxide fired powder. A light-emitting laminate having a phosphor layer formed through a wavelength conversion layer made of powder (γ-Al ₂ O ₃ .MgO) was produced.

[Example 32]
A lithium / fluorine-containing material was formed on the quartz substrate in the same manner as in Example 29 except that the lithium / fluorine-containing magnesium oxide fired material powder produced in Example 4 was used instead of the chlorine-containing magnesium oxide powder. The light emitting laminated body in which the fluorescent substance layer was formed through the wavelength conversion layer which consists of a magnesium oxide baked material powder (LiF * MgO) was manufactured.

[Example 33]
In place of the chlorine-containing magnesium oxide fired powder, the sodium / fluorine-containing magnesium oxide fired powder produced in Example 5 was used in the same manner as in Example 29 on the quartz substrate. The light emitting laminated body in which the fluorescent substance layer was formed through the wavelength conversion layer which consists of a magnesium oxide baked material powder (NaF * MgO) was manufactured.

[Example 34]
In place of the chlorine-containing magnesium oxide fired powder, the potassium / fluorine-containing powder was formed on the quartz substrate in the same manner as in Example 29 except that the potassium / fluorine-containing magnesium oxide fired powder produced in Example 6 was used. A light-emitting laminate having a phosphor layer formed through a wavelength conversion layer made of magnesium oxide fired powder (KF · MgO) was produced.

[Example 35]
A calcium / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 29 except that the calcium / fluorine-containing magnesium oxide fired powder produced in Example 7 was used instead of the chlorine-containing magnesium oxide fired powder. was prepared phosphor layer is formed through the wavelength conversion layer made of magnesium calcined powder oxide (CaF ₂ · MgO) luminescent laminate.

[Example 36]
A barium / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 29 except that the barium / fluorine-containing magnesium oxide fired material powder produced in Example 8 was used instead of the chlorine-containing magnesium oxide powder. was prepared phosphor layer is formed through the wavelength conversion layer made of magnesium calcined powder oxide (BaF ₂ · MgO) luminescent laminate.

[Example 37]
Instead of the chlorine-containing magnesium oxide fired powder, the aluminum / fluorine-containing magnesium oxide fired powder produced in Example 9 was used in the same manner as in Example 29 on the quartz substrate. was prepared phosphor layer is formed through the wavelength conversion layer made of magnesium calcined powder oxide (AlF ₃ · MgO) luminescent laminate.

[Example 38]
A zinc / fluorine-containing material was formed on the quartz substrate in the same manner as in Example 29 except that the zinc / fluorine-containing magnesium oxide fired powder produced in Example 10 was used instead of the chlorine-containing magnesium oxide fired powder. A light-emitting laminate having a phosphor layer formed through a wavelength conversion layer made of a magnesium oxide fired powder (ZnF ₂ .MgO) was produced.

[Example 39]
A tin / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 29 except that the tin / fluorine-containing magnesium oxide fired powder produced in Example 11 was used instead of the chlorine-containing magnesium oxide fired powder. was prepared phosphor layer is formed through the wavelength conversion layer made of magnesium calcined powder oxide (SnF ₂ · MgO) luminescent laminate.

[Example 40]
A cerium / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 29 except that the cerium / fluorine-containing magnesium oxide fired powder produced in Example 12 was used instead of the chlorine-containing magnesium oxide fired powder. was prepared phosphor layer is formed through the wavelength conversion layer made of magnesium calcined powder oxide (CeF ₃ · MgO) luminescent laminate.

[Example 41]
A yttrium / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 29 except that the yttrium / fluorine-containing magnesium oxide fired powder produced in Example 13 was used instead of the chlorine-containing magnesium oxide powder. A light-emitting laminate in which a phosphor layer was formed through a wavelength conversion layer made of magnesium oxide fired powder (YF ₃ .MgO) was produced.

[Example 42]
A gadolinium / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 29 except that the gadolinium / fluorine-containing magnesium oxide fired material powder produced in Example 14 was used instead of the chlorine-containing magnesium oxide fired material powder. A light-emitting laminate having a phosphor layer formed through a wavelength conversion layer made of magnesium oxide fired powder (GdF ₃ .MgO) was produced.

[Comparative Example 3]
A BaMgAl ₁₀ O ₁₇ : Eu having a thickness of 7 μm was formed on the quartz substrate in the same manner as in Example 29 except that the wavelength conversion layer made of the chlorine-containing fired magnesium oxide powder was not formed on the quartz substrate. A light-emitting laminate in which a ²⁺ blue light-emitting phosphor layer was formed was manufactured.

[Evaluation of luminous laminate]
The emission spectrum of visible light emitted from the laminate by irradiating with ultraviolet light having a wavelength of 146 nm and a wavelength of 172 nm from above the phosphor layers of the luminescent laminate produced in Examples 29 to 42 and Comparative Example 3. It was measured. Table 3 shows the maximum peak value of the obtained emission spectrum as the maximum emission luminance.

Table 3 (phosphor layer: BaMgAl ₁₀ O ₁₇ : Eu ²⁺ blue light emitting phosphor layer)
────────────────────────────────────────
Maximum luminance
──────────────────
Material of wavelength conversion layer Wavelength 146nm Wavelength 172nm
────────────────────────────────────────
Example 29 MgCl ₂ .MgO 188 200
Example 30 ZnO.MgO 192 193
Example 31 γ-Al ₂ O ₃ .MgO 182 194
Example 32 LiF · MgO 203 250
Example 33 NaF · MgO 210 251
Example 34 KF · MgO 218 238
Example 35 CaF ₂ .MgO 220 240
Example 36 BaF ₂ .MgO 223 244
Example 37 AlF ₃ .MgO 224 253
Example 38 ZnF ₂ .MgO 209 240
Example 39 SnF ₂ .MgO 206 240
Example 40 CeF ₃ .MgO 203 238
Example 41 YF ₃ .MgO 205 245
Example 42 GdF ₃ .MgO 227 241
────────────────────────────────────────
Comparative Example 3 None 100 100
──────────────────────────────────────── Note) The maximum light emission brightness is Comparative Example 3. The relative value with the value of 100 as 100.

[Example 43]
In the same manner as in Example 1 except that Zn ₂ SiO ₄ : Mn ²⁺ green light-emitting phosphor powder was used instead of CaMgSi ₂ O ₆ : Eu ²⁺ blue light-emitting phosphor powder, Luminescent laminate in which a 7 μm thick Zn ₂ SiO ₄ : Mn ²⁺ green light-emitting phosphor layer is formed through a wavelength conversion layer having a thickness of 3 μm and made of chlorine-containing magnesium oxide fired powder (MgCl ₂ · MgO) The body was manufactured.

[Example 44]
A zinc-containing magnesium oxide fired product is formed on a quartz substrate in the same manner as in Example 43 except that the zinc-containing magnesium oxide fired product powder produced in Example 2 is used instead of the chlorine-containing magnesium oxide fired product powder. A light-emitting laminate having a phosphor layer formed through a wavelength conversion layer made of powder (ZnO.MgO) was produced.

[Example 45]
An aluminum-containing magnesium oxide fired product is formed on a quartz substrate in the same manner as in Example 43 except that the aluminum-containing magnesium oxide fired powder produced in Example 3 is used instead of the chlorine-containing magnesium oxide fired powder. A light-emitting laminate having a phosphor layer formed through a wavelength conversion layer made of powder (γ-Al ₂ O ₃ .MgO) was produced.

[Example 46]
A lithium / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 43 except that the lithium / fluorine-containing magnesium oxide fired material powder produced in Example 4 was used instead of the chlorine-containing magnesium oxide powder. The light emitting laminated body in which the fluorescent substance layer was formed through the wavelength conversion layer which consists of a magnesium oxide baked material powder (LiF * MgO) was manufactured.

[Example 47]
Instead of the chlorine-containing magnesium oxide fired powder, the sodium / fluorine-containing magnesium oxide fired powder produced in Example 5 was used in the same manner as in Example 43 on the quartz substrate. The light emitting laminated body in which the fluorescent substance layer was formed through the wavelength conversion layer which consists of a magnesium oxide baked material powder (NaF * MgO) was manufactured.

[Example 48]
In place of the chlorine-containing magnesium oxide fired powder, the potassium / fluorine-containing magnesium oxide fired powder produced in Example 6 was used in the same manner as in Example 43 on the quartz substrate. A light-emitting laminate having a phosphor layer formed through a wavelength conversion layer made of magnesium oxide fired powder (KF · MgO) was produced.

[Example 49]
A calcium / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 43 except that the calcium / fluorine-containing magnesium oxide fired powder produced in Example 7 was used instead of the chlorine-containing magnesium oxide fired powder. was prepared phosphor layer is formed through the wavelength conversion layer made of magnesium calcined powder oxide (CaF ₂ · MgO) luminescent laminate.

[Example 50]
A barium / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 43 except that the barium / fluorine-containing magnesium oxide fired powder produced in Example 8 was used instead of the chlorine-containing magnesium oxide fired material powder. was prepared phosphor layer is formed through the wavelength conversion layer made of magnesium calcined powder oxide (BaF ₂ · MgO) luminescent laminate.

[Example 51]
In place of the chlorine-containing magnesium oxide calcined powder, the aluminum / fluorine-containing magnesium oxide calcined powder produced in Example 9 was used in the same manner as in Example 43 on the quartz substrate. was prepared phosphor layer is formed through the wavelength conversion layer made of magnesium calcined powder oxide (AlF ₃ · MgO) luminescent laminate.

[Example 52]
A zinc / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 43 except that the zinc / fluorine-containing magnesium oxide fired powder produced in Example 10 was used instead of the chlorine-containing magnesium oxide fired powder. A light-emitting laminate having a phosphor layer formed through a wavelength conversion layer made of a magnesium oxide fired powder (ZnF ₂ .MgO) was produced.

[Example 53]
A tin / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 43 except that the tin / fluorine-containing magnesium oxide fired powder produced in Example 11 was used instead of the chlorine-containing magnesium oxide fired powder. was prepared phosphor layer is formed through the wavelength conversion layer made of magnesium calcined powder oxide (SnF ₂ · MgO) luminescent laminate.

[Example 54]
A cerium / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 43 except that the cerium / fluorine-containing magnesium oxide fired powder produced in Example 12 was used instead of the chlorine-containing magnesium oxide fired powder. was prepared phosphor layer is formed through the wavelength conversion layer made of magnesium calcined powder oxide (CeF ₃ · MgO) luminescent laminate.

[Example 55]
A yttrium / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 43 except that the yttrium / fluorine-containing magnesium oxide fired material powder produced in Example 13 was used instead of the chlorine-containing magnesium oxide powder. A light-emitting laminate in which a phosphor layer was formed through a wavelength conversion layer made of magnesium oxide fired powder (YF ₃ .MgO) was produced.

[Example 56]
A gadolinium / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 43 except that the gadolinium / fluorine-containing magnesium oxide fired powder produced in Example 14 was used instead of the chlorine-containing magnesium oxide fired powder. A light-emitting laminate having a phosphor layer formed through a wavelength conversion layer made of magnesium oxide fired powder (GdF ₃ .MgO) was produced.

[Comparative Example 4]
A Zn ₂ SiO ₄ : Mn having a thickness of 7 μm is formed on the quartz substrate in the same manner as in Example 43 except that the wavelength conversion layer made of the chlorine-containing magnesium oxide fired powder is not formed on the quartz substrate. A light-emitting laminate in which a ²⁺ green light-emitting phosphor layer was formed was manufactured.

[Evaluation of luminous laminate]
The emission spectrum of visible light emitted from the laminate by irradiating with ultraviolet light having a wavelength of 146 nm and a wavelength of 172 nm from the phosphor layer of the luminescent laminate produced in Examples 43 to 56 and Comparative Example 4 It was measured. Table 4 shows the maximum peak value of the obtained emission spectrum as the maximum emission luminance.

Table 4 (phosphor layer: Zn ₂ SiO ₄ : Mn ²⁺ green light emitting phosphor layer)
────────────────────────────────────────
Maximum luminance
──────────────────
Material of wavelength conversion layer Wavelength 146nm Wavelength 172nm
────────────────────────────────────────
Example 43 MgCl ₂ .MgO 184 192
Example 44 ZnO.MgO 179 192
Example 45 γ-Al ₂ O ₃ .MgO 187 195
Example 46 LiF · MgO 217 258
Example 47 NaF · MgO 215 237
Example 48 KF · MgO 206 238
Example 49 CaF ₂ .MgO 212 243
Example 50 BaF ₂ .MgO 204 239
Example 51 AlF ₃ .MgO 229 259
Example 52 ZnF ₂ .MgO 200 236
Example 53 SnF ₂ .MgO 203 229
Example 54 CeF ₃ .MgO 199 227
Example 55 YF ₃ .MgO 220 237
Example 56 GdF ₃ .MgO 216 247
────────────────────────────────────────
Comparative Example 4 None 100 100
──────────────────────────────────────── Note) The maximum light emission brightness is Comparative Example 4 The relative value with the value of 100 as 100.

[Example 57]
In the same manner as in Example 1 except that (Y, Gd) BO ₃ : Eu ³⁺ red light emitting phosphor powder was used instead of CaMgSi ₂ O ₆ : Eu ²⁺ blue light emitting phosphor powder, On top of this, a 7 μm thick (Y, Gd) BO ₃ : Eu ³⁺ red light emitting phosphor layer is passed through a 3 μm thick wavelength conversion layer made of chlorine-containing sintered magnesium oxide powder (MgCl ₂ .MgO). The formed luminescent laminate was manufactured.

[Example 58]
A zinc-containing magnesium oxide fired product is formed on a quartz substrate in the same manner as in Example 57 except that the zinc-containing magnesium oxide fired powder produced in Example 2 is used instead of the chlorine-containing magnesium oxide fired powder. A light-emitting laminate having a phosphor layer formed through a wavelength conversion layer made of powder (ZnO.MgO) was produced.

[Example 59]
An aluminum-containing magnesium oxide fired product is formed on a quartz substrate in the same manner as in Example 57 except that the aluminum-containing magnesium oxide fired powder produced in Example 3 is used instead of the chlorine-containing magnesium oxide fired powder. A light-emitting laminate having a phosphor layer formed through a wavelength conversion layer made of powder (γ-Al ₂ O ₃ .MgO) was produced.

[Example 60]
A lithium / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 57 except that the lithium / fluorine-containing magnesium oxide fired material powder produced in Example 4 was used instead of the chlorine-containing magnesium oxide fired material powder. The light emitting laminated body in which the fluorescent substance layer was formed through the wavelength conversion layer which consists of a magnesium oxide baked material powder (LiF * MgO) was manufactured.

[Example 61]
A sodium / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 57 except that the sodium / fluorine-containing magnesium oxide fired material powder produced in Example 5 was used instead of the chlorine-containing magnesium oxide fired material powder. The light emitting laminated body in which the fluorescent substance layer was formed through the wavelength conversion layer which consists of a magnesium oxide baked material powder (NaF * MgO) was manufactured.

[Example 62]
In place of the chlorine-containing magnesium oxide calcined powder, the potassium / fluorine-containing magnesium oxide calcined powder produced in Example 6 was used in the same manner as in Example 57 except that potassium / fluorine-containing A light-emitting laminate having a phosphor layer formed through a wavelength conversion layer made of magnesium oxide fired powder (KF · MgO) was produced.

[Example 63]
A calcium / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 57 except that the calcium / fluorine-containing magnesium oxide fired powder produced in Example 7 was used instead of the chlorine-containing magnesium oxide fired powder. was prepared phosphor layer is formed through the wavelength conversion layer made of magnesium calcined powder oxide (CaF ₂ · MgO) luminescent laminate.

[Example 64]
A barium / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 57 except that the barium / fluorine-containing magnesium oxide fired material powder produced in Example 8 was used instead of the chlorine-containing magnesium oxide fired material powder. was prepared phosphor layer is formed through the wavelength conversion layer made of magnesium calcined powder oxide (BaF ₂ · MgO) luminescent laminate.

[Example 65]
In place of the chlorine-containing magnesium oxide fired powder, the aluminum / fluorine-containing magnesium oxide fired powder produced in Example 9 was used, except that the aluminum / fluorine-containing powder was formed on the quartz substrate in the same manner as in Example 57. was prepared phosphor layer is formed through the wavelength conversion layer made of magnesium calcined powder oxide (AlF ₃ · MgO) luminescent laminate.

[Example 66]
A zinc / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 57 except that the zinc / fluorine-containing magnesium oxide fired powder produced in Example 10 was used instead of the chlorine-containing magnesium oxide fired powder. A light-emitting laminate having a phosphor layer formed through a wavelength conversion layer made of a magnesium oxide fired powder (ZnF ₂ .MgO) was produced.

[Example 67]
A tin / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 57 except that the tin / fluorine-containing magnesium oxide fired powder produced in Example 11 was used instead of the chlorine-containing magnesium oxide fired powder. was prepared phosphor layer is formed through the wavelength conversion layer made of magnesium calcined powder oxide (SnF ₂ · MgO) luminescent laminate.

[Example 68]
A cerium / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 57 except that the cerium / fluorine-containing magnesium oxide fired material powder produced in Example 12 was used instead of the chlorine-containing fired magnesium oxide powder. was prepared phosphor layer is formed through the wavelength conversion layer made of magnesium calcined powder oxide (CeF ₃ · MgO) luminescent laminate.

[Example 69]
A yttrium / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 57 except that the yttrium / fluorine-containing magnesium oxide fired material powder produced in Example 13 was used instead of the chlorine-containing magnesium oxide fired material powder. A light-emitting laminate in which a phosphor layer was formed through a wavelength conversion layer made of magnesium oxide fired powder (YF ₃ .MgO) was produced.

[Example 70]
A gadolinium / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 57 except that the gadolinium / fluorine-containing magnesium oxide fired powder produced in Example 14 was used instead of the chlorine-containing magnesium oxide fired powder. A light-emitting laminate having a phosphor layer formed through a wavelength conversion layer made of magnesium oxide fired powder (GdF ₃ .MgO) was produced.

[Comparative Example 5]
A (Y, Gd) BO film having a thickness of 7 μm is formed on the quartz substrate in the same manner as in Example 57 except that the wavelength conversion layer made of the chlorine-containing fired magnesium oxide powder is not formed on the quartz substrate. ₃ : A light emitting laminate in which an Eu ³⁺ red light emitting phosphor layer was formed was manufactured.

[Evaluation of luminous laminate]
An emission spectrum of visible light emitted from the laminate by irradiating with ultraviolet light having a wavelength of 146 nm and a wavelength of 172 nm from the phosphor layer of the luminescent laminate produced in Examples 57 to 70 and Comparative Example 5. It was measured. Table 5 shows the maximum peak value of the obtained emission spectrum as the maximum emission luminance.

Table 5 (phosphor layer: (Y, Gd) BO ₃ : Eu ^{3 +} red light emitting phosphor layer)
────────────────────────────────────────
Maximum luminance
──────────────────
Material of wavelength conversion layer Wavelength 146nm Wavelength 172nm
────────────────────────────────────────
Example 57 MgCl ₂ .MgO 210 212
Example 58 ZnO.MgO 211 206
Example 59 γ-Al ₂ O ₃ .MgO 205 199
Example 60 LiF · MgO 221 249
Example 61 NaF · MgO 227 242
Example 62 KF · MgO 205 240
Example 63 CaF ₂ .MgO 218 242
Example 64 BaF ₂ .MgO 206 235
Example 65 AlF ₃ .MgO 219 258
Example 66 ZnF ₂ .MgO 202 240
Example 67 SnF ₂ .MgO 200 234
Example 68 CeF ₃ .MgO 208 237
Example 69 YF ₃ .MgO 204 232
Example 70 GdF ₃ .MgO 223 250
────────────────────────────────────────
Comparative Example 5 None 100 100
──────────────────────────────────────── Note) The maximum light emission brightness is Comparative Example 5 The relative value with the value of 100 as 100.

[Example 71]
On the quartz substrate in the same manner as in Example 1 except that Sr ₃ MgSi ₂ O ₈ : Eu ²⁺ blue light emitting phosphor powder was used instead of CaMgSi ₂ O ₆ : Eu ²⁺ blue light emitting phosphor powder. In addition, a 7 μm thick Sr ₃ MgSi ₂ O ₈ : Eu ²⁺ blue light emitting phosphor layer is formed through a wavelength conversion layer having a thickness of 3 μm made of a calcined magnesium oxide powder (MgCl ₂ · MgO). A luminescent laminate was produced.

[Example 72]
A zinc-containing magnesium oxide fired product is formed on a quartz substrate in the same manner as in Example 71 except that the zinc-containing magnesium oxide fired powder produced in Example 2 is used instead of the chlorine-containing magnesium oxide fired powder. A light-emitting laminate having a phosphor layer formed through a wavelength conversion layer made of powder (ZnO.MgO) was produced.

[Example 73]
An aluminum-containing magnesium oxide fired product is formed on a quartz substrate in the same manner as in Example 71 except that the aluminum-containing magnesium oxide fired powder produced in Example 3 is used instead of the chlorine-containing magnesium oxide fired powder. A light-emitting laminate having a phosphor layer formed through a wavelength conversion layer made of powder (γ-Al ₂ O ₃ .MgO) was produced.

[Example 74]
A lithium / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 71 except that the lithium / fluorine-containing magnesium oxide fired material powder produced in Example 4 was used instead of the chlorine-containing magnesium oxide fired material powder. The light emitting laminated body in which the fluorescent substance layer was formed through the wavelength conversion layer which consists of a magnesium oxide baked material powder (LiF * MgO) was manufactured.

[Example 75]
Instead of the chlorine-containing magnesium oxide fired powder, the sodium / fluorine-containing magnesium oxide fired powder produced in Example 5 was used in the same manner as in Example 71 on the quartz substrate. The light emitting laminated body in which the fluorescent substance layer was formed through the wavelength conversion layer which consists of a magnesium oxide baked material powder (NaF * MgO) was manufactured.

[Example 76]
In place of the chlorine-containing magnesium oxide fired powder, the potassium / fluorine-containing magnesium oxide fired powder produced in Example 6 was used in the same manner as in Example 71 on the quartz substrate. A light-emitting laminate having a phosphor layer formed through a wavelength conversion layer made of magnesium oxide fired powder (KF · MgO) was produced.

[Example 77]
A calcium / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 71 except that the calcium / fluorine-containing magnesium oxide fired powder produced in Example 7 was used instead of the chlorine-containing magnesium oxide fired powder. was prepared phosphor layer is formed through the wavelength conversion layer made of magnesium calcined powder oxide (CaF ₂ · MgO) luminescent laminate.

[Example 78]
A barium / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 71 except that the barium / fluorine-containing magnesium oxide fired material powder produced in Example 8 was used instead of the chlorine-containing magnesium oxide powder. was prepared phosphor layer is formed through the wavelength conversion layer made of magnesium calcined powder oxide (BaF ₂ · MgO) luminescent laminate.

[Example 79]
In place of the chlorine-containing magnesium oxide fired powder, the aluminum / fluorine-containing magnesium oxide fired powder produced in Example 9 was used, except that the aluminum / fluorine-containing powder was formed on the quartz substrate in the same manner as in Example 71. was prepared phosphor layer is formed through the wavelength conversion layer made of magnesium calcined powder oxide (AlF ₃ · MgO) luminescent laminate.

[Example 80]
A zinc / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 71 except that the zinc / fluorine-containing magnesium oxide fired powder produced in Example 10 was used instead of the chlorine-containing magnesium oxide fired powder. A light-emitting laminate having a phosphor layer formed through a wavelength conversion layer made of a magnesium oxide fired powder (ZnF ₂ .MgO) was produced.

[Example 81]
A tin / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 71 except that the tin / fluorine-containing magnesium oxide fired powder produced in Example 11 was used instead of the chlorine-containing magnesium oxide fired powder. was prepared phosphor layer is formed through the wavelength conversion layer made of magnesium calcined powder oxide (SnF ₂ · MgO) luminescent laminate.

[Example 82]
A cerium / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 71 except that the cerium / fluorine-containing magnesium oxide fired powder produced in Example 12 was used instead of the chlorine-containing magnesium oxide fired powder. was prepared phosphor layer is formed through the wavelength conversion layer made of magnesium calcined powder oxide (CeF ₃ · MgO) luminescent laminate.

[Example 83]
A yttrium / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 71, except that the yttrium / fluorine-containing magnesium oxide fired material powder produced in Example 13 was used instead of the chlorine-containing fired magnesium oxide powder. A light-emitting laminate in which a phosphor layer was formed through a wavelength conversion layer made of magnesium oxide fired powder (YF ₃ .MgO) was produced.

[Example 84]
A gadolinium / fluorine-containing material was formed on a quartz substrate in the same manner as in Example 71 except that the gadolinium / fluorine-containing magnesium oxide fired powder produced in Example 14 was used instead of the chlorine-containing magnesium oxide fired powder. A light-emitting laminate having a phosphor layer formed through a wavelength conversion layer made of magnesium oxide fired powder (GdF ₃ .MgO) was produced.

[Comparative Example 6]
A Sr ₃ MgSi ₂ O ₈ : Eu having a thickness of 7 μm was formed on the quartz substrate in the same manner as in Example 71 except that the wavelength conversion layer made of the chlorine-containing fired magnesium oxide powder was not formed on the quartz substrate. A light-emitting laminate in which a ²⁺ blue light-emitting phosphor layer was formed was manufactured.

[Evaluation of luminous laminate]
From the phosphor layer of the light emitting laminate manufactured in Examples 71 to 84 and Comparative Example 6, ultraviolet light having a wavelength of 146 nm and a wavelength of 172 nm is irradiated, and an emission spectrum of visible light emitted from the laminate is obtained. It was measured. Table 5 shows the maximum peak value of the obtained emission spectrum as the maximum emission luminance.

Table 6 (phosphor layer: Sr ₃ MgSi ₂ O ₈ : Eu ²⁺ blue light emitting phosphor layer)
────────────────────────────────────────
Maximum luminance
──────────────────
Material of wavelength conversion layer Wavelength 146nm Wavelength 172nm
────────────────────────────────────────
Example 71 MgCl ₂ .MgO 192 231
Example 72 ZnO.MgO 196 228
Example 73 γ-Al ₂ O ₃ .MgO 205 232
Example 74 LiF.MgO 223 268
Example 75 NaF · MgO 220 254
Example 76 KF · MgO 225 243
Example 77 CaF ₂ .MgO 228 248
Example 78 BaF ₂ .MgO 231 251
Example 79 AlF ₃ .MgO 222 257
Example 80 ZnF ₂ .MgO 219 236
Example 81 SnF ₂ .MgO 209 228
Example 82 CeF ₃ .MgO 205 225
Example 83 YF ₃ .MgO 211 230
Example 84 GdF ₃ .MgO 216 218
────────────────────────────────────────
Comparative Example 6 None 100 100
──────────────────────────────────────── Note) The maximum light emission brightness is Comparative Example 6 Relative value with the value of 100 as 100.

  As is clear from the results shown in Tables 1 to 6, the luminescent laminate in which the phosphor layer is formed through the wavelength conversion layer according to the present invention is compared with the luminescent laminate in which only the phosphor layer is formed. As a result, the emission luminance is remarkably increased.

Claims (8)

At least selected from the group consisting of the following (1) to (4), which emits ultraviolet light having a peak in the wavelength range of 230 to 260 nm when excited by ultraviolet light generated by discharge of Xe gas on the substrate. A phosphor layer including a phosphor that emits visible light when excited by ultraviolet light in the wavelength range of 230 to 260 nm is formed through a wavelength conversion layer containing a kind of magnesium oxide fired powder. Laminate:
(1) Chlorine-containing magnesium oxide fired powder containing chlorine in a range of 0.005 to 10% by mass;
(2) Zinc-containing magnesium oxide fired powder containing zinc in a range of 0.1 to 30% by mass;
(3) An aluminum-containing magnesium oxide fired powder having an aluminum content in the range of 2 to 38% by mass obtained by firing a powder mixture of γ-type aluminum oxide powder and magnesium oxide source powder;
(4) Fluorine is contained in an amount in the range of 0.01 to 24 mol with respect to 100 mol of magnesium, and selected from the group consisting of alkali metals, alkaline earth metals other than magnesium, rare earth metals, aluminum, zinc and tin. Magnesium oxide calcined powder containing fluorine and an auxiliary metal containing at least one auxiliary metal in an amount in the range of 0.01 to 30 mol with respect to 100 mol of magnesium.   The luminescent laminate according to claim 1, wherein the wavelength conversion layer has a thickness in the range of 0.5 to 10 μm.   The luminescent laminate according to claim 1, wherein the thickness of the phosphor layer is in the range of 0.1 to 30 μm. The phosphor layer is made of CaMgSi ₂ O ₆ : Eu ²⁺ , (Ca, Sr) MgSi ₂ O ₆ : Eu ²⁺ , Sr ₃ MgSi ₂ O ₈ : Eu ²⁺ , and BaMgAl ₁₀ O ₁₇ : Eu ^2+. The luminescent laminate according to claim 1, wherein the luminescent laminate is a blue-emitting phosphor layer containing a blue-emitting phosphor represented by at least one basic composition formula selected from the group. The luminescent laminate according to claim 1, wherein the phosphor layer is a green light-emitting phosphor layer containing a green light-emitting phosphor represented by a basic composition formula of Zn ₂ SiO ₄ : Mn ²⁺ . Phosphor _{layer, (Y, Gd) BO 3} : Eu 3+ emission laminate according to claim 1 which is a red-emitting phosphor layer containing the red light-emitting phosphor represented by the basic formula of.   The luminescent laminate according to claim 1, which is a back plate of an AC type plasma display panel.   The light emitting laminate according to claim 1, which is a light emitting element of a Xe lamp.