WO2005083035A1

WO2005083035A1 - Method for producing silicate phosphor and vacuum ultraviolet excited light-emitting device

Info

Publication number: WO2005083035A1
Application number: PCT/JP2005/003091
Authority: WO
Inventors: Yoshiko Nakamura; Keiji Ono; Susumu Miyazaki
Original assignee: Sumitomo Chemical Company, Limited
Priority date: 2004-02-27
Filing date: 2005-02-18
Publication date: 2005-09-09
Also published as: TW200528537A

Abstract

Disclosed is a method for producing a silicate phosphor. Also disclosed is a vacuum ultraviolet excited light-emitting device. The method for producing a silicate phosphor includes (i) a step for mixing a metal compound and a halide, and (ii) a step for firing the resulting mixture. The silicate phosphor contains a compound which is obtained by this method and represented by the formula (1) below, and at least one selected from the group consisting of Eu and Mn as an activator. mM1O·nM2O·2SiO2 (1) [In the formula (1), M1 represents at least one selected from the group consisting of Ca, Sr and Ba; M2 represents at least one selected from the group consisting of Mg and Zn; m is not less than 0.5 and not more than 3.5; and n is not less than 0.5 and not more than 2.5.]

Description

Technical Field Manufacturing method of silicate phosphor and vacuum ultraviolet ray excited light emitting device

The present invention relates to a method for producing a silicate phosphor, a silicate phosphor obtained by the method, and a vacuum ultraviolet ray excited light emitting device containing the silicate phosphor. Background art

The silicate phosphor is used for an ultraviolet-excited light-emitting element such as a fluorescent lamp, a cathode-ray-excited light-emitting element such as a cathode ray tube, a plasma display panel (PDP), and a vacuum ultraviolet-excited light-emitting element such as a rare gas lamp. , those represented by the formula _{C a ". 855 S r gs} E u 0. 05 MS i 2 0 6 are known. the Gay phosphor is oxidized Kei arsenide, calcium carbonate, strontium carbonate, oxide It is obtained by a method in which europium and basic magnesium carbonate are mixed, and the resulting mixture is calcined in a reducing atmosphere (for example, Japanese Patent Application Laid-Open No. 2003-186364).

On the other hand, from the viewpoint of improving the performance of PDP, it is essential to increase the luminance of the phosphor, and a method for producing a silicate phosphor having high luminance is required. Disclosure of the invention

An object of the present invention is to provide a method for producing a silicate phosphor having high luminance and a vacuum ultraviolet ray excited light emitting device.

The present inventors have studied a method for producing a silicate phosphor, and as a result, have completed the present invention.

That is, the present invention provides a method for producing a silicate phosphor including the steps (i) and (ii).

(i) a step of mixing a metal compound and an octalogenide,

(ii) firing the resulting mixture.

Further, the present invention provides a silicate phosphor obtained by the above-mentioned production method. Further, the present invention provides a vacuum ultraviolet ray excited light emitting device containing a silicate phosphor obtained by the above-mentioned production method. BEST MODE FOR CARRYING OUT THE INVENTION

The method for producing a silicate phosphor according to the present invention includes a step (i) of mixing a metal compound and an octalogenide.

The metal compound used in step ω is an element contained in the product silicate phosphor

(Si, Ca, Sr, Ba, Mg, Eu, Mn, Zn), for example, at least one hydroxide, carbonate, nitric acid of these elements It is a compound that becomes an oxide in a firing step described later, such as a salt or an oxalate, or at least one oxide of these elements.

Examples of metal compounds include

Oxide Kei containing [S i 0 _2], Kei-containing compounds such as silica gel [S i 0 _₂ · xH ₂ 〇],

Calcium oxide [C A_〇], calcium © beam compounds such as calcium carbonate [CaCO _s],

Strontium oxide [S R_〇], strontium compounds such as strontium carbonate [S r C_〇 _3],

Barium oxide [B A_〇], barium of compounds such as barium carbonate [B AC0 _3],

Magnesium compounds such as magnesium oxide [MgO], basic magnesium carbonate [(MgC_〇 _{_{3) 4 M g (OH)}} 2 · 5H 2 0 ],

Europium compounds such as europium oxide [Eu ₂ 〇 ₃ ],

Manganese compounds such as manganese oxide [Mn_〇 _2],

It is a zinc compound such as zinc oxide [Zn〇].

The metal compound may be a mixture thereof, or may be a compound of two or more of the above elements.

For example, Equation 〇3. ₉₆ £ 11. .. _When manufacturing the blue phosphor represented by ₄ 1 ^ 3 i ₂ 〇 ₆ , the metal compound is calcined. ₉₆ £ 1. . _{) § ₄ ^ [83 1 ₂ 0 ₆ become Compound It may be, for example, a mixture of a calcium compound, a magnesium compound, a silicon compound, and an europium compound.

In addition, when the metal compound is an element (Si, Ca, Sr, Ba, Mg, Eu, Mn, Zn), such as hydroxide, carbonate, nitrate, oxalate, etc. When the compounds are decomposed into oxides by the above, these compounds may be calcined before drying or firing described below. The calcination may be performed under the condition that water (adhering water) is removed from these compounds or crystallization water is removed from these compounds to form oxides. For example, temperature: 600 ° C. or more, It may be performed under a condition of less than 900 ° C. When the metal compound is a hydroxide or an inorganic salt such as a carbonate or a nitrate, the calcination may be performed in any of an oxidizing atmosphere (such as an air atmosphere) and a reducing atmosphere. When the metal compound is an organic salt such as oxalate, the calcination may be usually performed in an oxidizing atmosphere (such as an air atmosphere). It is preferable that the metal compound used in the step ω contains a gay oxide. Oxide Ke I arsenide, BET specific surface area is usually 1 O m ^ g or more, preferably 1 0 O m ² Z g or more on, still more preferably ² 0 O m 2 Z g or more, and usually 4 0 O m ² / g or less. By using a metal compound containing silicon oxide having a high BET specific surface area as a raw material, a silicate phosphor with higher luminance can be obtained. The halide used in the step ω is, for example, an ammonium halide or a metal halide. Examples of the halogenated ammonium include ammonium fluoride, ammonium chloride, and ammonium bromide. Metal halides are halides of one or more of the metals contained in the product silicate phosphor, such as metal chlorides such as magnesium chloride, calcium chloride, and strontium chloride. Metal fluorides such as magnesium fluoride, calcium fluoride, and strontium fluoride; and metal bromides such as magnesium bromide, calcium bromide, and strontium bromide. Of these, the halide is preferably a metal chloride or ammonium chloride, and more preferably a metal chloride. The amount of the halide is usually 1% by weight or more, preferably 3% by weight or more based on the total amount of the metal compound and the halide in terms of dry weight. And at most 50% by weight, preferably at most 20% by weight. The halide may be a powder or an aqueous solution.

For example, the formula 〇 &. ₉₆ £ 11. .. ₄ 1 ^ 83 in the manufacture of a blue phosphor represented by i ₂ 〇 _6, CaC 1 _2, Ca_〇, Mg_〇, the S I_〇 _2, Eu ₂ 〇 _3, CaC 1 ₂ and. & 〇 molar ratio of 1: 3, and the molar ratio of Ca: Eu: Mg: Si are 0.96: 0.04: 1: 2. Good. The mixtures thus obtained, C aC 1 _2: C _{_{A_〇: Eu z 0 3: MgO:}} S i 0 weight ratio of ₂ is 26.64: 40.32: 7.04: 40:60, halides the content of (C a C 1 ₂₎ is 15 wt%. The mixing in the step (i) may be performed either continuously or batchwise. The mixing may be performed by either a dry method or a wet method. Further, in the mixing, the entire amount of the metal compound and the entire amount of the halide may be mixed at once, or they may be separately mixed.

Dry mixing may be performed using, for example, a pole mill, a V-type mixer, or a stirrer, and wet mixing may be performed using a pole mill or a stirrer.

In the case of wet mixing, the resulting mixture is usually dried directly, or the solid is recovered by solid-liquid separation such as filtration or centrifugation, and dried. Drying may be performed using, for example, an evaporator or a spray dryer. The drying temperature is usually at least 20 ° C, preferably at least 90 ° C, and is at most 300 ° C, preferably at most 200 ° C. The method for producing a silicate phosphor of the present invention includes a step (ii) of firing the mixture obtained in the step (i).

The calcination in the step (ii) is performed, for example, using nitrogen (N ₂ ) containing about 0.1% to about 10% by volume of hydrogen, and argon (Ar) containing about 0.1% to about 10% by volume of hydrogen. What is necessary is just to perform under a reducing atmosphere. The firing temperature is usually 900 to 1400 ° C, and the firing time is usually 0.5 to 50 hours. Further, in the production method of the present invention, a flux may be added to the mixture before firing, and the mixture may be fired.

The phosphor obtained by firing may be subjected to treatments such as grinding, washing, and classification. The pulverization may be performed using, for example, a pole mill, a jet mill, or the like. Washing May be performed, for example, by washing with water. Further, the phosphor or treated phosphor may be further fired. By firing, a phosphor having higher luminance can be obtained. When firing is performed twice or more, the above-mentioned halide may be added to the fired product obtained in the firing step and fired. The silicate phosphor obtained by the above method is usually particles, has high crystallinity, and has high brightness. Further, this silicate phosphor has excellent color purity. The silicate phosphor emits light when excited by ultraviolet rays, cathode rays or X-rays in addition to vacuum ultraviolet rays.

Furthermore, equation (1)

mM'O nM ² 0 2 S i 0 ₂ (1)

[In the formula (1), M ¹ is at least one selected from the group consisting of Ca Sr and Ba, M ² is at least one selected from the group consisting of Mg and Zn, and m is 0 5 or more and 3.5 or less, and n is 0.5 or more and 2.5 or less. And a substance containing at least one selected from the group consisting of EuMn as an activator by the above method, a silicate phosphor having excellent luminance can be obtained. .

Incidentally, the above formula Ca. _G6 Eu ". Phosphor represented by _M MgS i ₂ 〇 ₆ is have you to equation (1) is M ¹ is the Ca M ² Mg, activator Eu, m = those satisfying 1 n = l. also, the formula S r _Q shown in _{_{example. 1 () C a. 892}} Eu Mg S i 2 〇 phosphor represented by _6, M in formula (1) ¹ S r and Ca M ² is Mg, activator is E u, fluorescence is to satisfy m = ln = 1. VUV-excited light-emitting display device of the present invention, obtained by the method In general, the device includes an electrode in addition to the phosphor described above Examples of the vacuum ultraviolet ray excited light emitting display device include a PDP, a rare gas lamp, etc. Next, a PDP is exemplified. Usually, it includes a back substrate, a phosphor layer, a transparent electrode, a bus electrode, a dielectric layer, and a surface substrate.A method of manufacturing such a PDP is disclosed in, for example, Japanese Patent Application Laid-Open No. H10-195428. of Steps (I) to (IV) are included. (I) Phosphor for green light emission, phosphor for red light emission, phosphor for blue light emission, and each phosphor mixed with phosphor, binder (cellulose-based compound, polyvinyl alcohol) and organic solvent Preparing a phosphor paste,

(II) The phosphor prepared in (I) for blue light emission, green light emission and red light emission on the stripe-shaped substrate surface provided with address electrodes and the partition surface on the inner surface of the rear substrate, which is partitioned by partitions. Applying paste (by screen printing, etc.) and baking at a temperature range of about 300 ° C to about 600 ° C to form a phosphor layer,

(III) a step of laminating and bonding a surface glass substrate provided with a transparent electrode and a bus electrode in the direction orthogonal to the obtained phosphor layer and having a dielectric layer and a protective layer on the inner surface thereof,

(IV) A process of evacuating the interior surrounded by the rear substrate and the front glass substrate, filling a reduced pressure rare gas (Xe, Ne, etc.), and forming a discharge space. Example

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The BET specific surface area of the metal compound (silicon oxide) was determined by the nitrogen adsorption method. Reference example 1

Calcium carbonate (Ube Material Industries, Ltd., CAC0 ₃₎ carbonate stolons lithium (manufactured by Sakai Chemical Industry Co., Ltd., S r C_〇 _3), europium oxide (manufactured by Shin-Etsu Chemical Co., Ltd., Eu ₂ 0 _3), basic carbonate magnesium (Kyowa chemical industry stock Company, Ltd., (MgC_〇 _{_{_{3) 4 M (OH) 2}}} · 5Η 2 0), oxidation Kei arsenide (Japan Aeroji Le Co., Ltd., S I_〇 _2, BET specific surface area: 200m ² / g) was mixed so that the molar ratio of Ca: Sr: Eu: Mg: Si was 0.782: 0.10: 0.008: 1: 2.

(Fired)

The obtained mixture was put in an alumina port, and then the alumina port was set in a firing furnace. The mixture Atmosphere: 2 vol% H ₂ containing argon gas, from room 1 Heating time to 165 ° C: 2 hours and 30 minutes, holding time at 1 165 ° C: 2 hours, and calcined by the formula C a _Q _.892 S

To give a compound represented by S i ₂ 0 ₆ a (phosphor). (Brightness evaluation of phosphor)

The resulting phosphor, 6. 7 P a (5 X 10- 2 To rr) following E in a vacuum chamber screeching 146 nm lamp (Ushio Denki Co., H0012 type) was irradiated with vacuum ultraviolet ray using When it emitted blue light. The luminance at this time is assumed to be 100. Example 1

Calcium carbonate (Ube Material Industries, Ltd., C AC_〇 _3), carbonate strike opening Nchiumu (manufactured by Sakai Chemical Industry Co., Ltd., S r C_〇 _3), europium oxide (manufactured by Shin-Etsu Chemical Industry Co., Ltd., Eu ₂ 〇 ₃ ), basic magnesium carbonate (manufactured by Kyowa chemical industry Co., Ltd., Ltd., (MgC_〇 _{_{_{3) 4 Mg (OH) 2}}} · 5Η 2 0), oxidation Kei arsenide (Japan Aero Jill Co., Ltd., S i 0 _2, BET specific surface area : 20 Om ² / g) so that the molar ratio of Ca: Sr: Eu: Mg: Si becomes 0.892: 0.10: 0.008: 1: 2 to form a metal compound. obtained, then, a metal compound, Anmoniumu chloride as halide (manufactured by Wako Pure chemical Industries, Ltd., NH ₄ C 1) were mixed to obtain a mixture containing chloride Anmoniumu 7 wt%.

The resulting mixture is subjected to the same procedure as Reference Example 1 [calcination], to give a formula _{_{_{Ca 0. 892 S r 0.}}} 10 Eu 0. 008 phosphor represented by Mg S i ₂ 0 _6. This phosphor was evaluated under the same conditions as in Reference Example 1 [Evaluation of Luminance of Phosphor]. This phosphor emitted blue light and had a luminance of 106. Example 2

Calcium carbonate (Ube Material Industries, Ltd., CaC0 _3), chloride strike opening Nchiumu hexahydrate (manufactured by Sakai Chemical Industry Co., _{_{Ltd., S rC 1 2 · 6Η 2}} 0), oxidized user port Piumu (Shin-Etsu Chemical Co., Ltd. Ltd., Eu ₂ 〇 _3), basic magnesium carbonate (manufactured by Kyowa chemical industry Co., Ltd., (MgC_〇 _{_{_{3) 4 Mg (OH) 2}}} · 5Η 2 0), oxidized Keimoto (Nippon Aerojiru Ltd., S i 0 ₂ , BET specific surface area: 20 OmV g) Mix each starting material so that the molar ratio of Ca: Sr: Eu: Mg: Si becomes 0.892: 0.10: 0.008: 1: 2, and strontium chloride 7 weight % Was obtained.

The obtained mixture was subjected to the same operation as [calcination] in Reference Example 1 to obtain a compound of the formula Ca. . ₈₉₂ S

to obtain a phosphor represented by i ₂ 〇 _6. This phosphor was evaluated under the same conditions as in Reference Example 1 [Evaluation of Luminance of Phosphor]. This phosphor emitted blue light and had a luminance of 123. Reference example 2.

Calcium carbonate (Ube Material Co., Ltd., CaC_〇 _3), carbonate strike opening Nchiumu (manufactured by Sakai Chemical Industry Co., Ltd., S r C0 _3), europium oxide (Shin-Etsu Chemical Industry Co., Ltd., Eu ₂ 〇 _3), basic magnesium carbonate (manufactured by Kyowa chemical industry Co., Ltd., Ltd., (MgC_〇 _{_{_{3) 4 Mg (OH) 2}}} · 5Η 2 〇), oxidation Kei arsenide (Japan Aero Jill Co., Ltd., S i 0 _2, BET specific surface area: 20 OrnVg) was mixed so that the molar ratio of Ca: Sr: Eu: Mg: Si was 0.778: 0.20: 0.012: 1: 2.

The resulting mixture is subjected to the same procedure as Reference Example 1 [calcination], to give the formula _{_{_{C a 0. 788 S r 0}}} . 20 Eu 0. 012 phosphor represented by Mg S i ₂ 0 _6. This phosphor was evaluated under the same conditions as in Reference Example 1 [Evaluation of Luminance of Phosphor]. This phosphor emitted blue light and had a luminance of 104. Example 3

Calcium carbonate (Ube Material Industries, Ltd., C AC_〇 _3), carbonate strike opening Nchiumu (manufactured by Sakai Chemical Industry Co., Ltd., S r C_〇 _3), europium oxide (manufactured by Shin-Etsu Chemical Industry Co., Ltd., Eu ₂ 〇 ₃ ), basic magnesium carbonate (manufactured by Kyowa chemical industry Co., Ltd., Ltd., (MgC_〇 _{_{_{3) 4 Mg (OH) 2}}} · 5Η 2 0), oxidation Gay arsenide (Japan Aero Jill Co., Ltd., S i 0 _2, BET specific surface area : 200m / g) to mix the metal compound by mixing so that the molar ratio of Ca: Sr: Eu: Mg: Si becomes 0.788: 0.20: 0.012: 1: 2. And then the metal compound and a halide Was mixed with ammonium chloride (manufactured by Wako Pure Chemical Industries, Ltd., NH ₄ C 1) to obtain a mixture containing 7% by weight of ammonium chloride.

The resulting mixture is subjected to the same procedure as Reference Example 1 [calcination], to give a formula _{_{_{Ca 0. 788 S r 0.}}} 20 Eu 0. 012 phosphor represented by Mg S i ₂ 0 _6. This phosphor was evaluated under the same conditions as in Reference Example 1 [Evaluation of Luminance of Phosphor]. This phosphor emitted blue light and had a luminance of 114. Example 4

Oxidation Gay arsenide (Japan Aerojiru Co., Ltd., S I_〇 _2, BET specific surface area: 20 0m ² / g) in place of the oxide gay arsenide (Co. Admatechs made, S I_〇 _2, BET specific surface area: 1 5 The same operation as in Example 3 was performed except that 〜25 m ² Zg) was used. The resulting phosphor _{(C a .. 788 S r ..} 2 .Eu.,. 12 Mg S i 2 0 6) is blue and emitting light, the luminance was 1 1 1. Example 5

Oxidation Kei arsenide (Japan Aerojiru Co., Ltd., S I_〇 _2, BET specific surface area: 20 OmVg) instead of, oxidation Kei arsenide (Co. Admatechs made, S I_〇 _2, BET specific surface area: 2~5m ² Zg ) Was performed, except that) was used. The resulting phosphor _{(C a .. 788 S r ..} 2 .Eu ... 12 Mg S i 2 0 6) emits a blue luminance was 106.

Claims

The scope of the claims

I. A method for producing a gaylate phosphor comprising steps (i) and (ii).

(i) a step of mixing a metal compound and an octalogenide,

(ii) firing the resulting mixture.

2. The method according to claim 1, wherein the metal compound includes a compound of at least one element selected from the group consisting of Si, Ca, Sr, Ba, Mg, Eu, Mn and Zn.

3. The method according to claim 2, wherein the metal compound includes a gay oxide.

4. The method according to claim 3, wherein the silicon oxide has a BET specific surface area of 10 m ² / g or more.

5. The method according to claim 1, wherein the halide is at least one selected from the group consisting of an ammonium halide and a metal halide.

6. The method according to claim 5, wherein the halide is a halogenated ammonium.

7. The method according to claim 6, wherein the halide is salted ammonia.

8. Obtained by the method of claim 1 and having the formula α)

mM ^ nM ² 0 2 S i 0 ₂ (1)

[In the formula (1), M ¹ is at least one selected from the group consisting of Ca, S r and Ba; M ² is at least one selected from the group consisting of Mg and Zn; m is 0.5 or more and 3.5 or less, and n is 0.5 or more and 2.5 or less. · ^Τ ,

And a silicate phosphor containing at least one selected from the group consisting of Eu and Mn as an activator.

9. A vacuum ultraviolet-excited light emitting device containing a silicate phosphor obtained by the method according to claim 1.

10. Use of a silicate phosphor obtained by the method according to claim 1 as a vacuum ultraviolet ray excited light emitting device.

I I. A VUV-excited light-emitting device comprising the silicate phosphor according to claim 8.

12. Use of the silicate phosphor according to claim 8 as a VUV-excited light emitting device.