KR20060115745A - Fluorescent material and fluorescent material paste - Google Patents

Abstract

A phosphor having high luminance after plasma exposure and a phosphor paste containing the phosphor. The fluorescent substance contains fluorescent substance A ¹ containing the compound represented by following formula (I), 1 or more types of activators selected from the group which consists of Eu and Mn, and fluorescent substance B ¹ which is an aluminate.

mM ¹ O.nM ² O.2M ³ O ₂ (I)

[In Formula (I), M <^1> is 2 or more types selected from the group which consists of Ca, Sr, and Ba, Ca alone, or Ba alone, M <^2> is 1 or more types chosen from the group which consists of Mg and Zn, M ³ is one or more selected from the group consisting of Si and Ge, and 0.5 ≦ m ≦ 3.5 and 0.5 ≦ n ≦ 2.5].

Description

Phosphor and Phosphor Paste {FLUORESCENT MATERIAL AND FLUORESCENT MATERIAL PASTE}

The present invention relates to a phosphor and a phosphor paste.

Phosphors are used in fluorescent lamps, luminous displays, X-ray inspection apparatuses, CRTs, vacuum ultraviolet excitation light emitting devices and the like. As red phosphor, aluminate [e.g. BaMg Al ₁₀ O ₁₇ : Eu] or borate [e.g. (Y, Gd) BO ₃ : Eu], silicate as blue phosphor [e.g. CaMgSi ₂ O ₆ : Eu], silicates as green phosphors [eg, Zn ₂ SiO ₄ : Mn] is known and is used for vacuum ultraviolet-excited light emitting elements such as plasma displays (hereinafter referred to as PDPs) and rare gas lamps.

A vacuum ultraviolet excitation light emitting element generates plasma by discharge in a rare gas, irradiates a vacuum ultraviolet-ray radiated | emitted from a plasma, and excites fluorescent substance, and visible light is radiated | emitted from a fluorescent substance, and it emits light.

When the conventional fluorescent substance is exposed to plasma, luminance may fall.

Disclosure of the Invention

An object of the present invention is to provide a phosphor having a high luminance and a phosphor paste containing the same, even when exposed to plasma.

The present inventors conducted extensive research in order to solve the said subject under such a situation, and, as a result of combining specific silicate and aluminate, the fluorescent substance which has high brightness came to be completed and this invention was completed.

That is, the present invention relates to a fluorescent substance A ¹ containing a compound represented by the following formula (I) and at least one activator selected from the group consisting of Eu and Mn, and a fluorescent substance B ¹ containing aluminate. Provided is a phosphor containing:

mM ¹ O.nM ² O.2M ³ O ₂ (I)

[In Formula (I), M <^1> is 2 or more types chosen from the group which consists of Ca, Sr, and Ba, Ca alone, or Ba alone,

M ² is one or more selected from the group consisting of Mg and Zn,

M ³ Is at least one selected from the group consisting of Si and Ge,

0.5 ≤ m ≤ 3.5,

0.5 <n <2.5].

Moreover, this invention provides the fluorescent substance paste containing the said fluorescent substance, a solvent, and a binder.

The phosphor of the present invention has high luminance after plasma exposure, and is particularly suitable for vacuum ultraviolet excitation light emitting devices such as PDPs and rare gas lamps. According to the phosphor and the phosphor paste of the present invention, a vacuum ultraviolet-excited light emitting element having a high brightness and a long life is provided.

Description of Embodiments of the Invention

The phosphor of the present invention contains the fluorescent substance A ¹ . This fluorescent substance A ¹ contains the compound represented by the said Formula (I) as 1 or more types chosen from the group which consists of Eu and Mn as an activator.

In formula (I), M ¹ Is at least 2 selected from the group consisting of Ca, Sr and Ba, Ca alone or Ba alone,

M ² Is one or more selected from the group consisting of Mg and Zn,

M ³ is one or more selected from the group consisting of Si and Ge,

0.5 ≤ m ≤ 3.5,

0.5 ≦ n ≦ 2.5.

The fluorescent substance A ¹ is preferably a compound represented by the following formula (II):

(M ¹ _{1 - a} Eu _a ) (M ² _{1 - b} Mn _b ) M ³ ₂ O ₆ (II)

[In Formula (II), M <^1> is 2 or more types chosen from the group which consists of Ca, Sr, and Ba, Ca alone, or Ba alone,

M ² is one or more selected from the group consisting of Mg and Zn,

M ³ Is at least one selected from the group consisting of Si and Ge,

0 ≤ a ≤ 0.5,

0 ≤ b ≤ 0.5,

0 <a + b].

The fluorescent substance A ¹ is more preferably a compound represented by the following formula (III):

Ca _{1 -c- d} Sr _c Eu _d MgSi ₂ O ₆ (III)

[In Formula (III), 0 <c <0.1,

0 <d ≤ 0.1].

Phosphor of the present invention, contains a non-fluorescent material A ^1, B ¹ fluorophore. This fluorescent substance B ¹ is an aluminate, Preferably it is a compound represented by following formula (IV):

p (M ⁴ _{1 - e} Eu _e ) O · q (M ⁵ _{1 - f} Mn _f ) OrAl ₂ O ₃ (IV)

[In formula (IV), M <^4> is 1 or more types chosen from the group which consists of Ca, Sr, and Ba,

M ⁵ is one or more selected from the group consisting of Mg and Zn,

0.5 ≤ p ≤ 1.5,

0.5 ≤ q ≤ 1.5,

4.5 ≤ r ≤ 5.5,

0 <e ≤ 0.5,

0 <f <0.1].

The fluorescent substance B ¹ is more preferably a compound represented by the following formula (V):

Ba _{1 - g} Eu _g MgAl ₁₀ O ₁₇ (V)

In formula (V), 0 <g <0.3.

The weight ratio of fluorescent substance A ¹ / fluorescent substance B ¹ is preferably in the range of 5/95 to 95/5, more preferably in the range of 20/80 to 90/10, and in the range of 30/70 to 85/15. Particularly preferred. If the weight ratio of fluorescent substance A ¹ / fluorescent substance B ¹ is in the said range, the fluorescent substance which has higher luminance can be obtained when it is exposed to plasma.

In the case where both the fluorescent material A ¹ and the fluorescent material B ¹ are particles, the primary particle diameter of the fluorescent material A ¹ is usually 0.1 μm to 5 μm, preferably 0.3 μm to 3 μm, and the fluorescent material the primary particle size of B ¹ is generally a 0.1㎛ ~ 5㎛, preferably 0.3㎛ ~ 3㎛. Further, the average primary particle diameter D _B ¹ of the fluorescent material B ^1, and a fluorescent material A being less than the average primary particle diameter of more than 0.2 times, 5 times the D _A ^{1 1,} i.e. D _A ¹ / D _B ¹ ≤ 5, and It is preferable to satisfy D _B ¹ / D _A ¹ ≦ 5.

Phosphor of the present invention, so long as it contains a fluorescent substance and a fluorescent material B ¹ A ^1, may be those containing a fluorescent substance other than the above.

The phosphor of the present invention can be excited by vacuum ultraviolet rays even when exposed to plasma, and has high luminance. In the production of PDPs and rare gas lamps, a process of obtaining a phosphor paste by mixing a phosphor, a binder, and a solvent, a process of applying the phosphor paste to a light emitting portion, and a process of heat-treating the applied light emitting portion (for example, 500 ° C.). By the manufacturing method containing a, the layer of fluorescent substance is formed. Since the phosphor of the present invention has the same luminance as before the heat treatment even when the heat treatment is performed, when the phosphor of the invention is used for vacuum ultraviolet-excited light emitting devices such as PDPs and rare gas lamps, PDP and rare gas having a long lifetime with high brightness A lamp is obtained.

In addition, since the fluorescent substance of this invention can be excited by ultraviolet-ray, X-ray, an electron beam, etc. other than vacuum ultraviolet-ray, it can also be applied to fluorescent lamp, luminous display, X-ray inspection apparatus, CRT, etc. which made these the excitation source. Do.

Phosphor of the present invention having a high luminance, for example, is when produced by the method of mixing the fluorescent material and the fluorescent material A ¹ B ^1. Mixing may be performed using apparatuses, such as a stirrer, a ball mill, and three roll mills, for example. The mixture, if necessary, may be conducted by adding a phosphor other than the phosphor A and phosphor B ^{1 1.}

A fluorescent material ¹ may, for example, can be prepared by firing a mixture which may be a fluorescent material by A ^1, firing a mixture of metal compounds.

Calcium source, strontium source or barium source of the mixture (M ¹ of formula (I) Corresponds to, for example, a compound which can be decomposed at an elevated temperature such as hydroxides, carbonates, nitrates, halides, and oxalates having a purity of 99% or higher, or an oxide of 99.9% or higher.

The magnesium or zinc source of the mixture (corresponding to M ² of formula (I)) is decomposed at high temperatures to oxides, for example, hydroxides, carbonates, nitrates, halides, oxalates of 99% or more purity. Compound, or an oxide having a purity of 99% or more.

The mixture silicon source or germanium source (corresponding to M ³ of formula (I)) may be decomposed at high temperature to an oxide, such as hydroxides, carbonates, nitrates, halides, oxalates of 99% or more purity, for example. Compound or an oxide having a purity of 99% or more.

The europium source or manganese source (which becomes the activator of the fluorescent substance A ¹⁾ of the mixture is, for example, at a high temperature, such as hydroxides, carbonates, nitrates, halides, and oxalates having a purity of 99% or more. It can be decomposed into an oxide, or an oxide having a purity of 99% or more.

A fluorescent substance ¹ is the compound, weighed and mixed so that a composition of a desired phosphor A ^1, is prepared by firing a mixture thereof.

Mixing may be performed using, for example, a ball mill, a V-type mixer, or a stirrer. In mixing, you may carry out by adding an appropriate amount of flux. By adding the flux, the production of the phosphor is promoted and it is possible to fire at low temperature.

It is preferable to perform baking in a reducing atmosphere, For example, it is preferable to carry out in nitrogen containing about 0.1 volume%-about 10 volume% of hydrogen, and argon containing about 0.1 volume%-about 10 volume% of hydrogen. Do. Baking may be normally performed under the conditions of temperature: about 1000 ° C to about 1500 ° C and time: about 1 hour to about 100 hours.

When the mixture contains a compound which can be decomposed at an elevated temperature such as hydroxides, carbonates, nitrates, halides, and oxalates to form an oxide, the mixture may be prefired before firing.

Preliminary baking may be performed either in an oxidizing atmosphere (for example, in air | atmosphere) or a reducing atmosphere. Preliminary baking may be normally performed in about 600 degreeC-about 900 degreeC temperature range.

The fluorescent substance A ¹ obtained by baking may be crushed, washed, or classified as needed. Grinding may be performed using a ball mill and a jet mill, for example. You may heat- ^process fluorescent substance A1 which grind | pulverized. By heat treatment, the crystallinity of the fluorescent substance A ¹ (reduced by grinding) can be increased. What is necessary is just to perform heat processing on the same conditions as the said baking normally.

In addition, the fluorescent substance A ¹ used for manufacture of the fluorescent substance of this invention may be manufactured by the method of Unexamined-Japanese-Patent No. 2002-332481 or Unexamined-Japanese-Patent No. 2003-183644, for example.

Phosphor B ¹ is, for example, can be prepared by a mixture of a metal compound and firing the mixture, which may be a fluorescent material B ¹ by firing.

For example, in the case of fluorescent material B ¹ containing barium (Ba), europium (Eu), magnesium (Mg), aluminum (Al) and oxygen (O),

The barium source, europium source, magnesium source and aluminum source of the mixture may be oxides by decomposing at high temperatures such as hydroxides, carbonates, nitrates, halides, and oxalates having a purity of 99% or more, or a purity of 99.9% or more. Oxide.

Phosphor B is ^1, the above compound, and mixing were weighed so that a composition of a desired fluorescent substance B ^1, is prepared by firing a mixture thereof.

Mixing and firing, and, optionally, calcination is carried out, and when carried out in the same condition as that for the fluorescent material A ^1. In addition, the fluorescent substance B ¹ obtained by baking may be crushed, washed, or classified as needed. What is necessary is just to grind | pulverize using a ball mill and a jet mill, for example. You may heat- ^process fluorescent substance B1 which grind | pulverized. By heat treatment, the crystallinity of the fluorescent substance B ¹ (reduced by pulverization) can be increased. What is necessary is just to perform heat processing on the same conditions as the said baking normally.

In addition, the fluorescent substance B ¹ used for manufacture of the fluorescent substance of this invention may be manufactured by the method of Unexamined-Japanese-Patent No. 2001-220582, for example.

Next, the phosphor paste of the present invention will be described.

The fluorescent substance paste of this invention contains the said fluorescent substance, a binder, and a solvent. When this phosphor paste is applied to a substrate and heated, the film or layer of the phosphor can be easily formed on the substrate. The heating is usually performed at or above the temperature at which the solvent volatilizes and below the decomposition temperature of the binder.

The phosphor paste of the present invention is, for example, by a method of mixing the fluorescent material A ¹ , the fluorescent material B ¹ , a solvent and a binder by using a device such as a ball mill, three roll mills, a bead mill, or a roller mill. It is good to manufacture.

The binder used for the phosphor paste may be, for example, a cellulose resin (ethyl cellulose, methyl cellulose, nitrocellulose, acetyl cellulose, cellulose propionate, hydroxypropyl cellulose, butyl cellulose, benzyl cellulose, modified cellulose, etc.) Resins (acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butylacryl Rate, n-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2- hydrate Roxypropyl methacrylate, benzyl acrylate, benzyl methacrylate, phenoxy Acrylate, phenoxy methacrylate, isobornyl acrylate, isobornyl methacrylate, glycidyl methacrylate, styrene, α-methylstyrene, acrylamide, methacrylamide, acrylonitrile, methacryl At least one polymer in monomers such as nitrile), ethylene-vinyl acetate copolymer resin, polyvinyl butyral, polyvinyl alcohol, propylene glycol, urethane resin, melamine resin, and phenol resin.

The content of the binder, is based on the total amount of the fluorescent material and the fluorescent material A ¹ B ^1, typically, 5% by weight to 50% by weight.

The solvent used for fluorescent paste is high boiling point in monohydric alcohol, for example; Polyhydric alcohols such as diols and triols represented by ethylene glycol glycerin; Compounds etherified and / or esterified with alcohols (ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol alkyl ether acetates, diethylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers) , Propylene glycol dialkyl ether, propylene glycol alkyl acetate).

The content of the solvent, based on the total amount of the fluorescent material and the fluorescent material A ¹ B ^1, typically, from 100% to 600% by weight.

Example

Next, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples.

The luminance of the sample (phosphor) was measured by the following method.

The sample was held in air at 500 ° C. for 30 minutes for heat treatment, and then pressure: 13.2 Pa, gas composition: 5 volume% xenon (Xe)-95 volume% Neon (Ne) was installed in a 50 W plasma. After exposing for a minute, the obtained sample was irradiated with vacuum ultraviolet rays using an excimer 146 nm lamp (manufactured by Ushio Electric Co., Ltd., H0012 type) in a vacuum chamber of 6.7 Pa (5 × 10 ^-2 Torr) or less. It was.

Reference Example 1

Aluminate for the _{(Ba 0 .9 Eu 0 .1 MgAl} 10 O 17, a blue fluorescent substance, and the average primary particle diameter of 0.4 ㎛), the brightness was measured by the above method. The brightness of this sample was 100.

Reference Example 2

Silicate (Ca Sr _{0 .9215 0 .0485 0 .03} Eu MgSi ₂ O _6, blue phosphor, and the average primary particle diameter 1.0㎛) for the result of measuring the brightness in the above manner, exhibited a luminance of 104.

Example 1

50 parts by weight of the fluorescent material used in Reference Example 2 and 50 parts by weight of the fluorescent material used in Reference Example 1 were wet mixed in ethanol, and the mixture was dried to obtain a phosphor. About this fluorescent substance, when the brightness was measured by the said method, it emitted blue light and the brightness was 127.

Example 2

80 parts by weight of the fluorescent material used in Reference Example 2 and 20 parts by weight of the fluorescent material used in Reference Example 1 were wet mixed in ethanol, and the mixture was dried to obtain a phosphor. About this fluorescent substance, when the brightness was measured by the said method, it emitted blue light and the brightness was 113.

Example 3

20 parts by weight of the fluorescent material used in Reference Example 2 and 80 parts by weight of the fluorescent material used in Reference Example 1 were wet mixed in ethanol, and the mixture was dried to obtain a phosphor. About this fluorescent substance, when the brightness was measured by the said method, it emitted light blue and the brightness was 107.

Claims (9)

Phosphor containing fluorescent substance A ¹ containing the compound represented by following formula (I), 1 or more types of activators selected from the group which consists of Eu and Mn, and fluorescent substance B ¹ which is an aluminate : mM ¹ O.nM ² O.2M ³ O ₂ (I) [In Formula (I), M <^1> is 2 or more types chosen from the group which consists of Ca, Sr, and Ba, Ca alone, or Ba alone, M <^2> Is at least one member selected from the group consisting of Mg and Zn, M ³ is at least one member selected from the group consisting of Si and Ge, and 0.5 ≦ m ≦ 3.5 and 0.5 ≦ n ≦ 2.5]. The method of claim 1, A phosphor having a weight ratio of the fluorescent substance A ¹ / fluorescent substance B ¹ of 5/95 to 95/5. The method according to claim 1 or 2, The fluorescent substance A ¹ is a phosphor represented by the following formula (II). (M ¹ _{1 - a} Eu _a ) (M ² _{1 - b} Mn _b ) M ³ ₂ O ₆ (II) In formula (II), M ¹ Is at least 2 selected from the group consisting of Ca, Sr and Ba, Ca alone or Ba alone, M ² is at least one selected from the group consisting of Mg and Zn, and M ³ is from the group consisting of Si and Ge At least one selected, and 0 ≦ a ≦ 0.5, 0 ≦ b ≦ 0.5, and 0 <a + b]. The method according to claim 1 or 2, Phosphor A ¹ is a phosphor represented by the following formula (III): Ca _{1 -c- d} Sr _c Eu _d MgSi ₂ O ₆ (III) In formula (III), 0 <c <0.1 and 0 <d <0.1. The method according to any one of claims 1 to 4, Aluminate salt is a compound represented by the following formula (IV): _{^{p (M 4 1 - e Eu}} e) O · q (M 5 1 - f Mn f) O · rAl 2 O 3 (IV) [In formula (IV), M <^4> is 1 or more types from the group which consists of Ca, Sr, and Ba, M <^5> is 1 or more types chosen from the group which consists of Mg and Zn, and 0.5 <= p <= 1.5, 0.5 <= q <1.5, 4.5 <r <5.5, 0 <e <0.5, 0 <f <0.1]. The method according to any one of claims 1 to 4, Aluminate salt is a compound represented by the following formula (V): Ba _{1 - g} Eu _g MgAl ₁₀ O ₁₇ (V) [0 <g ≦ 0.3 in Formula (V). The method according to any one of claims 1 to 6, B ¹ is a fluorescent material particles, and the average primary particle diameter D _B ¹ is from 0.2 to 5 times the phosphor of the average primary particle diameter D _A ¹ A ¹ of the fluorescent material. The method according to any one of claims 1 to 7, Phosphor for vacuum ultraviolet excitation light emitting element. A phosphor paste containing the phosphor, the solvent and the binder according to any one of claims 1 to 8.