JP2000034478A - Phosphor for vacuum ultraviolet ray, method for producing the same, phosphor paste composition and vacuum ultraviolet ray light emitting element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a high-luminance phosphor which is resistant to degradation in emission luminance in the step of forming a phosphor film by coating a phosphor with a silicate of at least one metal selected from among Mg, Ca, Sr, Ba, and Zn. SOLUTION: A phosphor is dispersed in a solvent such as water and then a solvent-soluble compd. of at least one metal selected from among Mg, Ca, Sr, Ba, and Zn and a silicon compd., such as water glass or a colloidal silica sol contg. an ionic silica component, which liberates silicic acid ions in a soln. are put into the above-prepd. phosphor dispersion under sufficient agitation, thus causing a metal silicate to be formed and attached to the phosphor in the dispersion. Then the resultant slurry is dehydrated and dried at 100-200 deg.C to give the objective phosphor. The silicate attached to the phosphor is the one represented by the formula: MxSiOx+2y [wherein M is Mg, Ca, Sr, Ba, or Zn; and 0.1<=(x/y)<=10]. Among such silicates, a silicate of Ba and/or Sr is esp. excellent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phosphor for vacuum ultraviolet rays which emits light when excited by vacuum ultraviolet rays used in plasma display panels, rare gas discharge lamps, etc., a method for producing the same, and a phosphor containing the phosphor. The present invention relates to a VUV-excited light emitting device including a paste composition and a phosphor film formed using the phosphor paste composition.

[0002]

2. Description of the Related Art In recent years, Ar, Xe, He, Ne, and Xe-
Development of a vacuum ultraviolet-excitation light-emitting element that encloses a rare gas such as Ne in a vacuum envelope such as glass and excites a fluorescent film inside the envelope with vacuum ultraviolet rays emitted by the discharge of the rare gas to emit light. Is being actively conducted.

One example is a thin tube lamp used as a light source for reading a scanner. Xe,
A rare gas such as Xe-Ne is sealed therein, and a fluorescent film made of a phosphor that emits light when excited by vacuum ultraviolet rays is formed on the inner surface of the tube. When electric energy is applied from electrodes provided at both ends of the thin tube, a rare gas discharge occurs in the thin tube, and vacuum ultraviolet rays are emitted. The phosphor is excited by the vacuum ultraviolet light to emit visible light.

The applied phosphor emits red, blue and green light.
A single-color phosphor and a three-color phosphor that emits a single color
There is something. The red light emitting phosphor is (Y, Gd) B
O_Three: Eu, green phosphor is LaPO_Four: Ce, T
b, the blue light emitting phosphor is BaMgAl _TenO₁₇: Eu, (B
a, Sr) MgAl_TenO₁₇: Eu, Mn, etc. are used
You.

[0005] In addition to the VUV-excited light emitting element, there is a plasma display panel (hereinafter referred to as "PDP"). In principle, the PDP can be considered to be such that the above-mentioned vacuum lamp excited by a vacuum ultraviolet ray is made smaller and three color lamps of different emission colors are arranged in a matrix. That is,
A narrow discharge space (hereinafter referred to as “cell”) is arranged in a matrix. Each cell is provided with an electrode,
A phosphor is applied inside or outside of each cell to form a phosphor film, and a rare gas such as Xe or Xe-Ne is sealed in each cell. When electric energy is applied from the electrode,
A rare gas discharge occurs in the cell, and vacuum ultraviolet rays are emitted. The fluorescent material is excited by the vacuum ultraviolet light to emit visible light, and an image is displayed by this light emission.

[0006] In the case of a full-color PDP, full-color display can be performed by applying phosphors that emit red, blue, and green when excited by vacuum ultraviolet rays in a matrix. Here, as the red light emitting phosphor, (Y, G
d) BO ₃ : Eu, Zn ₂ SiO as green emitting phosphor
₄ : Mn, BaMgAl ₁₀ O ₁₇ as a blue light emitting phosphor:
Eu or the like is used. (Issued by the Industrial Research Council, Electronic Materials Magazine, December 1997 issue)

When forming a fluorescent film by applying a fluorescent substance to both a thin tube lamp and a PDP, a fluorescent substance paste in which the fluorescent substance is dispersed in a binder resin is used. In the case of a thin tube lamp, usually, a phosphor and a resin such as nitrocellulose are mixed using a solvent such as butyl acetate, applied as a phosphor paste to the inner surface of the glass tube, dried, and then fired to fire the glass tube. A phosphor coating film is formed on the inner surface. Also,
In the case of PDP, a phosphor paste is prepared by mixing a phosphor, a resin such as ethylcellulose, and a solvent such as butyl carbitol, which is applied to the inner surface of the PDP by a screen printing method, dried, and fired. Generally, a phosphor coating film is formed in the cell.

[0008] As described above, in forming the fluorescent film of the VUV-excited light emitting device, a phosphor paste composition is applied,
It is essential that it be dried and then fired. In this firing step, there is a problem that the phosphor is deteriorated. In particular, the blue-emitting phosphor BaMgAl ₁₀ O ₁₇ : E
u, (Ba, Sr) MgAl ₁₀ O ₁₇ : Eu, Mn, etc.
Even if the aluminate phosphor using Eu as an activator is greatly degraded, even if the device is formed using a high-luminance blue light-emitting phosphor, the emission luminance of the blue light-emitting component of the obtained VUV-excited light-emitting device is reduced. I couldn't avoid it. Therefore, development of a phosphor and a phosphor paste with less deterioration of light emission luminance in the firing step has been desired.

[0009]

SUMMARY OF THE INVENTION Accordingly, the present invention has been made to overcome the above-mentioned drawbacks, and has provided a high-intensity phosphor for vacuum ultraviolet light which has little deterioration in light emission luminance in a process of forming a fluorescent film of a vacuum ultraviolet light-excited light emitting element. An object of the present invention is to provide a method for producing the same, a phosphor paste composition, and a vacuum ultraviolet ray excited light emitting device using the same.

[0010]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have intensively studied the effect of preventing the luminance deterioration by covering the surface of a phosphor emitting light by excitation with vacuum ultraviolet rays with various substances. As a result, it was found that by coating the surface of the phosphor with a divalent metal silicate, it was possible to suppress the luminance degradation in the above-mentioned firing step, and to complete a high-luminance phosphor for vacuum ultraviolet rays and a vacuum ultraviolet ray excited light emitting element. . That is,
The configuration of the present invention is as follows.

(1) A phosphor for vacuum ultraviolet rays, wherein the phosphor is coated with a silicate of at least one metal selected from the group consisting of magnesium, calcium, strontium, barium and zinc. (2) A phosphor for vacuum ultraviolet radiation, wherein a phosphor is mixed with a silicate of at least one metal selected from the group consisting of magnesium, calcium, strontium, barium and zinc.

(3) The coating according to (1) or (2), wherein the coating amount and / or the mixing amount of the silicate is in the range of 0.01 to 15 wt% based on the weight of the phosphor. Phosphor for vacuum ultraviolet rays. (4) wherein the phosphor is a phosphor activated by at least one selected from the group ^consisting of Eu2 ⁺ , Mn2 ⁺ , Tb3 ^+, and Ce3 ^+. (3) The phosphor for vacuum ultraviolet rays according to any one of (1) to (3).

(5) In a phosphor slurry obtained by dispersing the phosphor in a solvent, a compound of at least one metal selected from the group consisting of magnesium, calcium, strontium, barium and zinc, which is dissolved in the solvent, A phosphor for vacuum ultraviolet rays, wherein a silicate of the metal is generated by adding and mixing with a silicon compound which releases silicate ions in a solution, and the silicate of the metal is attached to the phosphor surface. Manufacturing method.

(6) In a phosphor paste composition obtained by dispersing a phosphor in a binder resin, the phosphor is selected from the vacuum ultraviolet phosphor described in any one of (1) to (4) above. A phosphor paste composition comprising:

(7) In a vacuum ultraviolet ray excited light emitting device in which a fluorescent film is formed in a vacuum envelope and a rare gas is sealed, the fluorescent film is any one of the above (1) to (4). A vacuum ultraviolet ray excited light emitting device, comprising the vacuum ultraviolet ray phosphor according to any one of the preceding claims.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The phosphor for vacuum ultraviolet rays of the present invention
The phosphor is dispersed in a solvent such as water and contains a compound of at least one metal element selected from the group consisting of Mg, Ca, Sr, Ba and Zn dissolved in the solvent, a water glass and an ionic silica component. A silicon compound that releases silicate ions in a solution, such as a colloidal silica sol, is charged and sufficiently stirred to form a silicate of the metal and adhere to the surface of the phosphor in the solution. Next, the slurry is dehydrated and dried at 100 to 200 ° C. to produce a phosphor for vacuum ultraviolet rays. The phosphor thus obtained was further added with 2
By baking at 00 to 1000 ° C., the hydroxyl groups bonded to the silicate and the attached moisture may be removed.

Here, Mg, C adhering to the phosphor surface
The silicates of a, Sr, Ba, and Zn are Mg ₂ SiO ₄ ,
Ca ₂ SiO ₄ , Sr ₂ SiO ₄ , Ba ₂ SiO ₄ , Z
orthosilicate such as n ₂ SiO ₄ , MgSiO ₃ , CaS
metasilicates such as iO ₃ , SrSiO ₃ , BaSiO ₃ ,
And Mg ₃ Si ₄ O ₁₁ , CaMg (SiO ₃ ) ₂ , Ba
General formula M _x Si _y O, such as Si ₂ O _5
It refers to the silicate represented by _{x + 2y} . (However, M is Mg,
At least one metal element selected from the group consisting of Ca, Sr, Ba and Zn, wherein x and y are 0.1 ≦ (x /
y) is a number that satisfies ≦ 10) Among them, Ba and / or
Sr silicate is particularly excellent in suppressing luminance deterioration during firing.

In the phosphor slurry, the metal silicate powder and the phosphor are mixed in a solvent such as water and then dehydrated, instead of attaching the metal silicate to the phosphor surface and coating the phosphor surface. Alternatively, the phosphor powder and the metal silicate powder can be mechanically mixed to increase the silicate coverage and covering power on the phosphor, but the luminance in the firing step in forming the phosphor film is increased. In order to more reliably control deterioration,
The method of producing silicate in the phosphor slurry and directly attaching the silicate to the phosphor is superior.

In the present invention, the coating amount and / or the mixing amount of the silicate on the phosphor surface is 0.01 to 0.01% based on the weight of the phosphor.
An appropriate range is from 15 to 15% by weight, preferably from 0.05 to 0.5% by weight. If less than 0.01% by weight,
When the effect of suppressing the luminance deterioration is small, and when the amount is more than 15% by weight, the penetration of the excitation light into the phosphor and the emission of the phosphor are inhibited by the silicate, and the luminous efficiency of the phosphor is reduced. Absent. The metal silicate may not be entirely coated with the phosphor, but it is preferable that a part of the metal silicate is attached to the phosphor surface.

The fluorescent material for vacuum ultraviolet rays used in the present invention
The light body is a fluorescent light that emits light with high efficiency when excited by vacuum ultraviolet light.
Any body may be used, but specifically, the general formula (M¹ _1-xEu
_x) O ・ a (M^Two _1-y, Mn_y) O. (5.5-0.5)
a) Al_TwoO_ThreePhosphor (where M¹Are Ba, Sr and C
at least one element selected from the group consisting of
Then M^TwoRepresents Mg and / or Zn, and a represents 0 <a ≦
2 represents a real number, and x and y are respectively 0 <x <1, 0 ≦
Eu represents a real number of y <1)²⁺And Mn ²⁺Activated by
Aluminate phosphor such as BaMgAl
_TenO₁₇: Eu phosphor, (Ba, Sr) MgAl_TenO₁₇:
Eu, Mn phosphor, other, Mn²⁺, Tb³⁺, Ce³⁺etc
Activated by Zn_TwoSiO_Four: Mn phosphor, LaP
O_Four: Ce, Tb phosphor, BaAl₁₂O₁₉: Such as Mn
Fireflies activated by an element that is oxidized and easily changes in valence
Light bodies can be mentioned.

[0021] Among these phosphors, BaMgAl ₁₀ O strong blue light emission requests for improvement luminance degradation _17: typified Eu, the general formula ^{_{(M 1 1-x Eu x}} ) O · a
^{_{(M 2 1-y, Mn}} y) O · (5.5-0.5a) Al 2
Particularly effective is an aluminate phosphor activated by Eu ²⁺ or Mn ²⁺ represented by O ₃ .

The phosphor paste composition of the present invention is produced by dispersing the above phosphor in a binder resin. As the binder resin, ethyl cellulose, nitrocellulose, acrylic resin, using a resin such as polystyrene oxide, butyl carbitol, butyl carbitol acetate, terpineol, butyl acetate, ethyl acetate,
It is uniformly mixed and dispersed with a solvent such as methyl ethyl ketone. The content of the phosphor in the phosphor paste composition is appropriately in the range of 5 to 80% by weight, preferably 20 to 60% by weight. The amount of the binder resin is 4
A range of from about 80% by weight to about 80% by weight, preferably from 8 to 50% by weight is appropriate. Further, the amount of the solvent added is 10 to 90% by weight,
Preferably, the range is 40 to 80% by weight.

The VUV-excited light emitting device of the present invention is prepared by applying the phosphor paste composition of the present invention in a glass tube of, for example, 4 to 12 mm and drying at 100 to 200 ° C.
After baking at 0 to 800 ° C. for 5 to 30 minutes, a phosphor layer is formed on the inner wall, nickel electrodes are attached to both ends of the glass tube, the inside of the tube is evacuated and evacuated, and then Ne98% -Xe 2.
% Or a rare gas such as a mixed gas of He 98% -Xe 2% is sealed to an internal pressure of about 50 Torr.

[0024]

[Example 1] (Ba, Eu) MgAl ₁₀ O ₁₇
100 g of the phosphor is put into 200 ml of water, mixed and sufficiently stirred to prepare a phosphor slurry, and 1.1 g of Zn ₂ SiO ₄ fine powder is put into the slurry, and heated while stirring to obtain a liquid volume. And finally evaporated to dryness to remove Zn ₂ S
The phosphor for vacuum ultraviolet rays of Example 1 in which iO ₄ was attached to and mixed with the phosphor was obtained.

Example 2 (Ba, Eu) MgAl ₁₀ O
₁₇ 100 g of a phosphor is put into 300 ml of water, mixed and sufficiently stirred to prepare a phosphor slurry, and 2 ml of a colloidal SiO ₂ solution containing 20% of ionic SiO ₂ is dropped into the slurry. Then, a ZnSO ₄ solution containing 0.55 g of Zn was added dropwise, stirred for 15 minutes, dehydrated, and dried at 120 ° C. for 5 hours, whereby zinc silicate was attached to the phosphor.
Was obtained.

Example 3 In Example 1, Zn ₂ S
Instead of iO ₂ fine powder 1.1g, BaSiO ₃ · 6H
Except for using ₂ O powder 2.3g, yield the VUV phosphor of Example 3 was adhered to and mixed with BaSiO _{3-6H 2} O in the same manner as in Example 1 to the phosphor.

Example 4 In Example 2, the amount of the colloidal SiO ₂ solution containing 20% of ionic SiO ₂ was changed from 2 ml to 4 ml, and Zn was added to 0.1 ml.
Instead of a ZnSO ₄ solution containing 55 g, Ba was added at 0.
A phosphor for vacuum ultraviolet rays of Example 4 was obtained in which barium silicate was adhered to the phosphor in the same manner as in Example 2 except that a Ba (NO ₃ ) ₂ solution containing 50 g was dropped.

Example 5 In Example 4, the amount of the colloidal SiO ₂ solution containing 20% ionic SiO ₂ was changed from 4 ml to 8 ml, and Ba (NO
₃ ) The phosphor for vacuum ultraviolet rays of Example 5 in which barium silicate was adhered to the phosphor in the same manner as in Example 4 except that the content of Ba in the _two solutions was changed from 0.50 g to 4.5 g. Was.

Example 6 In Example 4, the amount of the colloidal SiO ₂ solution containing 20% of ionic SiO ₂ was changed from 4 ml to 0.8 ml, and Ba was added.
The (NO ₃ ) ₂ solution has a Ba content of 0.50 g to 0.5%.
A phosphor for vacuum ultraviolet rays of Example 6 was obtained in which barium silicate was attached to the phosphor in the same manner as in Example 4 except that the phosphor was changed to 10 g.

Example 7 In Example 4, the amount of the colloidal SiO ₂ solution containing 20% of ionic SiO ₂ was changed from 4 ml to 0.4 ml, and Ba was added.
The (NO ₃ ) ₂ solution has a Ba content of 0.50 g to 0.5%.
A phosphor for vacuum ultraviolet rays of Example 7 was obtained in which barium silicate was adhered to the phosphor in the same manner as in Example 4 except that the phosphor was changed to 23 g.

Example 8 In Example 4, the amount of the colloidal SiO ₂ solution containing 20% of ionic SiO ₂ was dropped at 4 ml without changing, and Ba (NO ₃ ) was used.
₂ Instead of the solution, Sr containing 1.5 g of Sr (NO
₃ ) A phosphor for vacuum ultraviolet rays of Example 8 was obtained in which strontium silicate was adhered to the phosphor in the same manner as in Example 4 except that the _two solutions were dropped.

[0032] In Example 9 Example 4, the dropping amount of colloidal SiO ₂ solution containing ionic SiO ₂ 20% change from 4ml to 2 ml, in place of Ba (NO _{3) 2} solution, Ca (NO ₃ ) containing 0.33 g of Ca
_A phosphor for vacuum ultraviolet rays of Example 9 was obtained in which calcium silicate was adhered to the phosphor in the same manner as in Example 4 except that the _two solutions were dropped.

[0033] In Example 10 Example 4, the dropping amount of colloidal SiO ₂ solution containing ionic SiO ₂ 20% change from 4ml to 2ml, Ba (NO _{3) 2}
Instead of a solution, Mg containing 0.20 g of Mg (NO
₃ ) A phosphor for vacuum ultraviolet rays of Example 10 was obtained in which magnesium silicate was attached to the phosphor in the same manner as in Example 4 except that the _two solutions were dropped.

[Comparative Example 1] (B) used in Examples 1 to 10
a, Eu) MgAl ₁₀ O ₁₇ phosphor was used as a phosphor for vacuum ultraviolet rays of Comparative Example 1 without coating treatment.

Comparative Example 2 (Ba, Eu) MgAl ₁₀ O
_A phosphor slurry was prepared by charging 100 g of ₁₇ phosphor into 300 ml of water, mixing and sufficiently stirring, and 0.5 g of (NH ₄ ) ₂ HPO ₄ was added to the slurry and sufficiently stirred. Thereafter, the slurry was heated and evaporated to dryness to obtain a phosphor for vacuum ultraviolet rays of Comparative Example 2 in which the phosphor surface was coated with ammonium phosphate.

(Measurement of Si and Metal Equivalent Content in Phosphor) The phosphors for vacuum ultraviolet rays of Examples 1 to 10 were dissolved by using hydrofluoric acid, and were subjected to inductively coupled high frequency plasma emission spectrometry (ICP). ) Using SiO ₂ , Zn, Ba, Sr, C
The amounts of a and Mg were measured, and the results are shown in Table 1.

(Measurement of luminous efficiency of phosphor for vacuum ultraviolet ray)
The luminance of the blue phosphor used in the examples and the comparative examples greatly changes in proportion to the emission color (chromaticity point y value). As a simple method of comparing the luminous efficiencies of the phosphors having different luminescent colors, it is often performed to compare the luminous efficiency with a value obtained by dividing the luminance by the y value (luminous efficiency). Luminous efficiency (luminance / y value) in this evaluation
Luminous efficiency of each phosphor before firing treatment ()
And the luminous efficiency () after firing each of these phosphors at a temperature of 550 ° C. for 1 hour was measured, and the luminance maintenance ratio (/) after the calcination process was determined to obtain the luminous efficiency of each phosphor by the firing process. The results are shown in Table 1 below. At this time, the luminous efficiency (luminance / y value) of each phosphor was determined by irradiating each phosphor with 146 nm vacuum ultraviolet rays and measuring the luminous luminance and chromaticity (y value) at that time. The results are shown in Table 1. In Table 1, the luminous efficiency (luminance / y value) of each phosphor is the luminous efficiency of the (Ba, Eu) MgAl ₁₀ O ₁₇ phosphor of Comparative Example 1 whose surface is not covered with any material before the firing treatment. (Brightness / y value) is 100
And expressed as a relative value.

[0038]

[Table 1]

[Examples 11 to 20] 30 g of the phosphor for vacuum ultraviolet rays obtained in Examples 1 to 10 were weighed, and 25 g of ethyl cellulose resin, 10 g of butyl carbitol and 53 g of butyl carbitol acetate were kneaded. Thus, the phosphor pastes of Examples 11 to 20 were obtained.

Comparative Example 3 The phosphor paste of Comparative Example 3 was prepared in the same manner as in Example 11, except that the phosphor for vacuum ultraviolet rays was changed from that of Example 1 to that of Comparative Example 1. I got

(Evaluation of phosphor paste) Examples 11 and 2
Each of the phosphor paste compositions of Comparative Example 0 and Comparative Example 3 was applied on a glass plate to a thickness of 0.5 mm,
After drying for 450 minutes, a baking treatment was performed at 450 ° C. for 30 minutes to produce a phosphor coating film, which was used as an evaluation sample. Then, each of the evaluation samples is irradiated with 146 nm vacuum ultraviolet rays to measure the emission luminance and chromaticity (y value), and the luminous efficiency (luminance / y value,
) Was determined and the results are shown in Table 2. In Table 2, the luminous efficiencies () of the respective evaluation samples are all (Ba, E) of Comparative Example 1 used for the phosphor paste composition of Comparative Example 3.
u) The luminous efficiency (brightness / y value) of the MgAl ₁₀ O ₁₇ phosphor before the sintering treatment was shown as a relative value when 100.

[0042]

[Table 2]

As is clear from the results in Tables 1 and 2,
The phosphors of Examples 1 to 10 were compared with the phosphor of Comparative Example 1 in which no coating treatment was performed on the surface or the known phosphor treated with ammonium phosphate, that is, the phosphor of Comparative Example 2.
All of the luminous efficiencies (luminance / y value) after the phosphor baking treatment are high, and the degree of luminance degradation due to the baking treatment is greatly improved. In particular, when a silicate compound of Ba and Sr was coated or mixed, the luminous efficiency of the phosphor after the firing treatment was increased, and the luminance retention ratio was further improved.

The luminous efficiencies (brightness / y values) of the phosphor paste compositions of Examples 11 to 20 using the phosphors of Examples 1 to 10 were the same as those of the conventional phosphor paste composition of Comparative Example 3. The luminous efficiency was higher than the luminous efficiency (luminance / y value), and the luminous efficiency was high with little luminance deterioration due to the baking treatment during the production of the fluorescent film.

Example 21 30 g of the phosphor for vacuum ultraviolet rays obtained in Example 4 was weighed, and 25 g of nitrocellulose resin and 45 g of butyl acetate were kneaded to prepare a phosphor paste. This phosphor paste was applied to a glass tube having an outer diameter of 4 mm, dried at 120 ° C. for 60 minutes, and then dried at 600 ° C.
For 10 minutes to obtain a phosphor coated tube. Nickel electrodes were attached to both ends of the obtained phosphor-coated tube, and the inside of the tube was evacuated to a vacuum.
Then, a vacuum ultraviolet ray excited light emitting device of Example 21 was produced. An AC voltage of 1 kV was applied to the VUV-excited light-emitting device to emit light, and the luminous efficiency (luminance / y value) at the center of the tube of the VUV-excited light-emitting device was measured.

Comparative Example 4 The procedure of Example 21 was repeated, except that the phosphor for vacuum ultraviolet rays was changed from that of Example 4 to the phosphor of Comparative Example 1. An excitation light emitting device was manufactured. Then, in the same manner as in Example 21, an AC voltage was applied to emit light, and the luminous efficiency (luminance / y value) of the central portion of the tube of the VUV-excited light emitting element was measured.

(Evaluation of Vacuum Ultraviolet Light Excited Light Emitting Element) Assuming that the luminous efficiency (luminance / y value) at the center of the tube of the vacuum ultraviolet light excited light emitting element of Comparative Example 4 is 100%, the vacuum ultraviolet light excited light emitting element of Example 21 is used. Luminous efficiency (luminance / y) at the center of the tube
Value) was 121%.

[0048]

According to the present invention, by adopting the above structure, it is possible to suppress a decrease in luminance in the firing step when forming a fluorescent film, and to obtain a phosphor, a phosphor paste and a luminous efficiency having high luminous efficiency. Of the present invention has been made possible to provide a vacuum ultraviolet ray excited light emitting device which is improved.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C09K 11/64 CPM C09K 11/64 CPM (72) Inventor Masakazu Nabe 1060 Narita, Odawara-shi, Kanagawa Kasei Optonics Co., Ltd. (72) Inventor Takayuki Hisamune 1060 Narita, Odawara-shi, Kanagawa Prefecture DD00 DD13 5C043 EB01 EB04 EB07 EB08

Claims (7)

[Claims] 1. The phosphor according to claim 1, wherein the phosphor is magnesium, calcium,
A phosphor for vacuum ultraviolet rays, wherein the phosphor is coated with a silicate of at least one metal selected from the group consisting of strontium, barium and zinc. 2. A phosphor, comprising magnesium, calcium,
A phosphor for vacuum ultraviolet rays, wherein the phosphor is mixed with a silicate of at least one metal selected from the group consisting of strontium, barium and zinc. 3. The fluorescent material for vacuum ultraviolet rays according to claim 1, wherein the coating amount and / or the mixing amount of the silicate is in a range of 0.01 to 15 wt% based on the weight of the phosphor. body. 4. The phosphor according to claim 1, wherein the phosphor is activated by at least one selected from the group ^consisting of Eu ²⁺ , Mn ²⁺ , Tb ³⁺ and Ce ^3+. 4. The phosphor for vacuum ultraviolet rays according to any one of items 3 to 3. 5. A phosphor slurry obtained by dispersing a phosphor in a solvent, a solution of at least one metal selected from the group consisting of magnesium, calcium, strontium, barium and zinc dissolved in the solvent, and a solution A phosphor compound for vacuum ultraviolet radiation, wherein a silicate of the metal is generated by adding and mixing a silicon compound that releases silicate ions in the phosphor, and the silicate of the metal is attached to the phosphor surface. Production method. 6. A phosphor paste composition comprising a phosphor dispersed in a binder resin, wherein the phosphor comprises the phosphor for vacuum ultraviolet rays according to any one of claims 1 to 4. Phosphor composition. 7. A vacuum ultraviolet ray excited light emitting device in which a fluorescent film is formed in a vacuum envelope and a rare gas is sealed, wherein the fluorescent film is the vacuum ultraviolet light according to any one of claims 1 to 4. A vacuum ultraviolet ray excited light emitting device comprising a phosphor for use.