WO1991013124A1 - Process for producing rare earth oxysulfide phosphor - Google Patents
Process for producing rare earth oxysulfide phosphor Download PDFInfo
- Publication number
- WO1991013124A1 WO1991013124A1 PCT/JP1991/000276 JP9100276W WO9113124A1 WO 1991013124 A1 WO1991013124 A1 WO 1991013124A1 JP 9100276 W JP9100276 W JP 9100276W WO 9113124 A1 WO9113124 A1 WO 9113124A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- rare earth
- phosphor
- seed
- earth oxysulfide
- oxysulfide
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7784—Chalcogenides
- C09K11/7787—Oxides
- C09K11/7789—Oxysulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/288—Sulfides
- C01F17/294—Oxysulfides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7767—Chalcogenides
- C09K11/7769—Oxides
- C09K11/7771—Oxysulfides
Definitions
- the present invention relates to a method for producing a rare earth oxysulfide phosphor.
- Rare earth oxysulfide phosphor (Ln 2 0 2 S: with L n ') is for reasons of equal goodness and chemically stable handling of the luminous efficiency is easy, a red phosphor for a color one television job down and to Y 2 0 2 S: Eu is practically used, and a green phosphor for a projection tube G 0 2 S: Tb is into practical use.
- the present invention aims to solve the above-mentioned problems, and to provide a method capable of producing a rare earth oxysulfide phosphor having a good particle size distribution with a good dispersibility and a desired particle size. Things.
- 1 ⁇ is an element such as 0 (1, ⁇ , 3 (:, 1 ⁇ , 1 ⁇ , etc., and Ln 'is an element such as Eu, Tb, Sm, Pr, Dy, Tm. in it, Ln 2 0 3 and Ln 'use Les 2 0.
- Ln 2 O n S: Ln' is represented by a method for producing a good UNA rare earth oxysulfide phosphor that, rare earth Ruisan sulfide to the mixture (Ln 2 0.S: Ln 'and / or Ln.Rei 2 S) sheet - the de (seed crystal)
- the rare earth oxysulfide shield is 1 to 60% by weight based on the total amount of the rare earth oxide and the rare earth oxysulfide seed, especially It is preferable to add 5 to 30% by weight. In view of production cost and production efficiency, it is recommended to add the above-mentioned shade in an amount of 1 to 40% by weight, more preferably 3 to 30% by weight.
- the present invention provides a method of mixing a rare earth oxide and / or a rare earth compound (for example, rare earth carbonate, oxalate, sulfite, etc.) which easily becomes an oxide at a high temperature with a sulfidizing agent and a fluxing agent.
- a rare earth oxide and / or a rare earth compound for example, rare earth carbonate, oxalate, sulfite, etc.
- a rare earth compound for example, rare earth carbonate, oxalate, sulfite, etc.
- the rare earth oxysulfide seed to be added in the present invention has a particle diameter smaller than that of the target rare earth oxysulfide phosphor.
- Particle size of the sheet one de normally used, the central particle size of the phosphor (d 5.) Is used as 80% or less of the, in particular in the range of 10% to 70% and its main portion It is preferable to use such a shade as described above.
- the main part of the particle diameter of the phosphor is in the range of 25% to 65%.
- the rare earth oxysulfide Shi one de of the inner Ln 2 0 2 S: Ln, in the use of phosphors is shown benefit for Bok there is recommended to.
- the production method of the present invention has a significant effect only on rare earth oxysulfide phosphors, and well-known sulfide-based phosphors (for example, phosphors such as ZnS: Ag, ZnS: CuA, ZnCdS: Cu) and oxide phosphors In the case of a phosphor (Ln 20 : a phosphor such as Eu), the same effect was not observed.
- the median particle size ( d5Q ) is represented by a weight distribution.
- the present invention can obtain the rare earth oxysulfide phosphor which has a good dispersibility, a narrow particle size distribution, easy particle size control, and excellent coating characteristics. It became so.
- Example 1 and 2 are graphs showing the phosphor particle size d5Q and the particle size distribution obtained in Example 1 by changing the mixing ratio of the seeds.
- Y. 0 3 226g, Eu 2 0. was dissolved in 13.7 g of nitric acid, diluted with pure water to about 1.8, and heated to 70 ° C. Next, a solution of 565 g of oxalic acid dissolved in pure water 1 at 70 ° C. was added to the previous solution with stirring to coprecipitate, thereby producing oxalates of Y and Eu. After washing this with water several times, it was heated at 900 ° C for 1 hour to form an oxide. This (Y, Eu).
- (Y, Eu) 20 With respect to 160 g of sulfur, 70 g of sulfur, 70 g of sodium carbonate, and 20 g of calcium phosphate, having the same molar ratio as that of Y and Eu in the rare earth oxide, d 5 () is 4.5 mi of (Y, Eu) 2 0 o S Shi I rather added and mixed one de 40 g, was calcined placed in an alumina crucible for 2 hours at 1150 ° C. Wash the calcined product repeatedly with water, neutralize residual alkali with nitric acid, disperse with a ball mill, dehydrate and filter, dry at 120 ° C for 13 hours, and 250 mesh Nylon Mesh And sieve through Y 20 . An S: Eu red phosphor was obtained.
- Comparative Example 1 For comparison, in Comparative Example 1, a method was used in which the seed was not used under the above-described manufacturing conditions, and in Comparative Example 2, the firing temperature was 1250 ° C with no use of the seed. The temperature was increased to produce large particles.
- Table 1 shows the powder properties and coating properties of the obtained phosphor.
- the sedimentation volume of the underwater was measured by placing 5 g of the phosphor and 30 m € of pure water in a 30 m sedimentation tube, shaking the mixture sufficiently, and allowing it to stand still for 1 hour.
- the filling property of the coating properties refers to the degree of filling of the phosphor particles that make up the phosphor film (dots and stripes).
- X indicates that it does not have the required chargeability.
- the color mixture shows the degree of red phosphor particles adhering to the blue and picture elements (dots and stripes), indicating the effect on the color purity of blue. ⁇ means that there is substantially no effect on color purity, and X means that the effect is large.
- Phosphor of Example 2 though the particle diameter d 5Q is equivalent to the size rather growth and 8 / m, fine log (S) and clog (L) is minor, narrow particle size distribution min Call In addition, the sedimentation volume in water is small, the dispersibility is good, and the filling property and color mixture are excellent.
- Comparative Example 4 was manufactured by using a method without using a seed under the above manufacturing conditions, and Comparative Example 3 was performed without using a seed, and the firing temperature was 1200. Changed to C and manufactured.
- Table 2 shows the powder properties and coating properties of the obtained phosphor. Compared with Comparative Examples 3 and 4, the phosphor of Example 3 has excellent powder properties and coating properties as shown in the table. 1 and above, the force 5 ′ is exemplified as a parent element (Ln) in the case of Y, Gd, Sc, etc., and the activator element (Ln ′) is exemplified in the case of Eu, Tb, Sm as a representative example.
- the force 5 ′ is exemplified as a parent element (Ln) in the case of Y, Gd, Sc, etc.
- the activator element (Ln ′) is exemplified in the case of Eu, Tb, Sm as a representative example.
- the other activator elements are: Pr, Dy, Tm
- the effect of the present invention was also obtained in the case of using, and also in the case of co-activation of two or more including these elements.
- the method of the present invention it is possible to obtain a phosphor having a large particle size, which is impossible to obtain conventionally, such as obtaining a phosphor of 20 m using a 10 m shield, which is extremely useful. It is.
- Example 2 8.2 0.26 0.30 1.9 ⁇ ⁇ Comparative Example 1 8.0 0.44 0.47 2.6 X X
- Example 3 8.4 0.24 0.29 1.5 ⁇ ⁇ Comparative Example 3 8. ⁇ 0.0..45 1.8 X X Comparative Example 4 5.4 0.40 0.42 2.3 ⁇ X
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Luminescent Compositions (AREA)
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP91905333A EP0471091B1 (en) | 1990-03-01 | 1991-03-01 | Process for producing rare earth oxysulfide phosphor |
DE69110575T DE69110575T2 (de) | 1990-03-01 | 1991-03-01 | Verfahren zur herstellung von seltenerd-oxysulfidphosphor. |
KR1019910701508A KR0185153B1 (ko) | 1990-03-01 | 1991-03-01 | 희토류 산황화물 형광체의 제조방법 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2/47230 | 1990-03-01 | ||
JP2047230A JPH0737613B2 (ja) | 1990-03-01 | 1990-03-01 | 希土類酸硫化物蛍光体の製造方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1991013124A1 true WO1991013124A1 (en) | 1991-09-05 |
Family
ID=12769409
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1991/000276 WO1991013124A1 (en) | 1990-03-01 | 1991-03-01 | Process for producing rare earth oxysulfide phosphor |
Country Status (6)
Country | Link |
---|---|
US (1) | US5217647A (ja) |
EP (1) | EP0471091B1 (ja) |
JP (1) | JPH0737613B2 (ja) |
KR (1) | KR0185153B1 (ja) |
DE (1) | DE69110575T2 (ja) |
WO (1) | WO1991013124A1 (ja) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR0150725B1 (ko) * | 1995-02-20 | 1998-10-01 | 구자홍 | 칼라브라운관의 적색 형광체 |
US5853945A (en) * | 1996-06-03 | 1998-12-29 | Fuji Photo Film Co., Ltd. | High-contrast silver halide photographic material and photographic image forming system using the same |
WO2003078543A1 (en) * | 2002-03-13 | 2003-09-25 | University Of Florida | Novel methods for preparing rare-earth oxysulfide phosphors, and resulting materials |
US7829162B2 (en) | 2006-08-29 | 2010-11-09 | international imagining materials, inc | Thermal transfer ribbon |
US8545784B2 (en) * | 2006-10-20 | 2013-10-01 | Neo International Corp. | Method for the production of rare earth containing phosphates |
KR101458026B1 (ko) * | 2007-11-29 | 2014-11-06 | 삼성디스플레이 주식회사 | 희토류 나노형광체 및 그 제조 방법 |
EP3023831B1 (en) * | 2013-07-19 | 2018-08-01 | Shin-Etsu Chemical Co., Ltd. | Magneto-optical material, method for producing same and magneto-optical device |
JP6540784B2 (ja) * | 2017-03-15 | 2019-07-10 | 日亜化学工業株式会社 | アルミン酸塩蛍光体の製造方法、アルミン酸塩蛍光体及び発光装置 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55157678A (en) * | 1979-05-28 | 1980-12-08 | Hitachi Ltd | Preparation of fluorescent substance |
JPS57192484A (en) * | 1981-05-21 | 1982-11-26 | Toshiba Corp | Preparation of fluorescent material |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL6904459A (ja) * | 1969-03-22 | 1970-09-24 | ||
US3647707A (en) * | 1969-09-08 | 1972-03-07 | Gen Electric | Alkali monosulfide recrystallization of lanthanide oxysulfide luminescent material |
US3837882A (en) * | 1971-09-02 | 1974-09-24 | Kewanee Oil Co | Optical bodies with non-epitaxially grown crystals on surface |
JPS5183889A (en) * | 1975-01-20 | 1976-07-22 | Nippon Toki Kk | Tomeiseio jusuruketsushokagarasuyorinarukeikotai |
JPS55165983A (en) * | 1979-06-13 | 1980-12-24 | Toshiba Corp | Production of zinc sulfide phosphor |
JPS5943090A (ja) * | 1982-09-06 | 1984-03-09 | Toshiba Corp | 螢光体の製造方法 |
-
1990
- 1990-03-01 JP JP2047230A patent/JPH0737613B2/ja not_active Expired - Fee Related
-
1991
- 1991-03-01 WO PCT/JP1991/000276 patent/WO1991013124A1/ja active IP Right Grant
- 1991-03-01 KR KR1019910701508A patent/KR0185153B1/ko not_active IP Right Cessation
- 1991-03-01 EP EP91905333A patent/EP0471091B1/en not_active Expired - Lifetime
- 1991-03-01 US US07/773,881 patent/US5217647A/en not_active Expired - Lifetime
- 1991-03-01 DE DE69110575T patent/DE69110575T2/de not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55157678A (en) * | 1979-05-28 | 1980-12-08 | Hitachi Ltd | Preparation of fluorescent substance |
JPS57192484A (en) * | 1981-05-21 | 1982-11-26 | Toshiba Corp | Preparation of fluorescent material |
Also Published As
Publication number | Publication date |
---|---|
EP0471091B1 (en) | 1995-06-21 |
DE69110575D1 (de) | 1995-07-27 |
US5217647A (en) | 1993-06-08 |
DE69110575T2 (de) | 1996-03-21 |
KR0185153B1 (ko) | 1999-04-01 |
JPH03252495A (ja) | 1991-11-11 |
EP0471091A1 (en) | 1992-02-19 |
JPH0737613B2 (ja) | 1995-04-26 |
EP0471091A4 (en) | 1992-07-29 |
KR920701378A (ko) | 1992-08-11 |
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