KR930003702B1 - Production of red luminous fluorescent material - Google Patents
Production of red luminous fluorescent material Download PDFInfo
- Publication number
- KR930003702B1 KR930003702B1 KR1019890019192A KR890019192A KR930003702B1 KR 930003702 B1 KR930003702 B1 KR 930003702B1 KR 1019890019192 A KR1019890019192 A KR 1019890019192A KR 890019192 A KR890019192 A KR 890019192A KR 930003702 B1 KR930003702 B1 KR 930003702B1
- Authority
- KR
- South Korea
- Prior art keywords
- mol
- phosphor
- fluorescent material
- red light
- red
- Prior art date
Links
Images
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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
Description
제 1 도는 본 발명의 형광체와 종래의 형광체에 대하여 500시간 동안 여기했을때 여기 시간 변화에 대한 발광휘도 변화를 나타낸 그래프이다.FIG. 1 is a graph showing a change in emission luminance with respect to the excitation time when the phosphor of the present invention and the conventional phosphor are excited for 500 hours.
본 발명은 적색발광형광체에 관한 것으로, 특히 우수한 열화특성과 발광휘도특성을 갖는 조성식이 Y2O3: Eu, Er로 표기되는 적색발광형광체에 관한 것이다.The present invention relates to a red light emitting phosphor, and more particularly, to a red light emitting phosphor in which a composition formula having excellent deterioration characteristics and light emission luminance characteristics is represented by Y 2 O 3 : Eu, Er.
일반적으로 고휘도로 발광하는 적색발광형광체는 칼라 음극선관, 형광램프 또는 투사형 음극선관등에 사용되며, 지금까지 많은 적색발광형광체가 널리 공지되어 있다. 그중 대표적으로 자외선 여기하에서 밝은 적색발광을 나타내는 유로피움부활 산화이트륨형광체를 들 수 있다.In general, a red light emitting phosphor emitting high luminance is used in a color cathode ray tube, a fluorescent lamp or a projection cathode ray tube, and many red light emitting phosphors are well known. Representatively, europium-activated yttrium fluorescence phosphors exhibiting bright red light emission under ultraviolet excitation.
그러나 상기 형광체는 원료로 사용되는 산화이트륨(Y2O3)의 융점이 높기 때문에 고온에서 장시간 소성을 해야한다.However, since the phosphor has a high melting point of yttrium oxide (Y 2 O 3 ), which is used as a raw material, the phosphor should be baked at a high temperature for a long time.
이와 같이 장기간 소성을 해야하는 경우에는 많은 비용을 초래하게 되므로 저온에서 단시간 소성하여 우수한 발광휘도특성 및 열화특성을 갖는 형광체가 요망되고 있다.In the case where long-term firing is required, a large cost is incurred, and therefore, a phosphor having excellent luminescence brightness and deterioration characteristics by short-firing at low temperature is desired.
예컨대 일본특허공보 소 44-1416호, 소44-1417호에 기재된 바에 의하면, 융제로서 불화리튬(LiF), 붕소(B)를 단독으로 첨가하여 낮은 온도, 짧은 시간의 소정조건에서 형광체를 제조하도록 하고 있다.For example, as described in Japanese Patent Publication Nos. 44-1416 and 44-1417, lithium fluoride (LiF) and boron (B) are added alone as a flux to prepare phosphors at predetermined conditions of low temperature and short time. Doing.
그러나 형광램프, 칼라브라운관 및 투사형 음극선관에 융제를 단독으로 첨가하여 제조된 형광체 입자를 막으로 도포하는 경우에, 결정모양과 입도분포가 불균일하게 되고 그로 인해 자외선 여기에 의한 열화특성이 나빠지게 된다.However, when the phosphor particles prepared by adding flux alone to fluorescent lamps, color-brown tubes and projection-type cathode ray tubes are applied with a film, the crystal shape and particle size distribution become non-uniform, resulting in deterioration characteristics due to UV excitation. .
이와 같이 종래의 적색발광형광체는 형광체층의 온도가 상승되기 때문에 형광체의 열화특성이 나빠지게 되어 발광효율이 저하되는 문제가 있다.As described above, in the conventional red light-emitting phosphor, the temperature of the phosphor layer is increased, so that the deterioration characteristics of the phosphor deteriorate and the luminous efficiency is lowered.
본 발명의 목적은 상기 문제를 감안하여 자외선 여기하에서 고휘도로 발광하고, 소성 온도를 낮추고 소성시간을 단축시킴과 동시에 입도분포가 균일하고 우수한 발광휘도특성 및 열화특성을 갖는 적색발광형광체를 제공하는 것이다.SUMMARY OF THE INVENTION In view of the above problems, an object of the present invention is to provide a red light-emitting phosphor which emits light with high brightness under ultraviolet excitation, lowers the firing temperature, shortens the firing time, and has a uniform particle size distribution and excellent luminous luminance and deterioration characteristics. .
상기 목적을 달성하기 위하여 본 발명은 조성식이 Y2O3: Eu, Er로 표기되는 적색발광형광체에 있어서, Y2O31몰을 기준하여 Eu의 첨가량이 0.0001 내지 0.2몰이고, Er의 첨가량이 0.0001 내지 0.4몰인 것을 특징으로 한다.In order to achieve the above object, the present invention provides a red luminescent phosphor whose composition is represented by Y 2 O 3 : Eu, Er, wherein the amount of Eu is 0.0001 to 0.2 mol based on 1 mol of Y 2 O 3 , and the amount of Er added. It is characterized by being 0.0001-0.4 mol.
더우기 상기 조성식에 있어서 Eu의 첨가량은 0.001 내지 0.07몰이 바람직하고, Er의 첨가량은 0.005 내지 0.2몰이 바람직하다.Furthermore, in the composition formula, the amount of Eu added is preferably 0.001 to 0.07 mol, and the amount of Er added is preferably 0.005 to 0.2 mol.
이하 본 발명의 적색발광형광체의 제조방법은 다음과 같다.Hereinafter, the manufacturing method of the red light-emitting phosphor of the present invention is as follows.
형광체 원료로는, 이트륨원으로서 산화이트륨등의 이트륨화합물, 에르븀원으로서 산화에르븀등의 에르븀화합물, 유로피움원으로서 산화유로피움등의 유로피움화합물을 사용한다. 여기에 융제로서 불화나트륨(NaF), 탄산 나트륨(Na2CO3), 붕산(H3BO3)을 복합적으로 첨가하여 유봉이나 볼밀등의 혼합기로 충분히 혼합한다.As the phosphor raw material, an yttrium compound such as yttrium oxide is used as the yttrium source, an erbium compound such as erbium oxide as the erbium source, and a europium compound such as europium oxide as the europium source. Sodium fluoride (NaF), sodium carbonate (Na 2 CO 3 ), and boric acid (H 3 BO 3 ) are added to this as a flux, and the mixture is sufficiently mixed with a mixer such as a pestle or a ball mill.
그후 상기 혼합물을 석영이나 알루미나 도가니등의 내열성 용기에 넣은 후 대기중에서 1100 내지 1500℃로 1시간 내지 6시간 동안 소성한다.Thereafter, the mixture is placed in a heat-resistant container such as quartz or alumina crucible and then calcined at 1100 to 1500 ° C. for 1 to 6 hours in the air.
소성후 얻어진 형광체의 표면에 잔존해 있는 미반응한 붕소화합물과 기타 융제들을 제거하기 위해 상기에서 얻어진 형광체를 10% 묽은 염산용액으로 세척한 다음 수세, 건조 및 분급등의 공정을 수행하며 조성식이 Y2O3: Eu, Er로 표기되는 적색발광형광체를 얻었다.In order to remove the unreacted boron compound and other fluxes remaining on the surface of the phosphor obtained after firing, the phosphor obtained above is washed with 10% dilute hydrochloric acid solution, and then washed with water, dried and classified. 2 O 3 : A red light-emitting phosphor represented by Eu or Er was obtained.
상기 적색발광형광체의 제조방법에 있어서, 상기 혼합물은 단순한 건식법으로 혼합하는 방법이 있고 일정량의 옥살산용액으로 공침하여 혼합하는 방법이 있으며 이들중 어느 방법을 사용하여도 무방하지만, 형광체의 발광휘도 향상과 균일한 입자형성을 용이하게 하기 위하여 후자의 방법이 유리하다.In the method of manufacturing the red light-emitting phosphor, there is a method of mixing the mixture by a simple dry method, there is a method of coprecipitation and mixing with a certain amount of oxalic acid solution, and any of these may be used, The latter method is advantageous in order to facilitate uniform particle formation.
형광체 원료중 유로피움의 첨가량은 산화이트륨 1몰에 대하여 0.0001 내지 0.2몰이고 발광휘도면에서 0.001 내지 0.07몰이 바람직하고, 에르븀의 첨가량은 산화이트륨 1몰에 대하여 0.0001 내지 0.4몰이고 발광휘도와 발광색도점에 있어서, 0.005 내지 0.2몰이 바람직하다.The amount of europium in the phosphor raw material is preferably 0.0001 to 0.2 mol per mole of yttrium oxide, and 0.001 to 0.07 moles in terms of luminescence luminance, and the amount of erbium is 0.0001 to 0.4 mol per mole of yttrium oxide, and the luminance and emission color In that respect, 0.005-0.2 mol is preferable.
이와 같이 고출력, 고연색화를 실현시키는 형광체로는 발광피크파장이 611nm 부근에 존재하는 형광체가 가장 바람직하다.As such a phosphor that realizes high output and high color rendering, a phosphor having a light emission peak wavelength of around 611 nm is most preferable.
상기 특징을 갖는 본 발명의 적색발광형광체 제조방법을 다음의 실시예를 통하여 상세히 설명한다.The red light-emitting phosphor manufacturing method of the present invention having the above characteristics will be described in detail through the following examples.
[실시예 1]Example 1
적새발광형광체의 원료로As raw material of red light emitting phosphor
Y2O3: 1몰Y 2 O 3 : 1 mole
Eu2O3: 0.03몰Eu 2 O 3 : 0.03 mol
Er2O3: 0.05몰Er 2 O 3 : 0.05 mol
NaF : 0.2몰NaF: 0.2 mol
H3BO3: 0.09몰H 3 BO 3 : 0.09 mol
을 평량하고 이것을 볼밀로 충분히 분쇄하여 혼합하였다. 이와 같이 하여 얻어진 혼합물을 알루미나 도가니에 넣어 대기중에서 1350℃로 2시간 동안 소성하였다. 소성후 얻어진 소성물을 분쇄, 수세 건조등의 처리를 하여 본 발명의 적색발광형광체를 얻었다.Was weighed and mixed with a fine ball mill. The mixture thus obtained was placed in an alumina crucible and calcined at 1350 ° C. for 2 hours in air. The fired product obtained after firing was subjected to treatment such as pulverization and washing with water to obtain a red light-emitting phosphor of the present invention.
[실시예 2]Example 2
적색발광형광체의 원료로As a raw material of red light emitting phosphor
Y2O3: 1몰Y 2 O 3 : 1 mole
Eu2O3: 0.03몰Eu 2 O 3 : 0.03 mol
Er2O3: 0.05몰Er 2 O 3 : 0.05 mol
NaF : 0.05몰NaF: 0.05 mol
Na2CO3: 0.2몰Na 2 CO 3 : 0.2 mol
H3BO3: 0.09몰H 3 BO 3 : 0.09 mol
을 평량하여 실시예 1과 동일한 방법으로 소성, 분쇄, 수쇄 및 건조등의 처리를 하여 본 발명의 적색발광형광체를 얻었다.Was obtained by the same method as in Example 1, and then fired, pulverized, crushed and dried to obtain a red light-emitting phosphor of the present invention.
이와 같이 하여 얻어진 본 발명의 적색형광체는 254nm의 자외선 여기하에서 밝은 적색을 발광하고, 611nm부근에서 발광피크파장을 나타내고 있으며, 발광색도점은 X좌표가 0.6432이고 Y좌표는 0.3490으로 종래의 형광체의 발광색도점과 일치하는 것으로 판명되었다.The red phosphor of the present invention thus obtained emits bright red under 254 nm ultraviolet excitation and exhibits a peak emission wavelength near 611 nm. The emission chromaticity point is 0.6432 in the X coordinate and 0.3490 in the Y coordinate. It turned out to be consistent with the dot.
또한 제 1 도는 본 발명의 적색발광형광체와 종래의 적색발광형광체에 대하여 500시간 동안 여기했을때 여기시간 변화에 대한 발광휘도 변화를 나타낸 그래프로서, A는 종래의 형광체이고 B는 본 발명의 형광체이며, 본 발명의 적색발광형광체의 발광휘도는 종래의 형광체의 발광 휘도보다 3 내지 7% 향상되었다.1 is a graph showing the change in the luminance of light emission with respect to the change in excitation time when excited for 500 hours with respect to the red light emitting phosphor of the present invention and the conventional red light emitting phosphor, where A is a conventional phosphor and B is a phosphor of the present invention. The light emission luminance of the red light-emitting phosphor of the present invention is improved by 3 to 7% over that of the conventional phosphor.
이상에서 설명한 바와 같이, 본 발명에 의하면 조성식이 Y2O3: Eu, Er로 표기되는 형광체인 것으로, 자외선 여기하에서 고휘도로 발광하고 입도 분포가 균일하고 우수한 발광휘도특성과 열화특성을 갖는 적색발광형광체를 실현할 수 있었다.As described above, according to the present invention, the composition is a phosphor represented by Y 2 O 3 : Eu, Er, and emits red light with high luminance under ultraviolet excitation, uniform particle size distribution, and excellent luminous luminance and deterioration characteristics. The phosphor could be realized.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019890019192A KR930003702B1 (en) | 1989-12-22 | 1989-12-22 | Production of red luminous fluorescent material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019890019192A KR930003702B1 (en) | 1989-12-22 | 1989-12-22 | Production of red luminous fluorescent material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR910012163A KR910012163A (en) | 1991-08-07 |
| KR930003702B1 true KR930003702B1 (en) | 1993-05-08 |
Family
ID=19293365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019890019192A KR930003702B1 (en) | 1989-12-22 | 1989-12-22 | Production of red luminous fluorescent material |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR930003702B1 (en) |
-
1989
- 1989-12-22 KR KR1019890019192A patent/KR930003702B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| KR910012163A (en) | 1991-08-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| BRPI0517575B1 (en) | luminescent material | |
| CN102120931A (en) | Red fluorophor and preparation method thereof | |
| JP2005206841A5 (en) | ||
| CN111154488A (en) | Terbium-doped germanate green fluorescent powder for white light LED and preparation method thereof | |
| CN101486910B (en) | Green phosphor for white light LED and preparation thereof | |
| JP2001172626A (en) | Display and light emitting device | |
| JP2005179498A (en) | Red phosphor material, white light-emitting diode using the same, and illuminator using the white light-emitting diode | |
| JP5700306B2 (en) | Green light emitting material and preparation method thereof | |
| CN100415849C (en) | Rare earth red fluorescent powder and preparing method thereof | |
| KR930003702B1 (en) | Production of red luminous fluorescent material | |
| KR100539190B1 (en) | Phosphor for use with Low Speed Electron Beams | |
| JP2002003837A (en) | Phosphor and fluorescent lamp obtained by using the same | |
| EP1253181A2 (en) | Phosphors and fluorescent lamps comprising the phosphors | |
| CN100519694C (en) | Y3(Al, ga)5O12rare earth fluorescent powder | |
| KR930003975B1 (en) | Fluorescent material and fluorescent lamp used there | |
| KR101093979B1 (en) | High brightness green-emitting phosphor | |
| CN115261017B (en) | Blue light luminescent material capable of being excited by purple light and preparation method thereof | |
| KR930005691B1 (en) | Red-luminous phosphor | |
| JPH0345690A (en) | Phosphor and cathode ray tube made by using it | |
| JP3095220B2 (en) | New green light-emitting phosphor | |
| KR930012013B1 (en) | Green luminescent fluorescent containing boric acid-aluminum and fluorescent lamp use thereof | |
| CN108130080B (en) | Ce3+Activated Ca7(PO4)2(SiO4)2Fluorescent powder and preparation method thereof | |
| KR910010102B1 (en) | The fluorescent material and the cathode ray tube using the same | |
| KR910005818B1 (en) | Manufacturing method of a fluorescent screen | |
| CN109097048B (en) | Silicate blue fluorescent powder for white light LED and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| G160 | Decision to publish patent application | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20000429 Year of fee payment: 8 |
|
| LAPS | Lapse due to unpaid annual fee |