KR910004677B1 - Orange color fluorescent substance - Google Patents
Orange color fluorescent substance Download PDFInfo
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- KR910004677B1 KR910004677B1 KR1019880004267A KR880004267A KR910004677B1 KR 910004677 B1 KR910004677 B1 KR 910004677B1 KR 1019880004267 A KR1019880004267 A KR 1019880004267A KR 880004267 A KR880004267 A KR 880004267A KR 910004677 B1 KR910004677 B1 KR 910004677B1
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- 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
- C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J29/00—Details of cathode-ray tubes or of electron-beam tubes of the types covered by group H01J31/00
- H01J29/02—Electrodes; Screens; Mounting, supporting, spacing or insulating thereof
- H01J29/10—Screens on or from which an image or pattern is formed, picked up, converted or stored
- H01J29/18—Luminescent screens
- H01J29/20—Luminescent screens characterised by the luminescent material
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Abstract
Description
도면은 망간(Mn) 함량변화에 따른 CIE 색좌표 X 값의 변화를 나타낸 그래프이다.The figure is a graph showing the change of the CIE color coordinate X value according to the change of manganese (Mn) content.
본 발명은 황화물 형광체에 관한 것으로, 특히 디스플레이용 음극선관에 적합한 Mn 부활 등색발광 황하물 형광체에 관한 것이다.The present invention relates to a sulfide phosphor, and more particularly, to an Mn-activated isochromescent sulfide phosphor suitable for a cathode ray tube for display.
최근 정보화 사회에 즈음하여 각종 정보처리용 단말기, 수치제어용기기, 전산설계(CAD),교육, 사무합리화 분야에서 디스플레이용 음극선관의 수요가 급증하고 있다. 현재 사용되고 있는 대부분의 디스플레이용 음극선관은 녹색, 백색(paper white) 및 황등색으로 디스플레이 되고 있으나, 녹색은 장시간 바라볼 경우 눈에 많은 피로감을 주게되어, 최근에는 등색과 백색이 선호되고 있다.Recently, the demand for display cathode ray tubes is increasing rapidly in the field of information society, various information processing terminals, numerical control equipment, computer design, education, and office rationalization. Most of the cathode ray tubes for displays currently used are displayed in green, paper white, and yellow orange color. However, green color gives a lot of fatigue to eyes when viewed for a long time, and orange and white have recently been preferred.
여기서 종래 사용되고 있는 오렌지 및 등색발광을 하는 형광체의 종류 및 그 잔광특성을 표 1에서 기재하였다.Here, Table 1 shows the types of phosphors used for orange and orange light emission and their afterglow characteristics.
[표 1]TABLE 1
오렌지 및 등색형광체Orange and orange phosphor
상기 표 1에 도기된 바와같이 디스플레이용 등색형광체로서 가장 많이 사용되고 있는 3CD3(PO4)2· CdCl2:Mn은 카드뮴(Cd)을 함유하고 있어서 폐기물 처리에 엄격한 공해방지 시스템을 필요로 하기 때문에 실용상 제한이 따르고 있고, 또한 Zn2Sio4:Mn, As와 Zn3(PO4)2:Mn을 혼합한 형광체는 여기정지후 소광(Decay)하는 과정에서 발광색이 변화하게 되고, 색포화가 낮으며, 형성된 형광막이 불균일하게 되는 결점이 있다.As shown in Table 1, since 3CD 3 (PO 4 ) 2 · CdCl 2 : Mn, which is most commonly used as an orange phosphor for displays, contains cadmium (Cd), it requires a strict pollution prevention system for waste disposal. In practical use, the phosphor is mixed with Zn 2 Sio 4 : Mn, As and Zn 3 (PO 4 ) 2 : Mn, the emission color changes during decay after excitation and color saturation It is low and has the disadvantage that the formed fluorescent film becomes nonuniform.
일반적으로 CaS를 모체로 하는 형광체는 부활제의 종류에 따라 가시광선 및 적외선 영역까지 발광색을 다양하게 변화시킬 수 있고, 또 모체를 안정화시켜 발광색을 조절할 수도 있는바, 예컨대 일본특허공개 소 57-128772호에 의하면 Ca.T-xMgxS(0.05≤x≤0.95)에서의 Cu 부활 적색형광체는 최대(peak)가 414-441nm, Eu 부활 적색형광체는 최대(peak)가 625-655nm 범위로 변화하는 것을 나타내고 있어, 상당히 넓은 범위의 색조절이 가능하나, 그러나 x〈0.05 혹은 x〉0.95 조성범위에서는 모체혼정이 결정구조상 불안정하여 제어성이 나쁘기 때문에 재현성에 문제가 있음을 지적하고 있다.In general, phosphors based on CaS can vary the emission color to visible and infrared regions according to the type of activator, and can also stabilize the matrix to control the emission color. For example, Japanese Patent Application Laid-Open No. 57-128772 The Cu-activated red phosphor at Ca.T-xMgxS (0.05≤x≤0.95) showed a peak of 414-441 nm, while the Eu-activated red phosphor had a peak of 625-655 nm. Although it is possible to control a wide range of colors, however, it is pointed out that the composition of x <0.05 or x> 0.95 has a problem in reproducibility because the mother mixed crystals are unstable in crystal structure and have poor controllability.
한편 일본특허공고 소 62-23032호에 의하면, x〈0.05 범위에서도 Cu 부활 청색형광체, Eu 부활 적색 형광체의 안정성 및 재현성이 충분하고 음극선 자극 형광체로서의 실용성이 우수함을 밝힌바 있다.On the other hand, according to Japanese Patent Publication No. 62-23032, the stability and reproducibility of Cu-activated blue phosphor and Eu-activated red phosphor are sufficient even in the range of x <0.05, and it is excellent in practicality as cathode ray-stimulated phosphor.
그러나 본 발명자가 보다 상세히 실험하여 검토한바에 의하면, 0.011〈x0.05 조성범위에서 상기 예와는 별도로 Mn 부활 등색형광체가 얻어지는데, 이는 결정구조적으로 안정하고, 음극선 자극에 대해 고효율로 등색발광하며, 알칼리금속과 할라이드(halide)원소를 첨가시킴에 의해 발광효율이 보다 항상됨을 확인하였다.However, according to the present inventors' experiments, the Mn activating isophore is obtained separately from the above example in the 0.011 <x0.05 composition range, which is crystallographically stable and isochromatically emitted at high efficiency with respect to cathode stimulation. By adding alkali metal and halide element, it was confirmed that the luminous efficiency is more always.
본 발명에 의한 Ca1-xMgxS; Mn,A(0.01'x<0.05, A는 Na 또는 할라이드원소) 등색발광 형광체는 Cd을 포함하고 있지 않기 때문에 공해문제를 고려할 필요가 없으며, 단일조성이기 때문에 혼합형광체에서 나타나는 소광 기간의 발광색변화 또는 형광막의 불균일한 점등을 근원적으로 방지한 실용상 우수한 형광체가 얻어져 본 발명에 이르게 되었다.Ca 1- xMgxS according to the present invention; Since Mn, A (0.01'x <0.05, A is Na or halide element) isoluminescent phosphors do not contain Cd, there is no need to consider the pollution problem, and since it is a single composition, the emission color change of the extinction period appearing in the mixed phosphor or The practically excellent fluorescent substance which prevented the nonuniform lighting of a fluorescent film fundamentally was obtained and led to this invention.
이에 본 발명을 실시예를 들어 보다 상세하게 설명한다.Thus, the present invention will be described in more detail with reference to Examples.
[실시예]EXAMPLE
원료물질로서 CaCO3, MgSO4, MnSo4, Na2CO3, NH4CI을 사용하는바, 먼저 CaCO31mol 분말을 순수 2000ml에 넣고 교반기로 교반하여 골고루 분산되게 한 다음, MgSO4. 4H2O 0.5mol을 100ml에 녹인 용액을 상기 CaCO3분산용액에 첨가한다.CaCO 3 , MgSO 4 , MnSo 4 , Na 2 CO 3 , NH 4 CI are used as raw materials. First, 1 mol of CaCO 3 powder is added to 2000 ml of pure water, and stirred with a stirrer to disperse evenly, followed by MgSO 4 . A solution of 0.5 mol of 4H 2 O in 100 ml is added to the CaCO 3 dispersion.
이어 NH4OH를 피팻으로 한방울씩 적하하여 침전시키면 갈색침전이 점점 생성되는바, NH4OH를 계속 첨가하여도 더 이상 색깔이 변하지 않게되면(이때까지의 NH4Oh의 적하량은 약 5-10ml가 된다) 이 침전물을 여과하여 수분리한 다음, 이 갈색 침전물을 110℃의 건조기로 12시간동안 건조시키고 나서 #400메쉬 체분리하여 분산성이 좋은 분말로 만든다.Subsequently, when NH 4 OH is added dropwise with a pipet and precipitated, brown precipitates are gradually formed. If NH 4 OH is added continuously, the color does not change any more (the amount of NH 4 Oh added until this time is about 5- The precipitate was filtered and separated by water, and the brown precipitate was dried for 12 hours using a dryer at 110 ° C., and then separated into 400 mesh sieves to obtain a highly dispersible powder.
다음 MgSO₄1.5mol%, NaCO₃2mol%,NH₄Cl 0.5mol% 및 10wt%을 볼밀로써 건식 혼합하는바, 이때 상기 갈색 침전물로부터 얻은 원료분말을 가하여 30분동안 혼합한 뒤, #100메쉬 체분리하여 얻어진 분말을 알루미늄 도가니에 넣고 뚜껑을 덮은 다음, 통상의 가열로 1200℃로 4시간동안 소성하여 본 발명 Ca0.986Mg0.014S: Mn(0.8mol%), Cl(2.0mol%)을 만든다.Next, dry mix MgSO₄1.5mol%, NaCO₃2mol%, NH₄Cl 0.5mol% and 10wt% with a ball mill. At this time, add the raw powder obtained from the brown precipitate, mix for 30 minutes, and then remove the powder obtained by # 100 mesh sieve separation. Placed in an aluminum crucible and covered with a lid, it was calcined at 1200 DEG C for 4 hours by ordinary heating to make the present invention Ca0.986Mg0.014S: Mn (0.8 mol%), Cl (2.0 mol%).
이때 부활제 Mn의 함량을 0.1mol%에서 2.0mol%까지 변화시켜 얻어진 형광체의 CIE 색좌표 X 값의 변화를 첨부도면에 나타내었다.In this case, the change in the CIE color coordinate X value of the phosphor obtained by changing the content of the activator Mn from 0.1 mol% to 2.0 mol% is shown in the accompanying drawings.
도면에서 볼수 있는 바와 같이 Mn함량이 증가할수록 제한된 범위내에서 CIE 색좌표 X 값이 증가함을 알수 있는바, 색좌표 X가 증가하면 발광색이 등색에서 오렌지쪽으로 이동하게되어 시감효율을 고려할 때 휘도가 저하된다. 따라서 최적휘도를 얻기 위해서는 0.8mol% - 1.6mol% 범위로 Mn을 첨가하는 것이 바람직하다.As can be seen from the figure, it can be seen that as the Mn content increases, the CIE color coordinate X value increases within a limited range. As the color coordinate X increases, the emission color shifts from orange to orange, and the luminance decreases when considering luminous efficiency. . Therefore, in order to obtain the optimum luminance, it is preferable to add Mn in the range of 0.8 mol%-1.6 mol%.
모체조성비 x=0.03인 Ca0.97Mg0.03S : Mn(0.8mol%), Cl(2.0mol%)의 등색형광체는 CIE 색좌표(X=0.555, Y=0.455)가 3Cd(Po0)5CdCl2: Mn과 거의 일치하며 휘도는 약 10%더 높게되고, 또 본 발명에 의한 상기 등색발광 형광체는 Cd을 포함하고 있지않기 때문에 공해문제를 일으키지 않는 이점이 있다.Ca 0.97 Mg 0.03 S: Mn (0.8mol%), Cl (2.0mol%) isochromescent phosphor with mother composition ratio x = 0.03 has 3Cd (Po0) 5 CdCl 2 : Mn in CIE color coordinate (X = 0.555, Y = 0.455) The brightness is approximately 10% higher, and the orange light emitting phosphor according to the present invention does not contain Cd, and thus has no advantage of causing pollution.
그런데 알칼리토류 황화물 형광체에 있어서 실용상의 가장 큰 제약인 수분에 의해 분해되는 성질도 CaS 단일 모체에 비해 우수한 내수성을 나타내어 실용상에 문제가 생기지 않는바, 특히 디스플레이용 음극선관의 형광막 형성법으로 알려져 있는 중력침강법에 의해 형광막을 형성시켜도 본 발명에 의한 황화물 형광체는 균일한 막상태를 나타내었으며 음극선이 여기서 양호하게 등색발광함을 확인하였다.However, the property decomposed by moisture, which is the biggest practical limitation in alkaline earth sulfide phosphors, also shows excellent water resistance compared to a single CaS matrix, which does not cause practical problems. Especially, it is known as a fluorescent film forming method of cathode ray tubes for displays. Even when the fluorescent film was formed by gravity sedimentation, the sulfide phosphor according to the present invention showed a uniform film state, and it was confirmed that the cathode ray emitted satisfactorily here.
또한 2가지 이상의 형광체를 혼합한 형광체에서는 일반적으로 여기정지후 소광하는 동안 각 성분형광체의 잔광시간 차이로 인하여 발광색이 변화하게되나, 본 발명에 의한 황화물 형광체는 단일조성이기 때문에 음극선 여기정지후 소광하는 과정에서 발광색이 변화하지 않는 이점이 있다.In addition, in the phosphors in which two or more phosphors are mixed, the emission color is generally changed due to the difference in the afterglow time of each component phosphor during quenching after excitation. Since the sulfide phosphors according to the present invention have a single composition, There is an advantage that the emission color does not change in the process.
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KR1019880004267A KR910004677B1 (en) | 1988-04-14 | 1988-04-14 | Orange color fluorescent substance |
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KR910004677B1 true KR910004677B1 (en) | 1991-07-09 |
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