KR930005685B1 - Low-velocity electron excited phosphor - Google Patents
Low-velocity electron excited phosphor Download PDFInfo
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- KR930005685B1 KR930005685B1 KR1019890020443A KR890020443A KR930005685B1 KR 930005685 B1 KR930005685 B1 KR 930005685B1 KR 1019890020443 A KR1019890020443 A KR 1019890020443A KR 890020443 A KR890020443 A KR 890020443A KR 930005685 B1 KR930005685 B1 KR 930005685B1
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Abstract
Description
제1도는 본 발명과 종래의 방법에 의해 제조된 형광체의 발광 스펙트럼을 나타낸 그래프.1 is a graph showing emission spectra of phosphors produced by the present invention and conventional methods.
제2도는 슬러리 조합 후의 도전성 물질의 부착상태를 확인한 전자현미경 사진으로서, 제2a도는 본 발명에 의한 경우, 제2b도는 종래의 방법에 의한 경우의 것.Figure 2 is an electron micrograph confirming the adhesion state of the conductive material after the slurry combination, Figure 2a when the present invention, Figure 2b when the conventional method.
본 발명은 저속 전자선 여기 형광체의 제조방법에 관한 것으로서, 더욱 상세하게는 형광표시관(VFD)에 사용하는 적색, 청색 형광체에, 산화 인듐(In 203), 산화텅스텐(WO3), 이산화티탄(TiO2)등의 도전성 물질을 부착시키는 것을 특징으로 하는 저속 전자선 여기 형광체의 제조 방법에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a low speed electron beam excited phosphor, and more particularly, to red and blue phosphors used in fluorescent display tubes (VFD), indium oxide (In 203), tungsten oxide (WO 3), and titanium dioxide (TiO 2). It relates to a method for producing a low speed electron beam-excited phosphor characterized by attaching a conductive material such as).
형광표시관 등의 형광면에 피착되는 형광체는 전자 비임등의 작용에 의해 그 표면에서 발광현상을 일으킨다.Phosphors deposited on a fluorescent surface such as a fluorescent display tube emit light on the surface by the action of an electron beam or the like.
형광체 자체는 고 저항이기 때문에, 이를 발광시키기 위하여는 매우 높은(통상 10KV 이상)이 인가되어야만 한다.Since the phosphor itself has a high resistance, very high (usually 10 KV or more) must be applied to emit light.
그러나, 형광체에 도전성 물질을 부착시켜 주면 표면에서의 전류의 흐름이 원활하게 되어 발광 효율이 높아지게 되고, 또한 낮은 전압에서도 쉽게 여기될 수 있게 된다.However, when the conductive material is attached to the phosphor, the current flows smoothly on the surface, resulting in high luminous efficiency and easy excitation even at low voltage.
종래에, 형광표시관에 사용하는 적색, 청색 형광체에 도전성 물질을 부착시키는 방법으로는, 일정량의 형광체와 도전성 물질을 단순히 혼합하여 그대로 부착시키는 방법과, 일정량의 형광체와 도전성 물질을 폴리비닐알콜(P.V.A)을 바인더로 하여 부착시키는 방법 등이 알려져 있다.Conventionally, a method of attaching a conductive material to red and blue phosphors used in a fluorescent display tube includes a method of simply mixing a predetermined amount of phosphor and a conductive material as it is, and attaching a predetermined amount of phosphor and a conductive material to polyvinyl alcohol ( PVA) is used as a binder and a method is attached.
한편, 이러한 형광체를 형광표시관의 형광면에 도포하기 위하여는, 형광체를 슬러리로 제조하고 니트로 셀룰로우즈, 메틸 셀룰로우즈 및 고점도 유기용제 등을 첨가하는 데, 이 슬러리는 그 자체가 매우 높은 점도를 갖기 때문에, 형광체에 혼합되어 그 표면에 붙어 있는 도전성 물질이 형광체의 형광면에의 도포과정에서 쉽게 이탈되어 따로 응집하기 때문에 형광표시관 제조 후 형광체에 도전성 물질이 없어 발광강도가 상당히 저하하는 문제가 발생한다.On the other hand, in order to apply such a phosphor on the fluorescent surface of the fluorescent display tube, the phosphor is prepared as a slurry and nitro cellulose, methyl cellulose and a high viscosity organic solvent are added, which slurry itself has a very high viscosity. Since the conductive material admixed with the phosphor and adhered to the surface of the phosphor easily detaches and agglomerates separately during the application of the phosphor to the fluorescent surface, there is no conductive material in the phosphor after the manufacture of the fluorescent display tube, so that the emission intensity is considerably reduced. Occurs.
즉, 형광체에 도전성물질이 부착되어 있는 경우에는 저전압(통상 30V미만)에서도 형광체가 발광하지만, 도전성 물질이 이탈되는 경우에는 형광체 자체의 높은 저항으로 인해 저 전압에서 잘 발광되지 않는 단점이 있다.That is, when the conductive material is attached to the phosphor, the phosphor emits light even at low voltage (typically less than 30 V). However, when the conductive material is separated, the phosphor does not emit light well at low voltage due to the high resistance of the phosphor itself.
한편, 형광표시관(VFD)용 형광체에서 요구되는 특성은 다음과 같다.On the other hand, the characteristics required for the fluorescent substance for fluorescent display tubes (VFD) are as follows.
1) 형광체 표면에서 대전이 생기지 않도록 충분한 도전성을 갖고 있을 것.1) It should have sufficient conductivity to prevent electric charge from occurring on the surface of phosphor.
2) 형광체 발광시키는 데에 소요되는 전압이 본질적으로 낮을 것.2) The voltage required to emit phosphor is essentially low.
3) 저속 전자선 여기에서의 발광 효율이 양호하고, 휘도저하가 없을 것.3) Good luminous efficiency in low-speed electron beam excitation and no luminance deterioration.
4) 저속 전자선 여기에서의 수명이 길것 등이 요구된다.4) Long lifespan in low speed electron beam excitation is required.
본 발명은, 상기한 바와같은 종래 기술의 문제점을 해결하고, 특히 형광 표시관용 형광체로서 사용되기에 적합한 형광체의 제조방법을 제공하기 위하여 인출된 것으로서, 형광표시관의 형광면에 도포되는 형광체를 제조함에 있어, 형광체의 표면에 도전성물질을 부착시켜주는 과정에서, 부착 강도가 낮은 종래의 접착 바인더인 폴리비닐알콜이나 니트로 셀룰로오스를 사용하는 대신에, 종래 방법에서 보다 더욱 높은 부착 강도를 갖는 바인더인 카제인 및 젤라틴의 코아세베이션 방법을 이용하여 도전성 물질을 부착시킴으로써 낮은 전압하에서도 발광을 시킬 수 있는 형광체를 제조하는 데 그 목적이 있다.The present invention is drawn to solve the problems of the prior art as described above, and to provide a method for producing a phosphor suitable for use as a phosphor for a fluorescent display tube, and in particular, to produce a phosphor coated on a fluorescent surface of a fluorescent display tube. In the process of attaching the conductive material to the surface of the phosphor, instead of using polyvinyl alcohol or nitro cellulose, which is a conventional adhesive binder having a low adhesive strength, casein, which is a binder having a higher adhesive strength than the conventional method, and The purpose of the present invention is to prepare a phosphor capable of emitting light even under low voltage by attaching a conductive material by using a co-evaluation method of gelatin.
상기한 바와같은 목적을 달성하기 위하여, 본 발명은 하기와 같은 방법을 제공한다.In order to achieve the object as described above, the present invention provides a method as follows.
즉, 도전성물질을 적당량의 카제인에 분산시킨 액과, 형광체를 분산시킨 형광체 분산액, 그리고 젤라틴 수용액을 각각 제조한 후, 상기한 형광체 분산액에, 상기한 도전성 물질 분산액을 첨가하여 30분간 분산시킨 후, 다시 이 액에 젤라틴 수용액을 첨가하여 30분간 분산시키고, 5% 초산을 사용하여 전체액의 pH를 7로 조정한 후 냉각시키고, 포름알데히드를 더욱 첨가하여 최종 분산시키고 세정한 후 물을 분리, 건조시키는 것을 특징으로 하는 저속 전자선 여기 형광체의 제조방법을 제공한다.That is, after preparing a liquid in which the conductive material is dispersed in a suitable amount of casein, a phosphor dispersion in which the phosphor is dispersed, and a gelatin aqueous solution, respectively, the above-mentioned conductive material dispersion is added to the above-mentioned phosphor dispersion and dispersed for 30 minutes. Again, gelatin aqueous solution was added to this solution and dispersed for 30 minutes. The pH of the whole solution was adjusted to 7 with 5% acetic acid and then cooled. After further addition of formaldehyde, the final dispersion and washing were carried out to separate and dry the water. Provided is a method for producing a low speed electron beam excited phosphor.
[실시예 1]Example 1
입자크기가 0.1-0.5μm인 산화인듐(In203,99.99%)을 준비하여, 형광체[(Zn, cd) S : Ag,Cl 및 Zn S : Zn)양에 7%를 취하고, 동시에 카제인을 형광체 양에 3%를 위하여 유리용기에 넣고 잘 분산시켜 분산액 A를 얻었다. 이와 별도로 형광체를 300g 준비하여 비이커에 넣고 물500㎖를 첨가하여 잘 분산시켜 형광체 분산액을 얻었다.Indium oxide (In203,99.99%) having a particle size of 0.1-0.5 μm was prepared, taking 7% of the amount of phosphors ((Zn, cd) S: Ag, Cl and Zn S: Zn) and simultaneously adding casein to the amount of phosphor. To 3% in a glass container and dispersed well to obtain a dispersion A. Separately, 300 g of a phosphor was prepared, and the mixture was placed in a beaker and 500 ml of water was added to disperse well to obtain a phosphor dispersion.
별개의 용기에 젤라틴을 형광체 양의 3%를 취하여 온도 40-60℃ 순수에 용해하여 젤라틴 수용액을 얻었다.3% of the amount of the phosphor was taken in a separate container and dissolved in pure water at a temperature of 40-60 ° C. to obtain an aqueous solution of gelatin.
상기한 형광체 분산액에, 도전성 물질이 분산되어 있는 분산액 A를 주입하고 30분간 더욱 분산 시킨다. 다음에 이 분산액에 젤라틴 수용액을 더욱 첨가하고 30분간 분산시킨 후, 5%초산으로 pH를 조절하여 7이 되게 한 후, 5℃로 냉각시킨다. 냉각이 끝나면 포름 알데히드 3㎖를 첨가한 후 30분간 계속 분산시킨 후 방치한다. 세정을 실시하고 물을 분리, 100℃에서 12시간 건조시켜 도전성 물질이 부착된 형광체를 얻었다.The above-mentioned phosphor dispersion is injected with dispersion A in which the conductive material is dispersed, and further dispersed for 30 minutes. Next, the aqueous solution of gelatin was further added to the dispersion, dispersed for 30 minutes, and then adjusted to pH 7 with 5% acetic acid, followed by cooling to 5 ° C. After cooling, add 3 ml of formaldehyde, and continue to disperse for 30 minutes, then leave. After washing, water was separated and dried at 100 ° C. for 12 hours to obtain a phosphor with a conductive substance.
상기한 바와같은 방법으로 도전성 물질이 부착되어 얻어진 본 발명의 형광체와, 종래의 방법으로 도전성 물질을 부착시킨 형광체의 발광 스펙트럼을 측정한 바, 제1도와 같았다.The emission spectrum of the phosphor of the present invention obtained by adhering the conductive material to the above-described method and the phosphor to which the conductive material was adhered by the conventional method was measured.
제1도로부터 알 수있는 바와같이, 본 발명에 의한 형광체의 발광 스팩트럼(a)은 종래 방법에 의한 형광체의 발광 스펙트럼(b)보다 강도가 20-40% 높음을 알 수 있다.As can be seen from FIG. 1, it can be seen that the emission spectrum (a) of the phosphor according to the present invention is 20-40% higher in intensity than the emission spectrum (b) of the phosphor by the conventional method.
또한, 슬러리 조합 후의 도전성 물질의 부착상태에 있어서도 본 발명의 형광체는 형광체 표면 전반에 걸쳐서 도전성 물질이 골고루 부착되어 있음에 대하여 (제2a도) 종래방법에 의한 것은 도전성 물질이 서로 응집되어 있음을 알 수 있다.(제2b도)In addition, even in the adhered state of the conductive material after the slurry combination, the fluorescent material of the present invention shows that the conductive material is uniformly attached all over the surface of the phosphor (FIG. 2a). (Figure 2b)
도전성 물질의 탈락율을 계산하여 본 바, 종래의 방법에 있어서는 약 60%에 달하였던 것이 본 발명의 방법에 있어서는 0.5% 이하로 현저하게 감소되었음이 확인되었다.From the calculation of the dropout rate of the conductive material, it was confirmed that what was about 60% in the conventional method was significantly reduced to 0.5% or less in the method of the present invention.
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