KR920005960B1 - Red-fluorescent substance - Google Patents
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- KR920005960B1 KR920005960B1 KR1019880017524A KR880017524A KR920005960B1 KR 920005960 B1 KR920005960 B1 KR 920005960B1 KR 1019880017524 A KR1019880017524 A KR 1019880017524A KR 880017524 A KR880017524 A KR 880017524A KR 920005960 B1 KR920005960 B1 KR 920005960B1
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Abstract
Description
제1도는 본 발명에 따른 안료를 사용할때의 안료 반사율의 특성을 예시한 그래프이고,1 is a graph illustrating the characteristics of the pigment reflectance when using the pigment according to the present invention,
제2도는 본 발명에 따른 형광체의 반사율의 특성을 보인 그래프이다.2 is a graph showing the characteristics of the reflectance of the phosphor according to the present invention.
본 발명은 브라운관 형광면 제조시 사용되는 적색안료 부착형광체에 관한 것으로서, 종래의 사용안료인 적색산화철(α-Fe2O3)이나 카드뮴설퍼 설레나이드(Cds.nSeS)가 아닌 새로운 안료를 이용하여 제조한 적색 안료부착 형광체에 관한 것이다.The present invention relates to a red pigment-attached phosphor used in the manufacture of fluorescent tubes, and is prepared using a new pigment other than conventional red pigment iron oxide (α-Fe 2 O 3 ) or cadmium sulfenuride (Cds.nSeS). It relates to one red pigmented phosphor.
칼라브라운관의 형광면 제조시 사용되는 적색, 청색, 녹색 형광체는 각기 적색안료, 청색안료, 녹색안료를 입자표면에 피복시키면, 이들 안료의 필터(filter)효과에 의해서 각각 형광체의 발광 스펙트럼중 원하지 않은 파장의 빛을 흡수하거나 감소시켜 발광색이 선명하게 되고, 이를 이용하여 형광면 제조시 안료에 의한 외광의 흡수 효과로 영상의 콘트라스트가 비약적으로 향상되게 된다.Red, blue, and green phosphors used in the manufacture of fluorescent surfaces of color CRTs are coated with red pigments, blue pigments, and green pigments, respectively, on the surface of particles. The light emission color is made clear by absorbing or reducing light, and the contrast of the image is dramatically improved by absorbing external light by the pigment in manufacturing a fluorescent surface using the light.
따라서, 형광체 입자표면에 안료를 피복시키게 되는바, 종래에는 적색형광체의 경우 카드뮴 설퍼 설레나이드(Cds.nSeS)와 적색산화철(α-Fe2O3)이, 청색형광체의 경우 코발트 블루(CoO.nAl2O3)나 군청(3NaAl. SiO2, Na2S2)이, 녹색형광체의 경우에는 크롬 산화철(Cr2O3)이 대표적으로 사용되어 왔다.Therefore, the pigment is coated on the surface of the phosphor particle. Conventionally, cadmium sulfonide (Cds.nSeS) and red iron oxide (α-Fe 2 O 3 ) are used for the red phosphor and cobalt blue (CoO. nAl 2 O 3 ) and ultramarine (3NaAl.SiO 2 , Na 2 S 2 ) have been typically used in the case of green phosphors (chromium iron oxide (Cr 2 O 3 )).
특히 적색형광체의 경우 초기에는 카드뮴설퍼설레나이드(Cds.nSeS)가 사용되었으나 최근에는 카드뮴의 환경오염문제로 분광 반사율면에서 약간 불리한 적색산화철이 카드뮴 설퍼 셀레나이드를 대신하여 사용되고 있다.Particularly, in the case of the red phosphor, cadmium sulfersulenide (Cds.nSeS) was initially used, but recently, red iron oxide, which is slightly disadvantageous in terms of spectral reflectance due to environmental pollution of cadmium, is used in place of cadmium sulfur selenide.
이외에는 연단(: pb3O4) 및 카드뮴 수은적(Cds+HgS) 등의 사용도 검토되고 있는 등 적색 안료의 다양화가 이루어지고 있다.In addition, the use of podium (: pb 3 O 4 ) and cadmium mercury red (Cds + HgS) and the like have also been examined.
한편, 브라운관에 사용되는 안료로서는 분광 반사율이 양호할 것, 카드뮴, 납, 수은 등의 유해물질을 포함하지 말아야 할것, 슬러리 조합시 비수용성이어야할 것, 내열성에 있어서 브라운관의 베이킹 공정에서 용해, 변질, 변색되지 말아야 할것등의 특성에 필요하다.On the other hand, pigments used in CRT should have good spectral reflectance, should not contain harmful substances such as cadmium, lead, mercury, etc., should be water-insoluble during slurry combination, and dissolve and deteriorate in CRT baking process in heat resistance. It is necessary for characteristics such as not to discolor.
그러나 앞서 기술한 바와 같이 적색안료의 경우 Cds.nSeS나 Pb3O4등이 적색산화철(α-Fe2O3)을 제외하고는 모두 성분상 유해물질을 포함하고 있어 실용적으로 이용할 수 없는 상태이다.However, as described above, in the case of red pigment, Cds.nSeS or Pb 3 O 4 is not available for practical use because it contains harmful substances in all except red iron oxide (α-Fe 2 O 3 ). .
따라서, 본 발명에서는 적색 산화철 이외에 반사율이 양호하고, 유해물질을 포함하지 않으며, 내열성이 강한 새로운 안료를 즉, ZnO.Fe2O3안료를 개발하여 이를 이용해 제조한 적색안료 부착 형광체를 제공함을 목적으로 한다.Accordingly, the present invention provides a pigment having a red pigment prepared by using a new pigment, ie, ZnO.Fe 2 O 3 pigment, which has a good reflectance other than red iron oxide, does not include harmful substances, and has a high heat resistance. It is done.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은 종래의 대표적인 안료적색 산화철과는 상이한 새로운 적색안료인 산화아연(ZnO)과 산화철(Fe2O3)과의 혼정 화합물로서 피복하는 것을 특징으로 하는 바, 일반식 x ZnO.y Fe2O3로 표시하였을 경우 ZnO과 Fe2O3의 몰(ml)비 x/y는 (x/y≤0.84의 범위에 있다.The present invention is characterized by coating as a mixed compound of zinc oxide (ZnO) and iron oxide (Fe 2 O 3 ), which is a new red pigment different from conventional representative pigmented red oxide, and is represented by the general formula x ZnO.y Fe 2. If hayeoteul represented by O 3 ZnO and mole (ml) ratio x / y of Fe 2 O 3 is in the range of (x / y≤0.84.
본 발명에 따른 안료는 산화아연과 산화철의 혼합 및 소성에 의해서 제조되거나 탄산아연 및 황산아연등의 아연염과 황산철 수용액과의 공침화합물의 산화에 의해서도 제조될 수 있는 바, 산화아연과 산화철을 혼합, 소성하여 제조하는 경우에는 우선 산화아연과 산화철을 필요한 몰비로 섞고, 건식이나 습식 볼밀(ballmill)방법등을 이용하여 균일하게 혼합해준 다음 이 혼합물을 500 내지 800℃ 범위에서 2 내지 5시간 동안 소성해줌으로써 원하는 안료를 만들 수 있다.The pigment according to the present invention may be prepared by mixing and calcining zinc oxide and iron oxide, or may also be prepared by oxidation of a coprecipitation compound of zinc salts such as zinc carbonate and zinc sulfate and an aqueous solution of iron sulfate. In the case of mixing and calcining, first, zinc oxide and iron oxide are mixed in the required molar ratio, and uniformly mixed by dry or wet ball mill method, and then the mixture is mixed for 2 to 5 hours in the range of 500 to 800 ° C. By firing, the desired pigment can be produced.
제1도는 곡선 a와 b가 상기한 방법에 의해 제조한 ZnO.Fe2O3적색안료의 분광 반사율로써 5500Å 이하의 청색, 녹색 파장부분의 빛에 대해서는 반사율이 낮지만, 6000-7000Å의 적색 파장부분에서는 반사율이 높아 적색안료로서의 기본특성을 갖추었으며 현지 사용되고 있는 적색산화철(α-Fe2O3)의 분광반사율 곡선(제1도의 곡선 C)과 거의 유사하게 나타나 적색안료로써 사용가능함을 알 수 있다.1 is a spectral reflectance of ZnO.Fe 2 O 3 red pigment prepared by the method described above with curves a and b having a low reflectance for light in the blue and green wavelength region below 5500 Hz, but a red wavelength of 6000-7000 Hz. In the part, it has high reflectivity and has the basic characteristics as a red pigment, and it is almost similar to the spectral reflectance curve (curve C of FIG. 1) of red iron oxide (α-Fe 2 O 3 ) that is used locally. have.
이때, ZnO와 Fe2O3의 몰비 x/y가 커질수록 5500Å 이하의 파장반사율이 높아지고 대신 6000-7000Å의 적색파장의 빛에 대한 반사율이 감소되어 적색안료로써의 특성이 감소되는 경향이 있어 x/y값이 0.84보다 크게될 경우는 적색안료로써 부적합하게 된다.At this time, as the molar ratio x / y of ZnO and Fe 2 O 3 increases, the wavelength reflectance of 5500 Å or less increases, and instead, the reflectance of light with a red wavelength of 6000-7000 감소 decreases, which tends to decrease the characteristics as a red pigment. If the / y value is greater than 0.84, it is not suitable as a red pigment.
본 발명의 안료 x ZnO.y Fe2O3을 적색안료로써 이용할 수 있는 형광체는 통상의 적색형광체로서, 유로피움 부활이트륨옥시 설파이드 형광체(Y2O2S : Eu), 유로피움 부활 산화이트륨 형광체(Y2O3: Eu), 유로피움 부활 바나디움산 이트륨 형광체(YVO4: Eu), 망간산 부활 인산아연 형광체(Zn3(PO4) : Mn), 망간 부활 규산마그네슘 형광체(MgSiO3: Mn)은 부활 유화아연 카드뮴 형광체((Zn.Cd)S : Ag)등이 있고, 이들 형공체의 입경으로는 3-20μm인 것이 좋다.Phosphors which can use the pigment x ZnO.y Fe 2 O 3 of the present invention as a red pigment are ordinary red phosphors, and europium-activated yttrium oxy sulfide phosphors (Y 2 O 2 S: Eu) and europium-activated yttrium phosphors (Y 2 O 3 : Eu), europium-activated yttrium vanadium phosphor (YVO 4 : Eu), manganese-activated zinc phosphate phosphor (Zn 3 (PO 4 ): Mn), manganese-activated magnesium silicate phosphor (MgSiO 3 : Mn ) Are activated zinc cadmium phosphors ((Zn.Cd) S: Ag) and the like, and the particle diameter of these mold pores is preferably 3-20 μm.
[실시예 1]Example 1
산화아연(ZnO)과 산화철(Fe2O3)의 무게비를 1 : 9로 하여 섞은후, 알루미나 볼을 이용한 건식 볼밀(Ballmill)을 통하여 균일하게 혼합한 다음 600℃에서 소성하여 산화아연과 산화제이철의 혼정 화합물을 얻는다.Mix the weight ratio of zinc oxide (ZnO) and iron oxide (Fe 2 O 3 ) to 1: 9, uniformly mix through a dry ball mill using alumina balls, and then calcinate at 600 ° C to zinc oxide and ferric oxide Obtain the mixed crystal compound of
이와 같이하여 얻은 혼정 화합물은 ZnO와 Fe2O3의 몰비 x/y가 0.22인 0.22 ZnO.Fe2O3로 표시되는 적색안료로써 분광 반사율은 제1도의 곡선 a와 같이 나타나게 되어 종래의 적색산화철(α-Fe2O3, 98.5% 이상)의 분광반사율과 거의 동일하다.The mixed crystal obtained as described above is a red pigment represented by 0.22 ZnO.Fe 2 O 3 in which the molar ratio x / y of ZnO and Fe 2 O 3 is 0.22. The spectral reflectance is shown as a curve a in FIG. It is almost the same as the spectral reflectance of (α-Fe 2 O 3 , 98.5% or more).
한편 젤라틴(gellatin)을 40℃ 온수중에 용해시킨 0.3% 젤라틴 수용액에 평균입경 8.5μm인 유로피움 부활 산유화이트룸 적색 형광체(Y2O2S : Eu) 100중량부를 첨가해서 교반기등으로 균일하게 분산시켜 형광체 분산액을 준비한다.On the other hand, 100 parts by weight of europium-activated petroleum oil white room red phosphor (Y 2 O 2 S: Eu) with an average particle diameter of 8.5 μm was added to a 0.3% gelatin solution in which gelatin was dissolved in hot water at 40 ° C., and uniformly dispersed with a stirrer. To prepare a phosphor dispersion.
그리고, 앞에서 제조한 적색안료 0.22 ZnO.Fe2O30.3중량부와 0.3% 아라비아 고무를 혼합한 수용액을 만들어 안료분산액을 준비한다.Then, an aqueous solution is prepared by mixing 0.3 parts by weight of 0.32 parts by weight of red pigment 0.22 ZnO.Fe 2 O 3 prepared in the above and prepare a pigment dispersion.
상기의 형광체 분산액과 안료입자분산액을 교반하면서 혼합한 다음, 혼합액의 pH를 4로 조정하고 10℃이하로 냉각시킨 후 이에 포르말린 1중량부를 교반하면서 서서히 첨가한다.The above-mentioned phosphor dispersion and the pigment particle dispersion are mixed with stirring, and then the pH of the mixture is adjusted to 4 and cooled to 10 ° C. or lower, and then slowly added while stirring 1 part by weight of formalin.
이후, 침강, 세정 및 건조과정을 거쳐 적색안료부착 형광체를 얻는다.Subsequently, the red pigmented phosphor is obtained by sedimentation, washing and drying.
이와 같이하여 얻은 적색안료 부착 형광체는 제2도의 곡선 a와 같은 반사율을 가지고, 종래의 적색산화철(α-Fe2O3, 98.5% 이상)을 이용해 얻은 적색안료 부착형광체의 반사율 곡선인 곡선 b와 비교하여 볼때 거의 동일한 특성을 보여 양호한 것으로 나타났다.The red pigment attached phosphor obtained in this manner has the same reflectance as curve a in FIG. 2, and curve b, which is a reflectance curve of the red pigment attached phosphor obtained using a conventional red iron oxide (α-Fe 2 O 3 , 98.5% or more). In comparison, almost identical characteristics were found to be good.
[실시예 2]Example 2
산화아연과 산화철의 무게비를 2 : 8로 섞고, 이외에는 실시예 1과 동일하게 하여 산화아연과 몰비가 0.49인 0.49 ZnO.Fe2O3적색안료를 부착시킨 적색안료부착 형광체를 제조한다.A weight ratio of zinc oxide and iron oxide was mixed at 2: 8, except that 0.41 ZnO.Fe 2 O 3 red pigment having a zinc oxide and 0.49 ZnO.Fe 2 O 3 red pigment was prepared in the same manner as in Example 1.
이때의 안료분광 반사율은 제1도의 곡선 b와 같이 나타나 종래의 적색산화철의 분광반사율과 거의 유사함을 예시하며, 이를 이용해 제조한 적색 안료부착 형광체의 특성도 실시예 1과 동등하게 나타난다.The pigment spectroscopic reflectance at this time is shown as a curve b of FIG. 1, which is almost similar to the spectral reflectance of the conventional red iron oxide, and the characteristics of the red pigmented phosphor prepared by using the same are also shown in Example 1.
이상에서 설명한 바와 같이 본 발명에 의하면, 유해물질을 포함하지 않은 새로운 적색안료를 이용하여 형광체를 제조하므로써, 인체에 무해한 형광체를 제조할 수 있으며, 아울러 분광특성이 좋은 적색산화철의 안료와 동등한 분광 반사율을 갖고, 이를 이용하여 브라운관의 형광면 제조시 콘트라스트를 개선시킬 수 있다.As described above, according to the present invention, by producing a phosphor using a new red pigment that does not contain harmful substances, it is possible to produce a phosphor that is harmless to the human body, and has a spectral reflectance equivalent to that of a red iron oxide pigment having good spectral characteristics. It can be used to improve the contrast in the manufacture of fluorescent screen of the CRT.
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