KR950006081B1 - Red luminescent materials and its preparation method - Google Patents
Red luminescent materials and its preparation method Download PDFInfo
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Abstract
Description
제1도는 본 발명의 실시예 1에 따른 안료 부착 적색 발광 형광체의 입자 모양을 나타내는 확대 사진.1 is an enlarged photograph showing the particle shape of a red light-emitting phosphor with a pigment according to Example 1 of the present invention.
본 발명은 특히 휘도와 콘트라스트가 향상된 안료 부착 적색발광형광체 및 이의 제조방법에 관한 것이다.In particular, the present invention relates to a red light-emitting phosphor with a pigment having improved brightness and contrast, and a method for producing the same.
칼라 음극선관에 사용되고 있는 적색, 녹색, 청색의 형광체 입자 표면에는 형광체가 발하는 빛 중 일부 바람직하지 못한 영역의 광을 흡수시킴으로 형광체의 콘트라스트를 향상시키기 위해 안료 입자를 부착시키고 있다.Pigment particles are attached to the surface of the red, green, and blue phosphor particles used in the color cathode ray tube to improve the contrast of the phosphor by absorbing light in some undesired regions of the phosphor.
이들 중 Y2O2S : Eu, YVO4: Eu, Y2O3: Eu등의 적색 발광 형광체에 도입되는 안료로는 산화철(Fe2O3), 카드뮴 설포설레나이드[Cd(S1-x, Sex, O＜x＜1] 및 산화구리(Cu2O) 등이 있다.Among these pigments, iron oxide (Fe 2 O 3 ) and cadmium sulfosulfide [Cd (S 1 −) are introduced into the red light-emitting phosphors such as Y 2 O 2 S: Eu, YVO 4 : Eu, Y 2 O 3 : Eu, x, Sex, O <x <1] and copper oxide (Cu 2 O).
특히, 산화철 안료가 내산성, 내열성, 내알칼리성의 특성을 가지고 있어 널리 사용되고 있으나, 이 안료는 이를 형광체의 표면에 부착시 콘트라스트는 향상시키지만 휘도는 감소시킨다는 문제점을 가지고 있다. 따라서 선명한 색상을 가지고 있으면서도 독성이 없는 안료의 개발이 요구되고 있는 것이다.In particular, iron oxide pigments are widely used because they have properties of acid resistance, heat resistance, and alkali resistance, but these pigments have a problem in that the contrast is improved but the luminance is reduced when the pigment is attached to the surface of the phosphor. Therefore, it is required to develop a pigment having a vivid color and non-toxic.
본 발명의 목적은 상기한 요구에 부합하여 휘도와 콘트라스트가 향상되고 색상 조절이 용이해진 안료 부착 적색 발광 형광체를 제공하는 것이다.SUMMARY OF THE INVENTION An object of the present invention is to provide a pigment-emitting red light-emitting phosphor in which luminance and contrast are improved and color control is easily made in accordance with the above-mentioned requirements.
본 발명의 다른 목적은 상기한 안료 부착 적색 발광 형광체의 제조 방법을 제공하는 것이다.Another object of the present invention is to provide a method for producing the above-described pigment-emitting red light-emitting phosphor.
상기 목적을 달성하기 위하여 본 발명에서는 적색 발광 형광체와 그 표면에 부착된 안료로 이루어진 안료부착 적색 발광 형광체에 있어서, 상기 안료가 황화인듐인 것을 특징으로 하는 안료 부착 적색 발광형광체를 제공한다.In order to achieve the above object, the present invention provides a red light emitting phosphor with a pigment, wherein the pigment is indium sulfide in the pigmented red light emitting phosphor consisting of a red light emitting phosphor and a pigment attached to the surface thereof.
상기 황화인듐은 그 부착량이 상기 형광체의 양을 기준으로 하여 0.1 내지 10중량%인 것이, 상기 적색 발광 형광체는 유로피움 부활 산황화이트륨 형광체 (Y2SO : Eu) 것이 바람직하다.The indium sulfide preferably has an adhesion amount of 0.1 to 10% by weight based on the amount of the phosphor, and the red light emitting phosphor is europium-activated yttrium sulfate phosphor (Y 2 SO: Eu).
상기 다른 목적을 달성하기 위하여 본 발명에서는 적색발광형광체를 순수에 분산시킨 용액과 인듐염을 순수에 용해시킨 용액을 혼합하여 교반하는 단계와 ; 상기 혼합액에 염기를 가하여 용액의 pH를 4 내지 7로 조절하는 단계와 ; 상기 혼합액을 여과 및 건조하여 얻어지는 건조물을 체질하는 단계와 ; 체질된 건조물을 내열성 도가니에 넣고 황화 수소 분위기하에서 700 내지 950℃온도 범위로 2 내지 8시간 동안 소성하는 단계를 포함하는 황화인듐 안료 부착 적색 발광 형광체의 제조방법을 제공한다.In order to achieve the above object, the present invention includes the steps of mixing and stirring a solution in which the red light-emitting phosphor is dispersed in pure water and a solution in which an indium salt is dissolved in pure water; Adding a base to the mixed solution to adjust the pH of the solution to 4 to 7; Sieving the dried product obtained by filtering and drying the mixed solution; The sieved dried material is placed in a heat-resistant crucible and calcined for 2 to 8 hours in a temperature range of 700 to 950 ° C. under a hydrogen sulfide atmosphere.
상기 인듐염은 염화인듐(InCl3) 및 황산인듐[In2(SO4)3]중 적어도 하나인 것이 바람직하다.The indium salt is preferably at least one of indium chloride (InCl 3 ) and indium sulfate [In 2 (SO 4 ) 3 ].
상기 염기는 수산화암모늄(NH4OH), 수산화칼륨(KOH) 및 수산화 나트륨(NaOH)중 적어도 하나인 것이, 또한 상기 염기를 가하여 용액의 pH를 조절하는 단계를 통해 형광체 표면에 수산화인듐염[In(OH)3]이 석출되는 것이 바람직하다. 소성시 황화수소가스의 주입유량은 1.5ℓ/min의 속도로 조절 하도록 한다.The base is at least one of ammonium hydroxide (NH 4 OH), potassium hydroxide (KOH) and sodium hydroxide (NaOH), and indium hydroxide salts on the surface of the phosphor through the step of adding the base to adjust the pH of the solution [In (OH) 3 ] is preferably precipitated. During firing, the injection flow rate of hydrogen sulfide gas is controlled at a rate of 1.5ℓ / min.
본 발명의 안료 부착 적색 발광 형광체의 제조방법을 상세히 알아보면 다음과 같다.Looking at the manufacturing method of the red light-emitting phosphor with a pigment of the present invention in detail.
먼저 순수에 적색발광형광체를 넣고 충분히 교반시킨다. 염화인듐 또는 황산인듐을 순수에 용해 시킨 용액을 상기 형광체 분산액에 넣고 교반시킨다. 상기 혼합액을 교반하는 중 묽은 염기성 수용액을 투입하여 용액의 pH를 4 내지 7로 조절한다. 염기를 가하면 형광체의 표면에는 인듐염이 석출되는데 이 인듐염이 석출된 형광체를 여과, 건조시킨다. 건조물을 400메쉬 시이브로 체질한 후 내열성 알루미나 도가니에 넣는다. 도가니를 전기로 심체에 설치하고 양단을 밀폐시키면서 99.99%의 황하수소 가스 분위기하, 700 내지 950℃의 온도 범위에서 2 내지 8시간 동안 소성한다. 이러한 공정을 거친 소성물은 형광체 표면에 황화인듐(In2S3)이 부착된 것으로 붉은 체색을 갖는다. 소성물을 400메쉬 시이브로 체질하여 본 발명에 따른 안료 부착 적색 발광 형광체를 얻는다.First, add red luminescent phosphor to pure water and stir sufficiently. A solution obtained by dissolving indium chloride or indium sulfate in pure water is added to the phosphor dispersion and stirred. While stirring the mixed solution, a diluted basic aqueous solution is added to adjust the pH of the solution to 4 to 7. When a base is added, an indium salt precipitates on the surface of the phosphor, and the phosphor on which the indium salt is precipitated is filtered and dried. The dried product is sieved with a 400 mesh sieve and placed in a heat-resistant alumina crucible. The crucible is installed in the core by an electric furnace and fired for 2 to 8 hours in a temperature range of 700 to 950 ° C. under a 99.99% hydrogen sulfide gas atmosphere with both ends sealed. The calcined product passed through this process has indium sulfide (In 2 S 3 ) attached to the surface of the phosphor and has a red body color. The fired product is sieved with a 400 mesh sieve to obtain a red luminescent phosphor with a pigment according to the present invention.
이하 본 발명의 바람직한 실시예를 구체적으로 설명하기로 한다.Hereinafter, a preferred embodiment of the present invention will be described in detail.
[실시예 1]Example 1
심체 형광체인 유로피움 부활 산황화이트륨 형광체(Y2O2S : Eu) 100g을 순수 600g에 분산시킨다. 황산인듐[In2(SO4)3·9H2O]1.0435g(이후 얻어지는 황화인듐(In2S3) 0.5g에 해당되는 양이다)을 순수 50ml에 녹여 교반중인 상기 형광체 분산액에 가한다. 28% 수산화암모늄(NH4OH)을 순수에 희석한 후 상기 용액에 한방울씩 적하하여 용액의 pH를 7로 맞춘다. 용액을 여과하여 여과물을 건조한 후 이를 400메쉬시이브로 체질하고 내열성 알루미나 도가니에 충전한다. 황화수소 가스의 유량을 1.5ℓ/min로 하고 950℃에서 3시간 동안 소성한다. 실온으로 냉각시킨 후 다시 400메쉬 시이브로 체질하여 Y2O2S : Eu 형광체의 표면에 황화인듐(In2S3)이 부착된 적색 발광형광체를 얻는다.Europium-activated yttrium oxide phosphor (Y 2 O 2 S: Eu), which is a core phosphor, is dispersed in 600 g of pure water. 1.0435 g of indium sulfate [In 2 (SO 4 ) 3 .9H 2 O] (which is equivalent to 0.5 g of indium sulfide (In 2 S 3 ) obtained thereafter) is dissolved in 50 ml of pure water and added to the phosphor dispersion under stirring. Dilute 28% ammonium hydroxide (NH 4 OH) in pure water, and dropwise dropwise to the solution to adjust the pH of the solution to 7. The solution is filtered to dry the filtrate, sieved to 400 mesh and filled into a heat-resistant alumina crucible. The flow rate of hydrogen sulfide gas was 1.5 L / min and calcined at 950 ° C. for 3 hours. After cooling to room temperature, the resultant was sieved again with a 400 mesh sieve to obtain a red light-emitting phosphor having indium sulfide (In 2 S 3 ) attached to the surface of the Y 2 O 2 S: Eu phosphor.
[실시예 2-4]Example 2-4
실시예 1과 동일한 방법으로 수행하되 수화된 황산인듐 [In2(SO4)3·9H2O]의 양을 각 2.0871g(이후 얻어지는 황화인듐(In2S3) 1g에 해당된다 ; 실시예 2), 4.17g(황화인듐 2g에 해당된다 ; 실시예 3) 및 6.2613g(황화인듐 3g에 해당된다 ; 실시예 4)으로 하여 본 발명의 안료 부착 적색 발광 형광체를 얻는다.The same procedure as in Example 1, except that the amount of hydrated indium sulfate [In 2 (SO 4 ) 3 .9H 2 O] corresponds to 1 g of indium sulfide (In 2 S 3 ) obtained after each 2.0871 g; 2) and 4.17 g (corresponds to 2 g of indium sulfide; Example 3) and 6.2613 g (corresponds to 3 g of indium sulfide; Example 4) to obtain a red light-emitting phosphor with a pigment of the present invention.
[실시예 5-7]Example 5-7
실시예 1과 동일한 방법으로 수행하되 황산인듐 대신에 염화인듐을 사용하고 사용량을 각각 0.509g(이하 얻어지는 황하인듐 0.75g에 해당된다 ; 실시예 5), 0.679g(황화인듐 1g에 해당된다 ; 실시예 6) 및 0.849g(황화인듐 1.25g에 해당된다 ; 실시예 7)으로 하여 본 발명의 안료 부착 적색 발광 형광체를 얻는다.Perform the same method as in Example 1, but use indium chloride instead of indium sulfate, and the amount of use is 0.509 g (corresponding to 0.75 g of indium sulfide obtained below; Example 5) and 0.679 g (corresponding to 1 g of indium sulfide; Example 6) and 0.849 g (correspond to 1.25 g of indium sulfide; Example 7) yield a red light-emitting phosphor with a pigment of the present invention.
[비교예][Comparative Example]
절라틴 1.8g을 순수 600ml에 분산 시키고 40℃로 가열하여 젤라틴 수용액을 제조한다. Y2O2S : Eu형광체 300g을 젤라틴 수용액에 가하고 교반기로 균일해질 때까지 교반한다.1.8 g of gelatin is dispersed in 600 ml of pure water and heated to 40 ° C. to prepare a gelatin aqueous solution. Y 2 O 2 S: Eu phosphor 300g was added to the aqueous solution of gelatin and stirred until uniform with a stirrer.
아라비아 고무 1.2g을 순수 400ml에서 분산시켜 0.3%아라비아 고무 수용액을 제조한다. 적색 안료 Fe2O30.48g(0.16중량%)을 0.3%아라비아 고무 수용액에 가하고 충분히 교반하여 안료 분산액을 얻는다.1.2 g of Arabian rubber was dispersed in 400 ml of pure water to prepare a 0.3% aqueous solution of Arabic rubber. 0.48 g (0.16% by weight) of the red pigment Fe 2 O 3 is added to a 0.3% aqueous arabic rubber solution and sufficiently stirred to obtain a pigment dispersion.
얻어진 안료 분산액과 형광체 분산액을 혼합한 후 교반하면서 산을 가하여 pH를 4로 조정한다. 용액을 방치하여 침전물이 가라 앉으면 상등액은 따라 버리고 침전물은 물로 여러번 씻어 준다. 고체 덩어리를 100℃에서 함량이 될때까지 건조하여 산화철 안료가 부착된 형광체를 얻는다.After mixing the obtained pigment dispersion and phosphor dispersion, pH is adjusted to 4 by adding an acid while stirring. When the solution is left to settle down, the supernatant is poured out and the precipitate is washed several times with water. The solid mass is dried at a content of 100 ° C. to obtain a phosphor with iron oxide pigment attached.
이상의 각 실시예에 제조한 안료 부착 적색 발광 형광체의 휘도, 콘트라스트 및 색좌표를 표1에 나타내었다.Table 1 shows the luminance, contrast and color coordinates of the red light-emitting phosphor with pigments prepared in the above Examples.
[표 1]TABLE 1
* 표에서 휘도 및 콘트라스트는 산화철 안료를 부착한 형광체의 휘도 및 콘트라스트 값을 100으로 했을때의 상대값이다.In the table, the luminance and contrast are relative values when the luminance and contrast values of the phosphor to which the iron oxide pigment is attached are 100.
* 상기 각 값들을 디마운터블 시스템(Demountable System)을 사용하여 측정한 값이다.* Each of the above values is measured using a demountable system.
표 1의 결과로부터, 종래의 형광체와 비교하여 본 발명의 안료 부착 적색발광형체가 발광휘도는 비슷하거나 약간 향상되었고, 콘트라스트는 약 5 내지 17%수준으로 크게 향상 되었음을 알 수 있다.From the results of Table 1, it can be seen that the red light-emitting body with a pigment of the present invention has a similar or slightly improved luminescence brightness and a contrast of about 5 to 17%.
제1도는 본 발명의 실시예 1에 따른 안료부착 적색 발광 형광체의 입자 모양을 나타내는 확대사진으로서 입자가 깨끗하고 크기가 균일함을 알 수 있다.FIG. 1 is an enlarged photograph showing the particle shape of the pigmented red light emitting phosphor according to Example 1 of the present invention, and it can be seen that the particles are clean and uniform in size.
이상에서와 같이 본 발명의 황화이듐 부착된 형광체는 종래의 형광체와 비교할때 휘도와 콘트라스트가 향상되고 색재현 영역도 더욱 붉은색 쪽으로 이동된 것이라 할 수 있다.As described above, the phosphor having an indium sulfide according to the present invention has improved luminance and contrast, and the color reproduction region is shifted toward the red color as compared with the conventional phosphor.
그리고 본 발명의 안료 부착 형광체의 제조 방법에서는 인듐염을 형광체 표면에 석출 시키기 때문에 안료의 미립자 형성이 용이하게 되었고, 종래의 방법에서 처럼 안료 부착시 결합체를 사용하지 않기 때문에 공정 자체가 간단하다.In the method for producing a phosphor with a pigment of the present invention, the indium salt precipitates on the surface of the phosphor to facilitate the formation of fine particles of the pigment, and the process itself is simple because no binder is used when the pigment is attached as in the conventional method.
Claims (9)
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| KR1019910023723A KR950006081B1 (en) | 1991-12-20 | 1991-12-20 | Red luminescent materials and its preparation method |
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| Country | Link |
|---|---|
| KR (1) | KR950006081B1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100281292B1 (en) * | 1998-04-15 | 2001-02-01 | 구자홍 | Extension tube tightening structure of vacuum cleaner |
| KR100278174B1 (en) * | 1998-06-05 | 2001-01-15 | 김유혁 | Manufacturing method of red color lighting luminescence based on boron oxide |
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1991
- 1991-12-20 KR KR1019910023723A patent/KR950006081B1/en not_active IP Right Cessation
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| Publication number | Publication date |
|---|---|
| KR930013061A (en) | 1993-07-21 |
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