KR930006480B1 - Crt - Google Patents

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KR930006480B1
KR930006480B1 KR1019910011781A KR910011781A KR930006480B1 KR 930006480 B1 KR930006480 B1 KR 930006480B1 KR 1019910011781 A KR1019910011781 A KR 1019910011781A KR 910011781 A KR910011781 A KR 910011781A KR 930006480 B1 KR930006480 B1 KR 930006480B1
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South Korea
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phosphor
zns
blue light
laocl
mixing
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KR1019910011781A
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Korean (ko)
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KR930003205A (en
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양준모
정좌영
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삼성전관 주식회사
김정배
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Priority to KR1019910011781A priority Critical patent/KR930006480B1/en
Priority to JP4075007A priority patent/JPH0826308B2/en
Priority to DE4212671A priority patent/DE4212671A1/en
Publication of KR930003205A publication Critical patent/KR930003205A/en
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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
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7767—Chalcogenides
    • C09K11/7769—Oxides
    • C09K11/777—Oxyhalogenides
    • 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
    • C09K11/58—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing copper, silver or gold
    • C09K11/582—Chalcogenides
    • C09K11/584—Chalcogenides with zinc or cadmium
    • 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
    • C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
    • C09K11/611—Chalcogenides
    • C09K11/612—Chalcogenides with zinc or cadmium
    • 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
    • H01J29/187—Luminescent screens screens with more than one luminescent material (as mixtures for the treatment of the screens)
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/20—Manufacture of screens on or from which an image or pattern is formed, picked up, converted or stored; Applying coatings to the vessel
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/20—Manufacture of screens on or from which an image or pattern is formed, picked up, converted or stored; Applying coatings to the vessel
    • H01J9/22—Applying luminescent coatings

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Luminescent Compositions (AREA)

Abstract

The mixed blue light-emitting fluorescent material for the mfr. of CRT is produced by (a) mixing 1000 g ZnS, 0.158 g AgNO3, 2.082 g Al(NO3)3 9H2O and 10 g NH4I with 30 g S, and then firing the mixt. in the quartz crucible under the N2 gas atmosphere at 950 deg.C for 2 hr to obtain ZnS:Ag, Al fluorescent material (A), (b) mixing 100 g La2O3 and 50 g NH4Cl with 0.1 g Tm2O3, and then firing the mixt. in the quartz crucible at 400 deg.C for 2 hr and at 1200 deg.C for 2 hr. to obtain LaOCl:Tm fluorescent material (B), and (c) mixing the fluorescent materials of (A) and (B).

Description

청색 발광 형광체 및 이를 사용한 음극선관Blue light emitting phosphor and cathode ray tube using the same

제1도는 본 발명의 실시예에 따라 제조한 청색 발광 형광체의 전류변화에 따른 휘도 특성 변화를 나타내는 그래프이다.1 is a graph showing a change in luminance characteristic according to a current change of a blue light emitting phosphor manufactured according to an embodiment of the present invention.

본 발명은 고여기 조건하에서 사용되는 청색 발광 형광체 및 이를 사용한 음극선관에 관한 것이다.The present invention relates to a blue light emitting phosphor used under high excitation conditions and a cathode ray tube using the same.

일반적으로 사용되는 칼라 음극선관용 청색 발광 형광체로는 은 부활 염소 공부활 황화아열 형광체(ZnS : Ag,Cl)와, 은 부활 알루미늄 공부활 황화아연 형광체(ZnS : Ag,Al)등이 있다.Commonly used blue light-emitting phosphors for color cathode ray tubes include silver-activated chlorine-activated zinc sulfide phosphors (ZnS: Ag, Cl) and silver-activated aluminum-activated zinc sulfide phosphors (ZnS: Ag, Al).

최근 칼라 음극선관에의 인가 전압이 고압화되고 아울러 전자총이 고전류 밀도화되는 관계로, 상기한 두 형광체중 ZnS : Ag,Al 형광체가 ZnS : Ag,Cl 형광체 보다 발광 휘도에 있어서는 다소 낮지만 고자극 전류 밀도하에서는 비교적 좋은 특성을 나타내므로 현재 많이 사용되고 있다.Recently, the voltage applied to the color cathode ray tube becomes high and the electron gun becomes high current density. Among the above two phosphors, ZnS: Ag, Al phosphors are slightly lower in luminescence brightness than ZnS: Ag, Cl phosphors, but high stimulation It is widely used because it shows relatively good characteristics under current density.

그러나 투사관용 텔레비젼 등과 같은 고여기 조건하에서는 전류-휘도 포화 특성이 만족할 만큼 좋지는 못하여, 최근에는 휘도 포화 특성이 우수한 회토류계 청색 발광 형광체를 개발하기 위한 연구가 많은 관심을 끌고 있다.However, under high excitation conditions such as projection tube televisions, current-luminance saturation characteristics are not satisfactory enough. Recently, research for developing a rare earth-based blue light emitting phosphor having excellent luminance saturation characteristics has attracted much attention.

Ta, Er, Tm 및 Ce 등으로 부활된 La, Gd, Lu 등의 회토류 산화 할로겐화물 형광체는 X선, 음극선 및 UV선 등의 빛이 조사된 후 가시광선 또는 적외선 등의 전자파에 의해 여기됨으로써 UV 영역 내지 청색영역에 걸쳐 자극된 빛을 발하는 형광체로서 특히 대형 투나관용으로 각광을 받고 있다.Rare earth oxidizing halide phosphors such as La, Gd, and Lu, which are revived by Ta, Er, Tm, and Ce, are excited by electromagnetic waves such as visible or infrared rays after being irradiated with light such as X-rays, cathode rays, and UV rays. Phosphors that emit light stimulated over the UV region to the blue region have been in the spotlight, particularly for large tunnel tubes.

예커대 일본 특허 공보 소 62-18589호에는 톨륨 부활 산염화 란탄 형광체(LaOCl : Tm)와 이 형광체를 물유리와 질산바륨의 중량 농도비가 20 내지 40인 침강액을 사용하여 음극선관의 패널 내면에 침강시킴으로써 형광체 침강막을 형성하는 것을 통해 투사형 영상장치에 사용되는 청색 발광 스크린막을 제조하는 방법이 기술되어 있다.Japanese Patent Publication No. 62-18589 discloses sedimentation on the inner surface of a cathode ray tube using a tolium-activated lanthanum phosphate (LaOCl: Tm) and a sedimentation solution having a weight concentration ratio of water glass and barium nitrate of 20 to 40. A method of producing a blue light emitting screen film for use in a projection type imaging apparatus by forming a phosphor settling film is described.

그런데 이와 같은 방법으로 제조된 청색 발광 형광체는 수분에 불안정하므로 스크린막 형성시 형광특성에 바람직하지 못한 영향을 주며, 그 초기 발광 효율이 낮다는 문제점을 가지고 있다.However, the blue light-emitting phosphor prepared in this manner is unstable in moisture and thus has an undesirable effect on the fluorescence characteristics when forming the screen film, and has a problem of low initial emission efficiency.

본 발명의 목적은 상기한 문제점들을 감안하여 전체적인 형광체 특성이 우수해지고, 특히 전류-휘도 포화 특성이 향상된 혼합형 청색 발광 형광체를 제공하고자 하는 것이다.SUMMARY OF THE INVENTION In view of the above problems, an object of the present invention is to provide a mixed blue light emitting phosphor having excellent overall phosphor characteristics and particularly improved current-luminance saturation characteristics.

본 발명의 다른 목적은 상기한 혼합형 청색 발광 형광체를 사용함으로써 영상의 색순도와 휘도를 향상시킨 음극선관을 제공하고자 하는 것이다.Another object of the present invention is to provide a cathode ray tube with improved color purity and luminance of an image by using the mixed blue light emitting phosphor.

상기 목적을 달성하기 위하여 본 발명에서는 ZnS : Ag, Al 형광체에 5 내지 30중량%의 LaOCl : Tm 형광체를 혼합하여 제조되는 청색 발광 형광체를 제공한다.In order to achieve the above object, the present invention provides a blue light emitting phosphor prepared by mixing 5-30 wt% of LaOCl: Tm phosphor in a ZnS: Ag, Al phosphor.

본 발명의 또다른 목적을 달성하기 위하여 본 발명에서는 상기한 혼합 청색 발광 형광체를 사용하여 제조한 음극선관을 제공한다.In order to achieve another object of the present invention, the present invention provides a cathode ray tube manufactured using the mixed blue light emitting phosphor.

이하 본 발명에 따른 청색 발광 형광체의 제조 방법을 설명하기로 한다.Hereinafter, a method of manufacturing a blue light emitting phosphor according to the present invention will be described.

우선 ZnS : Ag, Al 형광체는 통상의 방법에 따라 주원료 ZnS과 AgNO3또는 Ag2SO4등의 은화합물과, 공부활제로서 Al2(SO4)3ㆍ18H2O 또는 Al(NO3)3ㆍ9H2O 등의 알루미늄 화합물을 혼합하고, 여기에 융제로서 NH4I, KI, NaI중 어느 하나를 첨가하여 충분히 혼합한다. 혼합물을 내열성 도가니에 충전하고 혼합물의 상부에 탄소분말을 덮은 후 뚜껑을 덮고 환원성 분위기하에서 2 내지 3시간 동안 900 내지 1000℃의 온도로 소성한다. 내용물이 식으면 수세 및 건조하여 ZnS : Ag,Al 형광체를 얻는다.First, ZnS: Ag, Al phosphors are silver compounds such as ZnS and AgNO 3 or Ag 2 SO 4 as the main raw materials according to a conventional method, and Al 2 (SO 4 ) 3 ㆍ 18H 2 O or Al (NO 3 ) 3 as an active agent. and mixing an aluminum compound, such as 9H 2 O, and sufficiently mixed by a flux to this was added any one of NH 4 I, KI, NaI. The mixture is charged into a heat-resistant crucible, covered with carbon powder on top of the mixture, covered with a lid, and calcined at a temperature of 900 to 1000 ° C. for 2-3 hours under a reducing atmosphere. When the contents cool, they are washed with water and dried to obtain a ZnS: Ag, Al phosphor.

다음 LaCOl : Tm 형광체는 산화란탄(La2O3), 산화툴륨(Tm2O3) 및 염화 암모늄(NH4Cl)을 적량 취하여 혼합한다. 얻어지는 혼합 분말을 내열성 도가니에 충전하고 400 내지 450℃ 온도로 1 내지 2시간 소성한다. 소성물을 분쇄하여 다시 내열성 용기에 충전한 후 약환원성 분위기하에서 1.5 내지 3시간 동안 1100 내지 1200℃ 온도에서 소성한다. 내용물이 식으면 수세 및 건조하여 LaOCl : Tm 형광체를 제조한다.LaCOl: Tm phosphor is mixed with a suitable amount of lanthanum oxide (La 2 O 3 ), thorium oxide (Tm 2 O 3 ) and ammonium chloride (NH 4 Cl). The resulting mixed powder is filled into a heat resistant crucible and calcined at a temperature of 400 to 450 ° C. for 1 to 2 hours. The fired product is pulverized and filled into a heat-resistant container and fired at a temperature of 1100 to 1200 ° C. for 1.5 to 3 hours in a weakly reducing atmosphere. After the contents cool, they are washed with water and dried to prepare a LaOCl: Tm phosphor.

이와같이 제조한 ZnS : Ag, Al 형광체와 LaOCl : Tm 형광체를 일정비율로 혼합하여 본 발명의 청색 발광 형광체를 얻는다. 제조된 형광체를 통상의 방법에 따라 음극선관의 패널 내면에 도포하여 스크린막을 제조하고 스크린막을 포함하는 벌브와 마운트를 봉착시키고, 배기, 에이징, 검사 등의 단계를 통해 본 발명의 음극선관을 제조한다.The ZnS: Ag, Al phosphor and LaOCl: Tm phosphor thus prepared are mixed at a constant ratio to obtain a blue light emitting phosphor of the present invention. The prepared phosphor is applied to the inner surface of the cathode ray tube panel according to a conventional method to prepare a screen membrane, the bulb and the mount including the screen membrane are sealed, and the cathode ray tube of the present invention is manufactured through steps such as exhaust, aging, and inspection. .

이하 본 발명에서 사용한 ZnS : Ag,Al 형광체와 LaOCl : Tm 형광체의 제조방법을 상세히 설명한다.Hereinafter, a method of preparing the ZnS: Ag, Al phosphor and LaOCl: Tm phosphor used in the present invention will be described in detail.

＜ZnS : Ag,Al 형광체의 제조＞<ZnS: Production of Ag, Al Phosphor>

ZnS 1000gZnS 1000g

AgNO30.158gAgNO 3 0.158 g

Al(NO3)3·9H2O 2.082gAl (NO 3 ) 3 .9H 2 O 2.082 g

NH4I 10gNH 4 I 10 g

S 30gS 30g

상기 원료를 균일하게 혼합한 후 석영 도가니에 충전하고 혼합물의 상부에 탄소를 첨가한 후 뚜껑을 덮는다. N2분위기하에서 2시간 동안 950℃ 온도에서 소성한다. 소성후 수세 및 건조하여 ZnS : Ag, Al 형광체를 얻는다.The raw materials are uniformly mixed and then filled into a quartz crucible and carbon is added to the top of the mixture and then covered with a lid. It is calcined at 950 ° C. for 2 hours under N 2 atmosphere. After firing, washing with water and drying yields a ZnS: Ag, Al phosphor.

＜LaOCl : Tm 형광체의 제조＞<Production of LaOCl: Tm Phosphor>

La2O3100gLa 2 O 3 100 g

NH4Cl 50gNH 4 Cl 50g

Tm2O30.1gTm 2 O 3 0.1g

상기 원료들을 평량하고 볼밀을 사용하여 잘 혼합한다. 얻어지는 혼합 분말을 석영 도가니에 충전한 후 400℃ 온도에서 2시간 동안 소성한다. 소성물을 다시 볼밀을 사용하여 분쇄한 후 다시 석영 도가니에 충전한 후 400℃ 온도에서 2시간 동안 소성한다. 소성물을 다시 볼밀을 사용하여 분쇄한 후 다시 석용 도가니에 넣고 약환원성 분위기하에서 2시간 동안 1200℃ 온도에서 소성한다. 내용물이 식으면 수세 및 건조하여 LaOCl : Tm 형광체를 얻는다.The raw materials are weighed and mixed well using a ball mill. The resulting mixed powder is charged into a quartz crucible and calcined at 400 ° C. for 2 hours. The calcined product is again ground using a ball mill, and then charged into a quartz crucible and calcined at 400 ° C. for 2 hours. The calcined product is pulverized again using a ball mill and then placed in a stone crucible and calcined at 1200 ° C. for 2 hours under a slightly reducing atmosphere. After the contents cool, they are washed with water and dried to obtain LaOCl: Tm phosphor.

이와 같이 제조한 ZnS : Ag, Al 형광체와 LaOCl : Tm 형광체를 혼합하여 본 발명의 청색 발광 형광체를 제조한다. 혼합비에 따른 각 실시예의 전류-휘도 포화 특성을 표 1에 나타내었다.The blue light emitting phosphor of the present invention is prepared by mixing the ZnS: Ag, Al phosphor and LaOCl: Tm phosphor thus prepared. Table 1 shows the current-luminance saturation characteristics according to the mixing ratios.

[표 1]TABLE 1

* 인가전압 ; 28KV, 래스터(raster)면적 ; 130×100㎟* Applied voltage; 28 KV, raster area; 130 × 100㎡

* *

표 1의 결과를 보면 LaOCl : Tm의 혼합량이 증가함에 따라 휘도 포화 특성(γ)은 향상되지만 과량첨가시 초기 휘도가 너무 낮다는 문제점이 있다. 휘도 포화 특성과 초기 휘도를 비교할 때 가장 바람직한 LaOCl : Tm의 혼합비는 10 내지 20중량%일때이다.The results of Table 1 show that as the mixing amount of LaOCl: Tm increases, the luminance saturation characteristic (γ) is improved, but there is a problem that the initial luminance is too low when it is added. When comparing the luminance saturation characteristics and the initial luminance, the most preferable LaOCl: Tm mixing ratio is 10 to 20% by weight.

제1도는 실시예 1, 3 및 5에 따라 제조한 본 발명의 청색 발광 형광체의 전류에 따른 휘도 포화 특성 변화를 나타내는 그래프이다.1 is a graph showing a change in luminance saturation characteristics according to the current of the blue light-emitting phosphor of the present invention prepared according to Examples 1, 3 and 5.

이상에서와 같이 본 발명의 청색 발광 형광체는 단일 형광체(ZnS : Ag,Al) 사용시보다 휘도 포화 특성이 약 7 내지 11% 향상된 것으로서 특히 고여기 조건하에서 그 특성이 우수한 형광체라고 할 수 있다.As described above, the blue light-emitting phosphor of the present invention is about 7 to 11% higher in luminance saturation characteristics than when using a single phosphor (ZnS: Ag, Al).

또한 본 발명의 방법에 따라 제조한 청색 발광 형광체를 사용하여 음극선관을 제조하게 되면 영상의 색순도와 휘도가 향상되어 우수한 품질의 음극선관을 얻을 수가 있다.In addition, when a cathode ray tube is manufactured using a blue light emitting phosphor manufactured according to the method of the present invention, color purity and luminance of an image may be improved to obtain a cathode ray tube having excellent quality.

Claims (4)

ZnS : Ag,Al 형광체에 5 내지 30중량%의 LaOCl : Tm 형광체를 혼합하여 얻어지는 청색 발광 형광체.A blue light emitting phosphor obtained by mixing 5-30 wt% LaOCl: Tm phosphor with a ZnS: Ag, Al phosphor. 제1항에 있어서, 상기 LaOCl : Tm 형광체의 혼합량이 ZnS : Ag, Al 형광체의 10 내지 20중량%인 것을 특징으로 하는 청색 발광 형광체.The blue light emitting phosphor according to claim 1, wherein the mixing amount of the LaOCl: Tm phosphor is 10 to 20% by weight of the ZnS: Ag, Al phosphor. ZnS : Ag, Al 형광체에 5 내지 30중량%의 LaOCl : Tm 형광체를 혼합하여 얻어지는 청색 발광 형광체를 사용하여 제조되는 음극선관.A cathode ray tube manufactured using a blue light emitting phosphor obtained by mixing 5-30 wt% LaOCl: Tm phosphor with a ZnS: Ag, Al phosphor. 제3항에 있어서, 상기 LaOCl : Tm 형광체의 혼합량이 ZnS : Ag, Al 형광체의 10 내지 20중량%인 것을 특징으로 하는 음극선관.The cathode ray tube according to claim 3, wherein the mixing amount of the LaOCl: Tm phosphor is 10 to 20% by weight of the ZnS: Ag, Al phosphor.
KR1019910011781A 1991-07-11 1991-07-11 Crt KR930006480B1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1019910011781A KR930006480B1 (en) 1991-07-11 1991-07-11 Crt
JP4075007A JPH0826308B2 (en) 1991-07-11 1992-03-31 Blue light emitting phosphor and cathode ray tube using the same
DE4212671A DE4212671A1 (en) 1991-07-11 1992-04-15 Blue luminescent material having high luminescence and good reproducibility - is produced by mixing silver-activated, aluminium-coactivated zinc sulphide with thulium-activated lanthanum oxychloride

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Application Number Priority Date Filing Date Title
KR1019910011781A KR930006480B1 (en) 1991-07-11 1991-07-11 Crt

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KR930003205A KR930003205A (en) 1993-02-24
KR930006480B1 true KR930006480B1 (en) 1993-07-16

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KR (1) KR930006480B1 (en)
DE (1) DE4212671A1 (en)

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DE4212671A1 (en) 1993-03-18
KR930003205A (en) 1993-02-24
JPH0826308B2 (en) 1996-03-13
JPH05117653A (en) 1993-05-14

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