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KR20010019297A - Green emitting phosphor compositions and cathod-ray tube having phosphor layer manufactured using the same - Google Patents

Green emitting phosphor compositions and cathod-ray tube having phosphor layer manufactured using the same Download PDF

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KR20010019297A
KR20010019297A KR1019990035638A KR19990035638A KR20010019297A KR 20010019297 A KR20010019297 A KR 20010019297A KR 1019990035638 A KR1019990035638 A KR 1019990035638A KR 19990035638 A KR19990035638 A KR 19990035638A KR 20010019297 A KR20010019297 A KR 20010019297A
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South Korea
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phosphor
sio
luminance
ray tube
weights
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KR1019990035638A
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Korean (ko)
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허경재
정좌영
윤원호
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김순택
삼성에스디아이 주식회사
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Publication of KR20010019297A publication Critical patent/KR20010019297A/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
    • 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
    • C09K11/59—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing silicon
    • C09K11/592—Chalcogenides
    • C09K11/595—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
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7743—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing terbium
    • C09K11/7749—Aluminates
    • 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
    • C09K11/7743—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing terbium
    • C09K11/77492—Silicates
    • 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
    • C09K11/7774—Aluminates
    • 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
    • C09K11/77742—Silicates
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

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

Abstract

PURPOSE: A green luminescent composition having improved deterioration property, color purity and light residue property is provided by using Y3(Al, Ga)5O12: Tb luminescent material. CONSTITUTION: A green luminescent composition is prepared by 63-92 weight part of Y3(Al, Ga)5O12: Tb, 5-30 weight part of Y2SiO5: Tb, and 3-7 wegiht part of Zn2SiO4 : Mn. The composition is manufactured into cathode-rays tube, particularly projective cathode-rays tube. In order to avoid low color purity, brightness and deterioration state, the composition comprises mixing fluorine compounds. The relative brightness is measured for 10 minutes under a condition of accelerating voltage of 20kV.

Description

녹색 발광 형광체 조성물 및 이를 이용하여 제조된 형광막을 구비한 투사형 음극선관{Green emitting phosphor compositions and cathod-ray tube having phosphor layer manufactured using the same}Green emitting phosphor compositions and cathod-ray tube having phosphor layer manufactured using the same

본 발명은 녹색 발광 형광체 조성물 및 이를 이용하여 제조된 형광막을 구비한 음극선관에 관한 것으로서, 더욱 상세하게는 휘도특성, 열화특성, 및 잔광특성이 모두 개선시킬 수 있는 녹색 발광 형광체 조성물 및 이를 이용하여 제조된 형광막을 구비한 음극선관에 관한 것이다.The present invention relates to a green light emitting phosphor composition and a cathode ray tube having a fluorescent film manufactured using the same, and more particularly, to a green light emitting phosphor composition which can improve luminance, deterioration characteristics, and afterglow characteristics. It relates to a cathode ray tube provided with a manufactured fluorescent film.

최근 고화질TV(high definition television : HDTV) 방송의 시작과 함께 40" 이상의 대형화면을 구현할 수 있는 투사형 음극선관(projection type cathode ray tube)에 대한 수요가 가정용뿐만 아니라 업무용으로서도 증가하고 있다. 투사형 음극선관의 경우에는 40" 또는 52" 이상의 대형화면으로 영상이 투사되므로 투사형 음극선관의 형광면은 직시형 음극선관의 형광면에 비해 수 배 ~ 수십 배의 밝기를 필요로 한다. 따라서, 직시형 음극선관의 경우에 비하여 수 배 ~ 수십 배의 고전류 밀도로 형광면을 여기하여야 하므로 형광체의 손상으로 형광면의 휘도가 열화되는 문제점이 있다. 이는 특히 화면 밝기의 약 70를 차지하는 녹색 발광 형광체에서 가장 큰 문제가 되고 있다.Recently, with the start of high definition television (HDTV) broadcasting, the demand for projection type cathode ray tube capable of realizing a large screen of 40 "or more is increasing not only for home use but also for business use. Since the image is projected on a large screen of 40 "or 52" or larger, the fluorescent screen of the projection type cathode ray tube requires several times to several tens of times the brightness of the fluorescent surface of the direct type cathode ray tube. Since the fluorescent surface must be excited at a high current density of several times to several tens of times, the luminance of the fluorescent surface is degraded due to the damage of the fluorescent substance, which is the biggest problem in the green light emitting phosphor which occupies about 70 of the screen brightness.

현재 통상적으로 사용되고 있는 녹색 발광 형광체로서는 종전의 Y2O2S:Tb, Gd2O2S:Tb, ZnS:Cu,Al 등의 특성을 개선한 Y3Al5O12:Tb, Y3(Al, Ga)5O12:Tb, LaOCl:Tb, Zn2SiO5:Tb, InBO3:Tb, Y2SiO5:Tb 등의 단일물질 형광체가 있다. 그러나, 이러한 단일물질 녹색 발광 형광체는 투사형 음극선관에 요구되는 모든 특성을 동시에 만족시킬 수 없기 때문에 실용적으로는 Y3(Al, Ga)5O12:Tb, Y2SiO5:Tb, 안료부착된 Y3(Al, Ga)5O12:Tb 등의 형광체에 Zn2SiO4:Mn 또는 InBO3:Tb 등의 형광체를 적정비율로 혼합한 녹색 발광 형광체가 사용되고 있다.Currently used green light emitting phosphors include Y 3 Al 5 O 12 : Tb, Y 3 (which improves the characteristics of conventional Y 2 O 2 S: Tb, Gd 2 O 2 S: Tb, ZnS: Cu, Al, etc.). Al, Ga) 5 O 12 : Tb, LaOCl: Tb, Zn 2 SiO 5 : Tb, InBO 3 : Tb, Y 2 SiO 5 : Tb and the like there is a single substance phosphor. However, since such a single material green light emitting phosphor cannot satisfy all the properties required for the projection cathode ray tube at the same time, practically Y 3 (Al, Ga) 5 O 12 : Tb, Y 2 SiO 5 : Tb, pigments attached Green luminescent phosphors in which phosphors such as Zn 2 SiO 4 : Mn or InBO 3 : Tb are mixed in a proper ratio with phosphors such as Y 3 (Al, Ga) 5 O 12 : Tb are used.

예를 들면, 일본 특개평 4-161483은 휘도특성과 열화특성이 우수하지만 색순도가 불량한 Y3(Al, Ga)5O12:Tb 형광체와 색순도가 매우 양호한 Zn2SiO4:Mn 형광체를 혼합한 녹색 발광 형광체를 개시하고 있다. USP 4,559,469도 역시 Y2SiO5:Tb 형광체에 색순도를 개선하기 위해서 Zn2SiO4:Mn 형광체를 혼합시킨 녹색 발광 형광체를 개시하고 있다.For example, Japanese Patent Laid-Open No. 4-161483 is a mixture of a Y 3 (Al, Ga) 5 O 12 : Tb phosphor having excellent luminance and deterioration characteristics but poor color purity and a Zn 2 SiO 4 : Mn phosphor having very good color purity. A green light emitting phosphor is disclosed. USP 4,559,469 also discloses a green light emitting phosphor in which a Zn 2 SiO 4 : Mn phosphor is mixed with Y 2 SiO 5 : Tb phosphors to improve color purity.

그러나, 이와 같이 투사형 음극선관용 혼합 녹색 발광 형광체에 있어서 색순도를 향상시키기 위해서 통상적으로 혼합되는 Zn2SiO4:Mn 형광체는 색순도는 우수하지만 고전류밀도 하에서의 열화가 심하고 시간경과에 따른 휘도감소율이 크고 잔광시간(약 30ms)이 길기 때문에 사용량이 증가할수록 휘도특성과 열화양상에 문제가 있어서 다른 형광체와 혼합될 때 혼합량이 제한된다.However, Zn 2 SiO 4 : Mn phosphors, which are commonly mixed to improve color purity in the projection type cathode ray tube mixed green light emitting phosphor, are excellent in color purity but have a high deterioration under high current density and have a high luminance decay rate over time and an afterglow time. (About 30 ms) is long, so that the amount of use increases, which causes problems in luminance characteristics and thermal degradation, thereby limiting the mixing amount when mixed with other phosphors.

일반적으로 Y3(Al, Ga)5O12:Tb 형광체 93 중량와 Zn2SiO4:Mn 형광체 7중량의 혼합물을 사용하고 있지만, 색순도, 휘도특성 및 열화양상면에서 개선이 이루어져야할 필요가 있다. 이러한 문제를 회피하기 위해서 USP 4,336,313과 같이 불소계 화합물을 혼합하여 휘도특성 및 잔광특성을 개선하려고 하는 시도가 있었지만 여전히 개선의 여지를 남기고 있다.Generally, a mixture of 93 weights of Y 3 (Al, Ga) 5 O 12 : Tb phosphors and 7 weights of Zn 2 SiO 4 : Mn phosphors is used, but improvements in color purity, luminance characteristics, and deterioration aspects need to be made. In order to avoid such a problem, attempts have been made to improve the luminance characteristics and the afterglow characteristics by mixing fluorine compounds such as USP 4,336,313, but there is still room for improvement.

따라서, 본 발명이 이루고자 하는 기술적 과제는 상기한 문제점을 해결하여 열화특성, 색순도 및 잔광특성이 향상된 신규의 녹색 발광 형광체 조성물을 제공하는데 있다.Accordingly, the technical problem to be achieved by the present invention is to solve the above problems to provide a novel green light emitting phosphor composition with improved deterioration characteristics, color purity and afterglow characteristics.

본 발명이 이루고자 하는 다른 기술적 과제는 열화특성, 색순도 및 잔광특성이 개선된 형광막을 구비한 음극선관, 특히 투사형 음극선관을 제공하는데 있다.Another object of the present invention is to provide a cathode ray tube, particularly a projection cathode ray tube, having a fluorescent film having improved deterioration characteristics, color purity, and afterglow characteristics.

상기 기술적 과제를 달성하기 위하여 본 발명은 Y3(Al,Ga)5O12:Tb 형광체 63 ~ 92중량, Y2SiO5:Tb 형광체 5 ~ 30중량및 Zn2SiO4:Mn 형광체 3 ~ 7 중량를 포함하는 녹색 발광 형광체 조성물을 제공한다.In order to achieve the above technical problem, the present invention provides Y 3 (Al, Ga) 5 O 12 : Tb phosphor 63 to 92 weight, Y 2 SiO 5 : Tb phosphor 5 to 30 weight and Zn 2 SiO 4 : Mn phosphor 3 to 7 It provides a green light emitting phosphor composition comprising a weight.

상기 다른 기술적 과제를 달성하기 위해서 본 발명은 상기 녹색 발광 형광체를 사용하여 제조된 형광막을 구비한 음극선관 특히 투사형 음극선관을 제공한다.In order to achieve the above technical problem, the present invention provides a cathode ray tube having a fluorescent film manufactured using the green light emitting phosphor, in particular a projection cathode ray tube.

이하 본 발명에 대하여 구체적으로 설명하기로 한다.Hereinafter, the present invention will be described in detail.

본 발명자들은 상기 목적을 달성하기 위해 최적의 형광체의 조합을 얻고자 기존의 형광체를 대상으로 여러 가지 실험을 실시한 결과 본 발명을 완성하게 되었다. 먼저, 몇가지 실험을 통해 Y2SiO5:Tb 형광체, Y3(Al,Ga)5O12:Tb 형광체 및 Zn2SiO4:Mn 형광를 선택하여 그 최적의 혼합비율을 설정하기 위해 이들 각각에 대한 특성을 좀더 상세하게 알아보았다. 이를 위해, 침강법으로 스크린막을 음극선관과 같은 구조의 디마운터블 시스템(demountable system)에 장착하여 상기 각각의 형광체에 대한 상대휘도, 색좌표, 휘도유지율을 평가하여 그 결과를 하기 표 1에 나타내었다. 평가조건은 가속전압이 20kV, 구동전류 Ik가 60㎂, 래스터(raster)의 크기는 2.7cm × 2.7cm, 그리고 휘도유지율 측정시간은 10분이었다.The present inventors have completed the present invention as a result of various experiments on the existing phosphor to obtain the optimal combination of phosphors to achieve the above object. First, several experiments were conducted to select the Y 2 SiO 5 : Tb phosphor, the Y 3 (Al, Ga) 5 O 12 : Tb phosphor, and the Zn 2 SiO 4 : Mn fluorescence to set the optimum mixing ratio for each of them. We looked at the properties in more detail. To this end, the screen film is mounted on a demountable system having a structure such as a cathode ray tube by the sedimentation method, and the relative luminance, color coordinates, and luminance retention of each phosphor are evaluated, and the results are shown in Table 1 below. . Evaluation conditions were 20 kV acceleration voltage, 60 kV drive current I k , the size of the raster was 2.7 cm x 2.7 cm, and the luminance measurement time was 10 minutes.

상대휘도1)()Relative luminance 1) () 색좌표Color coordinates 휘도유지율Luminance maintenance rate X좌표X coordinate Y좌표Y coordinate Y3(Al,Ga)5O12:TbY 3 (Al, Ga) 5 O 12 : Tb 100100 0.34860.3486 0.55340.5534 0.980.98 Y2SiO5:TbY 2 SiO 5 : Tb 9595 0.33370.3337 0.57780.5778 0.920.92 Zn2SiO4:MnZn 2 SiO 4 : Mn 8282 0.21430.2143 0.72680.7268 0.430.43 1)은 Y3(Al,Ga)5O12:Tb의 휘도를 100로 하였을 때 상대휘도를 나타냄1) shows the relative luminance when the luminance of Y 3 (Al, Ga) 5 O 12 : Tb is 100.

표 1을 보면 Zn2SiO4:Mn 형광체의 10분 후의 휘도유지율이 약 43로 열화가 빠르고 상대 휘도 또한 82로 좋지 않음을 알 수 있다. 이에 반해 Y2SiO5:Tb 형광체는 상대 휘도 95, 휘도 유지율 92로 Y3(Al,Ga)5O12:Tb 형광체의 특성에 근접하고 색좌표면에서도 양호하다. 따라서, 종래의 Y3(Al,Ga)5O12:Tb 형광체와 Zn2SiO4:Mn 형광체의 혼합물에 Y2SiO5:Tb 형광체를 첨가하면 기존의 색좌표를 유지하면서 Zn2SiO4:Mn 형광체의 혼합량을 줄일 수 있어서 Zn2SiO4:Mn 형광체의 사용으로 나타나는 문제를 해결할 수 있게 된다. 또한, Y3(Al,Ga)5O12:Tb 형광체의 일부를 Y2SiO5:Tb 형광체로 대치한다면 색순도가 향상될 수 있다.From Table 1, it can be seen that the luminance retention after 10 minutes of the Zn 2 SiO 4 : Mn phosphor is about 43, the deterioration is fast, and the relative luminance is also not good, 82. In contrast, the Y 2 SiO 5 : Tb phosphor is close to the characteristics of the Y 3 (Al, Ga) 5 O 12 : Tb phosphor with a relative luminance of 95 and a luminance retention of 92, and is good in color coordinate surfaces. Therefore, when a Y 2 SiO 5 : Tb phosphor is added to a mixture of a conventional Y 3 (Al, Ga) 5 O 12 : Tb phosphor and a Zn 2 SiO 4 : Mn phosphor, Zn 2 SiO 4 : Mn is maintained while maintaining the existing color coordinates. The mixing amount of the phosphor can be reduced, thereby solving the problem of using the Zn 2 SiO 4 : Mn phosphor. In addition, color purity may be improved when a part of the Y 3 (Al, Ga) 5 O 12 : Tb phosphor is replaced with the Y 2 SiO 5 : Tb phosphor.

본 발명에 따른 녹색 발광 형광체 조성물은 Y3(Al,Ga)5O12:Tb 형광체 63 ~ 92중량, Y2SiO5:Tb 형광체 5 ~ 30중량및 Zn2SiO4:Mn 형광체가 3 ~ 7중량를 포함한다.The green light emitting phosphor composition according to the present invention has Y 3 (Al, Ga) 5 O 12 : Tb phosphor 63 to 92 weight, Y 2 SiO 5 : Tb phosphor 5 to 30 weight and Zn 2 SiO 4 : Mn phosphor 3 to 7 Contains weight.

바람직하게는, Y3(Al,Ga)5O12:Tb 형광체가 83 ~ 88중량, Y2SiO5:Tb 형광체가 8 ~ 12중량, Zn2SiO4:Mn 형광체가 4 ~ 5중량포함된 것이다.Preferably, 83 to 88 weights of Y 3 (Al, Ga) 5 O 12 : Tb phosphor, 8 to 12 weights of Y 2 SiO 5 : Tb phosphor, and 4 to 5 weights of Zn 2 SiO 4 : Mn phosphors are included. will be.

Zn2SiO4:Mn 형광체가 3중량미만이면 색순도가 불량해지며, 7중량를 초과하면 휘도특성 및 열화특성이 나빠지게 된다. 그리고, Y2SiO5:Tb 형광체가 5중량이하이면 휘도특성과 열화특성에 대한 개선 효과가 거의 나타나지 않으며, 30중량를 초과하면 오히려 휘도특성과 열화특성이 나빠지게 된다.When the Zn 2 SiO 4 : Mn phosphor is less than 3 weights, the color purity is poor, and when the Zn 2 SiO 4 : Mn phosphor is more than 7 weights, the luminance and deterioration characteristics become worse. When the Y 2 SiO 5 : Tb phosphor is 5 weight or less, the improvement of the luminance characteristic and the deterioration characteristic is hardly exhibited. When the Y 2 SiO 5 : Tb phosphor is less than 30 weight, the luminance characteristic and the deterioration characteristic deteriorate.

본 발명에 따른 녹색 발광 형광체 조성물은 음극선관의 형광막 재료로 사용될 수 있으며, 특히 투사형 음극선관의 형광막 제조에 사용하기 적합하다.The green light emitting phosphor composition according to the present invention can be used as a fluorescent film material of a cathode ray tube, and is particularly suitable for use in manufacturing a fluorescent film of a projection cathode ray tube.

이하, 본 발명을 실시예를 통해 더욱 상세히 설명하고자 하는데, 본 발명의 범위가 하기 실시예로 한정되는 것이 아님은 물론이다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to the following Examples.

<실시예 1＞<Example 1>

Y3(Al,Ga)5O12:Tb 형광체 85중량, Y2SiO5:Tb 형광체 10중량와 Zn2SiO4:Mn 형광체 5중량를 건식혼합하였다. 상기 혼합물을 0.1K2SiO3용액에 분산시킨 후 충분히 혼합하였다. 상기 혼합물의 분산액을 Ba(NO3)2용액에 첨가하고, 여기에 글래스 패널을 넣은 후 침강법에 의해서 상기 글래스 패널상에 상기 혼합물로 이루어진 형광막을 형성하였다. 상기 형광막의 두께는 단위면적당 중량으로 5mg/cm2이 되도록 형광체 조성물의 도포양으로서 조절하였다. 소성에 의하여 제거될 수 있는 래커필름을 상기 형광막에 도포하고 이어서 얇은 알루미늄막을 진공증착하였다. 마지막으로 상기 스크린막을 소성하였다.85 weights of Y 3 (Al, Ga) 5 O 12 : Tb phosphor, 10 weights of Y 2 SiO 5 : Tb phosphor, and 5 weights of Zn 2 SiO 4 : Mn phosphor were dry mixed. The mixture was dispersed in 0.1K 2 SiO 3 solution and mixed well. A dispersion of the mixture was added to a Ba (NO 3 ) 2 solution, and a glass panel was placed therein to form a fluorescent film of the mixture on the glass panel by sedimentation. The thickness of the fluorescent film was adjusted as the coating amount of the phosphor composition so that the weight per unit area was 5 mg / cm 2 . A lacquer film that can be removed by firing was applied to the fluorescent film, and then a thin aluminum film was vacuum deposited. Finally, the screen film was fired.

이렇게 하여 제작한 스크린막을 음극선관과 같은 구조의 디마운터블 시스템(demountable system)에 장착하여 상대휘도, 색좌표, 휘도유지율을 측정하여 그 결과를 하기 표 2에 나타냈다. 평가조건은 가속전압이 20kV, 구동전류 Ik가 40㎂, 래스터(raster)의 크기는 2.7cm × 2.7cm, 그리고 휘도유지율 측정시간은 120분이었다.The screen film thus prepared was mounted on a demountable system having a structure such as a cathode ray tube, and the relative luminance, color coordinates, and luminance retention were measured, and the results are shown in Table 2 below. The evaluation conditions were acceleration voltage of 20 kV, driving current I k of 40 mA, raster size of 2.7 cm x 2.7 cm, and luminance maintenance measurement time of 120 minutes.

한편, 본 실시예와 아래의 실시예 및 비교예에 있어서 상대휘도는 비교예 1의 Y3(Al,Ga)5O12:Tb 형광체 93중량와 Zn2SiO4:Mn 형광체 7중량로 이루어진 혼합 녹색 발광 형광체를 이용하여 제작한 스크린막에 대하여 측정한 휘도를 100로 하고 이에 대한 상대치로 표시하였다.On the other hand, in this Example and the following examples and comparative examples, the relative luminance is a mixed green of 93 weights of Y 3 (Al, Ga) 5 O 12 : Tb phosphor of Comparative Example 1 and 7 weights of Zn 2 SiO 4 : Mn phosphor The luminance measured on the screen film produced using the light emitting phosphor was 100, and the relative value thereof was expressed.

<실시예 2＞<Example 2>

Y3(Al,Ga)5O12:Tb 형광체 75중량, Y2SiO5:Tb 형광체 20중량와 Zn2SiO4:Mn 형광체 5중량를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 스크린막을 제조하였다. 이렇게 하여 제작한 스크린막에 대하여 상대휘도, 색좌표, 휘도유지율을 측정하여 표 2에 나타냈다.A screen film was manufactured in the same manner as in Example 1, except that 75 weight of Y 3 (Al, Ga) 5 O 12 : Tb phosphor, 20 weight of Y 2 SiO 5 : Tb phosphor, and 5 weight of Zn 2 SiO 4 : Mn phosphor were used. . The relative brightness, color coordinates, and luminance retention of the screen film thus produced were measured and shown in Table 2.

<실시예 3＞<Example 3>

Y3(Al,Ga)5O12:Tb 형광체 83중량, Y2SiO5:Tb 형광체 10중량와 Zn2SiO4:Mn 형광체 7중량를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 스크린막을 제조하였다. 이렇게 하여 제작한 스크린막에 대하여 상대휘도, 색좌표, 휘도유지율을 측정하여 표 2에 나타냈다.A screen film was manufactured in the same manner as in Example 1, except that 83 weights of Y 3 (Al, Ga) 5 O 12 : Tb phosphors, 10 weights of Y 2 SiO 5 : Tb phosphors, and 7 weights of Zn 2 SiO 4 : Mn phosphors were used. . The relative brightness, color coordinates, and luminance retention of the screen film thus produced were measured and shown in Table 2.

<실시예 4＞<Example 4>

Y3(Al,Ga)5O12:Tb 형광체 73중량, Y2SiO5:Tb 형광체 20중량와 Zn2SiO4:Mn 형광체 7중량를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 스크린막을 제조하였다. 이렇게 하여 제작한 스크린막에 대하여 상대휘도, 색좌표, 휘도유지율을 측정하여 표 2에 나타냈다.A screen film was manufactured in the same manner as in Example 1, except that 73 weights of Y 3 (Al, Ga) 5 O 12 : Tb phosphors, 20 weights of Y 2 SiO 5 : Tb phosphors, and 7 weights of Zn 2 SiO 4 : Mn phosphors were used. . The relative brightness, color coordinates, and luminance retention of the screen film thus produced were measured and shown in Table 2.

<비교예＞<Comparative Example>

Y3(Al,Ga)5O12:Tb 형광체와 Zn2SiO4:Mn 형광체로 이루어진 종래의 녹색 발광 형광체 조성물에 있어서 Y3(Al,Ga)5O12:Tb 형광체 93중량와 Zn2SiO4:Mn 형광체 7중량로 이루어진 경우가 가장 좋은 휘도특성을 나타냈다. 따라서, Y3(Al,Ga)5O12:Tb 형광체 93중량와 Zn2SiO4:Mn 형광체 7중량를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 스크린막을 제조하여 이것을 비교예로 사용하였다. 이렇게 하여 제작한 스크린막에 대하여 상대휘도, 색좌표, 휘도유지율을 비교하여 표 2에 나타냈다.In the conventional green light emitting phosphor composition consisting of Y 3 (Al, Ga) 5 O 12 : Tb phosphor and Zn 2 SiO 4 : Mn phosphor, 93 weights of Y 3 (Al, Ga) 5 O 12 : Tb phosphor and Zn 2 SiO 4 The case of 7 weights of Mn phosphor showed the best luminance characteristic. Accordingly, except that 93 weights of Y 3 (Al, Ga) 5 O 12 : Tb phosphors and 7 weights of Zn 2 SiO 4 : Mn phosphors were used, a screen film was manufactured in the same manner as in Example 1 and used as a comparative example. The screen thus produced was compared with the relative luminance, color coordinates, and luminance retention, and is shown in Table 2.

Y3(Al,Ga)5O12:TbY 3 (Al, Ga) 5 O 12 : Tb Y2SiO5:TbY 2 SiO 5 : Tb Zn2SiO4:MnZn 2 SiO 4 : Mn 휘도1)()Brightness 1) () X좌표X coordinate Y좌표Y coordinate 휘도유지율Luminance maintenance rate 실시예 1Example 1 85중량85 weight 10중량10 weight 5중량5 weight 103.1103.1 0.34960.3496 0.56430.5643 96.796.7 실시예 2Example 2 75중량75 weight 20중량20 weight 5중량5 weight 101.5101.5 0.34800.3480 0.56530.5653 96.396.3 실시예 3Example 3 83중량83 weight 10중량10 weight 7중량7 weight 99.599.5 0.34690.3469 0.56850.5685 94.994.9 실시예 4Example 4 73중량73 weight 20중량20 weight 7중량7 weight 99.299.2 0.34480.3448 0.57110.5711 94.594.5 비교예Comparative example 97중량97 weight 7중량7 weight 100100 0.34900.3490 0.56480.5648 95.595.5 1) 비교예에서 얻은 휘도를 100로 했을 때의 상대휘도를 나타냄1) Relative luminance is shown when the luminance obtained in the comparative example is 100.

표 2를 참조하면, 실시예 1의 혼합 형광체, 즉 Y3(Al,Ga)5O12:Tb 형광체 85중량, Y2SiO5:Tb 형광체 10중량와 Zn2SiO4:Mn 형광체 5중량로 이루어진 경우는 비교예의 Y3(Al,Ga)5O12:Tb 형광체 93중량와 Zn2SiO4:Mn 형광체 7중량의 혼합물 형광체에 비하여 휘도 3.1, 휘도유지율 1.2가 향상되었음을 알 수 있다.Referring to Table 2, the mixed phosphor of Example 1, i.e., composed of 85 weights of Y 3 (Al, Ga) 5 O 12 : Tb phosphor, 10 weights of Y 2 SiO 5 : Tb phosphor, and 5 weights of Zn 2 SiO 4 : Mn phosphor In this case, it can be seen that the luminance 3.1 and the luminance maintenance ratio 1.2 were improved compared to the mixture phosphor of 93 weights of the Y 3 (Al, Ga) 5 O 12 : Tb phosphor and the 7 weight Zn 2 SiO 4 : Mn phosphor of the comparative example.

또한, 실시예 2의 혼합 형광체, 즉 Y3(Al,Ga)5O12:Tb 형광체 75중량, Y2SiO5:Tb 형광체 20중량와 Zn2SiO4:Mn 형광체 5중량로 이루어진 경우는 비교예의 Y3(Al,Ga)5O12:Tb 형광체 93중량와 Zn2SiO4:Mn 형광체 7중량의 혼합물 형광체에 비하여 휘도 1.5 휘도유지율 0.8가 향상되었음을 알 수 있다.In the case of the mixed phosphor of Example 2, that is, 75 weights of Y 3 (Al, Ga) 5 O 12 : Tb phosphor, 20 weights of Y 2 SiO 5 : Tb phosphor, and 5 weights of Zn 2 SiO 4 : Mn phosphor, It can be seen that the luminance 1.5 luminance retention 0.8 was improved compared to the mixture phosphor of 93 weights of Y 3 (Al, Ga) 5 O 12 : Tb phosphor and 7 weights of Zn 2 SiO 4 : Mn phosphor.

실시예 3과 4의 경우에는 비교예에 비하여 휘도 및 휘도유지율을 크게 감소시키지 않고 색순도를 향상시켰음을 알 수 있다.In the case of Examples 3 and 4, it can be seen that the color purity was improved without significantly reducing the luminance and the luminance maintaining ratio as compared with the comparative example.

상기에서 살펴본 바와 같이 본 발명에 따른 Y3(Al,Ga)5O12:Tb형광체, Y2SiO5:Tb 형광체 및 Zn2SiO4:Mn 형광체를 포함하는 녹색 발광 형광체 조성물은 고전류구동 하에서 색순도, 휘도특성 및 잔광특성이 개선되고 열화특성도 개선된다.As described above, the green light emitting phosphor composition including the Y 3 (Al, Ga) 5 O 12 : Tb phosphor, the Y 2 SiO 5 : Tb phosphor, and the Zn 2 SiO 4 : Mn phosphor according to the present invention has a color purity under high current driving. In addition, the luminance and afterglow characteristics are improved, and the deterioration characteristics are also improved.

Claims (3)

Y3(Al,Ga)5O12:Tb 형광체 63 ~ 92중량, Y2SiO5:Tb 형광체 5 ~ 30중량및 Zn2SiO4:Mn 형광체 3 ~ 7중량를 포함하는 것을 특징으로 하는 녹색 발광 형광체 조성물.Y 3 (Al, Ga) 5 O 12 : Tb phosphor 63 to 92 weight, Y 2 SiO 5 : Tb phosphor 5 to 30 weight and Zn 2 SiO 4 : Mn phosphor 3 to 7 weight, characterized in that the green light emitting phosphor Composition. 제 1항의 녹색 발광 형광체 조성물을 사용하여 제조된 형광막을 구비한 것을 특징으로 하는 음극선관.A cathode ray tube comprising a fluorescent film produced using the green light emitting phosphor composition of claim 1. 제 2항에 있어서, 상기 음극선관이 투사형 음극선관인 것을 특징으로 하는 음극선관.The cathode ray tube according to claim 2, wherein the cathode ray tube is a projection cathode ray tube.
KR1019990035638A 1999-08-26 1999-08-26 Green emitting phosphor compositions and cathod-ray tube having phosphor layer manufactured using the same KR20010019297A (en)

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KR20030036017A (en) * 2001-10-30 2003-05-09 가부시키가이샤 히타치세이사쿠쇼 Plasma display device, luminescent device and image and information display system using the same

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Publication number Priority date Publication date Assignee Title
KR20030036017A (en) * 2001-10-30 2003-05-09 가부시키가이샤 히타치세이사쿠쇼 Plasma display device, luminescent device and image and information display system using the same

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