JPS637594B2 - - Google Patents
Info
- Publication number
- JPS637594B2 JPS637594B2 JP18162481A JP18162481A JPS637594B2 JP S637594 B2 JPS637594 B2 JP S637594B2 JP 18162481 A JP18162481 A JP 18162481A JP 18162481 A JP18162481 A JP 18162481A JP S637594 B2 JPS637594 B2 JP S637594B2
- Authority
- JP
- Japan
- Prior art keywords
- phosphor
- amount
- gallium
- sulfur
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 155
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 85
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 57
- 239000011593 sulfur Substances 0.000 claims description 56
- 229910052717 sulfur Inorganic materials 0.000 claims description 56
- 239000013078 crystal Substances 0.000 claims description 52
- 229910052733 gallium Inorganic materials 0.000 claims description 47
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 45
- 239000005083 Zinc sulfide Substances 0.000 claims description 42
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 42
- 239000000460 chlorine Substances 0.000 claims description 36
- 229910052801 chlorine Inorganic materials 0.000 claims description 35
- 239000012190 activator Substances 0.000 claims description 30
- 239000011159 matrix material Substances 0.000 claims description 26
- 229910052709 silver Inorganic materials 0.000 claims description 26
- 239000004332 silver Substances 0.000 claims description 23
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 7
- 239000011737 fluorine Substances 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 6
- NYZGMENMNUBUFC-UHFFFAOYSA-N P.[S-2].[Zn+2] Chemical compound P.[S-2].[Zn+2] NYZGMENMNUBUFC-UHFFFAOYSA-N 0.000 claims description 4
- 230000004913 activation Effects 0.000 description 45
- 239000002994 raw material Substances 0.000 description 33
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 20
- 238000010304 firing Methods 0.000 description 18
- 238000000295 emission spectrum Methods 0.000 description 14
- 230000005284 excitation Effects 0.000 description 13
- 238000010894 electron beam technology Methods 0.000 description 12
- 230000003081 coactivator Effects 0.000 description 11
- -1 manganese- and arsenic-activated zinc silicate Chemical class 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 230000007423 decrease Effects 0.000 description 9
- 239000011572 manganese Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- 229940044658 gallium nitrate Drugs 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910001508 alkali metal halide Inorganic materials 0.000 description 2
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 description 2
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 229910004762 CaSiO Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052946 acanthite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 150000002259 gallium compounds Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical group [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical group [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- 229940056910 silver sulfide Drugs 0.000 description 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
Landscapes
- Luminescent Compositions (AREA)
Description
【発明の詳細な説明】
本発明は長残光性の青色発光硫化亜鉛螢光体に
関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to long afterglow blue emitting zinc sulfide phosphors.
細密な文字や図形の表示が行なわれるコンピユ
ーターの末端表示装置、航空機管制システムの表
示装置等には高解像度のブラウン管の使用が望ま
れている。ブラウン管の解像度を向上させるため
の有力な方法として、電子線による螢光膜走査速
度を普通の表示装置用ブラウン管のそれよりも２
〜３倍以上遅くすることが知られているが、その
ような高解像度ブラウン管の螢光膜を構成する螢
光体は10％残光時間（励起停止後発光輝度が励起
時の10％まで低下するのに要する時間）が普通の
表示装置用ブラウン管の螢光膜を構成する螢光体
よりも数十乃至数百倍長いことが必要である。 It is desired to use high-resolution cathode ray tubes for computer terminal display devices that display detailed characters and graphics, display devices for aircraft control systems, and the like. An effective way to improve the resolution of cathode ray tubes is to increase the scanning speed of the fluorescent film using an electron beam by 2 times higher than that of ordinary cathode ray tubes for display devices.
It is known that the phosphor that makes up the phosphor film of such a high-resolution cathode ray tube has a 10% afterglow time (after excitation stops, the luminance decreases to 10% of the excitation level). It is necessary that the time required for the phosphor film to be formed is several tens to hundreds of times longer than that of the phosphor that constitutes the phosphor film of a typical cathode ray tube for display devices.
従来、上記高解像度ブラウン管に使用可能な長
残光性螢光体として、マンガンおよび砒素付活珪
酸亜鉛緑色発光螢光体（Zn2SiO4：Mn、As）、マ
ンガン付活弗化カリウム・マグネシウム橙色発光
螢光体（KMgF3：Mn）、鉛およびマンガン付活
珪酸カルシウム橙色発光螢光体（CaSiO3：Pb、
Mn）、マンガン付活弗化マグネシウム赤色発光
螢光体（MgF2：Mn）、マンガン付活オルト燐酸
亜鉛・マグネシウム赤色発光螢光体〔（Zn、
Mg）3（PO4）2：Mn〕等が知られているが、上記
高解像度ブラウン管に使用可能な長残光性の青色
発光螢光体は全く知られていない。周知のように
白黒ブラウン管やカラーブラウン管を得るめには
青色発光螢光体は必要なものであり、このような
点から上記高解像度ブラウン管に使用可能な長残
光性の青色発光螢光体が望まれている。 Conventionally, long-afterglow phosphors that can be used in the above high-resolution cathode ray tubes include manganese- and arsenic-activated zinc silicate green-emitting phosphors (Zn 2 SiO 4 :Mn, As), and manganese-activated potassium/magnesium fluoride. Orange-emitting phosphor (KMgF 3 :Mn), lead- and manganese-activated calcium silicate orange-emitting phosphor (CaSiO 3 :Pb,
Mn), manganese-activated magnesium fluoride red-emitting phosphor (MgF 2 :Mn), manganese-activated zinc/magnesium orthophosphate red-emitting phosphor [(Zn,
Mg) 3 (PO 4 ) 2 :Mn] and the like are known, but there is no known long-afterglow blue-emitting phosphor that can be used in the above-mentioned high-resolution cathode ray tubes. As is well known, a blue-emitting phosphor is necessary to obtain black-and-white cathode ray tubes and color cathode ray tubes, and from this point of view, a blue-emitting phosphor with long afterglow that can be used in the above-mentioned high-resolution cathode ray tubes has been developed. desired.
上記要望に鑑みて、白黒テレビジヨン用ブラウ
ン管、カラーテレビジヨン用ブラウン管等に実用
されている銀を付活剤とし、塩素、臭素、沃素、
弗素およびアルミニウムのうちの少なくとも１種
を共付活剤とする短残光性の青色発光硫化亜鉛螢
光体（ZnS：Ag、Ｘ、但しＸは塩素、臭素、沃
素、弗素およびアルミニウムのうちの少なくとも
１種である）に上記長残光性の緑色発光螢光体お
よび赤色発光螢光体を特定の割合で混合し、この
混合螢光体（ライトブル螢光体と呼ばれている）
を上記高解像度ブラウン管の螢光膜を構成する青
色発光螢光体として使用し、人間の眼にあたかも
青色の発光に残光があるように感じさせることが
考えられている。しかしながら、上記混合螢光体
はZnS：Ag、Ｘ螢光体の10％残光時間が百数十
乃至数百マイクロ秒と非常に短かいために励起停
止後発光色に色ずれが生じ、また発光色の異なる
螢光体を混合したものであるので発光に色むらが
生じ易くまた発光色（青色）の色純度も悪い。 In view of the above requests, silver, which is used in cathode ray tubes for black and white television, cathode ray tubes for color television, etc., is used as an activator, and chlorine, bromine, iodine, etc.
A short-afterglow blue-emitting zinc sulfide phosphor (ZnS: Ag, X, where X is a coactivator of at least one of fluorine and aluminum) The above-mentioned long-afterglow green-emitting phosphor and red-emitting phosphor are mixed in a specific ratio with at least one type of phosphor (at least one type), and this mixed phosphor (called a light blue phosphor)
It has been proposed to use this material as a blue-emitting phosphor constituting the fluorescent film of the high-resolution cathode ray tube to make the human eye feel as if the blue light has an afterglow. However, the 10% afterglow time of the ZnS:Ag, Since it is a mixture of phosphors that emit light of different colors, color unevenness tends to occur in the emitted light, and the color purity of the emitted color (blue) is also poor.
上述のように上記高解像度ブラウン管に使用可
能な長残光性の青色発光螢光体は従来全く知られ
ておらず、このことが高解像度ブラウン管の普及
を阻害する大きな要因となつている。 As mentioned above, no long-afterglow blue-emitting phosphor that can be used in the above-mentioned high-resolution cathode ray tubes has been known, and this is a major factor hindering the spread of high-resolution cathode ray tubes.
本発明は上述のような状況の下で行なわれたも
のであり、長残光性の青色発光螢光体、特に上記
高解像度ブラウン管に使用するのに適した長残光
性の青色発光螢光体を提供することを目的とす
る。 The present invention was made under the above-mentioned circumstances, and provides a long afterglow blue emitting phosphor, particularly a long afterglow blue emitting phosphor suitable for use in the above-mentioned high resolution cathode ray tube. The purpose is to provide the body.
本発明者等は上記目的を達成するために、青色
発光螢光体として広く実用されている上記ZnS：
Ag、Ｘ螢光体を長残光性の螢光体にすることに
関して種々の研究を行なつてきた。その結果、適
当量の銀およびＸ（Ｘは塩素、臭素、沃素、弗素
およびアルミニウムのうちの少なくとも１種であ
る）と共に適当量のガリウム硫化亜鉛を付活する
場合には、ZnS：Ag、Ｘ螢光体よりも10％残光
時間が著しく長い青色発光螢光体を得ることがで
きることを見出した。この長残光性のZnS：Ag、
Ga、Ｘ青色発光螢光体においてはガリウムは発
光輝度にも影響を及ぼし、ガリウム付活量が増加
するに従つて螢光体の発光輝度は低下する。勿論
ZnS：Ag、Ga、Ｘ螢光体を高解像度ブラウン管
に使用するに当つてはその発光輝度はできるだけ
高いのが望ましく、このような点から本発明者等
はさらにZnS：Ag、Ga、Ｘ螢光体の発光輝度を
高めることに関して研究を行なつた。その結果、
製精時に多量の硫黄を含有させた硫化亜鉛生粉を
母体原料として使用し、得られる螢光体中に微量
の硫黄を含ませる場合には、残光特性にほとんど
影響を及ぼすことなくガリウムを付活したことに
よる発光輝度の低下をかなり抑制することができ
ることを見出した。 In order to achieve the above object, the present inventors developed the above-mentioned ZnS, which is widely used as a blue-emitting phosphor.
Various studies have been conducted on making Ag,X phosphors into phosphors with long afterglow properties. As a result, when activating an appropriate amount of gallium zinc sulfide with an appropriate amount of silver and X (where X is at least one of chlorine, bromine, iodine, fluorine, and aluminum), ZnS:Ag, It has been found that it is possible to obtain a blue-emitting phosphor with a significantly longer afterglow time by 10% than that of a phosphor. This long afterglow ZnS:Ag,
In Ga, Of course
When using ZnS:Ag, Ga, We conducted research on increasing the luminance of light bodies. the result,
When raw zinc sulfide powder containing a large amount of sulfur during refining is used as a base material and a small amount of sulfur is included in the resulting phosphor, gallium can be added without affecting the afterglow properties. It has been found that the decrease in luminance caused by activation can be significantly suppressed.
本発明は上述のような知見に基づいてなされた
ものである。すなわち、本発明の長残光性青色発
光螢光体は硫化亜鉛を母体とし、銀を付活剤と
し、ガリウムを第１の共付活剤とし、塩素、臭
素、沃素、弗素およびアルミニウムのうちの少な
くとも１種を第２の共付活剤とし、上記付活剤、
第１の共付活剤および第２の共付活剤の量がそれ
ぞれ上記硫化亜鉛母体の５×10-4乃至10-1重量
％、10-6乃至５×10-1重量％および５×10-6乃至
５×10-2重量％であり、かつ硫黄を上記硫化亜鉛
母体の10-5乃至８×10-1重量％含有することを特
徴とする。 The present invention has been made based on the above findings. That is, the long-afterglow blue-emitting phosphor of the present invention uses zinc sulfide as a matrix, silver as an activator, gallium as a first co-activator, and chlorine, bromine, iodine, fluorine, and aluminum. as a second co-activator, at least one of the above-mentioned activators,
The amounts of the first coactivator and the second coactivator are 5×10 −4 to 10 −1 % by weight, 10 −6 to 5×10 −1 % by weight, and 5× of the zinc sulfide matrix, respectively. 10 -6 to 5 x 10 -2 weight %, and sulfur is contained in an amount of 10 -5 to 8 x 10 -1 weight % of the zinc sulfide matrix.
上記本発明の青色発光硫化亜鉛螢光体は従来の
ZnS：Ag、Ｘ青色発光螢光体よりも電子線、紫
外線等による励起を停止した後の10％残光時間が
数十乃至数百倍長い。本発明の螢光体は製造時の
焼成温度に依存して立方晶系あるいは六方晶系を
主結晶相とするが、立方晶系を主結晶相とする螢
光体の方が六方晶系を主結晶相とする螢光体より
も高輝度の発光を示し、またより高い発光輝度お
よび発光色純度を示す螢光体を与えるガリウム付
活量範囲においては前者の方が後者よりも10％残
光時間が長い。このような点から、本発明の螢光
体のうち立方晶系と主結晶相とする螢光体は六方
晶系を主結晶相とする螢光体よりも高解像度ブラ
ウン管用青色発光螢光体としてより好ましいもの
である。 The above blue-emitting zinc sulfide phosphor of the present invention is similar to the conventional blue-emitting zinc sulfide phosphor.
ZnS: The 10% afterglow time after stopping excitation by electron beams, ultraviolet rays, etc. is several tens to hundreds of times longer than that of Ag and X blue-emitting phosphors. The phosphor of the present invention has a cubic or hexagonal crystal phase as its main crystal phase depending on the firing temperature during production, but phosphors with a cubic system as its main crystal phase tend to have a hexagonal crystal phase. In the range of gallium activation that provides a phosphor with higher luminance than the phosphor with the main crystal phase, and with higher luminance and color purity, the former is 10% more active than the latter. Long light hours. From this point of view, among the phosphors of the present invention, a phosphor having a cubic crystal system as a main crystal phase is more suitable for use as a blue-emitting phosphor for high-resolution cathode ray tubes than a phosphor having a hexagonal crystal system as a main crystal phase. It is more preferable as
以下本発明を詳細に説明する。 The present invention will be explained in detail below.
本発明の螢光体は以下に述べる製造方法によつ
て製造される。 The phosphor of the present invention is manufactured by the manufacturing method described below.
まず螢光体原料としては
(i) 製精時に多量の硫黄を含有させた硫化亜鉛生
粉（母体および硫黄の原料）
(ii) 硝酸銀、硫化銀、ハロゲン化銀等の銀化合物
（付活剤原料）
(iii) 硝酸ガリウム、硫化ガリウム、ハロゲン化ガ
リウム等のガリウム化合物（第１の共付活剤原
料）、および
(iv) アルカリ金属（Na、Ｋ、Li、RbおよびCs）
およびアルカリ土類金属（Ca、Mg、Sr、Zn、
CdおよびBa）の塩化物、臭化物、沃化物およ
び弗化物、並びに硝酸アルミニウム、硫酸アル
ミニウム、酸化アルミニウム、ハロゲン化アル
ミニウム等のアルミニウム化合物からなる化合
物群より選ばれる化合物の少なくとも１種（第
２の共付活剤原料）
が用いられる。上記(i)の母体および硫黄の原料は
例えばPH６乃至４の弱酸性硫酸亜鉛水溶液にその
水溶液のPH値を一定に維持しながら硫化アンモニ
ウムを添加して硫化亜鉛を沈殿させることによつ
て調製することができる。このようにして調製さ
れた硫化亜鉛生粉中に含まれる化学量論量以外の
硫黄の量は沈殿生成時の水溶液のPH値に依存し、
PH値が低い程（すなわち酸性度が高い程）その量
は多くなる。一般にPH６乃至４の水溶液から沈殿
せしめられた硫化亜鉛生粉は化学量論量以外の硫
黄を硫化亜鉛のコンマ数重量％乃至数十重量％含
有している。なおこの硫化亜鉛生粉中に含まれる
化学量論量以外の硫黄はその大部分が焼成時に失
なわれて得られる螢光体中にはごく一部しか残留
しない。従つて、母体原料であると同時に得られ
る螢光体中に微量含まれる硫黄の原料でもある上
記(i)の硫化亜鉛生粉は、螢光体製造時の焼成温
度、焼成時間等を考慮して、硫化亜鉛母体の10-5
乃至８×10-1重量％の範囲から選ばれる目的とす
る硫黄含有量を達成し得る量の化学量論量以外の
硫黄を含むものが用いられる。 First, the raw materials for the phosphor are (i) raw zinc sulfide powder containing a large amount of sulfur during refining (base material and raw material for sulfur), (ii) silver compounds such as silver nitrate, silver sulfide, and silver halide (activating agent). raw materials) (iii) gallium compounds such as gallium nitrate, gallium sulfide, and gallium halides (first coactivator raw materials), and (iv) alkali metals (Na, K, Li, Rb, and Cs)
and alkaline earth metals (Ca, Mg, Sr, Zn,
At least one compound selected from the group consisting of chlorides, bromides, iodides, and fluorides of Cd and Ba), and aluminum compounds such as aluminum nitrate, aluminum sulfate, aluminum oxide, and aluminum halide (second compound); activator raw material) is used. The base material and sulfur raw material in (i) above are prepared, for example, by adding ammonium sulfide to a weakly acidic zinc sulfate aqueous solution with a pH of 6 to 4 while maintaining the PH value of the aqueous solution constant to precipitate zinc sulfide. be able to. The amount of sulfur other than the stoichiometric amount contained in the raw zinc sulfide powder prepared in this way depends on the PH value of the aqueous solution at the time of precipitation,
The lower the PH value (that is, the higher the acidity), the greater the amount. Generally, raw zinc sulfide powder precipitated from an aqueous solution with a pH of 6 to 4 contains sulfur in an amount other than the stoichiometric amount, ranging from a few tenths of a percent to several tens of percent by weight of zinc sulfide. Most of the sulfur contained in the raw zinc sulfide powder other than the stoichiometric amount is lost during firing, and only a small portion remains in the resulting phosphor. Therefore, the raw zinc sulfide powder mentioned in (i) above, which is both the base material and the raw material for the trace amount of sulfur contained in the obtained phosphor, is prepared by taking into consideration the firing temperature, firing time, etc. during the production of the phosphor. 10 -5 of zinc sulfide matrix
A material containing sulfur in an amount other than the stoichiometric amount that can achieve the target sulfur content, which is selected from the range of 8 x 10 -1 % by weight, is used.
上記(i)の母体および硫黄の原料、(ii)の付活剤原
料および(iii)の第１の共付活剤原料は、(ii)の付活剤
原料中の銀の量および(iii)の第１の共付活剤原料中
のガリウムの量がそれぞれ(i)の母体および硫黄の
原料に含まれる硫化亜鉛の量の５×10-4乃至10-1
重量％および10-6乃至５×10-1重量％となるよう
な量比で用いられる。また(iv)の第２の共付活剤原
料は得られる螢光体中に含まれる塩素、臭素、沃
素、弗素およびアルミニウムのうちの少なくとも
１種の量（すなわち第２の共付活剤の量）が硫化
亜鉛母体の５×10-6乃至５×10-2重量％となるよ
うな量用いられる。すなわち、第２の共付活剤原
料中のアルミニウムは銀およびガリウムと同様に
そのほとんどが得られる螢光体中に残留して第２
の共付活剤となるが、第２の共付活剤原料中のハ
ロゲンはその大部分が焼成時に失なわれて得られ
る螢光体中にはごく一部しか残留しない。従つ
て、ハロゲンの原料である上記アルカリ金属ある
いはアルカリ土類金属のハロゲン化物は焼成温度
等に依存して目的とするハロゲン付活量の数十乃
至数百倍のハロゲンを含むような量用いられる。
なお、付活剤銀の原料としてハロゲン化銀が用い
られる場合、第１の共付活剤ガリウムの原料とし
てハロゲン化ガリウムが用いられる場合あるいは
アルミニウムの原料としてハロゲン化アルミニウ
ムが用いられる場合には、必要なハロゲンの一部
はそれら原料によつても供与される。 The base material and sulfur raw material in (i) above, the activator raw material in (ii) and the first co-activator raw material in (iii) are determined based on the amount of silver in the activator raw material in (ii) and the amount of silver in the activator raw material in (iii). The amount of gallium in the first co-activator raw material of (i) is 5×10 -4 to 10 -1 of the amount of zinc sulfide contained in the base material and sulfur raw material of (i), respectively.
It is used in an amount ratio of 10 -6 to 5×10 -1 weight %. The second coactivator raw material (iv) is the amount of at least one of chlorine, bromine, iodine, fluorine, and aluminum contained in the obtained phosphor (i.e., the amount of the second coactivator). The amount used is such that the amount (amount) is 5 x 10 -6 to 5 x 10 -2 % by weight of the zinc sulfide matrix. That is, like silver and gallium, most of the aluminum in the second co-activator raw material remains in the resulting phosphor and becomes part of the second coactivator.
However, most of the halogen in the second coactivator raw material is lost during firing, and only a small portion remains in the resulting phosphor. Therefore, the above-mentioned alkali metal or alkaline earth metal halide, which is a raw material for halogen, is used in an amount that contains several tens to hundreds of times as much halogen as the desired amount of halogen activation, depending on the firing temperature, etc. .
Note that when silver halide is used as a raw material for the activator silver, when gallium halide is used as a raw material for the first co-activator gallium, or when aluminum halide is used as a raw material for aluminum, A portion of the necessary halogen is also provided by these raw materials.
上記アルカリ金属あるいはアルカリ土類金属の
ハロゲン化物はハロゲン供与剤であると同時に融
剤としても作用する。 The alkali metal or alkaline earth metal halide acts both as a halogen donor and as a flux.
上記４つの螢光体原料を必要量秤取し、ボール
ミル、ミキサーミル等の粉砕混合機を用いて充分
に混合して螢光体原料混合物を得る。なおこの螢
光体原料の混合は上記(i)の母体および硫黄の原料
に上記(ii)の付活剤原料、(iii)の第１の共付活剤原料
および(iv)の第２の共付活剤原料を溶液として添加
して湿式で行なつてもよい。この場合、混合の後
得られた螢光体原料混合物を充分に乾燥させる。 Required amounts of the above four phosphor raw materials are weighed out and thoroughly mixed using a grinding mixer such as a ball mill or a mixer mill to obtain a phosphor raw material mixture. This phosphor raw material is mixed by adding the base material and sulfur raw material in (i) above, the activator raw material in (ii) above, the first co-activator raw material in (iii), and the second raw material in (iv). The co-activator raw material may be added as a solution and carried out in a wet manner. In this case, the phosphor raw material mixture obtained after mixing is sufficiently dried.
次に得られた螢光体原料混合物を石英ルツボ、
石英チユーブ等の耐熱性容器に充填して焼成を行
なう。焼成は硫化水素雰囲気、硫黄蒸気雰囲気、
二硫化炭素雰囲気等の硫化性雰囲気中で行なう。
焼成温度は600乃至1200℃が適当である。焼成温
度が1050℃よりも高い場合には六方晶系を主結晶
相とする螢光体が得られ、一方焼成温度が1050℃
以下である場合には立方晶系を主結晶相とする螢
光体が得られる。すなわち、本発明の螢光体は
1050℃付近に相転移点を有している。後に説明す
るように、立方晶系を主結晶相とする螢光体の方
が六方晶系を主結晶相とする螢光体よりも高解像
度ブラウン管用青色発光螢光体としてより好まし
いものである。従つて、焼成温度は600乃至1050
℃であるのが好ましく、より好ましくは800乃至
1050℃である。焼成時間は用いられる焼成温度、
耐熱性容器に充填される螢光体原料混合物の量等
によつて異なるが、上記焼成温度範囲では0.5乃
至７時間が適当である。焼成後、得られた焼成物
を水洗し、乾燥させ、篩にかけて本発明の螢光体
を得る。 Next, the obtained phosphor raw material mixture was placed in a quartz crucible.
It is filled into a heat-resistant container such as a quartz tube and fired. Firing is carried out in hydrogen sulfide atmosphere, sulfur vapor atmosphere,
The test is carried out in a sulfidic atmosphere such as a carbon disulfide atmosphere.
A suitable firing temperature is 600 to 1200°C. When the firing temperature is higher than 1050°C, a phosphor with a hexagonal system as the main crystal phase is obtained;
In the following cases, a phosphor having a cubic crystal system as the main crystal phase can be obtained. That is, the phosphor of the present invention is
It has a phase transition point around 1050℃. As will be explained later, a phosphor having a cubic crystal system as its main crystal phase is more preferable as a blue-emitting phosphor for a high-resolution cathode ray tube than a phosphor having a hexagonal system as its main crystal phase. . Therefore, the firing temperature is 600 to 1050
It is preferably 800°C to 800°C, more preferably 800 to
The temperature is 1050℃. The firing time depends on the firing temperature used,
Although it varies depending on the amount of the phosphor raw material mixture filled in the heat-resistant container, 0.5 to 7 hours is appropriate in the above firing temperature range. After firing, the obtained fired product is washed with water, dried, and sieved to obtain the phosphor of the present invention.
以上説明した製造方法によつて得られる本発明
の螢光体は硫化亜鉛を母体とし、銀を付活剤と
し、ガリウムを第１の共付活剤とし、塩素、臭
素、沃素、弗素およびアルミニウムのうちの少な
くとも１種を第２の共付活剤とし、上記付活剤、
第１の共付活剤および第２の共付活剤の量がそれ
ぞれ上記硫化亜鉛母体の５×10-4乃至10-1重量
％、10-6乃至５×10-1重量％および５×10-6乃至
５×10-2重量％であり、かつ硫黄を上記硫化亜鉛
母体の10-5乃至８×10-1重量％含有する螢光体で
ある。この螢光体は従来のZnS：Ag、Ｘ螢光体
と同じく電子線、紫外線等の励起下で高輝度の青
色発光を示すが、励起停止後の10％残光時間はガ
リウムの付活量に依存して従来のZnS：Ag、Ｘ
螢光体よりも数十乃至数百倍長い。このように本
発明の螢光体は長い残光を示し、その残光特性は
第１の共付活剤ガリウムの付活量に依存して変化
するが、ガリウムは発光輝度および発光色の純度
にも影響を及ぼす。すなわち、本発明の螢光体に
おいてはガリウム付活量が増加するに従つて発光
輝度は低下し、またガリウム付活量が非常に増加
すると発光色の純度は低下する。しかしながら、
先に述べたように本発明の螢光体に微量含まれる
硫黄はガリウムを付活したことによる発光輝度の
低下を抑制する作用を有しており、従つて本発明
の螢光体は微量の硫黄を含有しないこと以外は同
じ組成を有するZnS：Ag、Ga、Ｘ螢光体よりも
高輝度の発光を示す。 The phosphor of the present invention obtained by the manufacturing method described above uses zinc sulfide as a matrix, silver as an activator, gallium as a first co-activator, chlorine, bromine, iodine, fluorine, and aluminum. at least one of them is used as a second co-activator, the above-mentioned activator,
The amounts of the first coactivator and the second coactivator are 5×10 −4 to 10 −1 % by weight, 10 −6 to 5×10 −1 % by weight, and 5× of the zinc sulfide matrix, respectively. 10 -6 to 5 x 10 -2 weight %, and the phosphor contains sulfur in an amount of 10 -5 to 8 x 10 -1 weight % of the zinc sulfide matrix. Like conventional ZnS:Ag, Conventional ZnS depending on:Ag,X
It is several tens to hundreds of times longer than the fluorescent material. As described above, the phosphor of the present invention exhibits a long afterglow, and its afterglow characteristics vary depending on the activation amount of the first co-activator gallium. It also affects. That is, in the phosphor of the present invention, as the amount of gallium activation increases, the luminance of the emitted light decreases, and when the amount of gallium activation increases significantly, the purity of the emitted light color decreases. however,
As mentioned above, the sulfur contained in the phosphor of the present invention in a trace amount has the effect of suppressing the reduction in luminance caused by activating gallium. It exhibits higher luminance than ZnS:Ag, Ga, X phosphor, which has the same composition except that it does not contain sulfur.
また先に説明したように、本発明の螢光体は
1050℃付近に相転移点を有しており、1050℃以下
の温度で焼成することによつて得られた螢光体は
立方晶系を主結晶相とし、一方1050℃よりも高い
温度で焼成することによつて得られた螢光体は六
方晶系を主結晶相とする。立方晶系を主結晶相と
する螢光体と六方晶系を主結晶相とする螢光体を
比較する場合、前者は後者よりも発光輝度が約
1.3乃至２倍近く、また発光輝度および発光色純
度のより高いガリウム付活量が比較的少ない螢光
体については、前者は後者よりも10％残光時間が
長い。これらの点から、立方晶系を主結晶相とす
る螢光体の方が六方晶系を主結晶相とする螢光体
よりも高解像度ブラウン管用青色発光螢光体とし
てより好ましいものである。なお、立方晶系を主
結晶相とする螢光体の発光スペクトルは六方晶系
を主結晶相とする螢光体の発光スペクトルよりも
わずかに長波長側にある。 Furthermore, as explained earlier, the phosphor of the present invention
It has a phase transition point around 1050℃, and the phosphor obtained by firing at a temperature below 1050℃ has a cubic crystal system as the main crystal phase, while the phosphor obtained by firing at a temperature higher than 1050℃ has a cubic crystal phase. The phosphor obtained by this process has a hexagonal crystal system as its main crystal phase. When comparing a phosphor with a cubic crystal system as the main crystal phase and a phosphor with a hexagonal system as the main crystal phase, the former has a luminance that is approximately higher than the latter.
For phosphors with a relatively small amount of gallium activation, which is approximately 1.3 to 2 times higher and has higher emission brightness and emission color purity, the former has a 10% longer afterglow time than the latter. From these points of view, a phosphor having a cubic system as its main crystal phase is more preferable as a blue-emitting phosphor for a high-resolution cathode ray tube than a phosphor having a hexagonal system as its main crystal phase. Note that the emission spectrum of a phosphor having a cubic crystal system as its main crystal phase is slightly on the longer wavelength side than that of a phosphor having a hexagonal system as its main crystal phase.
第１図は本発明の螢光体の発光スペクトルを従
来のZnS：Ag、Ｘ螢光体の発光スペクトルと比
較して例示するものである。第１図において、曲
線ａは銀および塩素の付活量がそれぞれ硫化亜鉛
母体の10-2重量％および10-4重量％である従来の
立方晶系を主結晶相とするZnS：Ag、Cl螢光体
の発光スペクトル、曲線ｂおよびｃはそれぞれ銀
および塩素の付活量は上記と同じでありガリウム
付活量および硫黄含有量がそれぞれ硫化亜鉛母体
の10-2重量％および10-4重量％である本発明の立
方晶系および六方晶系を主結晶相とする硫黄含有
ZnS：Ag、Ga、Cl螢光体の発光スペクトル、曲
線ｄは銀および塩素の付活量および硫黄含有量は
上記と同じでありガリウム付活量が硫化亜鉛母体
の10-1重量％である本発明の立方晶系を主結晶相
とする硫黄含有ZnS：Ag、Ga、Cl螢光体の発光
スペクトルである。 FIG. 1 illustrates the emission spectrum of the phosphor of the present invention in comparison with that of a conventional ZnS:Ag,X phosphor. In Figure 1, curve a represents conventional ZnS whose main crystal phase is a cubic system in which the activation amounts of silver and chlorine are 10 -2 % and 10 -4 % by weight of the zinc sulfide matrix, respectively: Ag, Cl In the emission spectrum of the phosphor, curves b and c, the activation amounts of silver and chlorine are the same as above, and the activation amount of gallium and the sulfur content are 10 -2 % and 10 -4 % by weight of the zinc sulfide matrix, respectively. % of sulfur containing cubic and hexagonal crystalline main crystal phases of the present invention
Emission spectrum of ZnS: Ag, Ga, Cl phosphor, curve d shows that the activation amount of silver and chlorine and the sulfur content are the same as above, and the activation amount of gallium is 10 -1 % by weight of the zinc sulfide matrix. 1 is an emission spectrum of the sulfur-containing ZnS:Ag, Ga, Cl phosphor of the present invention whose main crystal phase is cubic system.
第１図に例示されるように、本発明の螢光体
（曲線ｂ，ｃおよびｄ）は従来のZnS：Ag、Ｘ螢
光体（曲線ａ）と同様に青色発光を示す。また曲
線ｂと曲線ｄの比較から明らかなように、本発明
の螢光体はガリウム付活量が非常に増加すると発
光スペクトルの半値幅が広くなり発光色の色純度
が低下する。ガリウム付活量が10-2重量％である
本発明の螢光体の発光スペクトル（曲線ｂ）は従
来のZnS：Ag、Ｘ螢光体の発光スペクトル（曲
線ａ）よりも半値幅が狭く、従つてガリウム付活
量が少なくとも10-2重量％以下である本発明の螢
光体は従来のZnS：Ag、Ｘ螢光体よりも色純度
の高い青色発光を示す。さらに曲線ｂと曲線ｃの
比較から明らかなように、本発明の螢光体におい
て立方晶系を主結晶相とする螢光体（曲線ｂ）は
六方晶系を主結晶相とする螢光体（曲線ｃ）より
もわずかに長波長側に発光スペクトルを有してい
る。 As illustrated in FIG. 1, the phosphor of the present invention (curves b, c and d) exhibits blue emission similar to the conventional ZnS:Ag,X phosphor (curve a). Furthermore, as is clear from the comparison of curves b and d, when the gallium activation amount of the phosphor of the present invention increases significantly, the half-width of the emission spectrum becomes wider and the color purity of the emitted color decreases. The emission spectrum (curve b) of the phosphor of the present invention with a gallium activation amount of 10 -2 % by weight has a narrower half-width than the emission spectrum (curve a) of the conventional ZnS:Ag,X phosphor. Therefore, the phosphor of the present invention having a gallium activation amount of at least 10 -2 % by weight or less emits blue light with higher color purity than the conventional ZnS:Ag,X phosphor. Furthermore, as is clear from the comparison between curve b and curve c, in the phosphor of the present invention, the phosphor having a cubic system as the main crystal phase (curve b) is different from the phosphor having a hexagonal system as the main crystal phase. (curve c) has an emission spectrum on the slightly longer wavelength side.
なお以上第１図によつて説明した本発明の螢光
体におけるガリウム付活量の変化に伴なう発光ス
ペクトルの変化（発光色の色純度の変化）の様子
は硫黄を含有しないZnS：Ag、Ga、Ｘ螢光体の
場合とほぼ同じである。すなわち、本発明の螢光
体に微量含まれる硫黄は螢光体の発光スペクトル
（発光色の色純度）にほとんど影響を及ぼさない。 Note that the changes in the emission spectrum (changes in the color purity of the emitted light color) due to changes in the amount of gallium activation in the phosphor of the present invention explained above with reference to FIG. , Ga, and X phosphors. That is, the trace amount of sulfur contained in the phosphor of the present invention has almost no effect on the emission spectrum (color purity of emitted light) of the phosphor.
第２図は本発明の螢光体の残光特性を従来の
ZnS：Ag、Ｘ螢光体の残光特性と比較して例示
するグラフである。第２図において、曲線ａは銀
および塩素の付活量がそれぞれ硫化亜鉛母体の
10-2重量％および10-4重量％である従来の立方晶
系を主結晶相とするZnS：Ag、Cl螢光体の電子
線励起停止後の残光特性、曲線ｂは銀および塩素
の付活量は上記と同じでありガリウム付活量およ
び硫黄含有量がそれぞれ硫化亜鉛母体の10-2重量
％および10-4重量％である本発明の立方晶系を主
結晶相とする硫黄含有ZnS：Ag、Ga、Cl螢光体
の電子線励起停止後の残光特性である。 Figure 2 shows the afterglow characteristics of the phosphor of the present invention compared to the conventional one.
It is a graph illustrating a comparison with the afterglow characteristics of ZnS:Ag and X phosphors. In Figure 2, curve a shows the activation amount of silver and chlorine, respectively, in the zinc sulfide matrix.
Curve b shows the afterglow characteristics of ZnS:Ag,Cl phosphors with the main crystalline phase of the conventional cubic system, which are 10 -2 and 10 -4 wt%, after electron beam excitation is stopped. The activation amount is the same as above, and the gallium activation amount and sulfur content are respectively 10 -2 % by weight and 10 -4 % by weight of the zinc sulfide matrix. ZnS: Afterglow characteristics of Ag, Ga, Cl phosphor after electron beam excitation is stopped.
第２図から明らかなように、本発明の硫黄含有
ZnS：Ag、Ga、Cl螢光体は従来のZnS：Ag、Cl
螢光体に比較して著しく長残光である。従来の
ZnS：Ag、Cl螢光体の10％残光時間が約150マイ
クロ秒であるのに対して本発明の硫黄含有ZnS：
Ag、Ga、Cl螢光体の10％残光時間は約40ミリ秒
であり、従来のZnS：Ag、Cl螢光体の250倍以上
である。 As is clear from FIG. 2, the sulfur-containing
ZnS:Ag,Ga,Cl phosphor is conventional ZnS:Ag,Cl
It has a significantly longer afterglow compared to fluorescent materials. Traditional
ZnS: The 10% afterglow time of Ag, Cl phosphor is about 150 microseconds, whereas the sulfur-containing ZnS of the present invention:
The 10% afterglow time of the Ag, Ga, Cl phosphor is approximately 40 milliseconds, which is more than 250 times that of the conventional ZnS:Ag, Cl phosphor.
第３図は本発明の螢光体におけるガリウム付活
量と10％残光時間との関係を例示するグラフであ
る。第３図において、曲線ａは銀および塩素の付
活量がそれぞれ硫化亜鉛母体の10-2重量％および
10-4重量％であり硫黄含有量が硫化亜鉛母体の
10-4重量％ある立方晶系を主結晶相とする硫黄含
有ZnS：Ag、Ga、Cl螢光体における上記関係、
曲線ｂは銀および塩素の付活量および硫黄含有量
が上記と同じである六方晶系を主結晶相とする硫
黄含有ZnS：Ag、Ga、Cl螢光体における上記関
係である。なお、第３図の10％残光時間を表わす
縦軸上に示される〇印は、銀および塩素の付活量
が上記と同じである従来の立方晶系を主結晶相と
するZnS：Ag、Cl螢光体の10％残光時間（約150
マイクロ秒）である。 FIG. 3 is a graph illustrating the relationship between the amount of gallium activation and the 10% afterglow time in the phosphor of the present invention. In Figure 3, curve a shows activation amounts of silver and chlorine of 10 -2% by weight and 10 -2 % by weight of the zinc sulfide matrix, respectively.
10 -4 % by weight and the sulfur content is higher than that of the zinc sulfide matrix.
The above relationship in the sulfur-containing ZnS: Ag, Ga, Cl phosphor with cubic crystal system as the main crystal phase with 10 -4 % by weight,
Curve b shows the above relationship in a sulfur-containing ZnS:Ag, Ga, Cl phosphor having a hexagonal system as the main crystal phase and having the same activation amounts of silver and chlorine and the same sulfur content as above. In addition, the mark ○ shown on the vertical axis representing the 10% afterglow time in Figure 3 indicates the conventional ZnS:Ag whose main crystal phase is the cubic system with the same activation amounts of silver and chlorine as above. , 10% afterglow time of Cl phosphor (approximately 150
microseconds).
第３図に例示されるように、ガリウム付活量が
硫化亜鉛母体の10-6乃至５×10-1重量％の範囲に
ある本発明の螢光体は主結晶相が立方晶系あるい
は六方晶系のいずれの場合も10％残光時間が従来
のZns：Ag、Ｘ螢光体よりも数十乃至数百倍長
い。特にガリウム付活量が５×10-4乃至10-1重量
％の範囲にある本発明の螢光体は10％残光時間が
著しく長い。しかしながら、先に説明したように
本発明の螢光体の発光輝度はガリウム付活量が増
加するに従つて低下し、また本発明の螢光体の発
光色純度はガリウム付活量が非常に増加すると低
下する。この発光輝度および発光色純度を考慮に
入れると、本発明の螢光体の好ましいガリウム付
活量は５×10-6乃至10-2重量％である。第３図に
例示されるようにガリウム付活量がこの範囲にあ
る本発明の螢光体の10％残光時間は約５乃至40ミ
リ秒であるが、この10％残光時間は高解像度ブラ
ウン管用青色発光螢光体として充分なものであ
る。 As illustrated in FIG. 3, the phosphor of the present invention in which the gallium activation amount is in the range of 10 -6 to 5 x 10 -1 weight % of the zinc sulfide matrix has a cubic or hexagonal crystal phase. In either case of the crystal system, the 10% afterglow time is several tens to hundreds of times longer than that of conventional Zns:Ag, X phosphors. In particular, the phosphor of the present invention having a gallium activation amount in the range of 5 x 10 -4 to 10 -1 % by weight has an extremely long 10% afterglow time. However, as explained above, the luminance of the phosphor of the present invention decreases as the amount of gallium activation increases, and the purity of the luminescent color of the phosphor of the present invention decreases as the amount of gallium activation increases. When it increases, it decreases. Taking into consideration the emission brightness and emission color purity, the preferred gallium activation amount of the phosphor of the present invention is 5 x 10 -6 to 10 -2 % by weight. As illustrated in FIG. 3, the 10% afterglow time of the phosphor of the present invention with a gallium activation amount within this range is about 5 to 40 milliseconds, but this 10% afterglow time is It is sufficient as a blue-emitting phosphor for cathode ray tubes.
先に説明したように、本発明の螢光体のうち立
方晶系を主結晶相とする螢光体は六方晶系を主結
晶相とする螢光体よりも発光輝度が約1.3乃至２
倍高い。また第３図から明らかなように上記好ま
しいガリウム付活量範囲（５×10-6乃至10-2重量
％）においては立方晶系を主結晶相とする螢光体
は六方晶系を主結晶相とする螢光体よりも10％残
光時間が長い。これらの点から、立方晶系を主結
晶相とする螢光体の方が六方晶系を主結晶相とす
る螢光体よりも高解像度ブラウン管用青色発光螢
光体としてより好ましいものである。特にガリウ
ム付活量が５×10-6乃至10-2重量％の範囲にある
立方晶系を主結晶相とする螢光体は高解像度ブラ
ウン管に最も適したものである。 As explained above, among the phosphors of the present invention, a phosphor having a cubic crystal system as a main crystal phase has a luminance of about 1.3 to 2 times higher than a phosphor having a hexagonal system as a main crystal phase.
twice as expensive. Furthermore, as is clear from FIG. 3, in the preferred gallium activation amount range (5 x 10 -6 to 10 -2 wt%), the phosphor having a cubic crystal system as its main crystal phase has a hexagonal system as its main crystal phase. The afterglow time is 10% longer than the phosphor used as the phase. From these points of view, a phosphor having a cubic system as its main crystal phase is more preferable as a blue-emitting phosphor for a high-resolution cathode ray tube than a phosphor having a hexagonal system as its main crystal phase. In particular, a phosphor having a cubic crystal system as a main crystal phase and having a gallium activation amount in the range of 5×10 -6 to 10 -2 weight % is most suitable for high-resolution cathode ray tubes.
なお第３図は硫黄含有ZnS：Ag、Ga、Cl螢光
体についてのガリウム付活量と10％残光時間との
関係を示すグラフであるが、第２の共付活剤が臭
素、沃素、弗素あるいはアルミニウムの場合もガ
リウム付活量と10％残光時間との関係は第３図と
同じような傾向にあることが確認された。 Figure 3 is a graph showing the relationship between the amount of gallium activation and the 10% afterglow time for a sulfur-containing ZnS:Ag, Ga, Cl phosphor. In the case of fluorine or aluminum, it was confirmed that the relationship between the amount of gallium activation and the 10% afterglow time had the same tendency as shown in Figure 3.
以上第３図によつて説明した本発明の螢光体に
おけるガリウム付活量と10％残光時間との関係は
硫黄を含有しないZnS：Ag、Ga、Ｘ螢光体にお
けるガリウム付活量と10％残光時間との関係とほ
ぼ同じである。すなわち、本発明の螢光体に微量
含まれる硫黄は螢光体の残光特性にほとんど影響
を及ぼさない。 The relationship between the amount of gallium activation and the 10% afterglow time in the phosphor of the present invention explained above with reference to FIG. The relationship is almost the same as the 10% afterglow time. That is, the trace amount of sulfur contained in the phosphor of the present invention has almost no effect on the afterglow properties of the phosphor.
上述のように本発明の螢光体に微量含まれる硫
黄は螢光体の発光色純度および残光特性にほとん
ど影響を及ぼさない。しかしながら、本発明の螢
光体に微量含まれる硫黄は螢光体の発光輝度を高
める作用を有している。従つて本発明の螢光体は
微量の硫黄を含有しないこと以外は同じ組成を有
するZnS：Ag、Ga、Ｘ螢光体よりも高輝度の発
光を示す。 As mentioned above, the trace amount of sulfur contained in the phosphor of the present invention has almost no effect on the luminous color purity and afterglow characteristics of the phosphor. However, the trace amount of sulfur contained in the phosphor of the present invention has the effect of increasing the luminance of the phosphor. Therefore, the phosphor of the present invention exhibits higher luminance than a ZnS:Ag, Ga, X phosphor having the same composition except that it does not contain a trace amount of sulfur.
第４図は本発明の螢光体におけるガリウム付活
量と発光輝度との関係を硫黄を含有しないZnS：
Ag、Ga、Ｘ螢光体におけるガリウム付活量と発
光輝度との関係と比較して例示するグラフであ
る。第４図において、曲線ａは銀および塩素の付
活量がそれぞれ硫化亜鉛母体の10-2重量％および
10-4重量％である立方晶系を主結晶相とする硫黄
を含有しないZnS：Ag、Ga、Cl螢光体における
上記関係、曲線ｂは銀および塩素の付活量は上記
と同じであり硫黄含有量が硫化亜鉛母体の10-4重
量％である本発明の立方晶系を主結晶相とする硫
黄含有ZnS：Ag、Ga、Cl螢光体における上記関
係である。 Figure 4 shows the relationship between the amount of gallium activation and the luminance in the phosphor of the present invention for sulfur-free ZnS:
It is a graph illustrating a comparison of the relationship between the amount of gallium activation and the luminance in Ag, Ga, and X phosphors. In Figure 4, curve a shows activation amounts of silver and chlorine of 10 -2% by weight and 10 -2 % by weight of the zinc sulfide matrix, respectively.
The above relationship in the sulfur-free ZnS:Ag, Ga, Cl phosphor with a cubic crystalline main crystal phase of 10 -4 % by weight, curve b, shows that the activation amounts of silver and chlorine are the same as above. This is the above relationship in the sulfur-containing ZnS:Ag, Ga, Cl phosphor of the present invention having a cubic system as the main crystal phase and having a sulfur content of 10 -4 % by weight of the zinc sulfide matrix.
第４図に例示されるように、本発明の螢光体あ
るいは硫黄を含有しないZnS：Ag、Ga、Ｘ螢光
体のいずれにおいてもガリウム付活量が増加する
に従つて発光輝度は低下する。しかしながら、第
４図から明らかなように本発明の螢光体は微量の
硫黄を含有しないこと以外は同じ組成を有する
ZnS：Ag、Ga、Ｘ螢光体よりも高輝度の発光を
示す。すなわち、本発明の螢光体に微量含まれる
硫黄はガリウムを付活したことによる発光輝度の
低下を抑制する作用を有している。このような作
用は硫黄含有量が硫化亜鉛母体の５×10-5乃至
10-3重量％の範囲にある場合に特に顕著であるよ
うである。先に説明したように本発明の螢光体の
発光色純度および残光特性は硫黄を含有しないこ
と以外は同じ組成を有するZnS：Ag、Ga、Ｘ螢
光体の発光色純度および残光特性とほぼ同じであ
る。従つて発光輝度を考慮に入れると、本発明の
螢光体は硫黄を含有しないZnS：Ag、Ga、Ｘ螢
光体よりも高解像度ブラウン管により適したもの
であると言うことができる。 As illustrated in Figure 4, the luminance of the phosphor of the present invention or the sulfur-free ZnS:Ag, Ga, X phosphor decreases as the amount of gallium activation increases. . However, as is clear from FIG. 4, the phosphor of the present invention has the same composition except that it does not contain a trace amount of sulfur.
ZnS: Exhibits higher luminance than Ag, Ga, and X phosphors. That is, the trace amount of sulfur contained in the phosphor of the present invention has the effect of suppressing the reduction in luminance caused by activating gallium. This effect occurs when the sulfur content is between 5×10 -5 and 5×10 −5 of the zinc sulfide matrix.
This appears to be particularly noticeable in the range of 10 -3 % by weight. As explained above, the luminescent color purity and afterglow characteristics of the phosphor of the present invention are the same as those of the ZnS:Ag, Ga, X phosphor having the same composition except that it does not contain sulfur. is almost the same. Taking into account the luminance, it can therefore be said that the phosphor of the present invention is more suitable for high resolution cathode ray tubes than the sulfur-free ZnS:Ag,Ga,X phosphor.
以上説明したように、本発明は特に高解像度ブ
ラウン管用青色発光螢光体として有用な長残光性
の青色発光螢光体を提供するものであり、その工
業的利用価値は非常に大きなものである。なお、
本発明の螢光体は第１の共付活剤ガリウムの一部
がインジウムあるいはスカンジウムあるいはその
両方で置換されてもよい。また本発明の螢光体は
銅、金、２価のユーロピウム、ビスマス、アンチ
モン等の付活剤でさらに付活されていてもよい。
さらに本発明の螢光体は発光波長を多少長波長側
へシフトさせるために硫化亜鉛母体の亜鉛の一部
がカドミウムによつてあるいは硫黄の一部がセレ
ンによつて置換されていてもよい。 As explained above, the present invention provides a long-lasting blue-emitting phosphor that is particularly useful as a blue-emitting phosphor for high-resolution cathode ray tubes, and its industrial utility value is extremely large. be. In addition,
In the phosphor of the present invention, a portion of the first coactivator gallium may be replaced with indium, scandium, or both. Further, the phosphor of the present invention may be further activated with an activator such as copper, gold, divalent europium, bismuth, or antimony.
Further, in the phosphor of the present invention, part of the zinc in the zinc sulfide matrix may be replaced by cadmium, or part of the sulfur may be replaced by selenium, in order to shift the emission wavelength to a somewhat longer wavelength side.
次に実施例によつて本発明を説明する。 Next, the present invention will be explained with reference to Examples.
実施例 １
硫酸亜鉛水溶液にその水溶液のPH値を硫酸の添
加により常に５に維持しながら硫化アンモニウム
を添加して硫化亜鉛を沈殿させた。このようにし
て調製した硫化亜鉛生粉は化学量論量以外の硫黄
を硫化亜鉛の７重量％含んでいた。この化学量論
量よりも多量の硫黄を含有する硫化亜鉛生粉2140
ｇ（すなわち硫化亜鉛2000ｇ＋硫黄140ｇ）、硝酸
銀（AgNO3）0.32ｇ、硝酸ガリウム〔Ga
（NO3）3・8H2O〕1.15ｇ、塩化ナトリウム
（NaCl）10ｇおよび塩化マグネシウム（MgCl2）
10ｇをボールミルを用いて充分に混合した後、硫
黄および炭素を適当量加えて石英ルツボに充填し
た。石英ルツボに蓋をした後、ルツボを電気炉に
入れ、950℃の温度で３時間焼成を行なつた。こ
の焼成の間ルツボ内部は二硫化炭素雰囲気になつ
ている。焼成後得られた焼成物をルツボから取り
出し、水洗し、乾燥させ、篩にかけた。このよう
にして銀、ガリウムおよび塩素の付活量および硫
黄含有量がそれぞれ硫化亜鉛母体の10-2重量％、
10-2重量％、10-4重量％および10-4重量％である
硫黄含有ZnS：Ag、Ga、Cl螢光体を得た。Example 1 Ammonium sulfide was added to a zinc sulfate aqueous solution while the pH value of the aqueous solution was constantly maintained at 5 by addition of sulfuric acid to precipitate zinc sulfide. The raw zinc sulfide powder thus prepared contained 7% by weight of zinc sulfide of non-stoichiometric sulfur. Zinc sulfide raw powder 2140 containing more sulfur than this stoichiometric amount
(i.e. 2000 g of zinc sulfide + 140 g of sulfur), 0.32 g of silver nitrate (AgNO 3 ), 0.32 g of gallium nitrate [Ga
(NO 3 ) 3・8H 2 O] 1.15 g, sodium chloride (NaCl) 10 g and magnesium chloride (MgCl 2 )
After thoroughly mixing 10 g using a ball mill, appropriate amounts of sulfur and carbon were added and the mixture was charged into a quartz crucible. After covering the quartz crucible, the crucible was placed in an electric furnace and fired at a temperature of 950°C for 3 hours. During this firing, the inside of the crucible is in a carbon disulfide atmosphere. The fired product obtained after firing was taken out from the crucible, washed with water, dried, and passed through a sieve. In this way, the activation amount of silver, gallium and chlorine and the sulfur content are respectively 10 -2 % by weight of the zinc sulfide matrix,
Sulfur-containing ZnS:Ag, Ga, Cl phosphors of 10 −2 wt. %, 10 −4 wt. % and 10 −4 wt. % were obtained.
上記螢光体は電子線励起下でその発光スペクト
ルが第１図曲線ｂで示される色純度の高い青色発
光を示し、またその電子線励起停止後の10％残光
時間は約40ミリ秒であつた。 The above-mentioned phosphor exhibits blue light emission with high color purity, whose emission spectrum is shown by curve b in Figure 1 under electron beam excitation, and the 10% afterglow time after the electron beam excitation is stopped is approximately 40 milliseconds. It was hot.
実施例 ２
硝酸ガリウムを0.23ｇ使用すること以外は実施
例１と同様にして銀、ガリウムおよび塩素の付活
量および硫黄含有量がそれぞれ硫化亜鉛母体の
10-2重量％、２×10- 3重量％、10-4重量％および
10-4重量％である硫黄含有Zns：Ag、Ga、Cl螢
光体を得た。Example 2 Same as Example 1 except that 0.23g of gallium nitrate was used.
10 -2 wt% , 2 x 10 -3 wt %, 10 -4 wt% and
A sulfur-containing Zns:Ag, Ga, Cl phosphor with a sulfur content of 10 -4 % by weight was obtained.
上記螢光体は電子線励起下で色純度の高い青色
発光を示し、またその電子線励起停止後の10％残
光時間は35ミリ秒であつた。 The above-mentioned phosphor exhibited blue light emission with high color purity under electron beam excitation, and the 10% afterglow time after the electron beam excitation was stopped was 35 milliseconds.
実施例 ３
硝酸ガリウムを0.046ｇ使用すること以外は実
施例１と同様にして銀、ガリウムおよび塩素の付
活量および硫黄含有量がそれぞれ硫化亜鉛母体の
10-2重量％、４×10-4重量％、10-4重量％および
10-4重量％である硫黄含有ZnS：Ag、Ga、Cl螢
光体を得た。Example 3 The activation amounts of silver, gallium, and chlorine and the sulfur content were determined to be the same as those of the zinc sulfide matrix in the same manner as in Example 1 except that 0.046 g of gallium nitrate was used.
10 -2 wt%, 4 x 10 -4 wt%, 10 -4 wt% and
A ZnS:Ag, Ga, Cl phosphor with a sulfur content of 10 -4 % by weight was obtained.
上記螢光体は電子線励起下で色純度の高い青色
発光を示し、またその電子線励起停止後の10％残
光時間は18ミリ秒であつた。 The above-mentioned phosphor exhibited blue light emission with high color purity under electron beam excitation, and the 10% afterglow time after the electron beam excitation stopped was 18 milliseconds.
実施例 ４
硝酸ガリウムを11.48ｇ使用すること以外は実
施例１と同様にして銀、ガリウムおよび塩素の付
活量および硫黄含有量がそれぞれ硫化亜鉛母体の
10-2重量％、10-1重量％、10-4重量％および10-4
重量％である硫黄含有ZnS：Ag、Ga、Cl螢光体
を得た。Example 4 The activation amount of silver, gallium, and chlorine and the sulfur content were the same as those of the zinc sulfide matrix in the same manner as in Example 1 except that 11.48 g of gallium nitrate was used.
10 -2 wt%, 10 -1 wt%, 10 -4 wt% and 10 -4
A ZnS:Ag, Ga, Cl phosphor containing sulfur in weight % was obtained.
上記螢光体は電子線励起下でその発光スペクト
ルが第１図曲線ｄで示される青色発光を示し、ま
たその電子線励起停止後の10％残光時間は約18ミ
リ秒であつた。 The above phosphor exhibited blue light emission whose emission spectrum was shown by curve d in Figure 1 under electron beam excitation, and the 10% afterglow time after the electron beam excitation stopped was about 18 milliseconds.
第１図は本発明の青色発光螢光体の発光スペク
トルを従来のZnS：Ag、Ｘ青色発光螢光体の発
光スペクトルと比較して例示するものである。第
２図は本発明の青色発光螢光体の残光特性を従来
のZnS：Ag、Ｘ青色発光螢光体の残光特性と比
較して例示するグラフである。第３図は本発明の
青色発光螢光体におけるガリウム付活量と10％残
光時間との関係を例示するグラフである。第４図
は本発明の青色発光螢光体におけるガリウム付活
量と発光輝度との関係を硫黄を含有しないZnS：
Ag、Ga、Ｘ青色発光螢光体におけるガリウム付
活量と発光輝度との関係と比較して例示するグラ
フである。
FIG. 1 illustrates the emission spectrum of the blue-emitting phosphor of the present invention in comparison with that of a conventional ZnS:Ag,X blue-emitting phosphor. FIG. 2 is a graph illustrating the afterglow characteristics of the blue-emitting phosphor of the present invention in comparison with the afterglow characteristics of a conventional ZnS:Ag,X blue-emitting phosphor. FIG. 3 is a graph illustrating the relationship between the amount of gallium activation and the 10% afterglow time in the blue-emitting phosphor of the present invention. Figure 4 shows the relationship between the amount of gallium activation and luminance in the blue-emitting phosphor of the present invention using sulfur-free ZnS:
It is a graph illustrating a comparison of the relationship between the amount of gallium activation and the luminance in Ag, Ga, and X blue light emitting phosphors.
Claims (1)
ウムを第１の共付活剤とし、塩素、臭素、沃素、
弗素およびアルミニウムのうちの少なくとも１種
を第２の共付活剤とし、上記付活剤、第１の共付
活剤および第２の共付活剤の量がそれぞれ上記硫
化亜鉛母体の５×10-4乃至10-1重量％、10-6乃至
５×10-1重量％および５×10-6乃至５×10-2重量
％であり、かつ硫黄を上記硫化亜鉛母体の10-5乃
至８×10-1重量％含有することを特徴とする長残
光性青色発光硫化亜鉛螢光体。 ２ 上記第１の共付活剤の量が５×10-6乃至10-2
重量％であることを特徴とする特許請求の範囲第
１項記載の螢光体。 ３ 上記硫黄の含有量が５×10-5乃至10-3重量％
であることを特徴とする特許請求の範囲第１項ま
たは第２項記載の螢光体。 ４ 主結晶相が立方晶系であることを特徴とする
特許請求の範囲第１項乃至第３項のいずれかの項
記載の螢光体。[Claims] 1 Zinc sulfide is used as a matrix, silver is used as an activator, gallium is used as a first co-activator, and chlorine, bromine, iodine,
At least one of fluorine and aluminum is used as a second co-activator, and the amounts of the above-mentioned activator, first co-activator and second co-activator are respectively 5× of the above-mentioned zinc sulfide matrix. 10 -4 to 10 -1 % by weight, 10 -6 to 5×10 -1 % by weight, and 5×10 -6 to 5×10 -2 % by weight, and the sulfur content is 10 -5 to 10 -5 of the zinc sulfide matrix. A long-afterglow blue-emitting zinc sulfide phosphor containing 8×10 -1 % by weight. 2 The amount of the first co-activator is 5×10 -6 to 10 -2
% by weight of the phosphor according to claim 1. 3 The above sulfur content is 5×10 -5 to 10 -3 % by weight
A phosphor according to claim 1 or 2, characterized in that: 4. The phosphor according to any one of claims 1 to 3, wherein the main crystal phase is cubic.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18162481A JPS5883084A (en) | 1981-11-12 | 1981-11-12 | Zinc sulfide fluorescent material |
| KR828204919A KR910001399B1 (en) | 1981-11-01 | 1982-11-01 | Zinc sulfide fluorescent materials |
| DE198282110097T DE78538T1 (en) | 1981-11-02 | 1982-11-02 | BLUE-EMITTING LUMINAIRE WITH LONG LUMINATION TIME AND A DISPLAY DEVICE USED BY THE SAME, EXPLORED BY ELECTRONES. |
| DE8282110097T DE3269876D1 (en) | 1981-11-02 | 1982-11-02 | Blue emitting phosphor exhibiting long afterglow and electron excited display device using the same |
| EP82110097A EP0078538B1 (en) | 1981-11-02 | 1982-11-02 | Blue emitting phosphor exhibiting long afterglow and electron excited display device using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18162481A JPS5883084A (en) | 1981-11-12 | 1981-11-12 | Zinc sulfide fluorescent material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5883084A JPS5883084A (en) | 1983-05-18 |
| JPS637594B2 true JPS637594B2 (en) | 1988-02-17 |
Family
ID=16104036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18162481A Granted JPS5883084A (en) | 1981-11-01 | 1981-11-12 | Zinc sulfide fluorescent material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5883084A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004031322A1 (en) * | 2002-09-30 | 2004-04-15 | Kabushiki Kaisha Toshiba | Fluorescent material for display unit, process for producing the same and color display unit including the same |
-
1981
- 1981-11-12 JP JP18162481A patent/JPS5883084A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5883084A (en) | 1983-05-18 |
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