200804562 (1) 九、發明說明 【發明所屬之技術領域】 本發明係一種關於複合氧化物、螢光體、螢光體膠漿 及發光元件。更詳細而言之，本發明係關於一種適合作胃 螢光體之複合氧化物、含有該等之螢光體、螢光體膠漿s 發光元件。 【先前技術】 由複合氧化物所組成之螢光體係廣泛使用於發光元件 。發光元件係螢光體之激發源爲電子線的電子線激發發光 元件（陰極射線管（CRT )、場發射型顯示器（FED )、 表面電界電子顯示器等）、螢光體之激發源爲紫外線的紫 外線激發發光元件（液晶顯示器用背光、3波長型燈管、 高負荷螢光燈管等）、螢光體之激發源爲真空紫外線的真 空紫外線激發發光元件（電槳電視（PDP )、稀有氣體燈 管之等）、螢光體之激發源爲藍色LED之發光或是紫外 LED之發光的白色LED等。作爲使用於此等之發光元件 的螢光體係已知例如，含有SrCaBaG.98Eu().G2MgSi208所表 示之複合氧化物的螢光體。 (特開2004-026922號公報） 由近年來發光元件之性能提升的觀點看來，可求得於 激發源之照射下的發光亮度的經時變化小之螢光體。 【發明內容】 -4- (2) 200804562 本發明之目的係提供一種於激發源之照射下的發光亮 度之經時變化小、適合於螢光體之複合氧化物。又，本發 明係提供於激發源之照射下的發光亮度的經時變化小之螢 光體及發光元件。再者，本發明係提供一種適合於此等之 發光元件的螢光層之形成的螢光體膠漿。 本發明者們係欲解決該課題而專心硏究之結果，以完 成本發明。 φ 即，本發明係提供一種複合氧化物，其特徵爲式（1 )所表示之化合物的Mg之一部份爲選自以5族元素及6 族元素所成群之至少1種的M3取代，且對於Mg及M3之 合計而言，M3之莫耳比M3/ (Mg+M3)爲0.003以上 〇 · 〇 〇 6以下， 3MlO · aMgO · bM202 ( 1 ) (式中，Μ1係選自Ba、Sr及Ca所成群之至少1種 ，Μ2係選自Si及Ge所成群之至少1種，0.003 ^ X ‘ _ 0.006、0.9^a^l.l 及 1.8^b$2.2)。 又，本發明係提供一種含有該複合氧化物之螢光體、 _ 螢光膠漿及發光元件。 用以實施本發明之最佳形態 複合氧化物及螢光體 本發明之複合氧化物係式（1 )所表示之化合物之M g 之一部份爲以Μ3取代。 式（1)中，Μ1係8&、31*、€&。3^1係可此等之單獨 (3) 200804562 或是2以上之組合。作爲螢光體使用時，由該亮度提 觀點看來，M1係最佳爲Ba單獨；Sr單獨；Ba與Sr 合，更佳爲B a與S r之組合，特別佳爲B a與S r之組 Ba : Sr之莫耳比爲1 : 3〜1 : 6 )。 M2係Si、Ge，最佳爲Si。M2係此等之單獨或是 上組合。 M3係5族元素、6族元素，例如，V、Nb、Ta、 W。由売度提升之觀點看來，Μ3係Mo、W爲佳。Μ3 此等之單獨或是2以上之組合。 對於Mg及Μ3之合計而言，Μ3之莫耳比Μ3/ ( Μ3 )爲0 · 0 〇 3以上0 · 0 0 6以下。 a係0.9以上、1 · 1以下，由亮度提升之觀點看 0.97以上、1.03以下爲佳。 b係1.8以上、2.2以下，由亮度提升之觀點看 1·97以上、2.03以下爲佳。 又，複合氧化物係於不阻礙本發明之效果的範圍 Mg之一部份爲可以Ζη取代。Ζη之量係一般對於Mg ，爲1 〇莫耳％以下。 複合氧化物係作爲螢光體使用時，一般含有M4 係例如以下之賦活劑，Ce、Pr、Nd、Sm、Eu、Tb、 Ho、Er、Tm、Yb之此等稀土類元素或是Mn。由螢 之亮度提升之觀點看來，Μ4係Eu、Tb、Ce、Dy，最 Eu，較佳爲2價之Eli。M4係可此等之單獨或是2以 合。螢光體係可以複合氧化物之Μ1之一部份爲Μ4 :升之 之組 ‘合（ 2以 Mo、 係可 Mg + 來， 來， 下， 而言 〇 M4 D y、 光體 佳爲 上組 代， -6 - (4) (4)200804562 由螢光體亮度提升之觀點看來，對於Μ1及Μ4之合計而言 ，Μ4之莫耳比Μ4/ (MhM4)爲0.0003以上〇.〇5以下爲 佳。作爲M4使用Eu時，將Eu之一部份可以其他元素取 代，作爲其他之元素係例如，Ce、Pr、Nd、Pm、Sm、Gd 、Tb、Dy、Ho、Er、Tm、Yb、Mn、Al、Y、La、Bi〇 其 他元素係可此等之單獨或是2以上組合。 又，複合氧化物係因爲提高螢光體之亮度的觀點，可 含有氟（F)、氯（C1)、溴（Br)、銪（I)之此等鹵素 。鹵素係此等之單獨或是2以上組合即可。鹵素含有量係 對於螢光體總重量而言，1 p p m以上1 0 〇 〇 〇 p p m以下，最佳 爲lppm以上lOOOppm以下。 該複合氧化物係經由將複合氧化物所組成之金屬化合 物的混合物燒成製造即可，例如，經由含有以下之步驟（ a— 1) 、（a— 2)之方法製造即可。 (a - 1 )將含有構成複合氧化物之金屬元素的化合物 ，以特定之方法秤取混合、 (a — 2 )將製得之混合物燒成。 又，複合氧化物所組成之金屬化合物的混合物係經由 晶析法，可將製得之混合物燒成。 關於步驟（a - 1 ) 、（ a - 2 )，詳細說明之。 含有金屬元素之化合物係例如，Ba、Sr、Ca、Mg、 Zn、Si、Ge、Ce、Pr、Nd、Pm、Sm、Eu、Tb、Dy、Ho、 Er、Tm、Yb、Mn、W及Mo之氧化物或是氫氧化物、碳 酸鹽、硝酸鹽、鹵素化合物、草酸鹽般在高溫中分解或氧 (5) (5)200804562 化成爲氧化物所得的物質。含有金屬元素之化合物係可爲 氟化物、氯化物。 混合，可舉例如使用球磨機、V型混合機、攪拌機進 行即可。混合係可使用乾式、濕式中任一種進行。 式（Ba〇_5Sr2.5) (MgG.995M0.005) Si2〇8 所表示之複合 氧化物之 Sr之一部份，以 Eu 取代之式（ Ba0.5Sr2.492E1i0.008 ) Si2〇8 所表示之複合 氧化物時，將 BaC03、SrC03、MgO、Mo03、Si02、Eu203 ，以 Ba: Sr: Mg: Mo: Si: Eu 之莫耳比爲 0.5: 2.492: 0.995 : 0.005 : 2·0 : 0.008之方法秤取、混合。混合物係 由提高複合氧化物之結晶性的觀點或是平均粒徑大之觀點 看來，可含有適量之助熔劑。助熔劑係列舉如下，LiF、 NaF、KF、LiCl、NaCl、KC1、Li2C03、Na2C03、K2C03、200804562 (1) Description of the Invention [Technical Field] The present invention relates to a composite oxide, a phosphor, a phosphor paste, and a light-emitting element. More specifically, the present invention relates to a composite oxide suitable for use as a gastric phosphor, a phosphor comprising the same, and a phosphor paste s light-emitting element. [Prior Art] A fluorescent system composed of a composite oxide is widely used for a light-emitting element. The light-emitting element is an electron beam excitation light-emitting element (cathode ray tube (CRT), field emission type display (FED), surface electrical boundary electronic display, etc.), and the excitation source of the phosphor is ultraviolet light. Ultraviolet-excited light-emitting elements (backlights for liquid crystal displays, three-wavelength lamps, high-load fluorescent tubes, etc.), and the excitation source of the phosphor is a vacuum ultraviolet light-emitting ultraviolet light-emitting element (PDP), rare gas The excitation source of the phosphor is the blue LED or the white LED of the ultraviolet LED. As a fluorescent system using such a light-emitting element, for example, a phosphor containing a composite oxide represented by SrCaBaG.98Eu().G2MgSi208 is known. (JP-A-2004-026922) From the viewpoint of improvement in performance of a light-emitting element in recent years, it is possible to obtain a phosphor having a small change in luminance of light emitted from an excitation source over time. SUMMARY OF THE INVENTION -4- (2) 200804562 An object of the present invention is to provide a composite oxide suitable for a phosphor which has a small change in luminescence brightness under irradiation of an excitation source. Further, the present invention provides a phosphor and a light-emitting element which are small in temporal change in luminance of light emitted by an excitation source. Furthermore, the present invention provides a phosphor paste which is suitable for the formation of a phosphor layer of such a light-emitting element. The inventors of the present invention focused on the subject and tried to solve the problem, and invented the invention. φ That is, the present invention provides a composite oxide characterized in that a part of Mg of the compound represented by the formula (1) is substituted with at least one selected from the group consisting of a group 5 element and a group 6 element. And for the total of Mg and M3, the molar ratio M3 of M3/(Mg+M3) is 0.003 or more 〇· 〇〇6 or less, 3MlO · aMgO · bM202 ( 1 ) (wherein Μ 1 is selected from Ba At least one of Sr and Ca is grouped, and Μ2 is at least one selected from the group consisting of Si and Ge, 0.003 ^X ' _ 0.006, 0.9^a^ll, and 1.8^b$2.2). Further, the present invention provides a phosphor comprising the composite oxide, a fluorescent paste, and a light-emitting element. BEST MODE FOR CARRYING OUT THE INVENTION Composite oxide and phosphor A part of the Mg of the compound represented by the formula (1) of the present invention is substituted with Μ3. In the formula (1), Μ1 is 8&, 31*, €&. 3^1 can be used alone (3) 200804562 or a combination of 2 or more. When used as a phosphor, from the viewpoint of brightness, M1 is preferably Ba alone; Sr alone; Ba is combined with Sr, more preferably a combination of B a and S r , particularly preferably B a and S r The group Ba: Sr molar ratio is 1: 3~1: 6). M2 is Si and Ge, and most preferably Si. M2 is a separate or a combination of these. M3 is a Group 5 element or a Group 6 element, for example, V, Nb, Ta, W. From the viewpoint of increasing the degree of enthalpy, the Μ3 series Mo and W are preferred. Μ3 These are separate or a combination of 2 or more. For the total of Mg and Μ3, the molar ratio Μ3/( Μ3 ) of Μ3 is 0·0 〇 3 or more and 0·0 0 6 or less. The a system is 0.9 or more and 1.1 or less, and 0.97 or more and 1.03 or less are preferable from the viewpoint of brightness enhancement. b is 1.8 or more and 2.2 or less, and it is preferable that it is 1.97 or more and 2.03 or less from the viewpoint of brightness enhancement. Further, the composite oxide is in a range which does not inhibit the effect of the present invention. One part of Mg is substituted by Ζη. The amount of Ζη is generally 1% or less for Mg. When the composite oxide is used as a phosphor, it generally contains an active agent such as M4, or a rare earth element such as Ce, Pr, Nd, Sm, Eu, Tb, Ho, Er, Tm, or Yb or Mn. From the viewpoint of the brightness enhancement of the fluorescing, the Μ4 series Eu, Tb, Ce, Dy, and most Eu, preferably the divalent Eli. The M4 system can be either alone or in combination. The fluorescent system can be a composite oxide of one of the Μ1 parts of Μ4: the group of liters' (2 is Mo, can be Mg +, come, down, 〇M4 D y, light body is the upper group Generation, -6 - (4) (4)200804562 From the viewpoint of brightness enhancement of the phosphor, for the total of Μ1 and Μ4, 莫4 has a molar ratio of /4/(MhM4) of 0.0003 or more 〇.〇5 or less. Preferably, when Eu is used as M4, one part of Eu may be substituted by other elements, for example, Ce, Pr, Nd, Pm, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb. Other elements such as Mn, Al, Y, La, and Bi may be used alone or in combination of two or more. Further, the composite oxide may contain fluorine (F) or chlorine from the viewpoint of improving the brightness of the phosphor. C1), halogen such as bromine (Br) or ruthenium (I). Halogen may be used alone or in combination of two or more. The halogen content is 1 ppm or more for the total weight of the phosphor. 〇〇ppm or less, preferably 1 ppm or more and 1000 ppm or less. The composite oxide is produced by firing a mixture of metal compounds composed of a composite oxide. For example, it may be produced by a method comprising the following steps (a-1) and (a-2). (a-1) A compound containing a metal element constituting the composite oxide is weighed by a specific method. Mixing, (a-2) the obtained mixture is fired. Further, the mixture of the metal compounds composed of the composite oxide is obtained by crystallization, and the obtained mixture can be fired. Regarding the step (a-1), (a - 2 ), which is described in detail. The compound containing a metal element is, for example, Ba, Sr, Ca, Mg, Zn, Si, Ge, Ce, Pr, Nd, Pm, Sm, Eu, Tb, Dy, Ho, Oxides of Er, Tm, Yb, Mn, W and Mo or hydroxides, carbonates, nitrates, halogen compounds, oxalates decompose at high temperatures or oxygen (5) (5)200804562 becomes oxides The compound to be obtained may be a fluoride or a chloride. The mixing may be carried out, for example, by using a ball mill, a V-type mixer or a stirrer. The mixing system may be carried out using either a dry type or a wet type. (Ba〇_5Sr2.5) (MgG.995M0.005) Composite oxidation represented by Si2〇8 When a part of Sr of the substance is substituted by Eu (Ba0.5Sr2.492E1i0.008), the composite oxide represented by Si2〇8, BaC03, SrC03, MgO, Mo03, SiO2, Eu203, Ba: Sr : Mg: Mo: Si: Eu The molar ratio is 0.5: 2.492: 0.995 : 0.005 : 2·0 : 0.008 method of weighing and mixing. The mixture may contain an appropriate amount of flux from the viewpoint of improving the crystallinity of the composite oxide or the viewpoint of a large average particle diameter. The flux series are as follows, LiF, NaF, KF, LiCl, NaCl, KC1, Li2C03, Na2C03, K2C03,
NaHC03、NH4CI > NH4I、MgF2、CaF2、SrF2、BaF2、 MgCl2、CaCl2、SrCl2、BaCl2、Mgl2、Cal2、Srl2、Bal2。 混合物爲含有氫氧化物、碳酸鹽、硝酸鹽、鹵素化合 物、草酸鹽等在高溫中分解成及/或是氧化成氧化物所得 的物質時，可在燒成前先將混合物假燒。假燒是將氫氧化 物、碳酸鹽、硝酸鹽、鹵素化合物、草酸鹽變爲氧化物的 條件，或是將結晶水除去的條件下進行即可，一般，於比 燒成溫度較爲低之條件下進行即可。假燒爲在惰性環境、 大氣中等的氧化性環境中或還原性環境中進行即可。可將 混合物假燒後，粉碎。 燒成係於例如，溫度：9 0 0 °C〜1 5 0 0 °C、時間：0 · 5〜 -8- (6) (6)200804562 1 0 0小時之條件下進行即可。燒成係於，氮、氬等惰性環 境中，空氣、氧氣、含有氧氣的氮氣、含有氧氣的氬氣般 之大氣中的氧化性環境中；含有〇.：[〜；!〇體積％之含有氫的 氮氣、含有〇·1〜10體積％氫的氬般的還原性環境中進行爲 佳。另外’燒成時在更爲強的還原性環境中進行，此時， 使用含有適量的碳之金屬混合物即可。 於製得之複合氧化物中，可實施例如粉碎、洗淨、分 級。粉碎係使用球磨機、精密粉碎機進行即可。又，將實 施粉碎、洗淨、分級之複合氧化物，再度燒成等，燒成可 進行2次以上。又，可對於複合氧化物實施表面處理。表 面處理係例如將複合氧化物之粒子的表面，以複合氧化物 相異之無機化合物被覆之方法進行即可。於此使用之無機 化合物係例如爲S i、A1、T i之此等元素之氧化物。 本發明之螢光體係含有該複合氧化物，一般，含有賦 活劑M4之複合氧化物。螢光體係於激發源之照射下發光 爲監先。激發源係真空紫外線、紫外線、電子線、X線、 可見光（藍），最佳爲真空紫外線。 螢光體膠漿及螢光體層 本發明之螢光體膠漿係含有螢光體，一般含有螢光體 及有機物。 有機物係形成螢光體膠漿者，其中將螢光體膠漿熱處 理時，經由揮發、燃燒、分解可除去，由螢光體形成實質 上之螢光體層即可，例如，溶劑、黏合劑。溶劑係例如1 -9- (7) 200804562 價醇中之高沸點者；代表乙二醇與甘油之二醇與三醇 多元醇；將醇經醚化及/或是酯化之化合物（乙二醇 基醚、乙二醇二烷基醚、乙二醇烷基醚乙酸酯、二乙 單烷基醚乙酸酯、二乙二醇二烷基醚、丙二醇單烷基 丙二醇二烷基醚、丙二醇烷基乙酸酯）等。溶劑之量 於營光體1〇〇重量份而言，一*般約爲80重量份以上 佳約爲1〇〇重量份以上，一般約爲406重量份以下， 爲3 00重量份以下。 黏合劑係例如纖維素系樹酯（乙基纖維素、甲基 素、硝化纖維素、乙醯纖維素、纖維素丙酸酯、羥基 纖維素、丁基纖維素、苄基纖維素、改性纖維素等） 烯酸系樹酯（丙烯酸、甲基丙烯酸、甲基丙烯酸酯、 甲基丙烯酸酯、乙基丙烯酸酯、乙基甲基丙烯酸酯、 丙烯酸酯、丙基甲基丙烯酸酯、異丙基丙烯酸酯、異 甲基丙烯酸酯、η-丁基丙烯酸酯、η-丁基甲基丙烯酸 tert-丁基丙烯酸酯、tert-丁基甲基丙烯酸酯、2-羥基 丙烯酸酯、2-羥基乙基甲基丙烯酸酯、2-羥基丙基丙 酯、2-羥基丙基甲基丙烯酸酯、苄基丙烯酸酯、苄基 丙烯酸酯、苯氧丙烯酸酯、苯氧甲基丙烯酸酯、異冰 丙烯酸酯、異冰片基甲基丙烯酸酯、環氧丙基甲基丙 酯、苯乙烯、甲基苯乙烯丙烯酸醯胺、甲基丙烯 胺、丙烯腈、甲基丙烯腈等之此等單量體中至少1種 合物）、乙烯一乙酸乙烯基共聚物樹脂、聚乙烯丁縮 聚乙烯醇、丙二醇、聚乙烯氧化物、尿烷系樹脂、三 等之 單烷 二醇 醚、 係對 ，最 最佳 纖維 丙基 、丙 甲基 丙基 丙基 酯、 乙基 烯酸 甲基 片基 烯酸 酸醯 之聚 醛、 聚氰 -10- (8) 200804562 胺系樹脂、苯酚樹脂等。黏合劑之量係對於螢光體粒子 100重量份而言，一般爲〇.〇1重量份以上，最佳約爲〇.；[ 重量份以上，更佳爲1重量份以上，一般約爲1 〇〇重量份 以下，最佳約爲8 0重量份以下，更佳約爲5 0重量份以下 〇 依據該螢光體膠漿，可形成於激發源之照射下的發光 亮度之經時變化小的發光元件之螢光體層。又，形成之螢 φ 光體層係濕潤性優異。 螢光體膠漿係經由例如特開平1 0-255 671號公報記載 之方法製造即可，例如將螢光體、黏合劑及溶劑，使用球 磨機、三輥球磨機混合即可。 螢光體層係經由例如含有以下之步驟（b-Ι )及（b-2 )之方法形成即可。 (b-1 )將螢光體膠漿塗佈於基板之步驟、 (b-2)將製得之基板經熱處理之步驟。 • 基板係例如爲玻璃、樹脂等所組成。基板係可爲易彎 者，形狀係可爲板狀、容器狀中任一種。 塗佈係例如可使用網板印刷法、噴墨法進行即可。 熱處理係於螢光體膠漿中有機物經揮發、燃燒或是分 解，且螢光特性（發光亮度等）爲不損害之條件下進行即 可’ 一般約加熱爲3 00 °C〜約600 °C即可。於塗佈後、熱 處理前，可將基板於室溫（約2 5 °C )〜約3 00 °C下乾燥。 發光元件 -11 - (9) 200804562 本發明之發光元件係含有該螢光體，一般含有將螢光 體粒子與激發螢光體之激發源。 發光元件係例如CRT、FED、SED之此等的電子線激 發發光元件；液晶顯示器用背光、3波長型螢光燈管、高 負荷螢光燈管之此等紫外線激發發光元件；PDP、稀有氣 燈管之此等真空紫外線激發發光元件，最佳爲真空紫外線 激發發光元件。 φ 電子線激發發光元件之激發源係電子槍或是電子發射 部、紫外線激發發光元件與真空紫外線激發發光元件係電 壓爲外加之放電空間部份。 高負荷螢光燈管（燈管之管壁之每單位面積的消費電 力爲大的小型之螢光燈管）係經由例如特開平1 〇 - 2 5 1 6 3 6 號公報記載之含有步驟（c -1 )〜（c - 7 )之方法製造即可 〇 (c-1)將紅色發光螢光體、綠色發光螢光體及該藍 • 色發光螢光體作爲發光元件之發光色求得之色（例如，白 色）之方式而秤取，將此等與溶劑（聚乙烯氧化物水溶液 )混合，製得塗佈液之步驟、 (c-2 )將塗佈液塗佈於玻璃管之內面的步驟、 (c-3)將製得之玻璃管於約3 00°C〜約60 0°C下，熱 處理而形成螢光體層之步驟、 (c-4 )對於玻璃管之端部裝設•封裝電極之步驟、 (c-5)將玻璃管內排熱、將低壓之稀有氣體（Aj*、 Kr、Ne等）及水銀封入之步驟、 -12- (10) (10)200804562 (c - 6 )將排氣管封切形成放電空間之步驟、 (心7)裝設燈頭之步驟。 高負荷螢光燈管以外之紫外線激發發光元件（例如， 液晶顯示器用背光）中，例如依據特開平2005-068403之 方法，進行相同製造即可。 PDP係經由特開平1 0- 1 95428號公報記載之含有步驟 (d-Ι)〜（d-4)之方法而製造即可。 (d-1 )對於綠色發光用螢光體、紅色發光用螢光體 及該藍色發光用螢光體，各自混合螢光體粒子、黏合劑及 溶媒，調製螢光體膠漿之步驟、 (d-2 )於背面基板之內面，以隔板區隔，於具備位 址電極之條狀的基板表面與隔板上，各自（以網狀印刷等 方式）塗佈藍色發光用螢光體膠漿、紅色發光用螢光體膠 漿及綠色發光用螢光體膠漿，於約3 00 °C〜約600 °C溫度 範圍下燒成，形成螢光體層之步驟、 (d-3)於製得之螢光體層上，具備垂直的方向之透 明電極及匯流電極，內面設有介電體層與保護層之表面玻 璃基板重疊黏附之步驟、 (d-4)將背面基板與表面玻璃基板包圍之內部排氣 ，封入減壓之稀有氣體（Xe、Ne等），形成放電空間之 步驟。 稀有氣體燈’除使用作爲原料之該螢光體膠漿以外， 經由公知之方法進行相同操作製造即可。 FED係經由例如特開平2002- 1 3 8279號公報記載之含 •13- (11) (11)NaHC03, NH4CI > NH4I, MgF2, CaF2, SrF2, BaF2, MgCl2, CaCl2, SrCl2, BaCl2, Mgl2, Cal2, Srl2, Bal2. When the mixture contains a hydroxide, a carbonate, a nitrate, a halogen compound, an oxalate or the like which is decomposed into a high temperature at a high temperature and/or oxidized to an oxide, the mixture may be pseudo-fired before firing. The calcination is carried out under the conditions of changing the hydroxide, carbonate, nitrate, halogen compound, or oxalate to an oxide, or removing the crystal water, and generally, the firing temperature is lower. It can be carried out under the conditions. The pseudo-sintering may be carried out in an oxidizing environment such as an inert environment or an atmosphere or in a reducing environment. The mixture can be smashed and pulverized. The firing is carried out, for example, at a temperature of from 190 ° C to 1 500 ° C, time: 0 · 5 to -8 - (6) (6) 200804562 under 1 hour. The firing is carried out in an inert atmosphere such as nitrogen or argon, in an oxidizing atmosphere such as air, oxygen, nitrogen containing oxygen, or argon containing oxygen; containing 〇.:[~;!〇% by volume It is preferred to carry out hydrogen in a hydrogen atmosphere and an argon-reducing atmosphere containing 〜1 to 10% by volume of hydrogen. Further, in the case of firing, it is carried out in a more reductive environment. In this case, a metal mixture containing an appropriate amount of carbon may be used. Among the obtained composite oxides, for example, pulverization, washing, and classification can be carried out. The pulverization system may be carried out using a ball mill or a precision pulverizer. Further, the composite oxide which is pulverized, washed, and classified is subjected to firing, and the like, and the firing can be carried out twice or more. Further, surface treatment can be performed on the composite oxide. The surface treatment may be carried out, for example, by coating the surface of the particles of the composite oxide with an inorganic compound having a composite oxide. The inorganic compound used herein is, for example, an oxide of such elements as Si, A1, and Ti. The fluorescent system of the present invention contains the composite oxide, and generally contains a composite oxide of the active agent M4. The fluorescent system is illuminated by the illumination of the excitation source. The excitation source is vacuum ultraviolet light, ultraviolet light, electron beam, X-ray, visible light (blue), and is preferably vacuum ultraviolet light. Phosphor Glue and Phosphor Layer The phosphor paste of the present invention contains a phosphor, and generally contains a phosphor and an organic substance. The organic substance forms a phosphor paste. When the phosphor paste is heat-treated, it can be removed by volatilization, combustion, and decomposition, and a substantially phosphor layer can be formed from the phosphor, for example, a solvent or a binder. The solvent is, for example, a high boiling point in the valence alcohol of 1 -9-(7) 200804562; a diol and a triol polyol representing ethylene glycol and glycerol; a compound which is etherified and/or esterified with an alcohol (Ethylene 2) Alcohol ether, ethylene glycol dialkyl ether, ethylene glycol alkyl ether acetate, diethyl ether alkyl ether acetate, diethylene glycol dialkyl ether, propylene glycol monoalkyl propylene glycol dialkyl ether , propylene glycol alkyl acetate) and the like. The amount of the solvent is usually about 80 parts by weight or more, preferably about 1 part by weight or more, usually about 406 parts by weight or less, and 300 parts by weight or less. Binders such as cellulose-based resins (ethyl cellulose, methyl ketone, nitrocellulose, acetamidine cellulose, cellulose propionate, hydroxy cellulose, butyl cellulose, benzyl cellulose, modified Cellulose, etc.) Acrylic resin (acrylic acid, methacrylic acid, methacrylic acid ester, methacrylic acid ester, ethyl acrylate, ethyl methacrylate, acrylate, propyl methacrylate, isopropyl Acrylate, isomethacrylate, η-butyl acrylate, tt-butyl methacrylate tert-butyl acrylate, tert-butyl methacrylate, 2-hydroxy acrylate, 2-hydroxyethyl methacrylate Ester, 2-hydroxypropylpropyl ester, 2-hydroxypropyl methacrylate, benzyl acrylate, benzyl acrylate, phenoxy acrylate, phenoxy methacrylate, iso-ice acrylate, isobornyl At least one of such monoliths of methacrylate, propylene propyl propyl acrylate, styrene, methyl styrene decyl amide, methacrylamide, acrylonitrile, methacrylonitrile, and the like ), ethylene vinyl acetate Resin, polyvinyl butyral polyvinyl alcohol, propylene glycol, polyethylene oxide, urethane resin, tri-alkaline monoalkyl glycol ether, pair, most optimal fiber propyl, propyl methyl propyl propyl ester, Polyacetal of methacrylic acid methyl succinate, polycyanide-10-(8) 200804562 Amine resin, phenol resin, and the like. The amount of the binder is generally 〇.〇1 parts by weight or more, preferably about 〇.; [parts by weight or more, more preferably 1 part by weight or more, and usually about 1 part by weight of the phosphor particles. The content of the bismuth or less is preferably about 80 parts by weight or less, more preferably about 50 parts by weight or less. Depending on the phosphor paste, the change in luminescence brightness which can be formed under the irradiation of the excitation source is small. The phosphor layer of the light-emitting element. Further, the formed φ φ light layer is excellent in wettability. The phosphor paste may be produced by a method described in, for example, JP-A-H05-255671. For example, a phosphor, a binder, and a solvent may be mixed using a ball mill or a three-roll ball mill. The phosphor layer may be formed by, for example, a method comprising the following steps (b-Ι) and (b-2). (b-1) a step of applying a phosphor paste to a substrate, and (b-2) a step of subjecting the obtained substrate to heat treatment. • The substrate is made of, for example, glass, resin, or the like. The substrate may be a bendable one, and the shape may be any of a plate shape and a container shape. The coating system can be carried out, for example, by a screen printing method or an inkjet method. The heat treatment is carried out in the phosphor paste. The organic matter is volatilized, burned or decomposed, and the fluorescence characteristics (luminous brightness, etc.) are carried out under conditions of no damage. Generally, the heating is about 300 ° C to about 600 ° C. Just fine. The substrate may be dried at room temperature (about 25 ° C) to about 300 ° C after coating and before heat treatment. Light-emitting element -11 - (9) 200804562 The light-emitting element of the present invention contains the phosphor, and generally contains an excitation source for the phosphor particles and the excited phosphor. The light-emitting element is an electron beam-excited light-emitting element such as CRT, FED, or SED; a UV-excited light-emitting element such as a backlight for a liquid crystal display, a 3-wavelength fluorescent tube, or a high-load fluorescent tube; PDP, rare gas Such vacuum ultraviolet light-exciting light-emitting elements of the lamp tube, preferably vacuum ultraviolet light-excited light-emitting elements. The excitation source of the φ electron line excitation light source is an electron gun or an electron emission portion, an ultraviolet excitation light-emitting element, and a vacuum ultraviolet excitation light-emitting element voltage is an additional discharge space portion. A high-intensity fluorescent tube (a small-sized fluorescent tube having a large power consumption per unit area of the tube wall) is a step (for example) described in Japanese Laid-Open Patent Publication No. Hei. The method of c -1 ) ~ (c - 7 ) can be used to produce yttrium (c-1), which is obtained by using a red luminescent phosphor, a green luminescent phosphor, and the blue luminescent phosphor as the luminescent color of the illuminating element. The color is collected (for example, white), the solvent is mixed with a solvent (polyethylene oxide aqueous solution) to prepare a coating liquid, and (c-2) the coating liquid is applied to a glass tube. Step of the inner surface, (c-3) a step of heat-treating to form a phosphor layer at a temperature of about 300 ° C to about 60 ° C, and (c-4) for the end of the glass tube Step of installing and encapsulating the electrode, (c-5) Step of discharging heat in the glass tube, enclosing the low-pressure rare gas (Aj*, Kr, Ne, etc.) and mercury, -12- (10) (10)200804562 (c - 6) The step of sealing the exhaust pipe to form a discharge space, and (the core 7) the step of installing the lamp cap. In the ultraviolet light-emitting element (for example, a backlight for a liquid crystal display) other than the high-intensity fluorescent tube, the same production may be carried out, for example, according to the method of JP-A-2005-068403. The PDP may be produced by the method of the steps (d-Ι) to (d-4) described in JP-A-10-109424. (d-1) a step of modulating the phosphor paste by mixing the phosphor particles, the binder, and the solvent with the phosphor for green light emission, the phosphor for red light emission, and the phosphor for blue light emission (d-2) The inner surface of the rear substrate is partitioned by a spacer, and each of the strip-shaped substrate surfaces and the spacer having the address electrode is coated with a blue light-emitting flame (for mesh printing or the like). Light body glue, red light-emitting phosphor paste and green light-emitting phosphor paste, fired at a temperature ranging from about 300 ° C to about 600 ° C to form a phosphor layer, (d- 3) on the obtained phosphor layer, a transparent electrode and a bus electrode having a vertical direction, a step of superimposing and bonding the dielectric layer on the inner surface of the protective layer, and (d-4) the back substrate The internal exhaust gas surrounded by the surface glass substrate is sealed with a decompressed rare gas (Xe, Ne, etc.) to form a discharge space. The rare gas lamp can be produced by the same operation in a known manner except for using the phosphor paste as a raw material. The FED is described in, for example, Japanese Patent Publication No. 2002-138878, including: 13-(11) (11)
200804562 有步驟（e-1)〜（e-4)之方法而製造即可。 (e-1 )對於綠色螢光體、紅色螢光體及該藍t 體，各自混合螢光體粒子、黏合劑及溶媒而調製螢为 漿之步驟， (e-2 )於玻璃基板上塗佈各種液體，乾燥，名 成螢光體層而製作螢光屏（face plate)之步驟、 (心3 )將形成螢光屏（face plate )與多數之電 射部之背板，經由支持框組裝之步驟、 (e-4) 將螢光屏（face plate )與背板之間隙， 排氣，封裝之步驟。 SED係與FED進行相同製造即可，例如以特開 8 3 5 3 7號公報之段落號0 1 82-0 1 89揭示之方法進行· 可 〇 又，發光元件係可含螢光體與LED之白色LED « 係螢光體之激發源，例如，產生波長200nm〜410nm 的紫外LED、波長410〜55〇11111之光的藍色1^0，f 藍色LED。LED係使用市面販售商品即可。 白色LED係混合螢光體粒子與樹脂（環氧樹靡 碳酸酯、矽橡膠之此等透明性樹脂），以製得之螢为 子分散之樹脂，包圍LED之方法（例如’特開 1 52609號公報、特開平7-993 45號）、將LED以棱 如環氧樹脂之此等透明性樹脂）封裝，經由於其上® 光體之方法（例如，特開平1 1-3 1 845號公報、特開 226846號公報）進行製造即可。 ί螢光 5體膠 •自形 〖子發 真空 2 0 0 2 - έ造即 =LED 之光 Η圭爲 卜聚 i體粒 平 5-ί脂（ 丨定螢 2002- -14 - (12) 200804562 【實施方式】 實施例 度 以 份 外 限 純 公 股 工 式 入 2 成 光 表 將本發明經由實施例，更進一步詳細說明。發光亮 係將螢光體放置於真空槽內，保持6.7Pa ( 5xl0_2t〇rr ) 下之真空下，使用準分子146nm燈管（USHIO電機股 有限公司製作、H0012型），照射波長146nm之真空紫 線，使螢光體發光，使用分光放射計（TOP CON股份有 公司製、SR - 3 )，測定發光亮度。發光亮度係於初期、 小時後、24小時後進行。 參照例1 將秤取碳酸鋇（日本化學工業股份有限公司製作： 度99%以上）、碳酸緦（堺化學工業股份有限公司製作 純度99%以上）、鹼性碳酸鎂（協和化學工業股份有限 司製作：純度99%以上）、二氧化矽（日本AEROSIL 份有限公司製作：純度9 9.9 9 % )、氧化銪（信越化學 業股份有限公司製作：純度99.99%)，以B a: Sr: Mg Si: Eu 之莫耳比爲 〇·5: 2.492: 1·0: 2·0: 0.008 之方 秤取，使用乾式球磨機混合4小時。將製得之混合物放 氧化鋁皿（Alumina boat )。將混合物於混合氣（氫： 體積％、氮：98體積％)之還原環境下、於120(rc下燒 2 小時，製得（BaG.5Sr2.492Eu(KGG8) MgSi208 所表示之螢 體1。螢光體1係於照射波長146nm之真空紫外線下， -15- (13) (13)200804562 示爲藍色發光，此時之發光亮度爲1 〇 0。發光亮度之測定 係將螢光體1之初期亮度，以1 00之相對値表示。測定結 果表示如表1。 參照例2 秤取碳酸鋇（日本化學工業股份有限公司製作：純度 99%以上）、碳酸緦（堺化學工業股份有限公司製作：純 度 99%以上）、碳酸鈣（UBEMATERIALS股份有限公司 製作··純度99%以上）、鹼性碳酸鎂（協和化學工業股份 有限公司製作：純度 99%以上）、二氧化矽（日本 AEROSIL股份有限公司製作：純度99.99% )、氧化銪（ 信越化學工業股份有限公司製作：純度99.99% )、氧化 鉬（高純度化學股份有限公司：純度99.9%)，以Ba : Sr :Mg: Si: Eu: Mo 之莫耳比爲 0·5: 2·492: 0.998: 2.0 :0.008 : 0.002之方式秤取之外，進行與參照例1相同之 操作，製得式（Ba0.5Sr2.492EU0.0G8) ( Mg〇.99 8M〇〇.〇〇2)200804562 It can be manufactured by the method of steps (e-1) to (e-4). (e-1) For the green phosphor, the red phosphor, and the blue body, the phosphor particles, the binder, and the solvent are mixed to prepare a slurry, and (e-2) is coated on the glass substrate. A step of making a face plate by various liquids, drying, and forming a phosphor layer, (heart 3) will form a face plate and a back plate of a plurality of electric parts, assembled through a support frame Step, (e-4) The step of venting and encapsulating the gap between the face plate and the back plate. The SED system can be manufactured in the same manner as the FED. For example, the method disclosed in the paragraph No. 0 1 82-0 1 89 of JP-A-8 3 5 3 7 can be carried out. The light-emitting element can contain a phosphor and an LED. The white LED « is an excitation source of a phosphor, for example, an ultraviolet LED having a wavelength of 200 nm to 410 nm, a blue 1^0 having a wavelength of 410 to 55 〇 11111, and a blue LED. LEDs can be sold on the market. The white LED is a method in which a phosphor particle and a resin (epoxy resin such as epoxy eucalyptus carbonate or ruthenium rubber) are mixed to obtain a resin which is dispersed as a sub-particle, and a method of enclosing the LED (for example, 'Special opening 1 52609 No. 7-993, No. 45-993), and a method in which an LED is encapsulated by a transparent resin such as an epoxy resin, and a method of applying a light-emitting body thereto (for example, JP-A No. 1-3 1 845) It is sufficient to manufacture it by the gazette and the special opening 226846. ί荧光光5体胶•自形〗 〖子发真空2 0 0 2 - έ造即=LED light Η 为 卜 i i i 体 体 体 体 体 5 5 - 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 200804562 [Embodiment] The present invention is further described in detail by way of an embodiment of the present invention. The illuminating system places the phosphor in a vacuum chamber and maintains 6.7 Pa (for example). Under the vacuum of 5xl0_2t〇rr), an excimer 146nm lamp tube (manufactured by USHIO Motor Co., Ltd., H0012 type) was used to irradiate a vacuum violet line with a wavelength of 146 nm to illuminate the phosphor, using a spectroradiometer (TOP CON shares have The company's system, SR - 3), measures the luminosity. The illuminance is performed after the initial period, after the hour, and after 24 hours. Reference Example 1 The cesium carbonate (manufactured by Nippon Chemical Industry Co., Ltd.: 99% or more), carbonated缌(堺Chemical Industries Co., Ltd. produces more than 99% purity), alkaline magnesium carbonate (produced by Xiehe Chemical Industry Co., Ltd.: purity over 99%), cerium oxide (produced by Japan AEROSIL Co., Ltd.: purity 9 9.9 9 % ),oxygen Huayu (Shin-Etsu Chemical Co., Ltd. produced: purity 99.99%), with the molar ratio of B a: Sr: Mg Si: Eu is 〇·5: 2.492: 1·0: 2·0: 0.008 The mixture was mixed for 4 hours using a dry ball mill. The obtained mixture was placed on an Alumina boat. The mixture was fired at 120 (rc) under a reducing atmosphere of a mixed gas (hydrogen: % by volume, nitrogen: 98% by volume). 2 hours, the fluorescein 1 represented by BaG.5Sr2.492Eu(KGG8) MgSi208 was obtained. The phosphor 1 was under vacuum ultraviolet light with an irradiation wavelength of 146 nm, and -15-(13) (13)200804562 was shown as blue. When the light is emitted, the light emission luminance is 1 〇 0. The measurement of the light-emitting luminance is expressed by the relative 値 of 100 in the initial luminance of the phosphor 1. The measurement results are shown in Table 1. Reference Example 2 Weighing of strontium carbonate (Japan) Chemical Industry Co., Ltd.: purity: 99% or more), strontium carbonate (manufactured by 堺Chemical Industries Co., Ltd.: purity: 99% or more), calcium carbonate (manufactured by UBEMATERIALS Co., Ltd., purity: 99% or more), alkaline magnesium carbonate (Concord Chemical Industry Co., Ltd. produced: purity over 99% ), cerium oxide (produced by Japan AEROSIL Co., Ltd.: purity 99.99%), cerium oxide (manufactured by Shin-Etsu Chemical Co., Ltd.: purity 99.99%), molybdenum oxide (high-purity chemical company: purity 99.9%), The same operation as in Reference Example 1 was carried out except that the molar ratio of Ba : Sr :Mg: Si: Eu: Mo was 0·5: 2·492: 0.998: 2.0 : 0.008: 0.002. (Ba0.5Sr2.492EU0.0G8) ( Mg〇.99 8M〇〇.〇〇2)
Si2〇8所表示之螢光體2。螢光體2之亮度測定結果如表1 所示。 參照例3 將秤取碳酸鋇（日本化學工業股份有限公司製作：純 度99%以上）、碳酸鋸（堺化學工業股份有限公司製作： 純度99%以上）、碳酸鈣（UBEMATERIALS股份有限公 司製作··純度99%以上）、鹼性碳酸鎂（協和化學工業股 -16- (14) (14)200804562 份有限公司製作：純度99%以上）、二氧化砍（日本 AEROSIL股份有限公司製作：純度99.99% )與氧化銪（ 信越化學工業股份有限公司製作：純度99.99%)、氧化 鉬（高純度化學股份有限公司：純度99.9%)，以Ba : Sr :Mg : Si : Eu : Mo 之莫耳比爲 05:2.48:0.99:2.0: 0.02: 0·01之方式坪取之外，進行與參照例1相同之操作 ，製得式（Ba〇.5Sr2.48Eu〇.()2) ( Mg〇.99MoG ()1) si208 所表 示之螢光體3。螢光體3之亮度測定結果如表1所示。 實施例1 將秤取碳酸鋇（日本化學工業股份有限公司製作：純 度99%以上）、碳酸緦（堺化學工業股份有限公司製作： 純度99%以上）、碳酸鈣（UBEMATERIALS股份有限公 司製作：純度99%以上）、鹼性碳酸鎂（協和化學工業股 份有限公司製作：純度99%以上）、二氧化矽（日本 AEROSIL股份有限公司製作：純度99.99% )、氧化銪（ 信越化學工業股份有限公司製作：純度99.99% )、氧化 鎢（高純度化學股份有限公司：純度9 9.9 % )，以B a : S r :Mg : Si : Eu : W 之莫耳比爲 〇·5 : 2.492 ·· 0.995 : 2.0 : 0·008: 0.005之方式秤取之外，進行與參照例1相同之操 作，製得式（Ba〇.5Sr2.4 92 Eu〇.〇〇8 ) ( Mg〇.9 9 5 W〇.〇〇5 ) Si2〇s 所表示之螢光體4。螢光體4之亮度測定結果如表1所示 -17- (15) 200804562 實施例2Phosphor 2 represented by Si2〇8. The results of the luminance measurement of the phosphor 2 are shown in Table 1. Reference Example 3 Weighed strontium carbonate (manufactured by Nippon Chemical Industry Co., Ltd.: purity: 99% or more), carbonic acid saw (produced by 堺Chemical Industries Co., Ltd.: purity: 99% or more), calcium carbonate (manufactured by UBEMATERIALS Co., Ltd. Purity of more than 99%), basic magnesium carbonate (Xiehe Chemical Industry Co., Ltd. - 16 - (14) (14) 200,804,562 parts Co., Ltd.: purity: 99% or more), dioxide oxidation (produced by Japan AEROSIL Co., Ltd.: purity 99.99% ) with yttrium oxide (manufactured by Shin-Etsu Chemical Co., Ltd.: purity 99.99%), molybdenum oxide (high-purity chemical company: purity 99.9%), and the molar ratio of Ba : Sr :Mg : Si : Eu : Mo 05: 2.48: 0.99: 2.0: 0.02: 0. 01, the same operation as in Reference Example 1 was carried out to obtain the formula (Ba〇.5Sr2.48Eu〇.()2) (Mg〇.99MoG () 1) The phosphor 3 represented by si208. The results of the luminance measurement of the phosphor 3 are shown in Table 1. Example 1 Bismuth carbonate (manufactured by Nippon Chemical Industry Co., Ltd.: purity: 99% or more), strontium carbonate (manufactured by Suga Chemical Industry Co., Ltd.: purity: 99% or more), calcium carbonate (manufactured by UBEMATERIALS Co., Ltd.: purity) 99% or more), basic magnesium carbonate (produced by Kyowa Chemical Industry Co., Ltd.: purity: 99% or more), cerium oxide (produced by Japan AEROSIL Co., Ltd.: purity 99.99%), cerium oxide (manufactured by Shin-Etsu Chemical Co., Ltd.) : purity: 99.99%), tungsten oxide (High Purity Chemical Co., Ltd.: purity: 9.9.9%), and the molar ratio of B a : S r :Mg : Si : Eu : W is 〇·5 : 2.492 ·· 0.995 : 2.0 : 0·008: In the same manner as in the case of 0.005, the same operation as in Reference Example 1 was carried out to obtain a formula (Ba〇.5Sr2.4 92 Eu〇.〇〇8 ) ( Mg〇.9 9 5 W〇 .〇〇5) The phosphor 4 represented by Si2〇s. The results of the luminance measurement of the phosphor 4 are shown in Table 1. -17- (15) 200804562 Example 2
將秤取碳酸鋇（日本化學工業股份有限公司製作：純 度99%以上）、碳酸緦（堺化學工業股份有限公司製作： 純度99%以上）、碳酸鈣（UBEMATERIALS股份有限公 司製作：純度99%以上）、鹼性碳酸鎂（協和化學工業股 份有限公司製作：純度99%以上）、二氧化矽（日本 AEROSIL股份有限公司製作：純度99.99%)與氧化銪（ 信越化學工業股份有限公司製作：純度99.99% )、氧化 鉬（高純度化學股份有限公司：純度99.9% )，以Ba : Sr • Mg ： Si ： Eu ： Mo 之莫耳比爲 0·5 : 2.492 : 0.995 : 2.0 :0.008 : 0.005之方式秤取之外，進行與參照例1相同之 操作，製得式（Ba〇.5Sr2.492Eu〇_〇〇8 ) ( Mg〇.99 5M〇〇 〇〇5)The scale is taken from strontium carbonate (manufactured by Nippon Chemical Industry Co., Ltd.: purity: 99% or more), strontium carbonate (produced by 堺Chemical Industries Co., Ltd.: purity: 99% or more), and calcium carbonate (produced by UBEMATERIALS Co., Ltd.: purity: 99% or more) ), basic magnesium carbonate (produced by Kyowa Chemical Industry Co., Ltd.: purity of 99% or more), cerium oxide (produced by Japan AEROSIL Co., Ltd.: purity 99.99%) and cerium oxide (manufactured by Shin-Etsu Chemical Co., Ltd.: purity 99.99 %), molybdenum oxide (High Purity Chemical Co., Ltd.: purity 99.9%), the molar ratio of Ba:Sr • Mg : Si : Eu : Mo is 0·5 : 2.492 : 0.995 : 2.0 :0.008 : 0.005 Except for weighing, the same operation as in Reference Example 1 was carried out to obtain a formula (Ba〇.5Sr2.492Eu〇_〇〇8) (Mg.99 5M〇〇〇〇5)
Si2〇8所表示之螢光體5。螢光體5之亮度測定結果如表1 所示。 表1螢光體之亮度測定結果 發3 έ亮度 發光色 初期 1小時後 24小時後 參 照 例 1 螢 光 體 1 藍 100 88 ___74 參 照 例 2 螢 光 體 2 藍 97 90 _28 參 照 例 3 螢 光 體 3 藍 9 2 76 實 施 例 1 螢 光 體 4 藍 98 93 ___9^0 實 施 例 2 螢 光 m. Μ 5 藍 93 93 於此，將螢光體之發光特性，經由於真空紫外線τ之 亮度變化評價，但是螢光體即使於電子線、紫外線、X線 、可見光（藍色）照射下’顯示同樣之發光特性。 •18- (16) (16)200804562 〔產業上之可利用性〕 本發明之複合氧化物係可使用作爲螢光體。螢光體係 可使用於真空紫外線、電子線、紫外線、X線之此等激發 源之長時間照射下發光亮度高，例如電槳電視（PDP )、 稀有氣體燈管之此等真空紫外線激發發光元件、液晶顯示 器用背光之此等紫外線激發發光元件、場發射型顯示器（ FED )之此等電子線激發發光元件、白色LED之此等發光 元件。The phosphor 5 represented by Si2〇8. The results of the luminance measurement of the phosphor 5 are shown in Table 1. Table 1 Luminance measurement results of the phosphors 3 έ Brightness Luminescence color 1 hour after the first hour and 24 hours later Reference Example 1 Phosphor 1 Blue 100 88 ___74 Reference Example 2 Phosphor 2 Blue 97 90 _28 Reference Example 3 Phosphor 3 Blue 9 2 76 Example 1 Phosphor 4 Blue 98 93 ___9^0 Example 2 Fluorescent m. Μ 5 Blue 93 93 Here, the luminescence characteristics of the phosphor are evaluated by the change in brightness of the vacuum ultraviolet τ However, the phosphor exhibits the same luminescence characteristics even under the irradiation of electron beams, ultraviolet rays, X-rays, and visible light (blue). 18-(16) (16)200804562 [Industrial Applicability] The composite oxide of the present invention can be used as a phosphor. The fluorescent system can be used for high-intensity illumination of ultraviolet light, electron beam, ultraviolet light, X-ray, etc. for a long time, such as a vacuum ultraviolet light-emitting element such as a power paddle television (PDP) or a rare gas lamp. The ultraviolet light-excited light-emitting element of the liquid crystal display, the electron-emitting element of the field emission type display (FED), the light-emitting element, and the light-emitting element of the white LED.
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