1331167 ⑴ 玖、發明說明 【發明所屬之技術領域】 本發明係一種關於螢光體及螢光體糊料。 【先前技術】 螢光體係使用於螢光燈、夜光顯示、X線檢查裝置、 CRT、真空紫外線激發發光元件等。已知一種紅色螢光體 係鋁酸鹽〔例如，B aM g A1 i 〇 0 ! 7 : E u〕與硼酸鹽〔例如， (Y，Gd ) B〇3 : Eu〕、藍色螢光體係矽酸鹽〔例如， CaMgSi06 : Eu〕、綠色螢光體係矽酸鹽〔例如，Zn2Si〇4 :Μη〕，且可使用於電漿顯示器與稀有氣體燈之真空紫 外線激發發光元件。 真空紫外線激發發光元件係經由稀有氣體中之放電而 產生電漿，且將電漿放射之真空紫外線，照射螢光體而激 發螢光體，再由螢光體之可見光放射、發光者。 以往之螢光體係電漿處理與亮度低者。 【發明內容】 本發明之目的係提供一種即使電漿處理，亦具有高亮 度之螢光體及含有其螢光體之螢光體糊體。 本發明者們於此情況下，欲解決上述之課題而專心硏 究之結果，發現經由組合特定之矽酸鹽與鋁酸鹽而具有高 亮度之螢光體，已完成本發明。 即，本發明係提供一種螢光體，其係含有下式（I ) -4 - (2) (2)1331167 所示之化合物與含有1種以上選自Eu、Μη所成群之活化 劑的螢光物質Α1及鋁酸鹽之螢光物質Β1之螢光體， mM'O · ηΜ20 · 2M3 02 ( I ) - 〔式（I )中，M1係2種以上選自Ca、Sr及Ba所成之群 ，Ca單獨或Ba單獨， Μ2係1種以上選自Mg及Zn所成之群， φ M3係1種以上選自Si及Ge所成之群，且0.5 S 3.5' 0.5^n^2.5]。 又，本發明係提供一種含有上述之螢光體、溶劑及膠 粘劑之螢光體糊料。 本發明之螢光體，最適合使用於電漿處理後之亮度高 ，特別是PDP與稀有氣體燈之真空紫外線激發發光元件 。依據本發明之螢光體及螢光體糊料，提供一種於高亮度 下壽命長之真空紫外線激發發光元件。 · 【實施方式】 發明實施形態之說明 、 本發明之螢光體係含有螢光物質A1。其螢光物質A1 係上述式（I)所示之化合物，且含有1種選自以上Eu、 Μη所成群之活化劑。 式中，Μ1係2種以上選自Ca、Sr及Ba所成之群， Ca單獨或Ba單獨， -5- (3) (3)1331167 Μ2係1種以上選自Mg及Zn所成之群， M3係1種以上選自Si及Ge所成之群，且 0.5 ^ m ^ 3.5 > 0.5 S n S 2.5。 螢光物質Α1，最佳爲下述式（II)所示之化合物， (M'l-aEua) ( M2,.bM n b) M32〇6 (II) 〔式（II)中，M1係2種以上選自Ca、Sr及Ba所成 之群，而Ca單獨或Ba單獨，且 M2係1種以上選自Mg及Zn所成之群， M3係1種以上選自Si及Ge所成之群，且 0 ^ a ^ 0.5 ' 5 ^ b ^ 0.5 ' 0 < a + b〕。 螢光物質A1，最佳爲下述式（III)所示之化合物， Φ1331167 (1) Description of the Invention [Technical Field of the Invention] The present invention relates to a phosphor and a phosphor paste. [Prior Art] The fluorescent system is used for a fluorescent lamp, a luminous display, an X-ray inspection device, a CRT, a vacuum ultraviolet excitation light-emitting element, and the like. A red fluorescent system aluminate (for example, B aM g A1 i 〇0 ! 7 : E u) and a borate [for example, (Y, Gd ) B〇 3 : Eu], a blue fluorescent system are known. An acid salt (for example, CaMgSi06: Eu), a green fluorescent system phthalate (for example, Zn2Si〇4: Μη), and can be used for a vacuum ultraviolet ray-exciting luminescent element for a plasma display and a rare gas lamp. The vacuum ultraviolet ray-excited light-emitting element generates a plasma by discharge in a rare gas, and irradiates the phosphor with a vacuum ultraviolet ray radiated from the plasma to excite the phosphor, and then emits and emits light from the visible light of the phosphor. In the past, the fluorescent system was treated with plasma and the brightness was low. SUMMARY OF THE INVENTION An object of the present invention is to provide a phosphor having high brightness even a plasma treatment, and a phosphor paste containing the same. The present inventors have found that the present invention has been accomplished by focusing on the above-mentioned problems and focusing on the above-mentioned problems, and found that a phosphor having high luminance by combining a specific citrate and an aluminate has been found. That is, the present invention provides a phosphor comprising a compound represented by the following formula (I) -4 - (2) (2) 1331167 and an activator containing one or more selected from the group consisting of Eu and Μη. Fluorescent substance Α1 and phosphor of luminescent substance 铝1 of aluminate, mM'O · ηΜ20 · 2M3 02 ( I ) - [In formula (I), two or more types of M1 are selected from Ca, Sr and Ba In the group, Ca alone or Ba alone, Μ2 is one or more selected from the group consisting of Mg and Zn, and φ M3 is one or more selected from the group consisting of Si and Ge, and 0.5 S 3.5' 0.5^n^ 2.5]. Further, the present invention provides a phosphor paste containing the above-described phosphor, solvent and adhesive. The phosphor of the present invention is most suitably used for high brightness after plasma treatment, in particular, a vacuum ultraviolet light-emitting element of a PDP and a rare gas lamp. According to the phosphor and the phosphor paste of the present invention, a vacuum ultraviolet excitation light-emitting element having a long life under high luminance is provided. [Embodiment] Description of Embodiments of the Invention The fluorescent system of the present invention contains a fluorescent substance A1. The fluorescent substance A1 is a compound represented by the above formula (I), and contains one activator selected from the group consisting of Eu and Μη above. In the formula, Μ1 is a group of two or more selected from the group consisting of Ca, Sr, and Ba, and Ca alone or Ba alone, -5-(3) (3) 1331167 Μ 2 is one or more selected from the group consisting of Mg and Zn. One or more types of M3 are selected from the group consisting of Si and Ge, and 0.5 ^ m ^ 3.5 > 0.5 S n S 2.5. The fluorescent substance Α1 is preferably a compound represented by the following formula (II), (M'l-aEua) (M2,.bM nb) M32〇6 (II) [in the formula (II), two types of the M1 system The above is selected from the group consisting of Ca, Sr, and Ba, and Ca alone or Ba alone, and one or more M2 systems are selected from the group consisting of Mg and Zn, and one or more M3 systems are selected from the group consisting of Si and Ge. And 0 ^ a ^ 0.5 ' 5 ^ b ^ 0.5 ' 0 < a + b]. The fluorescent substance A1 is preferably a compound represented by the following formula (III), Φ
Cai-c-a SrcEudMgSi2〇6 ( III ) 〔式（ΠΙ)中、0‘ 01、 - 0 < d g 0.1〕。 本發明之螢光體係含有螢光物質A1以外之螢光物質 B1。其螢光物質B1係鋁酸鹽’最佳爲下述式（IV)所述 之化合物， -6- (4) (4)1331167 P ( Μ4 卜 eEue ) Ο · q ( Μ5 卜 fMnf ) Ο . r Al2〇3 ( IV ) 〔式（IV)中，M4係1種以上選自Ca、Sr及Ba所 成之群， M5係1種以上選自Mg及Zn所成之群’且 0.5 ^ p ^ 1 .5 'Cai-c-a SrcEudMgSi2〇6 (III) [in the formula (ΠΙ), 0' 01, - 0 < d g 0.1]. The fluorescent system of the present invention contains a fluorescent substance B1 other than the fluorescent substance A1. The fluorescent substance B1 is an aluminate' is preferably a compound of the following formula (IV), -6-(4) (4) 1331167 P ( Μ 4 b eEue ) Ο · q ( Μ 5 b fMnf ) Ο . r Al2〇3 ( IV ) [In the formula (IV), one or more of the M4 systems are selected from the group consisting of Ca, Sr, and Ba, and one or more of the M5 systems are selected from the group consisting of Mg and Zn' and 0.5 ^ p ^ 1 .5 '
4.5 ^ r ^ 5.5 ' 0 < e < 0.5、 0 < f S 0 . 1〕。 螢光物質B1，最佳爲下述式（v)所示之化合物，4.5 ^ r ^ 5.5 ' 0 < e < 0.5, 0 < f S 0 . 1]. The fluorescent substance B1 is preferably a compound represented by the following formula (v).
Bai .gEugMg A110〇 】7 〔式（V)中、〇<gg〇.3〕。 螢光物質A1/螢光物質B1之重量比，最佳爲5/95〜 95/5之範圍，更佳爲20/80〜90/10之範圍，特別佳爲 30/70〜85/15之範圍。螢光物質八~螢光物質B1之重量比 若於上述範圍內，則電漿處理時，可得到具有更高亮度的 螢光體。 螢光物質A1/螢光物質B1之兩者爲粒子時，螢光物質 A1之一次粒子徑一般爲O.lym〜5//m，最佳爲〇_3;zm〜 3//m，而營光物質B1之一次粒子徑一般爲〜5//m ，最佳爲〇.3//m〜3ym。螢光物質B1之平均一次粒子徑 Db1若爲螢光物質A1之平均一次粒子徑Da1之2倍以上 (5) (5)1331167 、5倍以下’即滿足〇//〇81芸5及d// Da^5之式爲佳 〇 本發明之螢光體若含有光物質A1/螢光物質B1，則含 有此些以外之螢光體亦爲佳。 本發明之螢光體係電漿即使被處理，爲可經由真空紫 外線激發而具有高亮度者。PDP及稀有氣體燈之製造中， 經由含有一般混合螢光體、膠粘劑及溶媒製得螢光糊體之 步驟、將其螢光體糊料塗佈於發光部之步驟、將被塗佈之 發光部熱處理（例如5 00 °C )之步驟的製造方法而形成螢 光體之層。本發明之螢光體即使經由上述熱處理時，因爲 具有與熱處理前相同之亮度，若將本發明之螢光體使用於 PDP及稀有氣體燈之真空紫外線激發發光元件，可製得高 売度且壽命長之PDP及稀有氣燈。 又，本發明之螢光體係可經由真空紫外線以外之紫外 線' X線或電子線等激動，故將此些作爲激動源，亦可適 合使用於螢光燈、夜光顯示、X線檢查 置、CRT等β 一種具有高亮度之本發明之螢光體係以混合例如螢光 物質Α1與螢光物質Β1之方法製造爲佳。混合係使用例如 攪拌機、球磨機、三輥球磨機之裝置進行爲佳。混合，必 要時，添加螢光物質Α1與螢光物質Β1以外之螢光體進行 爲佳。 螢光物質A 1係例如金屬化合物之混合物且可將經由 燒結製得之螢光物質A1製得之混合物經由燒結而可調製 -8- (6) (6)1331167 上述之混合物的鈣源 '錁源或鋇源（對應式（I )之 Μ1 )係例如純度9 9 %以上之氫氧化物、碳酸鹽、硝酸鹽 、鹵化物、草酸鹽等於高溫下分解而氧化物製得之化合物 或純度99.9%以上之氧化物。 上述之混合物之鎂源或鋅源（對應式（I)之Μ2)係 例如純度99%以上之氫氧化物、碳酸鹽、硝酸鹽、鹵化 物、草酸鹽等於高溫下分解製得之化合物或純度99.9%以 上之氧化物。 上述之混合物之鹵源或鎳源（對應式（I)之Μ3)係 例如純度99%以上之氫氧化物、碳酸鹽、硝酸鹽、鹵化 物、草酸鹽等於高溫下分解製得之化合物或純度9 9.9%以 上之氧化物。 上述之混合物之銪源或錳源（螢光物質 Α1之活化劑 )係例如純度99%以上之氫氧化物、碳酸鹽、硝酸鹽、 鹵化物 '草酸鹽等於高溫下分解製得者或純度9 9.9%以上 之氧化物。 螢光物質Α1係將上述之化合物與所期望之螢光物質 A 1之組成方法秤量而混合，再將此些混合物經由燒結而 調製。 混合係使用例如球磨機、V型混合機或攪拌機進行爲 佳。混合係適量添加而進行爲佳。經由添加助熔劑，可促 進螢光體之產生且於低溫燒結。 燒結係於還原氣氛下進行爲佳，例如含有氫約0.1體 (7) (7)1331167 積％之氬中進行爲佳。燒結，一般於溫度：約1 0 0 0 °c〜 約1 500°c、時間：約1小時〜約1〇〇小時之條件下進行 爲佳。 於上述之混合物中，將含有氫氧化物、碳酸鹽、硝酸 鹽、鹵化物、草酸鹽，於高溫下分解製得之化合物時，於 燒結前預燒混合物爲佳。 預燒係於氧化性氣氛（例如氣氛中）、還原性氣氛中 任一種進行爲佳。預燒，一般於約600 °c〜約900 °c之溫 度範圍下進行爲佳。 燒結製成之螢光物質A1，必要時，粉碎、洗淨或分 級爲佳。粉碎係使用球磨機、噴射磨爲佳。使粉碎之螢光 物質A1經由熱處理爲佳。經由熱處理，可提高（經由粉 碎而降低之）螢光物質A1之結晶性。熱處理，一般係與 上述之燒結相同條件下進行爲佳。 又，本發明之螢光體的製造使用之螢光物質 A1係以 例如特開2002-332481號公報或特開2003-183644號公報 記載之方法製造者爲佳。 螢光物質B1係例如金屬化合物之混合物，且將經由 燒結之螢光物質B1製得之混合物經由燒結而可調製。 例如’含有鋇（Ba)、銪（Eu) '鎂（Mg)、銘（ A1 )及氧（Ο )時， 上述之混合物之鋰源、銪源、鎂源、鋁源係純度99 %以上之氫氧化物、碳酸鹽、硝酸鹽、鹵化物、草酸鹽， 於高溫下分解製成者或純度99.9%以上之氧化物。 -10- (8) (8)1331167 螢光物質B 1係將上述之化合物與所期望之螢光物質 B1之組成方法秤量而混合，再將此些混合物經由燒結而 調製。 混合、燒結及任意進行之預燒係與高螢光物質A1相 同條件下進行爲佳》又，燒結製得之螢光物質B 1，必要 時，粉碎、洗淨或分級爲佳。粉碎係使用例如球磨機、噴 射磨進行爲佳。粉碎之螢光物質B 1係熱處理爲佳。經由 熱處理|可提高（經由粉碎降低之）螢光物質B1之結晶 性。 熱處理，一般與以上述之燒結相同條件下進行爲佳。 又，本發明之螢光體的製造使用之螢光物質B1係例 如以特開2001-220582號公報記載之方法製造者爲佳。 以下係對於螢光體糊料之說明。 本發明之螢光體糊料係含有上述之螢光體、膠粘劑及 溶劑。將其螢光糊體塗佈於基材，若加熱，可容易形成螢 光體之膜與層。加熱，一般爲溶劑輝發之溫度以上且未達 膠粘劑之分解溫度下進行。 本發明之螢光體糊料係例如將上述之螢光物質A1、 螢光物質B1、溶劑及膠粘劑，使用球磨機、三輥球磨機 '濕式分散機、輥輾機之裝置，經由混合之方法製造爲 佳。 螢光體糊料使用之膠粘劑係例如纖維素系樹脂（乙基 纖維素、甲基纖維素、硝基纖維素、乙酸纖維素、纖維素 丙酸酯、羥基丙基纖維素、丁基纖維素 '苄基纖維素、改 -11 - (9) (9)1331167 性纖維素等）、丙烯基系樹脂（丙烯酸、甲基丙烯酸、甲 基丙烯酸酯、甲基甲基丙烯酸酯、乙基丙烯酸酯、乙基甲 基丙烯酸酯、丙基丙烯酸酯、丙基甲基丙烯酸酯、異丙基 丙烯酸酯、異丙基甲基丙烯酸酯、正丁基丙烯酸酯、正丁 基甲基丙烯酸酯 '第三丁基丙烯酸酯、第三丁基甲基丙烯 酸酯、2 —羥基乙基丙烯酸酯、2 -羥基乙基甲基丙烯酸酯 、2-羥基丙基丙烯酸酯、2_羥基丙基甲基丙烯酸酯、苄 基丙烯酸酯、苄基甲基丙烯酸酯、苯基丙烯酸酯、苯基甲 基丙烯酸酯、異冰片基丙烯酸酯、異冰片基甲基丙烯酸酯 '甘氨醯基甲基丙烯酸酯、苯乙烯、甲基苯乙烯、丙 烯基醯胺基、甲基丙烯基醯胺基、丙烯腈、甲基丙烯腈等 之單量體中至少1種之聚合體）、乙烯-乙酸乙烯基共聚 合體樹脂、聚乙烯醇縮丁醛、聚乙烯醇、丙烯醇、尿烷系 樹脂、三聚氰胺系樹脂、苯酚樹脂。 摻雜基之含有量，對於螢光物質Α1螢光物質Β1之 合計量而言，一般爲5重量％〜50重量％ 。 螢光體糊料使用之溶劑係例如1價醇中之高沸點者； 乙二醇與甘油代表之二醇與三醇等之多價醇·，將醇醚化或 酯化之化合物（乙二醇單烷基醚、乙二醇二烷基醚、乙二 醇烷基醚乙酸酯、二乙二醇單烷基醚乙酸酯、二乙二醇二 烷基酯、丙二醇單烷基醚、丙二醇二烷基醚、丙二醇烷基 乙酸酯）。 溶劑之含有量，對於螢光物質Α1螢光物質Β1之合 計量而言，一般爲1〇〇重量！〜600重量％ 。 (10) 1331167 實施例 以下，經由實施例更進一步詳細地說明本發明，但本 發明並不特別限定於此些實施例。 試料（螢光體）之亮度係使用以下之方法測定。 將試料保持30分鐘於500 °C之空氣中，進行熱處理 後，設定壓力：13.2pa、氣體組成：5體積％氙（xe) -95 體積％氛（Ne)之氣氛中，於50W之電獎中處理15分鐘 後製得之試料，於6.7pa(5xl(T2Torr)以下之真空槽內 ，使用Excimer 146nm燈（USHIO電機股份有限公司製作 、H0012型），進行照射真空紫外線。 參照例1 對於銘酸鹽（Bao.gEuo.iMgAlioO"、藍色螢光物質、 平均一次粒徑) ’使用上述方法測定亮度。其試 料之亮度爲100。 參照例2 0 · 〇 3 M g s i 0 5、藍色螢光 使用上述方法測定亮 對於砂酸鹽（Ca〇.9215Sr〇.()485Eu 物質、平均一次粒徑) » 度之結果*売度爲127。 實施例1 照例Bai .gEugMg A110〇 】7 [Formula (V), 〇 < gg〇.3]. The weight ratio of the fluorescent substance A1/fluorescent substance B1 is preferably in the range of 5/95 to 95/5, more preferably in the range of 20/80 to 90/10, and particularly preferably 30/70 to 85/15. range. When the weight ratio of the fluorescent substance VIII to the fluorescent substance B1 is within the above range, a phosphor having higher brightness can be obtained by plasma treatment. When both of the fluorescent substance A1/fluorescent substance B1 are particles, the primary particle diameter of the fluorescent substance A1 is generally O.lym~5//m, and most preferably 〇_3; zm~3//m, and The primary particle diameter of the camping material B1 is generally 〜5//m, and most preferably 〇.3//m~3ym. The average primary particle diameter Db1 of the fluorescent material B1 is twice or more the average primary particle diameter Da1 of the fluorescent substance A1 (5) (5) 1331167 or less than 5 times 'that satisfies 〇//〇81芸5 and d/. / Da^5 is a preferred embodiment. If the phosphor of the present invention contains the light substance A1/fluorescent substance B1, it is preferable to contain a phosphor other than the above. The phosphor system of the present invention, even if it is treated, is high in brightness which can be excited by vacuum ultraviolet rays. In the production of a PDP and a rare gas lamp, a step of preparing a phosphor paste by using a general mixed phosphor, an adhesive, and a solvent, a step of applying a phosphor paste to the light-emitting portion, and a coating light to be applied The layer of the phosphor is formed by a manufacturing method of a step of heat treatment (for example, 500 ° C). When the phosphor of the present invention has the same brightness as that before the heat treatment, the phosphor of the present invention can be used in a vacuum ultraviolet light-emitting element of a PDP or a rare gas lamp to obtain a high degree of turbulence. Long life PDP and rare gas lamps. Further, the fluorescent system of the present invention can be excited by ultraviolet rays other than vacuum ultraviolet rays, such as X-rays or electron lines. Therefore, these may be used as an excitation source, and may be suitably used for fluorescent lamps, luminous displays, X-ray inspections, and CRTs. Etc. β A fluorescent system of the present invention having high brightness is preferably produced by mixing, for example, a fluorescent substance Α1 with a fluorescent substance Β1. The mixing is preferably carried out using a device such as a stirrer, a ball mill, or a three-roll ball mill. It is preferable to add a fluorescent substance Α1 and a phosphor other than the fluorescent substance Β1 as necessary. The fluorescent substance A 1 is, for example, a mixture of metal compounds and a mixture of the fluorescent substance A1 obtained by sintering can be prepared by sintering to prepare a calcium source of the mixture of the above - 8 - (6) (6) 1331167. The source or the source (corresponding to Μ1 of the formula (I)) is, for example, a hydroxide, a carbonate, a nitrate, a halide, or an oxalate having a purity of 99% or more, which is equivalent to a compound obtained by decomposing at a high temperature and having an oxide or purity. More than 99.9% of oxides. The magnesium source or the zinc source of the above mixture (corresponding to Μ2 of the formula (I)) is, for example, a hydroxide, a carbonate, a nitrate, a halide or an oxalate having a purity of 99% or more, which is equivalent to a compound obtained by decomposition at a high temperature or An oxide having a purity of 99.9% or more. The halogen source or nickel source of the above mixture (corresponding to Μ3 of the formula (I)) is, for example, a hydroxide, a carbonate, a nitrate, a halide or an oxalate having a purity of 99% or more, which is equivalent to a compound obtained by decomposition at a high temperature or An oxide having a purity of 9.9% or more. The source of the above mixture or the source of manganese (the activator of the fluorescent substance Α1) is, for example, a hydroxide, a carbonate, a nitrate, or a halide of oxalate having a purity of 99% or more, which is equivalent to the decomposition at a high temperature or purity. 9 9.9% or more of oxides. The fluorescent substance Α 1 is obtained by weaving a mixture of the above-mentioned compound and a desired fluorescent substance A 1 , and then pulverizing the mixture. The mixing system is preferably carried out using, for example, a ball mill, a V-type mixer or a mixer. It is preferred that the mixing is carried out in an appropriate amount. By adding a flux, the generation of the phosphor can be promoted and sintered at a low temperature. The sintering is preferably carried out in a reducing atmosphere, and it is preferably carried out, for example, in an argon containing hydrogen of about 0.1% (7) (7) of 1331167% by weight. Sintering is generally carried out at a temperature of about 1 0 0 °c~ about 1 500 ° C, and a time of about 1 hour to about 1 hour. In the above mixture, when a compound obtained by decomposing a hydroxide, a carbonate, a nitrate, a halide or an oxalate at a high temperature is used, it is preferred to pre-fire the mixture before sintering. It is preferred that the calcination is carried out in an oxidizing atmosphere (for example, in an atmosphere) or a reducing atmosphere. The calcination is preferably carried out at a temperature ranging from about 600 ° C to about 900 ° C. The phosphor material A1 produced by sintering is preferably pulverized, washed or classified as necessary. It is preferable to use a ball mill or a jet mill for the pulverization. It is preferred that the pulverized fluorescent substance A1 is subjected to heat treatment. The crystallinity of the fluorescent substance A1 (reduced by pulverization) can be improved by heat treatment. The heat treatment is generally carried out under the same conditions as those described above for sintering. Further, it is preferable that the phosphor material A1 used in the production of the phosphor of the present invention is produced by a method described in, for example, JP-A-2002-332481 or JP-A-2003-183644. The fluorescent substance B1 is, for example, a mixture of metal compounds, and the mixture obtained through the sintered fluorescent substance B1 can be prepared by sintering. For example, when 'containing Ba (Ba), Eu (Eu) 'Mg (Mg), Ming (A1) and Oxygen (Ο), the lithium source, the source of the source, the source of the magnesium, and the source of the aluminum of the above mixture are 99% or more. A hydroxide, a carbonate, a nitrate, a halide, or an oxalate is decomposed at a high temperature to produce an oxide having a purity of 99.9% or more. -10- (8) (8) 1331167 The fluorescent substance B 1 is prepared by mixing the above-mentioned compound and the desired composition of the fluorescent substance B1, and these mixtures are prepared by sintering. The mixing, sintering, and arbitrarily performed calcination are carried out under the same conditions as in the case of the high-fluorescent substance A1. Further, the phosphor material B1 obtained by sintering is preferably pulverized, washed or classified. The pulverization system is preferably carried out using, for example, a ball mill or a jet mill. The pulverized phosphor material B 1 is preferably heat treated. The crystallinity of the fluorescent substance B1 (reduced by pulverization) can be improved by heat treatment. The heat treatment is generally carried out under the same conditions as those described above for sintering. Further, the fluorescent material B1 used in the production of the phosphor of the present invention is preferably manufactured by a method described in JP-A-2001-220582. The following is a description of the phosphor paste. The phosphor paste of the present invention contains the above-mentioned phosphor, adhesive and solvent. The phosphor paste is applied to the substrate, and if heated, the film and layer of the phosphor can be easily formed. Heating, generally above the temperature of the solvent, does not occur at the decomposition temperature of the adhesive. The phosphor paste of the present invention is produced by, for example, mixing a phosphor material A1, a phosphor material B1, a solvent, and an adhesive using a ball mill, a three-roll ball mill 'wet disperser, and a roll mill. It is better. The adhesive used for the phosphor paste is, for example, a cellulose resin (ethyl cellulose, methyl cellulose, nitrocellulose, cellulose acetate, cellulose propionate, hydroxypropyl cellulose, butyl cellulose). 'Benzyl cellulose, modified -11 - (9) (9) 1331167 cellulose, etc.), propylene-based resin (acrylic acid, methacrylic acid, methacrylic acid ester, methyl methacrylate, ethyl acrylate) , ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate 't-butyl Acrylate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, benzyl acrylate , benzyl methacrylate, phenyl acrylate, phenyl methacrylate, isobornyl acrylate, isobornyl methacrylate 'glycidyl methacrylate, styrene, methyl styrene Propenyl decylamine a polymer of at least one of a monovalent body such as a methacrylamide group, an acrylonitrile or a methacrylonitrile, an ethylene-vinyl acetate copolymer resin, polyvinyl butyral, or polyvinyl alcohol. Acryl alcohol, urethane resin, melamine resin, phenol resin. The content of the doping group is generally 5% by weight to 50% by weight based on the total amount of the fluorescent substance Α1 fluorescent substance Β1. The solvent used for the phosphor paste is, for example, a high boiling point in a monovalent alcohol; a polyvalent alcohol such as a glycol or a triglyceride represented by glycerin, and a compound which etherifies or esterifies an alcohol (Ethylene 2) Alcohol monoalkyl ether, ethylene glycol dialkyl ether, ethylene glycol alkyl ether acetate, diethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ester, propylene glycol monoalkyl ether , propylene glycol dialkyl ether, propylene glycol alkyl acetate). The content of the solvent is generally 1 〇〇 for the measurement of the fluorescent substance Α1 fluorescent substance Β1! ~600% by weight. (10) 1331167 EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples. However, the invention is not particularly limited thereto. The brightness of the sample (fluorescent body) was measured by the following method. The sample was kept in air at 500 ° C for 30 minutes, and after heat treatment, set pressure: 13.2 pa, gas composition: 5 vol% 氙 (xe) - 95 vol% atmosphere (Ne) atmosphere, 50 W electric prize The sample prepared after the treatment for 15 minutes was irradiated with vacuum ultraviolet rays using an Excimer 146 nm lamp (manufactured by USHIO Electric Co., Ltd., model H0012) in a vacuum chamber of 6.7 Pa (5×1 (T2 Torr) or less.) Reference Example 1 Acid salt (Bao.gEuo.iMgAlioO", blue fluorescent material, average primary particle diameter) 'The brightness was measured by the above method. The brightness of the sample was 100. Reference Example 2 0 · 〇3 M gsi 0 5, blue fluorescein The light was measured by the above method for the sulphate (Ca 〇 92 92 92 92 92 92 92 92 92 92 485 485 485 485 » » » » » » » » » » » » » 売 売 127 127 127 127 127 127 127 127 127
將參照例2使用之螢光物質5 〇重4 {分_ & -13- 1331167 (11)The fluorescent substance 5 used in Reference Example 2 is 44 {分_ & -13- 1331167 (11)
* I 用之螢光物質50重量份’於乙醇中濕式混合，將其混合 物乾燥製得螢光體。對於螢光體，使用上述方法測定亮度 之結果，發光爲藍色，亮度爲127。 實施例2 將參照例2使用之螢光物質8 0重量份與參照例1使 用之螢光物質20重量份’於乙醇中濕式混合，將其混合 物乾燥製得螢光體。對於螢光體’使用上述方法測定亮度 之結果，發光爲藍色’亮度爲113。 實施例3 將參照例2使用之螢光物質2〇重量份與參照例i $ 用之螢光物質80重量份，於乙醇中濕式混合， 物乾燥製得螢光體。對於螢光體，使用上述方法彻」$胃p 之結果，發光爲藍色，亮度爲1〇7。* I used 50 parts by weight of the fluorescent material in wet mixing in ethanol, and the mixture was dried to obtain a phosphor. For the phosphor, the result of measuring the brightness by the above method was that the light emission was blue and the luminance was 127. Example 2 80 parts by weight of the fluorescent material used in Reference Example 2 and 20 parts by weight of the fluorescent material used in Reference Example 1 were wet-mixed in ethanol, and the mixture was dried to obtain a phosphor. As a result of measuring the brightness of the phosphor using the above method, the light emission was blue and the luminance was 113. Example 3 Two parts by weight of the fluorescent material used in Reference Example 2 and 80 parts by weight of the fluorescent material used in Reference Example i were wet-mixed in ethanol and dried to obtain a phosphor. For the phosphor, the above method was used to "go stomach p", the light was blue, and the brightness was 1〇7.