201109422 六、發明說明： 【發明所屬之技術領域】 本發明有關經表面處理之螢光體粒子的製造方法及經 表面處理之螢光體粒子。 【先前技術】 螢光體所採用之發光元件而言，可例舉：螢光體的激 發源（excitation source)爲紫外線之紫外線激發發光元 件(ultravoletray excitation luminescent element )(例如 ，液晶顯示器用背光板（backlight ) 、3波長型螢光燈（ 3 - wavelength type fluorescent lamp )、高負載登光燈（ high load fluorescent lamp)等），激發源爲真空紫外線 (vacuum ultravioletray )之真空紫外線激發發光元件（ vacuum ultravioletray excitation luminescent element )( 例如，電榮顯示器面板（plasma display panel) '稀有氣 體燈（rare gas lamp )等），激發源爲藍色LED ( li ght emitting diode，發光二極體）或紫外LED所發出之光之白 色LED，激發源爲電子束之電子束激發發光元件（electron beam excitation luminescent element)(例如，陰極射線 管（Braun tube )、場致發射顯示器（f i e 1 d em i s s i ο η display )、表面電場顯示器（surface electric field display )等），激發源爲X射線之發光元件（x射線攝像 裝置（X-ray pick-up camera)等）等。 螢光體，係因照射如上所述之激發源而發光者。一般 -5- 201109422 ，關於亮度（luminance)、色度（chromaticity)、耐久 性、帶電特性（electrification characteristics)、粒徑等 的特性而言，則按照所使用之環境而選擇適當的螢光體。 例如，紫外線激發發光元件、真空紫外線激發發光元件的 藍色螢光體而言，在來周知，有BaMgAl1Q017 : Eu2+ (通 稱BAM)、或〇3^^5丨206:£112+(通稱^^5)。綠色螢光 體而言，周知有 LaP04 : Ce3+，Tb3 +或 Zn2Si04 : Mn2+，紅 色螢光體而言，周知有Y2〇3 : Eu3+或（Y，Gd ) B〇3 : Eu3、 如將此螢光體採用於顯示器等的裝置（device)上時 ，通常，如將螢光體粒子與溶劑或黏合劑（binder ) —起 混合以製備料漿（slurry)或糊膏（paste)，並將此塗佈 或印刷於將成爲基板等的發光面之部位，然後，利用乾燥 及加熱以去除溶劑或黏合劑等方法，即可形成螢光層。當 如此方式製造裝置時，由於螢光體將遭受熱歷程（thermal hysteresis )之故，有時螢光體的亮度會降低。此種現象， —般稱爲螢光體的燒成劣化（burning deterioration)等。 又，如長時期使用（點燈）裝置時，則可能有繼續接受激 發源之紫外線、真空紫外線等的高能量的入射之螢光體的 亮度之降低、或螢光體的發光色（發光波長）之變化之情 形。此等現象，係一般認爲螢光體的長期劣化、壽命問題 等所致。 爲此種螢光體的劣化的對策，有時會採用例如，利用 耐久性優異的材料以被覆螢光體粒子表面之方法（例如， -6 - 201109422 參考專利文獻1至5 )。爲被覆所使用之材料而言，例如， 除ai2o3或Si02等單純氧化物之外，尙有氮化物、氟化物 、碳酸鹽、複合氧化物（compound oxide)、有機物等。 〔先前技術文獻〕 〔專利文獻〕 專利文獻1:日本專利特開平1 1 -73 8 8 7號公報 專利文獻2:美國專利7,223,48 2號說明書 專利文獻3:日本專利特開20 00-3 03 065號公報 專利文獻4:日本專利特開2003 -82 3 43號公報 專利文獻5 :日本專利特表2007-52 8426號公報 【發明內容】 如採用於上述之利用耐久性優異的材料以被覆螢光體 粒子表面之方法，則關於螢光體的燒成劣化或壽命問題而 言，亦能獲得某程度的效果。但，由於利用各種材料被覆 螢光體粒子時所需要的加熱等的影響，而有螢光體粒子的 初期的亮度會降低之問題。 於是，本發明之主要目的在於使初期亮度維持於十分 高之下且能充分抑制在製造採用螢光體粒子之各種裝置之 階段所遭受之因熱歷程所引起之亮度的低落。 〔用以解決課題之手段〕 爲解決上述課題起見，本發明提供一種經表面處理之 201109422 螢光體粒子的製造方法，其特徵爲：具備；於將含有鑭（ La)之水溶液與含有磷酸之水溶液，在螢光體粒子的存在 下混合所得分散液中，形成具有該螢光體粒子及附著於其 表面之磷酸鑭之經表面處理之螢光體粒子之過程。 於上述分散液中，因共沈澱反應（Co-precipitation reaction )而生成磷酸鑭，並於螢光體粒子表面附著磷酸 鑭之結果，不實施燒成處理，即可製造經表面處理之螢光 粒子。因此，可使螢光體粒子的初期亮度維持於十分高的 水準。再者，如採用本經表面處理之螢光體粒子，則亦能 充分抑制在製造具備螢光體粒子之各種裝置之階段所遭受 之因熱歷程所引起之亮度的低落。 於本發明之製造方法中，螢光體粒子較佳爲含有可以 (Ba|.x-zSrxEuz ) MgAll0O17 ( X符合 0 $ X $ 0.5、z符合 0.01 SzS0.2)表示之螢光體、可以（Cai.y.zSryEuz) MgSi206 (y 符合 OSygl、Z符合 O.OOlSzSO.l，而 y + zgl)表示 之螢光體，或者可以（Zn2-wMnw) Si04(w符合O.OOlSw S 0.1)表示之螢光體。 如螢光體粒子含有BaMgAl1()017: Eu2+時，特別是在 螢光體的燒成劣化及長期劣化方面有待改進之課題。另一 方面，螢光體粒子含有可以Cai-ySryMgSi206 : Eu2+ ( y表 示0至1之數）表示之螢光體時，容易發生所謂溫度熄滅效 應（temperature quenching)的問題。如將採用蛮光體之 裝置加以點燈時，則因入射能量或電子電路的發熱等而裝 置的溫度上升，隨著螢光體的溫度亦上升，以致其亮度可 -8 - 201109422 能降低。此種現象，一般稱爲溫度熄滅效應，而 成爲顯示器或照明之著色（tinting)變化之原因 體粒子含有可以Zn2Si04 : Mn2+表示之螢光體時 的吸附所引起之亮度低落會容易成爲問題。本發 迴避此種問題來看1亦屬有用者。 於本發明之製造方法中，較佳爲再具備：藉 處理之螢光體粒子不致於被加熱爲200°C以上之 從分散液中回收經表面處理之螢光體粒子之過程 利用不致於被加熱爲200 °C以上之方法，而 中回收經表面.處理之螢光體粒子之結果，可將經 之螢光體粒子，不致於經過例如約300至600°C的 燒成之下，採用爲裝置之製造等上。其結果，可 地防止螢光體粒子的初期亮度之低落。 又，本發明提供一種經表面處理之螢光體粒 徵爲：具備；螢光體粒子、及藉由將含有鑭之水 有磷酸之水溶液在螢光體粒子的存在下混合之方 附著於螢光體粒子表面之磷酸鑭。 如採用有關上述本發明之經表面處理螢光體 使初期亮度維持於十分高之下且能充分抑制在製 光體粒子之各種裝置之階段所遭受之因熱歷程所 度的低落。 於本發明之上述經表面處理之螢光體粒子中 粒子較佳爲含有可以（Bai-x_zSrxEuz) MgAli〇〇i7 SxS0.5、z符合O.OlSzSO.2)表示之螢光體 該效應即 。如螢光 ，則因汞 明，從能 由經表面 方法，而 〇 從分散液 表面處理 高溫下的 特別有效 子，其特 溶液與含 法而使其 粒子，則 造使用螢 引起之亮 ，螢光體 (X符合〇 ，可以（ -9 - 201109422201109422 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for producing surface-treated phosphor particles and a surface-treated phosphor particle. [Prior Art] The light-emitting element used in the phosphor may be an ultraviolet excitation light-emitting element (for example, a backlight for a liquid crystal display). (backlight), 3 - wavelength type fluorescent lamp, high load fluorescent lamp, etc., the excitation source is vacuum ultraviolet ray (vacuum ultraviolet ray) Ultraviolet Ray luminescent element ) (for example, a plasma display panel 'rare gas lamp, etc.'), the excitation source is a blue LED (light luminescent diode) or an ultraviolet LED a white LED that emits light, an excitation beam is an electron beam excitation luminescent element (for example, a cathode ray tube (Braun tube), a field emission display (fie 1 d em issi ο η display) Surface electric field display Or the like, the excitation source is an X-ray light-emitting element (such as an X-ray pick-up camera). The phosphor is a person who emits light by irradiation with an excitation source as described above. In general, -5-201109422, regarding the characteristics of luminance, chromaticity, durability, electrification characteristics, particle size, etc., an appropriate phosphor is selected in accordance with the environment to be used. For example, a blue phosphor that emits an ultraviolet-ray-excited light-emitting element or a vacuum ultraviolet-excited light-emitting element is known as BaMgAl1Q017: Eu2+ (commonly known as BAM), or 〇3^^5丨206: £112+ (commonly known as ^^) 5). For green phosphors, LaP04 : Ce3+, Tb3 + or Zn2Si04 : Mn2+ is known, and red phosphors are known to have Y2〇3: Eu3+ or (Y, Gd) B〇3: Eu3, such as this When the light body is used on a device such as a display, usually, the phosphor particles are mixed with a solvent or a binder to prepare a slurry or a paste, and this is The phosphor layer is formed by coating or printing on a portion to be a light-emitting surface of a substrate or the like, and then drying or heating to remove a solvent or a binder. When the device is manufactured in this manner, the brightness of the phosphor may be lowered because the phosphor will suffer from thermal hysteresis. Such a phenomenon is generally called "burning deterioration" of a phosphor. In addition, when the device is used for a long period of time (lighting), there is a possibility that the luminance of the incident fluorescent light that continues to receive high-energy ultraviolet rays, vacuum ultraviolet rays, or the like, or the luminescent color of the fluorescent body (light-emitting wavelength) The situation of change. These phenomena are generally caused by long-term deterioration of the phosphor, life problems, and the like. For the purpose of the deterioration of the phosphor, for example, a method of coating the surface of the phosphor particles with a material having excellent durability (for example, -6 - 201109422, refer to Patent Documents 1 to 5). The material used for the coating is, for example, a nitride, a fluoride, a carbonate, a compound oxide, an organic substance or the like in addition to a simple oxide such as ai2o3 or SiO2. [Prior Art Document] [Patent Document] Patent Document 1: Japanese Patent Laid-Open Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Patent Document 4: Japanese Patent Laid-Open Publication No. 2003-82 No. 2003-52 No. 2007-52-8426. SUMMARY OF THE INVENTION The present invention is applied to a material which is excellent in durability as described above. The method of the surface of the phosphor particles can also achieve a certain degree of effect regarding the deterioration of the phosphor or the problem of the lifetime. However, there is a problem that the initial brightness of the phosphor particles is lowered due to the influence of heating or the like required when the phosphor particles are coated with various materials. Accordingly, the main object of the present invention is to maintain the initial luminance at a very high level and to sufficiently suppress the deterioration of the luminance caused by the thermal history which is suffered at the stage of manufacturing various devices using the phosphor particles. [Means for Solving the Problems] In order to solve the above problems, the present invention provides a method for producing a surface-treated 201109422 phosphor particle, which comprises: providing an aqueous solution containing barium (La) and containing phosphoric acid The aqueous solution is mixed in the dispersion liquid in the presence of the phosphor particles to form a surface-treated phosphor particle having the phosphor particles and the yttrium phosphate adhered to the surface. In the dispersion liquid, yttrium phosphate is formed by a co-precipitation reaction, and strontium phosphate is attached to the surface of the phosphor particles, and the surface-treated luminescent particles can be produced without performing a baking treatment. . Therefore, the initial luminance of the phosphor particles can be maintained at a very high level. Further, by using the surface-treated phosphor particles, it is possible to sufficiently suppress the decrease in luminance due to the heat history which is suffered at the stage of manufacturing various devices having the phosphor particles. In the manufacturing method of the present invention, the phosphor particles preferably contain a phosphor which can be represented by (Ba|.x-zSrxEuz) MgAll0O17 (X conforms to 0$X$0.5, z corresponds to 0.01 SzS0.2), and can be ( Cai.y.zSryEuz) MgSi206 (y conforms to OSygl, Z conforms to O.OOlSzSO.l, and y + zgl) represents a phosphor, or may be represented by (Zn2-wMnw) Si04 (w in accordance with O.OOlSw S 0.1) Fluorescent body. When the phosphor particles contain BaMgAl1() 017: Eu2+, there is a problem that needs to be improved particularly in the case of firing deterioration and long-term deterioration of the phosphor. On the other hand, when the phosphor particles contain a phosphor which can be represented by Cai-ySryMgSi206: Eu2+ (y represents a number from 0 to 1,), a so-called temperature quenching problem easily occurs. When a light-emitting device is used for lighting, the temperature of the device rises due to incident energy or heat generation of the electronic circuit, and the temperature of the phosphor also rises, so that the brightness can be lowered by -8 - 201109422. Such a phenomenon is generally called a temperature quenching effect, and is a cause of a change in tinting of a display or illumination. When the bulk particles contain a phosphor which can be represented by Zn2Si04: Mn2+, the decrease in luminance is likely to be a problem. This issue is also useful for avoiding such problems. In the production method of the present invention, it is preferable to further provide that the process of recovering the surface-treated phosphor particles from the dispersion liquid by the processed phosphor particles not being heated to 200 ° C or higher is not utilized The method of heating to a temperature above 200 ° C, and recovering the surface-treated phosphor particles, can pass the phosphor particles without being subjected to firing at, for example, about 300 to 600 ° C. For the manufacture of the device, etc. As a result, the initial luminance of the phosphor particles can be prevented from being lowered. Further, the present invention provides a surface-treated phosphor particle: comprising: a phosphor particle, and an aqueous solution containing phosphoric acid in water in the presence of phosphor particles to be attached to the firefly Barium phosphate on the surface of the light body particles. The use of the surface-treated phosphor of the present invention described above maintains the initial luminance at a very high level and sufficiently suppresses the deterioration of the thermal history suffered at the stage of various devices of the toner particles. Preferably, the particles in the surface-treated phosphor particles of the present invention contain a phosphor which can be represented by (Bai-x_zSrxEuz) MgAli〇〇i7 SxS0.5 and z in accordance with O.OlSzSO.2). For example, if it is fluorescent, it can be made from a surface-based method, and the surface of the dispersion can be treated with a special solution at a high temperature, and the special solution and the inclusion method can cause the particles to be bright. Light body (X conforms to 〇, can ( -9 - 201109422
Ca,.y.zSryEuz ) MgSi206 ( y符合 1、z符合 O.OOlgz $0.1，而y + zgl)表示之螢光體，或者可以（Zn2-wMnw )Si04(w符合O.OOlSwSO.l)表示之螢光體。 於本發明之上述經表面處理之螢光體粒子中，以螢光 體粒子的質量作爲基準之磷酸鑭的質量比，較佳爲0.01至 5質量％。 如磷酸鑭的質量增加時，則由於螢光體粒子的質量比 即降低，相對性的亮度即降低之故，以螢光體粒子的質量 作爲基準之磷酸鑭的質量比，較佳爲在上述範圍。 〔發明之效果〕 如採用本發明之經表面處理之螢光體粒子的製造方法 ，則因共沈澱反應而生成磷酸鑭，並附著於螢光體粒子表 面之結果，在不實施燒成處理之下，即可製造經表面處理 之螢光體粒子。因此，可使螢光體粒子的初期亮度維持於 十分高的水準。再者，如採用本經表面處理之螢光體粒子 ，則亦能充分抑制在製造具備螢光體粒子之各種裝置之階 段所遭受之因熱歷程所引起之亮度的低落。 〔發明之最佳實施形態〕 以下’就本發明之最佳實施形態詳細加以說明。惟本 發明並不因下述之實施形態而有所限定。 有關本實施形態之製造方法，係具備；於使含有鑭之 水溶液與含有磷酸之水溶液’在螢光體粒子的存在下混合 -10- 201109422 所得分散液中，形成具有螢光體粒子及附著於其表面之磷 酸鑭之經表面處理之螢光體粒子之過程、和從分散液回收 經表面處理之螢光體粒子之過程。 構成螢光體粒子之螢光體，並不特別加以限定，惟從 能改善燒成劣化之觀點來看，很適合採用BaMgAl1Q017 : Eu2+。另一方面，從能改善溫度熄滅效應之觀點來看，很 適合採用CahySryMgShOe : Eu2+ ( y表示0至1 )。又，就 在屬於螢光體的主要用途之液晶顯示器用背光板等，利用 泵以生成作爲激發源之紫外線之裝置而言，因螢光體的汞 吸附所引起之劣化即成爲亮度低落的原因。由於磷酸鑭亦 具有阻礙汞的吸附之效果之故，從此種觀點來看，特別適 合採用 Zn2Si04 : Μ]ι2+。又，BaMgAll0O17 : Eu2 +以及〇31· ySryMgSi206 : Eu2+ ( y表示0至1 )亦很適用使用。就經將 BaMgAl10O17 ： Eu2+ 的 Ba 的一部分取代爲 Sr 2Bai. xSrxMgAli〇〇i7: Eu2+(x表示0至0.5)而言，亦可獲得同 樣的效果。 螢光體粒子的製法，並不特別加以限定，除一般性的 固體相反應（Solid -phase reaction method)之外，尙可採 用共沈澱法、溶膠—凝膠法（sol-gel method)、水熱法 (hydrothermal method)等。於最爲一般性的固體相反應 法中，係將含有構成螢光體之金屬元素之氧化物、碳酸鹽 、氫氧化物等作爲原料，按能成爲與目標組成之螢光體的 莫耳比同樣之方式加以稱重量，並將此等混合、粉碎後進 行燒成。在藍色螢光體BaMgAllc017 : Eu2+的情形，例如 -11 - 201109422 ’將 BaC03、3MgC03· Mg(OH) 2、Al2〇3 以及 Eu2〇3 作爲 原料使用’並將此等按能成爲Ba: Mg: Al: Eu=l_z: i: · z之旲耳比之方式加以稱重量。在此，z表示將Ba的— 部分取代爲Eu之比例，一般性而言，2 = 〇〇1至〇2程度的値 。如將所稱重量之原料混合後，在l4〇〇°C程度的含氫之還 原氣氛下進行燒成’即可製得作爲目的之螢光體。需要時 ’亦可重複複數次的燒成、洗滌以及粉碎。 在0&1151^1^3丨206:£112+的情形，例如，將（：3(：〇3、 SrC03、3MgC03 · Mg ( OH ) 2 ' 3102及 Eu203 作爲原料使 用’並按既定的莫耳比將此等混合。又，在Zn2Si04 : Mn2 +的情形’例如’將ZnO、Si02、以及Μη02作爲原料使 用，並按既定的莫耳比將此等混合。其他則利用與Ca,.y.zSryEuz ) MgSi206 (y corresponds to 1, z conforms to O.OOlgz $0.1, and y + zgl) represents a phosphor, or may be represented by (Zn2-wMnw)Si04 (w in accordance with O.OOlSwSO.l) Fluorescent body. In the surface-treated phosphor particles of the present invention, the mass ratio of barium phosphate based on the mass of the phosphor particles is preferably 0.01 to 5% by mass. When the mass of the strontium phosphate is increased, the mass ratio of the phosphor particles is lowered, and the relative luminance is lowered. Therefore, the mass ratio of the strontium phosphate based on the mass of the phosphor particles is preferably range. [Effects of the Invention] According to the method for producing a surface-treated phosphor particle of the present invention, yttrium phosphate is formed by the coprecipitation reaction and adheres to the surface of the phosphor particle, and the firing treatment is not performed. The surface treated phosphor particles can then be produced. Therefore, the initial luminance of the phosphor particles can be maintained at a very high level. Further, by using the surface-treated phosphor particles, it is possible to sufficiently suppress the decrease in luminance due to the heat history which is suffered in the stage of manufacturing various devices having the phosphor particles. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the best mode for carrying out the invention will be described in detail. However, the invention is not limited by the embodiments described below. In the production method of the present embodiment, the dispersion liquid obtained by mixing the aqueous solution containing ruthenium and the aqueous solution containing phosphoric acid in the presence of the phosphor particles -10-201109422 is formed to have phosphor particles and adhere thereto. The process of surface-treated phosphor particles on the surface of the strontium phosphate and the process of recovering the surface-treated phosphor particles from the dispersion. The phosphor constituting the phosphor particles is not particularly limited, but BaMgAl1Q017: Eu2+ is suitably used from the viewpoint of improving the deterioration of firing. On the other hand, it is suitable to use CahySryMgShOe : Eu2+ (y represents 0 to 1) from the viewpoint of improving the temperature extinction effect. In addition, in a backlight device for a liquid crystal display, which is a main use of a phosphor, a device that generates ultraviolet rays as an excitation source by a pump, deterioration due to mercury adsorption of the phosphor is a cause of low brightness. . Since strontium phosphate also has an effect of hindering the adsorption of mercury, from this viewpoint, Zn2Si04 : Μ]ι 2+ is particularly suitable. Further, BaMgAll0O17: Eu2+ and 〇31·ySryMgSi206: Eu2+ (y represents 0 to 1) are also suitable for use. The same effect can be obtained by substituting a part of Ba of BaMgAl10O17: Eu2+ for Sr 2Bai. xSrxMgAli〇〇i7: Eu2+ (x represents 0 to 0.5). The method for producing the phosphor particles is not particularly limited. In addition to the general solid-phase reaction method, the coprecipitation method, the sol-gel method, and the water may be used. Hydrothermal method, etc. In the most general solid phase reaction method, an oxide, a carbonate, a hydroxide, or the like, which contains a metal element constituting a phosphor, is used as a raw material, and a molar ratio which can be a phosphor of a target composition is used. In the same manner, the weight is weighed, and these are mixed, pulverized, and fired. In the case of the blue phosphor BaMgAllc017: Eu2+, for example, -11 - 201109422 'Use BaC03, 3MgC03·Mg(OH) 2, Al2〇3, and Eu2〇3 as raw materials, and use this as Ba: Mg : Al: Eu=l_z: i: · z is the weight of the ear. Here, z represents the ratio of the substitution of Ba to the Eu, and in general, 2 = 〇〇1 to 〇2. The desired phosphor can be obtained by mixing the raw materials of the weighed weight and then firing in a hydrogen-containing reducing atmosphere of about 14 °C. When necessary, the firing, washing, and pulverization may be repeated a plurality of times. In the case of 0 & 1151 ^ 1 ^ 3 丨 206: £ 112 + , for example, (: 3 (: 〇 3, SrC03, 3MgC03 · Mg ( OH ) 2 ' 3102 and Eu203 are used as raw materials] and according to the established Mo In the case of Zn2Si04 : Mn2 +, for example, ZnO, SiO 2 , and Μ η 02 are used as raw materials, and these are mixed according to a predetermined molar ratio.
BaMgAl1()017 : Eu2+同樣的操作，即可製得各螢光體粒子 〇 螢光體粒子的表面處理（coating，塗層），係藉由所 謂共沈澱法而實施。對螢光體粒子表面，主要將附著磷酸 鑭，惟需要時，亦可倂用其他材料。 如將含有鑭之水溶液與含有磷酸之水溶液加以混合， 則因共沈澱反應而生成磷酸鑭。如將此共沈澱反應在螢光 體粒子的存在下進行時，則所生成之磷酸鑭即附著於螢光 體粒子表面，而生成經表面處理之螢光體粒子。此時並不 需要螢光體粒子表面全面爲經磷酸鑭所被覆’亦可爲營光 體粒子本身的表面的一部分在露出。 含有磷酸之水溶液中，含有水、和經溶解於水之憐酸 -12- 201109422 (H3P04 )或其鹽。又，水溶液可以氨等調整pH値。磷酸 的鹽而言，例如，可採用磷酸銨（（NH4 ) 2HP04 )。如 使用此等含有磷酸或磷酸鹽之水溶液，則可抑制其他金屬 離子之混入。含有磷酸之水溶液的磷濃度，較佳爲0.001 莫耳（mol) /公升至O.lmol/公升，更佳爲0.005mol/公升 至0.05mol/公升、特佳爲o.oimol/公升程度。如濃度過高 時，則有螢光體被酸所溶解、或所生成之磷酸鑭的粒子會 凝聚之傾向。如濃度過低時，則有磷酸鑭難於附著於螢光 體粒子表面之傾向。 例如，於此含葙磷酸之水溶液中使螢光體粒子分散以 調製分散液，並對此添加含有鑭之水溶液。分散液中之螢 光體粒子的量，並不特別加以限定，惟對含有磷酸之水溶 液1公升’較佳爲10g至l〇,〇〇〇g、更佳爲l〇〇g至l〇〇〇g程度 。按照螢光體粒子的比重、粒徑等，調整爲最適量。按磷 酸鑭能均句附著於螢光體粒子表面起見，螢光體粒子實質 上未沈降於分散液中爲宜。爲此，在共沈澱反應中，使用 攪拌棒、磁力攪拌器（magnetic stirer)等，繼續攪拌分 散液爲宜。 含有鑭之水溶液，例如，將硝酸鑭（La ( N03 ) 3 )、 乙酸鑭（La ( CH3 COO ) 3 )等鑭化合物溶解於水中即可製 得。含有鑭之水溶液的鑭濃度，較佳爲〇.〇〇 lm〇l/公升至 O.lmol/公升、更佳爲〇.0〇5m〇i/公升至0.05m〇丨/公升、特佳 爲O.Olmol /公升程度》 將含有鑭之水溶液添加於含有磷酸之分散液中之速度 -13- 201109422 ，係因溶液的濃度或溫度等之故最適當條件會變動而並不 能特別加以限定，惟在O.OOOlmol/分鐘至O.Olmol/分鐘程 度。鑭與磷酸的比例，可爲化學計量比（stoichiometric ratio )之La: P = l: 1，惟亦可防止未反應的鑭離子漏出或 恢復原來的鑭鹽起見，亦可作成如La : P = 1 : 3之方式之磷 過剩條件下實施。由於未反應的磷，係可由洗滌而容易去 除者之故。 將含有鑭之水溶液與含有磷酸之水溶液，在螢光體粒 子的存在下混合以製得分散液之方法，係並不特別限定於 如上述般之使螢光體粒子分散於含有磷酸之水溶液中後， 添加含有鑭之水溶液之方法。亦可作成使螢光體粒子分散 於含有鑭之水溶液中後，對此添加含有磷酸之水溶液之方 式。 由於因混合所引起之磷酸鑭的生成，即使在室溫下仍 能略瞬間完成之故，不需要特別加以加熱之操作。但，爲 使反應完全完成起見，或爲控制所生成之磷酸鑭的粒徑或 結晶性起見，亦可在混合前後的任意時間（混合前、混合 中或混合後）將溶液加溫》此時，溫度爲液體的沸點以下 ，在水溶液的情形爲約100°C以下，較佳爲70至90°c。 將分散液中所生成之經表面處理之螢光體粒子，利用 過濾等方法取出，並從所取出之經表面處理之螢光體粒子 ，利用使用純水之洗滌以去除過剩部分。然後，將所洗滌 之螢光體粒子，利用200 °C以下，較佳爲60至120 °C的加熱 而加以乾燥。按照此種方法，即可在不需要200 °C以上的 -14- 201109422 加熱之下，從分散液中回收經表面處理之螢光體粒子。如 因乾燥而經表面處理之螢光體粒子凝聚時，亦可實施撕碎 (shredding ) ° 就螢光體粒子表面的磷酸鑭的附著量而言，並不特別 加以限定，只要是在能獲得作爲目的之特性改善之最低需 要限度內即可。由於磷酸鑭實質上不會吸收紫外線之故， 對螢光體粒子表面之因附著所引起之亮度的影響很少。但 ，如本身爲非發光材料之磷酸鑭的附著量增加時，則螢光 體粒子的體積分率（volume fraction)降低，以致有相對 性的亮度會降低之傾向。從此種觀點來看，磷酸鑭的附著 量，係以螢光體粒子的質量爲基準計，較佳爲0.01至5質 量％，更佳爲0. 1至1質量％。 【實施方式】 以下，舉出實施例以更具體方式說明本發明內容。但 ，本發明並不因下述之實施例而有所限定。本實施例中， 爲測定螢光體粒子的亮度起見，採用光譜光度計（spectro photometer) FP-6500 (製品名，日本分光社製）。 爲製作藍色螢光體BaMgAl1()017: Eu2 +起見，將BaC03 、3MgC03 · Mg ( OH ) 2、A1203 以及 Eu203 作爲原料使用 ，並將此等，按以莫耳比計，能成爲Ba : Mg : A1 : Eu=l 至0·1 : 1 : 1〇 : 0.1之方式加以稱重量。在此，0.1表示將 Ba的一部分取代爲Ell之比例。將經稱量之原料加以混合後 ’在1 400 °C程度的含氫氣之還原氣氛下加以燒成之結果， -15- 201109422 製得作爲目的之螢光體粒子。 (實施例1 ) 作爲含有磷之水溶液，採用磷酸（Η 3 P 0 4 )水溶液， 作爲含有鑭之水溶液，則採用硝酸鑭（La ( Ν03 ) 3 )水溶 液。於0.01Μ (莫耳）的磷酸水溶液37.5ml中，在攪拌之 下添加本身爲藍色螢光體粒子之BaMgAl1C)〇17 : Eu2 + 5.0g， 以製作料漿狀的分散液。對此分散液，滴下0.01 Μ的La ( Ν Ο 3 ) 3水溶液1 2 · 5 m 1 ’並將液溫升溫爲7 5 後，完成共沈 澱反應。然後，將此料漿（分散液）加以過濾，並將所取 出之固體成分加以水洗（50mlx3次）。水洗後的固體成分 ’則在1 2 0 °C下加熱1小時以使其乾燥，使用瑪瑙硏鉢（ agate mortar)加以撕碎之結果，製得經於螢光體粒子表 面附著0.2質量％之磷酸鑭（LaP04)之經表面處理之螢光 體粒子。 (實施例2 ) 於0.01M的磷酸水溶液37.5ml中，在攪拌下添加本身 爲藍色螢光體粒子BaMgAl1Q〇17: Eu2+ 12.5g,以製作料漿 狀的分散液。對此分散液，滴下0 · 0 1 Μ的L a ( Ν Ο 3 ) 3水溶 液12.5ml ’並將液溫升溫爲75 t後，完成共沈澱反應。然 後’將此料漿（分散液）加以過濾，並將所取出之固體成 分加以水洗（50ml X3次）。水洗後的固體成分，則在120 °C下加熱1小時以使其乾燥，使用瑪瑙硏鉢加以撕碎之結 -16- 201109422 果，製得經於螢光體粒子表面附著〇. 5質量％之磷酸鑭（ LaP04 )之經表面處理之螢光體粒子。 (實施例3 ) 於0.01M的磷酸水溶液60.Oml中，在攪拌下添加本身 爲藍色螢光體粒子之BaMgAl1()017 : Eu2+ 4.0g，以製作料 漿狀的分散液。對此分散液，滴下0.01M的La(N03) 3水 溶液2 0 . Oml，並將液溫升溫爲7 5 °C後，完成共沈澱反應。 然後，將此料漿（分散液）加以過濾，並將所取出之固體 成分加以水洗（50ml X 3次）。水洗後的固體成分，則在 1 20°C下加熱1小時以使其乾燥，使用瑪瑙硏鉢加以撕碎之 結果，製得經於螢光體粒子表面附著1 .〇質量％之磷酸鑭（ LaP04 )之經表面處理之螢光體粒子。 (藉由熱處理之亮度變化之評價） 將在實施例1至3所得經表面處理之螢光體粒子、及未 經表面處理之螢光體粒子，在600 °C下加以熱處理，並測 定熱處理前後的各螢光體粒子在室溫下之亮度（以熱處理 前的未經表面處理的螢光體粒子的亮度作爲1 0 0時之相對 値）。將其結果表示於表1中。 -17- 201109422 〔表1〕 磷酸鑭附著量 處理溫度 亮度 實施例1 0.2質量％ 熱處理前 102.6 600°C 101.1 實施例2 0.5質量％ 熱處理前 102.0 600°C 101.4 實施例3 1.0質量％ 熱處理前 102.0 600。。 101.7 比較例 (未經表面處理） 0% 熱處理前 100.0 600°C 96.0 (以未經表面處理且熱處理前者作爲100.0) 如表1所示，經表面處理螢光體粒子，係與熱處理前 且未經表面處理之螢光體粒子相比較之下，顯然顯現有高 的亮度，且在經過600 °C之熱處理後，其亮度的低落情況 爲非常少。由此可確認，如採用經表面處理之螢光體粒子 ，則能充分抑制在製造使用螢光體粒子之各種裝置之階段 所遭受之因熱歷程所引起之亮度的低落之事實。另一方面 ，於未經表面處理之螢光體粒子的情形，在熱處理後，其 亮度有比較大的低落。 (亮度的溫度依賴性評價（temperature dependency evaluation )) 將在實施例1至3所得經表面處理之螢光體粒子、及未 經表面處理之螢光體粒子，從室溫（25 °C )加熱至100 °C ，並測定當時的各螢光體粒體的亮度的變化。將其結果表 示於表2中。第1圖，係表示實施例2及比較例（未經表面 -18- 201109422 處理）的各螢光體粒子的亮度與溫度之間的關係之曲線圖 〔表2〕 表面附著量 處理溫度 亮度 實施例1 0.2質量％ 25〇C 100.0 100°C 96.7 實施例2 0.5質量％ 25〇C 100.0 10(TC 97.1 實施例3 1.0質量％ 25〇C 100.0 100°C 96.1 比較例 (未經表面處理） 0% 25〇C 100.0 100°C 94.4 (以分別在2 5 °c下的亮度作爲1 00·0 ) 如表2及第1圖中所示，經表面處理螢光體粒子，係與 未經表面處理的螢光體粒子相比較之下，溫度當從室溫上 升爲1 00°C時的亮度的情況顯然爲少。 第2圖，係在實施例2中所得經表面處理螢光體粒子（ 表面附著量爲0.5質量％ )的電子顯微鏡照片。從第2圖亦 可確認於螢光體粒子表面附著有磷酸鑭之情況。 〔產業上之利用可能性〕 如採用本發明之經表面處理之螢光體粒子的製造方法 ，則因共沈澱反應而生成磷酸鑭，並附著於螢光體粒子表 面之結果，在不實施燒成處理之下，即可製造經表面處理 之螢光體粒子。因此，可使螢光體粒子的初期亮度維持於 -19- 201109422 十分高的水準。再者，如採用本經表面處理之螢光體粒子 ，則亦能充分抑制在製造具備螢光體粒子之各種裝置之階 段所遭受之因熱歷程所引起之亮度的低落。 【圖式簡單說明】 第1圖：表示經表面處理之螢光體粒子及未經表面處 理之螢光體粒子的亮度與溫度之間的關係之曲線圖。 第2圖：係經表面處理之螢光體粒子之電子顯微鏡照 片。 -20-The surface treatment (coating) of each of the phosphor particles 萤 phosphor particles can be carried out by the same operation of BaMgAl1() 017 : Eu2+, and is carried out by a so-called coprecipitation method. For the surface of the phosphor particles, strontium phosphate is mainly attached, but other materials may be used if necessary. When an aqueous solution containing cerium is mixed with an aqueous solution containing phosphoric acid, cerium phosphate is formed by the coprecipitation reaction. When the coprecipitation reaction is carried out in the presence of phosphor particles, the generated strontium phosphate adheres to the surface of the phosphor particles to form surface-treated phosphor particles. In this case, it is not necessary for the surface of the phosphor particles to be completely covered with yttrium phosphate, or a part of the surface of the luminescence particle itself may be exposed. The aqueous solution containing phosphoric acid contains water and a pity acid -12-201109422 (H3P04) or a salt thereof dissolved in water. Further, the aqueous solution can be adjusted to pH 氨 by ammonia or the like. As the salt of phosphoric acid, for example, ammonium phosphate ((NH4) 2HP04) can be used. If such an aqueous solution containing phosphoric acid or phosphate is used, the incorporation of other metal ions can be suppressed. The phosphorus concentration of the aqueous solution containing phosphoric acid is preferably 0.001 mol/mol to 0.1 mol/liter, more preferably 0.005 mol/liter to 0.05 mol/liter, and particularly preferably o. oimol/liter. If the concentration is too high, there is a tendency that the phosphor is dissolved by the acid or the particles of the produced strontium phosphate are aggregated. If the concentration is too low, there is a tendency that the strontium phosphate is hard to adhere to the surface of the phosphor particles. For example, in this aqueous solution containing cesium phosphoric acid, the phosphor particles are dispersed to prepare a dispersion, and an aqueous solution containing ruthenium is added thereto. The amount of the phosphor particles in the dispersion is not particularly limited, but 1 liter of the aqueous solution containing phosphoric acid is preferably 10 g to 10 Å, 〇〇〇 g, more preferably 1 〇〇 g to 1 〇〇. 〇g degree. The amount is adjusted to the optimum amount according to the specific gravity and particle diameter of the phosphor particles. It is preferable that the phosphor particles are substantially not deposited in the dispersion liquid insofar as the bismuth phosphite can be attached to the surface of the phosphor particles. For this reason, in the coprecipitation reaction, it is preferred to continue stirring the dispersion using a stirring bar, a magnetic stirrer or the like. An aqueous solution containing ruthenium, for example, can be obtained by dissolving a ruthenium compound such as lanthanum nitrate (La(N03)3) or lanthanum acetate (La(CH3COO)3) in water. The cerium concentration of the aqueous solution containing cerium is preferably 〇.〇〇lm〇l/liter to 0.1 mol/liter, more preferably 〇.0〇5 m〇i/liter to 0.05 m〇丨/liter, particularly preferably O.Olmol / liter degree" The rate at which the aqueous solution containing cerium is added to the dispersion containing phosphoric acid -13,094,044, the optimum conditions of the solution may vary depending on the concentration or temperature of the solution, and is not particularly limited. In the range of O.O00lmol/min to O.Omolol/min. The ratio of bismuth to phosphoric acid can be stoichiometric ratio of La: P = l: 1, but it can also prevent unreacted strontium ions from leaking out or recovering the original strontium salt, or can be made as La: P = 1 : The mode of 3 is implemented under excess phosphorus conditions. Since unreacted phosphorus is easily removed by washing, it is easy to remove. The method of mixing an aqueous solution containing cerium and an aqueous solution containing phosphoric acid in the presence of phosphor particles to obtain a dispersion is not particularly limited to dispersing the phosphor particles in an aqueous solution containing phosphoric acid as described above. Thereafter, a method of adding an aqueous solution containing hydrazine is added. Alternatively, the phosphor particles may be dispersed in an aqueous solution containing cerium, and then an aqueous solution containing phosphoric acid may be added thereto. Since the formation of cesium phosphate caused by the mixing is completed in a momentary manner even at room temperature, no special heating operation is required. However, in order to completely complete the reaction, or to control the particle size or crystallinity of the produced strontium phosphate, the solution may be heated at any time before (mixing, mixing or after mixing) before and after mixing. In this case, the temperature is below the boiling point of the liquid, and in the case of the aqueous solution, it is about 100 ° C or lower, preferably 70 to 90 ° C. The surface-treated phosphor particles generated in the dispersion are taken out by filtration or the like, and the surface-treated phosphor particles are removed by washing with pure water to remove excess portions. Then, the washed phosphor particles are dried by heating at 200 ° C or lower, preferably 60 to 120 ° C. According to this method, the surface-treated phosphor particles can be recovered from the dispersion without heating at -14 to 201109422 of 200 ° C or higher. When the surface-treated phosphor particles are aggregated by drying, shredding may be performed. The amount of the barium phosphate deposited on the surface of the phosphor particles is not particularly limited as long as it is obtained. It can be within the minimum required limit of the purpose of improving the characteristics. Since barium phosphate does not substantially absorb ultraviolet rays, it has little effect on the brightness caused by the adhesion of the surface of the phosphor particles. However, when the amount of yttrium phosphate which is itself a non-luminescent material is increased, the volume fraction of the phosphor particles is lowered, so that the relative brightness tends to decrease. From the viewpoint of the above, the amount of the yttrium phosphate is preferably from 0.01 to 5% by mass, more preferably from 0.1 to 1% by mass, based on the mass of the phosphor particles. [Embodiment] Hereinafter, the present invention will be described in more detail by way of examples. However, the invention is not limited by the following examples. In the present embodiment, in order to measure the brightness of the phosphor particles, a spectrophotometer FP-6500 (product name, manufactured by JASCO Corporation) was used. For the production of blue phosphor BaMgAl1() 017: Eu2 + , BaC03 , 3MgC03 · Mg ( OH ) 2, A1203 and Eu203 are used as raw materials, and these can be used as Ba in terms of molar ratio. : Mg : A1 : Eu=l to 0·1 : 1 : 1〇: Weigh the weight by 0.1. Here, 0.1 represents a ratio in which a part of Ba is substituted with Ell. After the weighed raw materials were mixed and fired at a hydrogen-containing reducing atmosphere of about 1,400 °C, -15-201109422 was used as the target phosphor particles. (Example 1) As an aqueous solution containing phosphorus, an aqueous solution of phosphoric acid (Η 3 P 0 4 ) was used, and as an aqueous solution containing cerium, an aqueous solution of lanthanum nitrate (La ( Ν03 ) 3 ) was used. To a solution of 0.01 Torr (mole) of phosphoric acid in 37.5 ml, BaMgAl1C) 〇17: Eu2 + 5.0 g, which is itself a blue phosphor particle, was added under stirring to prepare a slurry-like dispersion. To the dispersion, a 0.01 Torr La ( Ν Ο 3 ) 3 aqueous solution of 1 2 · 5 m 1 ' was dropped and the liquid temperature was raised to 7 5 to complete the coprecipitation reaction. Then, the slurry (dispersion) was filtered, and the taken solid component was washed with water (50 ml x 3 times). The solid component after washing was heated at 120 ° C for 1 hour to be dried, and was shredded with agate mortar to obtain 0.2% by mass of the surface of the phosphor particles. Surface treated phosphor particles of barium phosphate (LaP04). (Example 2) Into 37.5 ml of a 0.01 M aqueous phosphoric acid solution, 12.5 g of blue phosphor particles BaMgAl1Q〇17: Eu2+ was added under stirring to prepare a slurry-like dispersion. To the dispersion, 12.5 ml of a water solution of 0 · 0 1 Torr of L a ( Ν Ο 3 ) 3 was added dropwise, and the temperature of the liquid was raised to 75 t, and then the coprecipitation reaction was completed. Then, the slurry (dispersion) was filtered, and the taken solid component was washed with water (50 ml X 3 times). The solid component after washing was heated at 120 ° C for 1 hour to dry it, and the agate was shredded with agate -16-16-201109422, and the surface of the phosphor particles was attached. 5 mass% Surface treated phosphor particles of barium phosphate (LaP04). (Example 3) BaMgAl1() 017: Eu2+ 4.0 g, which is a blue phosphor particle itself, was added to 60. Oml of a 0.01 M aqueous phosphoric acid solution under stirring to prepare a slurry-like dispersion. To the dispersion, 0.01 M of a La(N03) 3 aqueous solution of 20. 0 ml was dropped, and the temperature of the liquid was raised to 75 ° C to complete the coprecipitation reaction. Then, the slurry (dispersion) was filtered, and the taken solid component was washed with water (50 ml X 3 times). The solid component after washing with water was heated at 1 to 20 ° C for 1 hour to be dried, and was shredded with agate crucible to obtain a cerium phosphate adhered to the surface of the phosphor particles. LaP04) surface treated phosphor particles. (Evaluation of Change in Luminance by Heat Treatment) The surface-treated phosphor particles obtained in Examples 1 to 3 and the non-surface-treated phosphor particles were heat-treated at 600 ° C, and were measured before and after heat treatment. The brightness of each of the phosphor particles at room temperature (the relative luminance of the untreated surface-treated phosphor particles before the heat treatment is taken as 100 Å). The results are shown in Table 1. -17- 201109422 [Table 1] Barium Phosphate Adsorption Treatment Temperature Brightness Example 1 0.2% by mass 102.6 600 ° C before heat treatment 101.1 Example 2 0.5% by mass 102.0 600 ° C before heat treatment 101.4 Example 3 1.0% by mass 102.0 before heat treatment 600. . 101.7 Comparative Example (without surface treatment) 0% 100.0 600 °C before heat treatment 96.0 (without surface treatment and heat treatment before 100.0) As shown in Table 1, the surface treated phosphor particles are not treated before heat treatment. Compared with the surface-treated phosphor particles, it is apparent that the existing high brightness is obtained, and after the heat treatment at 600 ° C, the brightness is extremely low. From this, it was confirmed that the use of the surface-treated phosphor particles can sufficiently suppress the fact that the brightness caused by the heat history at the stage of manufacturing various devices using the phosphor particles is low. On the other hand, in the case of the phosphor particles which are not surface-treated, the brightness thereof is relatively large after the heat treatment. (temperature dependency evaluation) The surface-treated phosphor particles obtained in Examples 1 to 3 and the non-surface-treated phosphor particles were heated from room temperature (25 ° C). To 100 ° C, and measure the change in brightness of each phosphor granule at that time. The results are shown in Table 2. Fig. 1 is a graph showing the relationship between the luminance and temperature of each of the phosphor particles of Example 2 and Comparative Example (not treated by Surface-18-201109422) [Table 2] Surface adhesion amount processing Temperature brightness implementation Example 1 0.2% by mass 25〇C 100.0 100°C 96.7 Example 2 0.5% by mass 25〇C 100.0 10 (TC 97.1 Example 3 1.0% by mass 25〇C 100.0 100°C 96.1 Comparative example (without surface treatment) 0 % 25〇C 100.0 100°C 94.4 (with brightness at 2 5 °C as 1 00·0) As shown in Table 2 and Figure 1, the surface treated phosphor particles are unsurfaced. In comparison with the treated phosphor particles, the case where the temperature rises from room temperature to 100 ° C is apparently small. Fig. 2 shows the surface-treated phosphor particles obtained in Example 2 ( An electron micrograph of the surface adhesion amount of 0.5% by mass. It can also be confirmed from the second figure that yttrium phosphate adheres to the surface of the phosphor particles. [Industrial Applicability] If the surface treatment is used in the present invention A method for producing a phosphor particle, which generates phosphorus due to a coprecipitation reaction As a result of adhering to the surface of the phosphor particles, the surface-treated phosphor particles can be produced without performing the firing treatment. Therefore, the initial luminance of the phosphor particles can be maintained at -19- 201109422 Very high level. In addition, if the surface-treated phosphor particles are used, the brightness caused by the heat history at the stage of manufacturing various devices with phosphor particles can be sufficiently suppressed. [Simple description of the diagram] Fig. 1 is a graph showing the relationship between the brightness of the surface-treated phosphor particles and the non-surface-treated phosphor particles and the temperature. Fig. 2: Surface treatment Electron micrograph of the phosphor particles. -20-