201243028 六、發明說明： 【發明所屬之技術領域】 *月係關於隹茧T1Q遐祖于的表面且有 本鞅鉍4SL 叫八’钣覆層之螢 光體材科之製造方法、及藉此 用其之發光裝置 【先前技術 « # ^ ^ 蛩光體材料、及使 用其之發光裝置。 目前以液晶電視的背光或次世代照明而言，led燈 備^矚目。為了使LED燈發光成白色，必須將led元件 本^發光通過塗布或混揉有紅/藍/綠等螢光體的透鏡 措將來自螢光體的發光相疊合來獲得白色。但是， 蝥光體若曝露在水分 '熱、或紫外線時，會有發：特性 降低的弱點。因此，藉由以陶瓷被覆螢光體粒子，來進 灯防止特性劣4匕’且達成長壽命化（參照例如專利文獻1) 。以被覆方法而言雖有各種方法，但是若將陶曼微粒子 使用在原料來進行被覆，可得較高的特性，故較為理想 具體而§，例如將螢光體粒子與陶瓷微粒子與液體混 合而形成為由噴霧乾燥、溫風乾燥、或自然乾 燥來使其乾燥的方法已為人所知（參照例如專利文獻2) 〇 [先前技術文獻] [專利文獻] [專利文獻1]曰本特開2010-280877號公報 [專利文獻2]日本特開2008-29125 1號公報 【發明内容】 • 4- 201243028 (發明所欲解決之課題） 但是，噴霧乾燥或溫風乾燥係必須藉由使大量的氣 體與叙末在空氣中混合或流動而使液體乾燥，因此會有 螢光體粒子及陶瓷微粒子亦從用以逸逃所送入的氣體的 路徑逸逃的問題。為了防止該問題，例如設法藉由透過 袋濾器來捕集粉末來減少損《’但是即使如此亦不易提 冋產率。此外，即使產率的問題獲得改善，亦由於以袋 濾器未完全捕集到的小粒徑側的粒子會通過過濾器而逸 逃，因此作為母材的螢光體粒子的粒度分布會改變，亦 會有在實用上發生故障的情形的問題。此外，螢光體粒 子大多數非常昂貴，即使少量亦發生損失時損害會變 得極大。此外，亦會有發生陶瓷微粒子不會附著在螢光 體粒子而發生乾燥的情形的問題。 ' 方面，右為自然乾燥的情形，與喷霧乾燥或溫 風乾燥相比’接觸到乾燥氣體的比表面積明顯變小，因 此會有在乾燥時需要長時間，而且在乾燥中環境中的 水分會吸附而使螢光體粒子劣化的問題。例士口，以控制 環境而在脫水環境中使其乾燥的方法而言，係有利用手 套，（81〇〜1>〇幻等，但是必須一面常時排氣，一面導入脫 水環境氣體’在成本、時間上均大量耗費，並不具現實 性。 、 本發明係根據如上所示之問題所研創者，目的在提 ^效率佳地在螢Μ粒子的表面形成被覆層，而且可 得高特性及高產率之螢光體材料之製造方法、及藉此 得之螢光體材料 '以及使用其之發光裝置。 201243028 (解決課題之手名 本發明之螢 子的表面具有被 減壓蒸發乾燥法 體的漿體乾燥， 形成被覆層。 本發明之螢 製造方法所製造 造的螢光體材料 (發明之效果） 依據本發明 發乾燥法，使包 漿體乾燥，因此 螢光體粒子及陶 因此，可提高螢 子的粒度分布的 外’可減少陶瓷 燥的量，而可提 效率地製造，並 此外，在使 例如在包含氮及 中的至少1種的 止螢光體粒子的 此外，若在 燥時間。 光體材料之劁γ 製k方法係製造在螢光體粒 復層之螢光體材料之方法，其中，藉由 使包含螢光體粒子、陶瓷微粒子、及液 藉由將液體去除，纟螢光體粒子的表面 光體材料係藉由本發明之螢光體材料之 者，本發明之發光裝置係包含藉此所製 含螢光體粒子、陶瓷微粒子、及液體的 進行排氣的氣體的量極少，T極為減少 竞微粒子被排出至處理裝置之外的量。 光體粒子的產車，* 早並且可防止螢光體粒 匕，而可維持螢光體材料的品質。此 :粒子不會附著在螢光體粒子而單獨乾 冋成膜效率。Λ外’乾燥時間短，可有 且水分的影響小，可防止特性劣化。 漿體乾燥之後，若在惰性氣體環境中， 由長週期表第18族元素所組成之群組之 惰性氣體環境中進行熱處理，可_面防 特性劣化，-面提高被覆層的密接性。 使漿體乾燥時賴I挫將g · f撹拌漿體，可更加縮短乾 201243028 此外，若將陶究微粒子的平均粒徑設為4〇nm以下 ’或陶瓷微粒子包含由稀土類氧化物、氧化锆、氧化鈦 、氡化鋅、氧化铭、釔與紹的複合氧化物、氧化鎮及紹 與鎂的複合氧化物所組成之群組之中的至少】種金屬氧 化物，則可使财水性或耐紫外光等特性更加提升。 【實施方式】 以下參照圖不’詳加說明本發明之實施形態。 ，第1圖係表示本發明之—實施形態之螢光體材料之 製造方法之製程者，第2圖係以模式表示藉此所製作之 螢光體材# 10者。本實施形態之螢光體材料ι〇之製造 方法係製造在螢光體粒+ u的表面具有被覆層Η的螢 光體材料10纟’本實施形態之螢光體材料1〇係藉由該 螢光體材料10之製造方法所得者。 在該螢光體材料10之製造方法中，首先調製例如包 含勞光體粒子U、陶瓷微粒子12A、及液體的漿體(步驟 si〇i)。以螢光體粒子u而言，可使用任意者列舉如 • BaMgAl10〇17 : Eu . ZnS ： Ag ^ Cl > BaAl2S4 : Eu caMgsi2〇6 : Eu 等藍色系螢光體、（Ba，Ca，201243028 VI. Description of the Invention: [Technical Fields of the Invention] * A method for manufacturing a fluorescent body material having a surface of the 隹茧T1Q 遐 且 and having a SL4SL 八八钣 coating, and A illuminating device using the same [previous technique « # ^ ^ 蛩 light material, and a illuminating device using the same. At present, in terms of backlighting of LCD TVs or next-generation lighting, LED lights are available. In order to cause the LED lamp to emit white light, it is necessary to superimpose the light emitted from the phosphor by a lens coated or mixed with a phosphor such as red/blue/green to obtain white color. However, if the phosphor is exposed to moisture 'heat or ultraviolet rays, there will be a weak point in which the characteristics are lowered. Therefore, by coating the phosphor particles with ceramics, the lamp prevention characteristics are inferior and the life is shortened (see, for example, Patent Document 1). Although there are various methods for the coating method, if the ceramic particles are used for coating with a ceramic material, high characteristics can be obtained. Therefore, it is preferable to mix the phosphor particles and the ceramic fine particles with the liquid. A method of drying by spray drying, warm air drying, or natural drying is known (refer to, for example, Patent Document 2) 〇 [Prior Art Document] [Patent Document] [Patent Document 1] 曰本特[Patent Document 2] Japanese Laid-Open Patent Publication No. 2008-29125 No. 1 (Invention): 4-201243028 (Problems to be Solved by the Invention) However, spray drying or warm air drying must be performed by making a large amount of The gas is mixed with or flows in the air to dry the liquid, so that the phosphor particles and the ceramic particles are also escaped from the path for escaping the gas to be fed. In order to prevent this problem, for example, it is tried to reduce the damage by collecting the powder through the bag filter, but even this is not easy to improve the yield. Further, even if the problem of the yield is improved, since the particles on the small particle diameter side which are not completely trapped by the bag filter escape through the filter, the particle size distribution of the phosphor particles as the base material changes. There will also be problems in the case of a practical failure. In addition, most of the phosphor particles are very expensive, and the damage becomes extremely large even if a small amount is lost. Further, there is a problem in that the ceramic fine particles do not adhere to the phosphor particles and are dried. On the right side, the right is naturally dry. Compared with spray drying or warm air drying, the specific surface area of the exposed dry gas is significantly smaller, so there is a need for a long time during drying and moisture in a dry environment. There is a problem that the phosphor particles are adsorbed and deteriorated. In the method of controlling the environment and drying it in a dehydrated environment, it is possible to use gloves, (81〇~1> illusion, etc., but it is necessary to vent one side at a time, and introduce dehydrated ambient gas at the cost) In terms of time and cost, it is not realistic. The present invention is based on the problems described above, and aims to form a coating layer on the surface of the cerium particles with high efficiency and high yield and high yield. A method for producing a phosphor material, a phosphor material obtained therefrom, and a light-emitting device using the same. 201243028 (Hands to solve the problem) The surface of the firefly of the present invention has a method of evaporating and drying the body under reduced pressure. The slurry is dried to form a coating layer. The phosphor material produced by the method for producing a firefly of the present invention (effect of the invention) According to the drying method of the present invention, the slurry is dried, so that the phosphor particles and the ceramics can be Increasing the particle size distribution of the fluorescers can reduce the amount of ceramic drying, and can be efficiently produced, and further, at least one kind of phosphorescent granules containing, for example, nitrogen and In addition, in the drying time, the 劁γ method of the light material is a method of manufacturing a phosphor material in a phosphor particle layer, wherein the phosphor particles, the ceramic particles, and the liquid are contained. By removing the liquid, the surface light material of the bismuth phosphor particles is the phosphor material of the present invention, and the light-emitting device of the present invention comprises the phosphor-containing particles, the ceramic fine particles, and the liquid. The amount of gas to be vented is extremely small, and T is extremely small in reducing the amount of particles that are excreted to the processing device. The production of the light particles, * prevents the phosphor particles from colliding, and maintains the phosphor material. Quality: This is because the particles do not adhere to the phosphor particles and dry up separately. The drying time is short, and the influence of moisture is small, which prevents deterioration of properties. After the slurry is dried, if it is in an inert gas In the environment, heat treatment is performed in an inert gas atmosphere of a group consisting of elements of Group 18 of the long-period table, and the surface resistance property is deteriorated, and the surface is improved in adhesion of the coating layer. · f Mixing the slurry, the drying can be further shortened 201243028. In addition, if the average particle size of the ceramic particles is set below 4 〇 nm or the ceramic microparticles contain rare earth oxides, zirconia, titanium oxide, zinc hydride, oxidized, At least one of the metal oxides of the composite oxide of lanthanum and sulphur, the oxidized town and the composite oxide of sulphate and magnesium, can further improve the properties such as water solubility or ultraviolet light resistance. The embodiment of the present invention will be described in detail below with reference to the drawings. Fig. 1 is a diagram showing a process for producing a phosphor material according to an embodiment of the present invention, and Fig. 2 is a schematic representation of the process. The phosphor material #10. The method for producing the phosphor material ι of the present embodiment is to produce a phosphor material 10' having a coating layer on the surface of the phosphor particles + u. The light material 1 is obtained by the method for producing the phosphor material 10. In the method for producing the phosphor material 10, first, for example, a slurry containing the mortar particles U, the ceramic fine particles 12A, and the liquid is prepared (step si〇i). For the phosphor particles u, any of the blue phosphors such as BaMgAl10〇17: Eu. ZnS: Ag ^ Cl > BaAl2S4 : Eu caMgsi2〇6 : Eu, (Ba, Ca, etc.) may be used.
Eu ’ Zn2Si04 : Μη ’（Y，Gd)B〇3 : Tb，ZnS : Cu，：〆 (Ba’ Sr，Mg)0 . aAl2〇3: Mn 等綠色系螢光體、（¥，叫= :Eu’ Y2〇2S: Eu或γρν〇4: Eu等紅色系螢光體。3 體粒子1 1的粒子徑基本上不拘，但是較佳為平 為5μιη至20μηι左右，粒子徑係以儘可能一致為佳。 係基於可使特性安定之故。 〃 201243028 陶瓷微粒子12A係用以形成被覆 如包含由稀土類氧化物、氧化錯、氧 ’車父佳為例 化銘、紀·紹·石權石(garnet)等纪與麵的複物氧 氧化鎂、及MgAl2〇4等铭與鎮的 。氧化物、 組之中的至少！種金屬氧化物為主成=所組成之群 耐水性及耐紫外光等特性提升之故。’、係基於可使 ... ^亦以稀土類負 化物為佳，以包含由紀、亂、鈽及鑭所組成之二二 的至少1種元素的稀土類氧化物為較佳，尤其以γ〇 為宜。其係基於可得更高的效果，亦抑 太、23 瓷微粒子12Α係可單獨使用}種之故。陶 種以上。此外，亦可使用包含…—;氧=合使用2 拉子2Α’但是亦可使用包含2種以上的金 陶瓷微粒子1 2 Α。 “屬氧化物的 :究微粒子12A的平均粒子徑係以形成為利⑽以 下為佳，以3〇nm以下為較佳，以25nm以下 職:平均粒子徑較小者，使陶究微粒子i2A、較易於附 :於：：體粒子"，可在粒子間的間隙極小的狀態下堆 子12A的❹覆層12之故°此外’陶究微粒 、：均拉子徑係以lOnm以上為佳’以l5nm以上 ‘、' 。若陶瓷微粒子1 2 A的平均粒子徑太小，容县膝 生粗大的二次凝聚粒子，且不易均—被覆勞光體粒子^Eu ' Zn2Si04 : Μ η '(Y, Gd) B 〇 3 : Tb, ZnS : Cu, : 〆 (Ba' Sr, Mg) 0 . aAl 2 〇 3: green phosphor such as Mn, (¥, called = : Eu' Y2〇2S: Eu or γρν〇4: Eu-based red-based phosphor. The particle diameter of the 3-body particle 1 1 is substantially non-limiting, but it is preferably about 5 μm to 20 μm, and the particle diameter is as uniform as possible. It is based on the stability of the characteristics. 〃 201243028 Ceramic microparticles 12A is used to form coatings, including rare earth oxides, oxidized faults, and oxygen, as the example of the father, Ji Shao, Shi Quanshi (garnet) complex and surface complex magnesium oxyhydroxide, and MgAl2〇4, etc.. Oxide, at least one of the group of metal oxides as the main = group of water resistance and UV resistance The characteristics such as light are improved. ', based on rare earth oxides that can be used to make at least one element of rare earths, including at least one element consisting of quarantine, chaos, bismuth and bismuth. Preferably, γ 〇 is preferred. It is based on a higher effect, and it is also possible to use 23 porphyry micro-particles. In addition, it can also be used to contain...-;oxygen=combined with 2 puller 2Α' but it is also possible to use two or more kinds of gold ceramic fine particles 1 2 Α. "Oxide: The average of the fine particles 12A The particle diameter system is preferably formed to be (10) or less, preferably 3 Å or less, and 25 nm or less, and the average particle diameter is smaller, so that the granule i2A is more easily attached to:: body particles " In the state where the gap between the particles is extremely small, the ruthenium coating layer 12 of the stack 12A can be used. In addition, the ceramic particles are generally more than lOnm, and more preferably l5 nm or more ', '. The average particle diameter of 1 2 A is too small, and the secondary agglomerated particles of Rong County are coarse and uneven, and it is not easy to cover the coated light body particles ^
之故令是微粒子12A的平均粒子徑係以螢光體粒子U 的平均粒子㈣"100以下至1/5〇〇以下左右為佳。其 係基於可更加安定形成被覆層12之故。此外，平约 徑係指一次粒子的平均粒子徑。 十句杻子 201243028 此外’陶瓷微粒子12A的异+』 為5〇nm以下為# 以的最大粒子徑係例如以形成 露出營光體教子存在較大的粒子時1容易發生 徑係例如以形成為40二=微：子似的最大粒子 下為更佳。 乂下為較佳，以形成為30nm以 溶媒在= ; = =的液f較佳為使例如有機 ΙΡΑΓ s a ffi- λ 土 不拘，但是較佳為使用乙醇、 二：醉)來作為廉價且在常溫常 性較低的材料。1 Α 、，丄，· 刃…如兄毋 @ _ /、 ，1由對作為母材的螢光體粒子1 1 的影響的觀點來看，会k 此外，在常、3大！水的材質並不理想。 ! 申壓下不易蒸發的材質亦不理想。 接著’藉由減壓蒗發齡怿 卞法使漿體乾燥來去除液體 =微粒子12A附著在營光體粒子"的表面，而形 為減燃二二2(步驟S102)。減麗蒸發乾燥法係指藉由形成 :’衣兄而促進液體蒸發且使其乾燥的方法。此外， :、：二了促進乾燥而由容器外部加熱而使黎體溫度上升 乾烨84 P… 見件聚-為佳。其係基於可縮短 祀你吟間之故。此外，在使漿 社使水體作外部加熱時，藉由攪 择亦可得防止暴沸的效果。攪拌 ^ 將_ Μ〜 係例如可藉由使收納有 的一:谷器旋轉來進行，此外’亦可藉由設在收納聚體 的…的旋轉翼等授拌裝置來進行。具體而言，例如 以使用旋轉蒸發器或急速蒸發器為佳。 接著，較佳為在使衆體乾燥之後，將附著陶曼微粒 子12Α的螢光體粒子u在惰性氣體環境 步驟⑽3)。其係基於可-面防止營光體粒子“的特性 201243028 劣化，一面提高被覆層1 2的密接性 言，係列舉如包含氮及 接f之故。以惰性氣體而 群組之中的至少丨種+ # +表第8私兀素所組成之 以下甘〆 者。熱處理溫度係例如較佳Λ 45(ΤΓTherefore, the average particle diameter of the fine particles 12A is preferably equal to or less than the average particle size of the phosphor particles U (four) and less than or equal to 1/5 Å. This is based on the fact that the coating layer 12 can be formed more stably. Further, the flat diameter refers to the average particle diameter of the primary particles. Ten sentences 2012子 201243028 In addition, the 'different + of the ceramic fine particles 12A' is 5 〇 nm or less. The maximum particle diameter is, for example, when a large particle is formed to expose the camping body, and the diameter is likely to occur, for example, to form 40 two = micro: the sub-like maximum particle is better. It is preferred that the underlayer is formed so that the liquid f of the solvent at 30 nm is preferably made of, for example, organic ΙΡΑΓ sa ffi- λ, but preferably ethanol, two: drunk, as inexpensive and A material with a low temperature and normality. 1 Α 、 丄 · 刃 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如The material of the water is not ideal. The material that does not evaporate under pressure is not ideal. Then, the slurry is dried by decompression and aging, and the liquid is removed. The fine particles 12A adhere to the surface of the luminescence particle ", and the shape is reduced to 222 (step S102). The evaporative drying method refers to a method of promoting evaporation of a liquid and drying it by forming a fabric. In addition, :, : Two to promote drying and heating from the outside of the container to raise the temperature of the body. Dry 烨 84 P... See the pieces - preferably. It is based on the fact that it can shorten your life. Further, when the slurry is used to externally heat the water body, the effect of preventing the bumping can be obtained by stirring. The stirring can be carried out, for example, by rotating the stored one: the barn, or by adding the mixing device such as a rotating blade provided in the container. Specifically, for example, a rotary evaporator or a rapid evaporator is preferably used. Next, it is preferred that after drying the body, the phosphor particles u to which the Taman particles 12 are attached are placed in an inert gas atmosphere (step) (10) 3). It is based on the deterioration of the characteristics of the coating layer of the surface of the surface of the surface of the surface of the surface of the surface of the surface of the surface of the surface of the surface of the surface of the surface of the surface of the coating layer. Kind of + # + table 8th private sputum composed of the following glutinous rice. The heat treatment temperature is, for example, preferably Λ 45 (ΤΓ
以下。其係基於可防止特性劣化之故。佳為45〇C 此外，漿體的調製（步驟 熱處理(步驟_)的各(步驟S释 反覆複數次。例如，亦 /、卩久即可’但是亦可 ςιη„ 了進行漿體的調製（步驟sioi)、 紅各（步驟S102).、熱處理（步 層12的勞光體粒子u驟S1〇3)，關於形成有被覆 體一起再-人連同陶瓷微粒子12A及液 :=衆體(步驟S1〇1)，使其乾燥(步驟 進 ^ . n ^ ”係基於可更加確實被覆螢光體 ^子1之故。此外，在反覆複數次時 不同種類的陶竞微粒子12A # ^ ^ 此外，被覆層12較佳為將 陶邊子12A朝厚度方向層冑3粒子層以上，被覆層 12的厚度較佳為10nm以上1μιη以下。其係基於陶曼微 拉子12Α的層積數較少時’或者被㈣12的厚度較薄時 ’防止特性劣化的效果較小’若厚度較厚時，光透過性 會降低而使發光效率降低之故。藉此，可得以被覆層12 被覆螢光體粒子I 1的表面的螢光體材料丨〇。 第3圖係表示使用該螢光體材料1〇的發光裝置2〇 之一構成例。該發光裝置2〇係在基板2丨之上裝載有發 光兀件22,發光元件22係藉由形成在基板21之上的配 線23與線材24作電性連接。此外，在發光元件22的周 圍係形成有例如反射器框體2 5，在發光元件2 2之上係 以覆蓋發光元件2 2的方式形成有密封層2 6。密封層2 6 係例如藉由使螢光體材料10分散的樹脂所構成。 -10- 201243028 綠 如 \ 或 包 燥 子 此 子 質 子 時 特 例 之 面 的 燥 以 在發光元件22係使用例如發出紫外光、藍色光、或 色光來作為激發光者。以螢光體材料1 0而言，使用例 藉由由發光元件22所發出的激發光來發出紅色光者 發出藍色光者、發出綠色光者、發出黃色光者等丨種 視需要混合2種以上。 如上所示藉由本實施形態，藉由減壓蒸發乾燥法使 含螢光體粒子1 1、陶瓷微粒子12A、及液體的漿體乾 因此所排氣的氣體的量極少，可極其減少螢光體粒 11及陶瓷微粒子12A被排出至處理裝置之外的量。因 ，可提尚螢光體粒子u的產率，並且可防止螢光體粒 11的粒度分布的變化’而可維持螢光體材料10的品 。此外’ W陶兜微粒子12A不會附著在榮光體粒 1 1而單獨乾燥的量，而可提高成膜效率。此外，乾燥 間短，可有效率地製造，並且水分的影響 性劣化。 此外’在使漿體乾燥之後，若在惰性氣體環境中， 中：包含氮及由長週期表第18 _元素所組成之群組 中的至少1種的惰性氣體環境中進行熱處自，則可一 防止榮光體粒子U的特性劣]匕 、 密接性。 面^间被覆層12 此外’若在使漿體教操本 時間。 &乾知時攪拌漿體，可更加縮短乾 此外，若將陶瓷微粒 T . . ^ g 子12A的平均粒徑形成為40nm 下’或者陶瓷微粒子句人士链丄上 3由稀土類氧化物、氧化錯、 -11- 201243028 氧化鈦、氧化鋅、氧化鋁、釔與鋁的複合氧化物、氧化 鎂及鋁與鎂的複合氧化物所組成之群組之中的至少丨種 金屬氧化物，可使耐水性或耐紫外光等特性更加提升。 [實施例] (實施例1) 隹便由平均粒子徑20nm、最大粒子徑5〇nm的氧化 釔（丫2〇3)所構成的陶瓷微粒子12A分散在 混合平均粒子徑一左右的綠色系榮光體粒二 調製出毁體(步驟S101)。接著’使用旋轉蒸發器，藉由 減壓蒸發乾燥法使該製體乾燥’而將有機溶媒去除(步驟 S 102)。此時，藉由使收納有漿體的容器旋轉，一面攪拌 漿體-面使其乾燥。接著，將附著經乾燥的粉末，亦即 =竞微粒子12A的勞光體粒子u在氮環境中以彻。〔軌 广小時(步驟S1〇3)。之後’關於所得粉末，亦即形、 =層U的螢光體粒子U，同樣地再反覆i次聚體 ，、：^::…㈣燥❻㈣叫熱處理㈣·) 體材料1〇。關於所得的勞光體材料1〇,經調 :所：：的螢光體粒子"的產率，結果為_上 螢光胁# ; θ 灸〇 ~重量/(處理前的 蝥先胆拉子重罝+陶究微粒子的重量 (比較例1 -1 ) ® !由喷霧乾燥使1體乾燥以外，其他”施例 1冋樣地製作螢光體材料。 ^ π 1 查原料所使用的勞光體粒子材料’經調 ，、、σ果為約70%。 -12- 201243028 (比較例1-2) 除了错由自然乾燥而使漿體乾燥以外， 例1同樣地製作螢光體材料。在比較例丨^他”貝她 實施例1同量的漿體乾燥時，耗費 在使與 的時間。 f ““列^的10倍以上 •2的結果。 體乾燥，可 時間，故較 在表1中顯示實施例1及比較例丨_丨、i 如上所示，可知若藉由減壓蒸發乾燥法使渡 提高螢光體粒子11的產率，而且可縮短乾燥 為理想。 卜表1] 乾燥方法 裝料量 (g) 回收量 (g) 產率 (%) 乾燥時間(分鐘） 評估 評估要因 貫施例1 減壓4發乾燥 100 97 97 30 一 — 〇 比較例1-1 ---- 喷霧乾癌~~ ~Ϊ00~ Hr- 20 •牧例1-2 自然乾燥 100 94 94 500 X 乾燥所需時間 (實施例2-1) 使用藉由實施例1所製作的螢光體材料1 〇，製作出 如第3圖所示的發光裝置2〇。在發光元件22係使用發 出紫外光者。 (實施例2-2) 除了在氧化環境中（大氣環境中）進行熱處理以外， 其他與實施例1同樣地製作螢光體材料1 〇 ’與實施例2 _ i 同樣地製作發光裝置20。 (比較例2) 在螢光體粒子未形成被覆層，直接使用作為螢光體 材料，與實施例2-1同樣地製作發光裝置。 -13- 201243028 (劣化試驗） 關於貫施例2-1、2-2及比較例2的各發光裝置2〇 ，進行發光s式驗，以調查亮度的經時變化。將所得結果 顯不於表2。在表2中，相對亮度係指將未形成有被覆 層的比較例2的初期亮度設為1 〇〇%時的相對値。 [表2]the following. It is based on the prevention of deterioration of characteristics. Preferably, 45 〇C In addition, the preparation of the slurry (step heat treatment (step _) each (step S is repeated several times. For example, also /, long time can be 'but can also be η „ 了 进行 进行 浆 浆 浆 浆 浆 ( Steps sioi), red (step S102), heat treatment (slaughter particles of step 12, step S1〇3), regarding the formation of the coated body together with the person together with the ceramic fine particles 12A and the liquid: = body (step S1〇1), let it dry (step into ^. n ^ ” based on the fact that the phosphor can be more reliably covered. In addition, different kinds of Tao Jing particles 12A # ^ ^ in the repeated multiple times The coating layer 12 preferably has a layer of the ceramic layer 12A in the thickness direction of the layer 3 or more, and the thickness of the coating layer 12 is preferably 10 nm or more and 1 μm or less. The number of layers of the coating layer 12 is less than that of the Tauman micro-pillar 12 较少. 'When the thickness of (4) 12 is thin, the effect of preventing deterioration of characteristics is small. When the thickness is thick, the light transmittance is lowered to lower the luminous efficiency. Thereby, the coating layer 12 can be coated with the phosphor particles. Phosphor material 丨〇 on the surface of I 1. Fig. 3 shows the use of the phosphor A configuration example of one of the light-emitting devices 2 is mounted on the substrate 2A with the light-emitting element 22 mounted thereon, and the light-emitting element 22 is formed by the wiring 23 and the wire 24 formed on the substrate 21. Further, for example, a reflector housing 25 is formed around the light-emitting element 22, and a sealing layer 26 is formed on the light-emitting element 22 so as to cover the light-emitting element 22. The sealing layer 2 is formed. 6 is formed, for example, by a resin in which the phosphor material 10 is dispersed. -10- 201243028 Green such as \ or the dried proton of the proton is dried on the surface of the special element to emit ultraviolet light, blue, for example. The color light or the color light is used as the excitation light. In the case of the phosphor material 10, the use case emits red light by the excitation light emitted from the light-emitting element 22, and emits blue light, emits green light, and emits yellow. As described above, in the present embodiment, the phosphor-containing particles 1 1 , the ceramic fine particles 12A, and the slurry of the liquid are dried by the vacuum evaporation drying method. The amount of gas is very small, The amount by which the phosphor particles 11 and the ceramic fine particles 12A are discharged to the processing apparatus is extremely reduced. Therefore, the yield of the phosphor particles u can be raised, and the change in the particle size distribution of the phosphor particles 11 can be prevented. The product of the phosphor material 10 can be maintained. In addition, the 'W ceramic pockets 12A do not adhere to the glory body particles 1 and are dried separately, and the film forming efficiency can be improved. Moreover, the drying chamber is short and can be efficiently manufactured. And the influence of moisture is deteriorated. Further, 'after drying the slurry, if in an inert gas atmosphere, at least one inert gas containing nitrogen and a group consisting of the 18th element of the long-period table The heat in the environment can prevent the characteristics of the glory particles U from being inferior. The surface of the coating layer 12 is in addition to the teaching of the slurry. & knowing to stir the slurry, the drying can be further shortened. If the average particle diameter of the ceramic particles T. . g g 12A is formed to be 40 nm or the ceramic particles are on the chain, 3 are made of rare earth oxides. Oxidation error, -11- 201243028 at least a metal oxide among titanium oxide, zinc oxide, aluminum oxide, a composite oxide of cerium and aluminum, magnesium oxide, and a composite oxide of aluminum and magnesium. Improves water resistance or UV resistance. [Examples] (Example 1) The ceramic fine particles 12A composed of cerium oxide (丫2〇3) having an average particle diameter of 20 nm and a maximum particle diameter of 5 〇 nm were dispersed in a green glory of a mixed average particle diameter of about one. The body particle 2 modulates the deficiencies (step S101). Then, the organic solvent is removed by using a rotary evaporator to dry the body by a vacuum evaporation drying method (step S102). At this time, the slurry-surface is stirred and dried by rotating the container in which the slurry is accommodated. Next, the dried powder, i.e., the colloidal particles u of the microparticles 12A, is adhered to in a nitrogen atmosphere. [Average hours (step S1〇3). Then, regarding the obtained powder, that is, the phosphor particles U of the shape and the layer U, the i-times are again repeated, and: ^:: (4) dry (four) is called heat treatment (four) ·) body material 1 〇. Regarding the obtained labor light material 1〇, the yield of the phosphor particles::: 上上萤光#; θ Moxibustion ~ weight / (pre-treatment 胆 胆 拉The weight of the sub-heavy enamel + ceramic granules (Comparative Example 1-1) ® ! The other materials were dried by spray drying, and the other examples were used to prepare a phosphor material. ^ π 1 The light-emitting particle material was adjusted, and the σ fruit was about 70%. -12- 201243028 (Comparative Example 1-2) The phosphor material was produced in the same manner as in Example 1 except that the slurry was dried by natural drying. In the comparative example, the same amount of slurry is dried in the same amount of the slurry. The time is the time of the application. f "The result of the column ^ 10 times or more • 2. The body is dry, the time is available, so In Table 1, it is shown that the first embodiment and the comparative examples 丨_丨 and i are as shown above, and it is understood that the yield of the phosphor particles 11 is improved by the evaporation under reduced pressure, and drying is preferably shortened. 1] Drying method Charge amount (g) Recovery amount (g) Yield (%) Drying time (minutes) Evaluation evaluation should be applied to Example 1 Decompression 4 drying 100 97 97 30 I—〇Comparative Example 1-1 ---- Spray dry cancer~~~Ϊ00~ Hr- 20 • Pasture 1-2 Natural drying 100 94 94 500 X Time required for drying (Example 2-1 The light-emitting device 2A shown in Fig. 3 was produced by using the phosphor material 1 〇 produced in Example 1. The light-emitting element 22 was used to emit ultraviolet light. (Example 2-2) A light-emitting device 20 was produced in the same manner as in Example 1 except that the heat treatment was performed in an oxidizing atmosphere (in the atmosphere). (Comparative Example 2) In the phosphor A light-emitting device was produced in the same manner as in Example 2-1, except that the particles were not formed as a coating material. -13-201243028 (Deterioration test) About the examples 2-1, 2-2 and Comparative Example 2 Each of the light-emitting devices 2 was subjected to a luminescence s test to investigate the temporal change in luminance. The results obtained are shown in Table 2. In Table 2, the relative luminance refers to the initial stage of Comparative Example 2 in which the coating layer was not formed. Relative 値 when the brightness is set to 1 〇〇% [Table 2]
熱處理環境 相 初期亮膚 亮度(％) 2000小時後 評估 實施例2-1 實施例2-2 1" - — 氮 ----- ---- 99 82 〇 大氣 94 74 △ 比較例2 - 100 30 X 〇·（亮度維持率)80%以上，△ : 5〇〜79%，X :未達49〇/〇 如上所不，可知在使漿體乾燥之後，若在惰性氣體 環境中進行熱處理，可大幅改善初期亮度的降低及亮度 維持率。此外，可知若在大氣環境中進行熱處理，雖然 初期亮度會降低，但是與未處理的比較例2相比，可改 善亮度維持率。 (實施例3 -1〜3 - 5) 除了使陶竟微粒子12A的平均粒子徑及最大粒子經 改變以外’其他與實施例i同樣地製作螢光體材料ι〇， 與實施例W同樣地製作發光裝置2〇。在實施例31十 係使用平均粒子徑為4〇nm、最大粒子徑為遍爪的陶瓷 微粒子12A，在實施例U中係使用平均粒子徑為30nm 、最大粒子徑& 5〇nm的陶瓷微粒子12A，在實施例3·3 中係使用平均粒子和太 二為25nm、最大粒子徑為5〇nm的陶 竟微粒子12八，尤银h 汽施例3_4中係使用平均粒子徑為 20nm、最大粒子栌Α ι 十仫為4〇nm的陶：文微粒子12A，在實 -14- 201243028 例3-5中係使用平均粒子徑為15nm、最大粒子徑為 的陶瓷微粒子12A。關於所得的發光裝置2〇，與實施例 hi同樣地進行發光試驗，以調查亮度的經時變化;將所 得結果連同實施例2·〗及比較例2的結果一起顯示於表3 。在表3巾’ 2GGG小時後的亮度維持率係指#將未形成 有被覆層的比較例2的初期亮度設為⑽％時的相對値。 [表 3]Heat treatment environment phase initial brightness brightness (%) Evaluation after 2000 hours Example 2-1 Example 2-2 1" - - Nitrogen----- ---- 99 82 〇 atmosphere 94 74 △ Comparative Example 2 - 100 30 X 〇 · (brightness maintenance ratio) 80% or more, △ : 5 〇 to 79%, X: less than 49 〇 / 〇 as above, it is understood that after drying the slurry, if heat treatment is performed in an inert gas atmosphere, The initial brightness reduction and the brightness maintenance rate can be greatly improved. Further, it is understood that when the heat treatment is performed in the air atmosphere, the initial luminance is lowered, but the luminance maintenance ratio can be improved as compared with the untreated Comparative Example 2. (Examples 3 -1 to 3 - 5) A phosphor material ι was produced in the same manner as in Example i except that the average particle diameter and the maximum particle size of the ceramic fine particles 12A were changed, and the same procedure as in Example W was carried out. Light-emitting device 2〇. In Example 31, ceramic fine particles 12A having an average particle diameter of 4 〇 nm and a maximum particle diameter of ubiquitous claws were used, and in Example U, ceramic fine particles having an average particle diameter of 30 nm and a maximum particle diameter & 5 〇 nm were used. 12A, in the embodiment 3·3, the average particle diameter is 20 nm, the maximum particle diameter is 5 〇nm, and the average particle diameter is 20 nm, and the maximum particle diameter is 20 nm. The particle 栌Α ι 十仫 is a 4 〇 nm pottery: the granule 12A, and in the real-14-201243028 3-5, the ceramic fine particle 12A having an average particle diameter of 15 nm and a maximum particle diameter is used. With respect to the obtained light-emitting device 2, a luminescence test was carried out in the same manner as in Example hi to investigate the temporal change in luminance; and the results obtained are shown in Table 3 together with the results of Example 2 and Comparative Example 2. In the table 3, the brightness retention rate after 2 GGG hours is the relative enthalpy when the initial luminance of Comparative Example 2 in which the coating layer is not formed is (10)%. [table 3]
平均粒子徑 (mm) 最大粒子徑 fmm) 2000小時後的亮度維持率 (%) 評估 __實施例3-1 -i-V 40 ___寬施例3·2 30 50 一 50 80 〇 80 〇 例 3-3 25 50 -----麵 81 〇 __實施例3~4 20 20 -_ 40 82 — 〇 85 r\ 例 3-5 15 40 82 「〇 較例2 - ' —-— 30 X 一 '-----—…〜/y%，X :禾達49% 如上所示，可知若將陶瓷微粒子12A的平均粒子徑 形成為40nm以τ、1 η ， m以下1〇nm以上，可得較高的特性。此外 :可：若將微粒子12A的最大粒子徑形成為5〇請以下 ’可得較高的特性。 以上列舉實施形態來說明本發明’惟本發明可為各 形、2而非限疋於上述實施形態。例如，在上述實施 二——係關於發光體材料1〇的各製造製程加以說明， 產疋亦可未包括所有製程，而且亦可包括其他製程。 L座業上可利用性] 可使用在LED等發光裝置。 -15- 201243028 【圖式簡單說明】 第1 圖係表示發明之一 造方法之製程的流程圖。 第2 圖係表示藉由本發 料之製造 方法所製作的螢光 第3 圖係表示使用藉由 體材料之製造方法所製作的 成圖。 【主要元件符號說明】 10 螢光體材料 11 螢光體粒子 12 被覆層 12A 陶瓷微粒子 20 發光裝置 21 基板 22 發光元件 23 配線 24 線材 25 反射器框體 26 密封層 貫施形嘘之螢光體材料之製 明之一實施形態之螢光體材 體材料的構成的模式圖。 本發明之一實施形態之螢光 螢光體材料的發光裝置的構 16 -Average particle diameter (mm) Maximum particle diameter fmm) Brightness maintenance rate after 2000 hours (%) Evaluation __Example 3-1 - iV 40 ___ Width Example 3·2 30 50 A 50 80 〇 80 Example 3 -3 25 50 -----面81 〇__Example 3~4 20 20 -_ 40 82 — 〇85 r\ Example 3-5 15 40 82 〇 〇 Example 2 - ' —- — 30 X '------...~/y%, X:: 49% As shown above, it is understood that the average particle diameter of the ceramic fine particles 12A is 40 nm to τ, 1 η, m or less and 1 〇 nm or more. Further, it is possible to: when the maximum particle diameter of the fine particles 12A is 5 Å, the following characteristics can be obtained. The present invention will be described by way of embodiments. However, the present invention can be various shapes, 2 Rather than being limited to the above embodiments, for example, in the above-mentioned second embodiment, the manufacturing process for the illuminant material 1 加以 is described, and the pudding may not include all the processes, and may also include other processes. Usability] It can be used in light-emitting devices such as LEDs. -15- 201243028 [Simple description of the drawings] Figure 1 shows the process of one of the inventions. Fig. 2 is a view showing the fluorescence produced by the manufacturing method of the present invention. Fig. 3 is a diagram showing the use of a method of manufacturing a bulk material. [Major component symbol description] 10 Phosphor material 11 Phosphor particles 12 Coating layer 12A Ceramic particles 20 Light-emitting device 21 Substrate 22 Light-emitting element 23 Wiring 24 Wire 25 Reflector frame 26 Sealing layer 贯 嘘 萤 萤 萤 实施 实施 实施 实施 实施Schematic diagram of the structure of the material of the material. The structure of the light-emitting device of the fluorescent material of one embodiment of the present invention -