201042006 六、發明說明： 【發明所屬之技術領域】 本發明是有關於一種將鈦酸鹽作為母材的紅色螢光體 及其製造方法。 【先前技術】 近年來，將藍色二極體加以實用，已知有大量的將該 -極體作為發光賴自色發光二極體的研究。發光二極體 具有重量輕'不使用水銀、壽命長的優點。 例如，已知有一種將lALOu : Ce塗佈於藍色發光元 ^上的白色發光二極體。然而’該發光二極體嚴格而言並 ^白色，而成為混有藍綠色的白色。因此，提出了將 =15〇12 · Ce與吸收藍色光而發出紅色螢光的紅色營光體 以調整色調。吸收藍色光而發出紅色螢光的紅色螢 相關報告大多是與有機系材料有關，⑽無機系材 枓有關的報告較少。 ❹：一：為通常的紅色螢光體，已提出有氧化物 :無機系材料’亦提二 Ϊ驗=文中提出有一種於通式:卿“M表 而』所表示的鈦酸鹽中使3價的Eu活化 =獲传的紅色發光螢光體。另外，下料利 : Mnz ( ^ t , MgI ^^ Γ價的陽離*、x為使電荷平衡 的 α 或 F、、〇gn^4、〇么9、〇〈 201042006 ζ$0.5)所表示的紅色螢光體等。 該些先前技術中的將鈦酸鹽作為母材的螢光體是以乾 式或濕式將驗土類金屬源、鈦酸源及活化成分混合，獲得 該些原料的均勾混合物後，進行煅燒而獲得，但所得的紅 色發光體於發光強度方面有問題，量子產率亦較低。 [先行技術文獻] [專利文獻] [專利文獻1]曰本專利特開2006-232948號公報 [專利文獻2]曰本專利特開2〇〇7_297643號公報 【發明内容】 因此’本發明提供—種由藍色光激發並以高發光強度 發出紅色光的紅色螢光體 及其工業上有利的制；矣古、土。201042006 VI. Description of the Invention: [Technical Field] The present invention relates to a red phosphor having a titanate as a base material and a method for producing the same. [Prior Art] In recent years, a blue diode has been put into practical use, and a large number of studies have been known as a light-emitting color-emitting diode. The light-emitting diode has the advantage of being light-weighted without using mercury and having a long life. For example, a white light-emitting diode in which lALOu : Ce is coated on a blue light-emitting element ^ is known. However, the light-emitting diode is strictly white and becomes white mixed with cyan. Therefore, it has been proposed to adjust the color tone by using =15〇12· Ce and a red camping body that absorbs blue light and emits red fluorescence. The red firefly that emits red light and absorbs red fluorescence is mostly related to organic materials, and (10) there are few reports on inorganic materials. ❹: One: for the usual red phosphor, an oxide has been proposed: the inorganic material is also referred to as a test. In the text, a titanate represented by the formula: "M-meter" is used. Trivalent Eu activation = red-emitting phosphor that is transmitted. In addition, the lower material is: Mnz (^ t , MgI ^^ 阳 的 * *, x is the charge balance α or F, 〇 gn ^ 4. 〇 9 9, 〇 2010 2010 2010 2010 2010 2010 2010 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 0.5 2010 0.5 2010 0.5 0.5 0.5 0.5 0.5 0.5 The titanium acid source and the activating component are mixed to obtain a homogenous mixture of the raw materials, and then obtained by calcination, but the obtained red illuminant has a problem in terms of luminescence intensity, and the quantum yield is also low. [Previous Technical Literature] [ [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. 2006-232948 [Patent Document 2] Japanese Patent Laid-Open Publication No. Hei. No. Hei. a red phosphor that emits red light with high luminous intensity and its industrially advantageous system; earth.
❹ 本發明是根據上述見解而成， 體，該紅色螢光體的特徵在於： 示的鈦酸鹽中使Μη活化而形成， ’對發光強度The present invention is based on the above findings, and the red phosphor is characterized in that: TiO is activated in the titanate shown, and the luminescence intensity is formed.
M2Ti〇4 上的鹼土類金屬元 (式中，Μ表示一種或者兩種以 201042006 素）’ 且Si含量為24000 ppm以下。 另外，本發明提供一種紅色螢光體的製造方法，其是 用以製造上述紅色螢光體的較佳方法，其特徵在於：包括 將鹼土類金屬源、錳源及鈦源混合，對所得的混合物進行 煅燒而獲得煅燒物後，對該煅燒物進行退火處理的步驟； 且上述各金屬源是使用具有如下純度的金屬源，其中上述 純度為該些金屬源中所含的Si量為使所得釭色螢光體的 Si含量成為24000 ppm以下的量。 [發明之效果] 根據本發明，可提供一種红色光的發光強度高的紅色 螢光體。另外，根據本發明的製造方法，可藉由工業上有 利的方法來製造該紅色螢光體。 為讓本發明之上述和其他目的、特徵和優點能更明顯 易懂，下文特舉較佳實施例，並配合所附圖式，作詳細說 明如下。 【實施方式】 以下’根據本發明的較佳實施形態對其加以說明。 本發明的紅色螢光體基本上是由藍色光激發而發出紅 色光。具體而言，至少藉由270 nm〜550 nm、較佳的是 380 nm〜490nm的激發光而激發。另外，於600nm〜75〇 nm、較佳的是650 nm〜700 mn的區域中具有發光帶（即 具有紅色光譜）。 本發明的紅色螢光體是於下述通式（丨）所表示的鈦酸 (1) (1) 素）0 ο Ο 201042006 中使Μη活化而成 M2Ti04 (式中’Μ表示—種或者兩種以上的驗土類金屬元 通式（1)中的Μ是選自由H銷及鋇所組成的 組群中的-種或者兩種以上的鹼土類金屬元素，該些驗土 類金屬疋素中，就藉由藍色區域的波長的光而激發、且言 效地發出紅色光的方面而言，Μ較佳的是鎮。另外，當= 為兩種以上的鹼土類金屬元素時，二 祕…Μ'鳥Χ1、Χ2'』為為 + Χη=2 的-正數。 ... 於=酸鹽中活化的Μη為二價〜四價的—種或者兩種 以，特別是就紅色區域的發光的強度高的方面而言 ?η。，活化的施的含量’若相對於鈦酸 ==子計為°·。1 m〇1% (莫耳百分比）〜2.5 mol%、 度優;的方 外，色螢光體的特徵除了在於具有上述組成以 以下。Si含量較佳體而言是Si含量為24000 PPm 以下。於本發明以下’更佳的是10一 故Si體中，Si會導致發缝度下降， 3越^越好。目前的情況下，Si含量可下降至20 201042006 ppm左右。若為該水準的^含量’則表現出充分高的發光 強度。 以於通式（1)所表示的鈦酸鹽中使Mn活化而形成的 紅色螢光體為代表，作為紅色螢光體而先前已知的無機系 材料中j通常含有來源於成為肩料的金屬料的各種雜 貝。但疋，關於雜質對紅色螢光體的性能所造成的影響， 迄今為止未有報告。本發明者們特別對在通式（1)所表示 的鈦酸鹽中使施活化而形成的紅色螢光體的性能，著眼 於雜貝而進行了研究，結果發現雜質會影響發光強度。進 2進行研究得知，雜#中，Si對發光強度有大的影響。 先别已知的於通式⑴所表示的鈦酸鹽中使Μη活化而形 成的紅色螢光體（例如利料散獻2所記載的方法而製 備的紅色§光體）含有25GGQppm左右的的&。若如本發 月中對其加以規定般而設定為24000 ppm以下，則發光強 度可見明顯的改善效果。 本發明的紅色螢光體中的Si含量例如可利用Rigaku 公司製造的螢光X射線分析裝置（zsxl〇〇e)，以ι〇8度 〜110度的範圍内的Κα線波蜂強度值進行分析而定量。另 外雖不月確，但一般認為於本發明的紅色螢光體中，sj 疋以作為Si4+*於螢紐結晶巾固熔的狀態存在。 本發明的紅色螢光體為粉體，其粒子形狀並無特別限 制。粒子形狀例如除了球狀、多面體狀、紡錘形狀、針狀 以外，亦可為不定形。就激發光的吸收效率等的進一步提 高的觀點而言，較佳的是球狀。 201042006 本發明的紅色螢光體較佳的是平均粒徑為i μιη〜3〇 μιη、特別是10 μιη〜25 μιη。若平均粒徑小於叫，則有 激發光容易散射、激發光的吸收效率下降的傾向。若平均 粒，過30 μιη，則粒子表面積變小，仍然是激發光的吸 收容易變得不充分。另外，本發明中所述的平均粒徑均是 指一次粒子凝聚而形成的二次粒子的平均粒徑。該平均粒 徑為中值徑。二次粒子的平均粒徑（中值徑）例如可利用 堀場製作所製造的雷射繞射/散射式粒度分布測定裝置（型 號LA920)來進行測定，並將樣品的折射率設為丨8丨、將 分散介質的折射率設為h33而以體積基準計算。 平均粒徑例如能以如下方式來調節。即，對後述煅燒 步驟中獲得的锻燒物實施利用自動研蛛或球磨機等的粉碎 處理三視情形而使用與目標粒徑相符的網眼的_來進行分 級’藉此可獲得具有所需平均粒徑的粉體。 2本發明的紅色螢光體較佳的是ΒΕΤ比表面積為〇〇5 m2/g〜1.0 m2/g、特別是 〇] m2/g〜〇 5 m2/g。若 Μτ 比表 Ο 面積小於0.05m2/g，則激發光的吸收容易變得不充分。若 BET比表面積超過L〇 m2/g，則伴隨著表面積大而平均粒 徑小，因此有時激發光發生散射而激發光的吸收變得不充 分。BET比表面積例如可使用島津製作所製造的BET法單 吸附比表面積測定裝置（FlowS〇rbII23〇〇)來測定。 BET比表面積例如能以如下方式來進行調節。即，對 後述的烺燒步驟中獲得的煅燒物實施利用自動研缽或球磨 機等的粉碎處理，視情形而使用與目標粒徑相符的網眼的 201042006 篩來進行分級’藉此可獲得具有所需的BET比表面積的粉 體。 繼而，對本發明的紅色螢光體的較佳製造方法加以說 明。 本發明的紅色螢光體的製造方法包括將鹼土類金屬 源、錳源及鈥源混合，對所得的混合物進行煅燒而獲得煅 燒物後，對該煅燒物進行退火處理的步驟。即，本發明的 紅色螢光體的製造方法大致包括（A)混合步驟、（B)煅 燒步驟及（c)退火處理步驟。 (A)混合步驟中，製備將鹼土類金屬源、錳源及鈦 源均勻混合的均勻混合物。 第，料的鹼土類金屬源例如可使用鹼土類金屬的氧 化物、氫氧化物、碳酸鹽、硝酸鹽、硫酸鹽、有機酸鹽等。 該些化合物可使用一種或者兩種以上。該些化合物中，就 緞燒後不殘留雜質的方面及原料彼此的反應性高的方面而 言，較佳的是氫氧化物。鹼土類金屬源是以固體（粉體） 的狀態而並非水溶液等溶液的狀態來使用。鹼土類金屬源 右使用平均粒徑為5 μηι以下、特別是〇 2 μπι〜2 的物 質’則就可料地均勻混合的觀點而言較佳。 *第2原料的錳源例如可使用錳的氧化物、氫氧化物、 <酸鹽 '、硝_、琉gH有機酸鹽等。該些化合物可使 用_種或者兩種以上。該些化合物中，就锻燒後不殘留雜 質，方面及相翁母體組成而容易眺的方面而言 ，較佳 的是碳酸猛。缝源亦是以固體（粉體）的狀態來使用。猛 201042006 ϋ使用卜平均ϊ徑為10㈣以下、特別是1哗〜9 Mm的 貝’則就可容易地㈣混合的觀點而言較佳。 、 j3原料的鈦源例如可使用鈦的氧化物、氫氧化 綠化物等。㈣化合物可制—種或者兩種以 A化合物中’就锻燒後不殘留雜質的方面及 Ο 〇An alkaline earth metal element (wherein Μ means one or two of 201042006) and an Si content of 24000 ppm or less on M2Ti〇4. In addition, the present invention provides a method for producing a red phosphor, which is a preferred method for producing the red phosphor described above, comprising: mixing an alkaline earth metal source, a manganese source, and a titanium source, and obtaining the obtained After the mixture is calcined to obtain a calcined product, the calcined product is subjected to an annealing treatment step; and each of the above metal sources is a metal source having a purity in which the amount of Si contained in the metal source is such that The Si content of the ochre phosphor is 24,000 ppm or less. [Effect of the Invention] According to the present invention, a red phosphor having a high luminous intensity of red light can be provided. Further, according to the production method of the present invention, the red phosphor can be produced by an industrially advantageous method. The above and other objects, features and advantages of the present invention will become more <RTIgt; [Embodiment] Hereinafter, the present invention will be described based on preferred embodiments of the present invention. The red phosphor of the present invention is substantially excited by blue light to emit red light. Specifically, it is excited by at least excitation light of 270 nm to 550 nm, preferably 380 nm to 490 nm. Further, the light-emitting band (i.e., having a red spectrum) is present in a region of 600 nm to 75 Å, preferably 650 nm to 700 mn. The red phosphor of the present invention activates Μη to form M2Ti04 in the titanic acid (1) (1) element represented by the following formula (丨)) 0 ο Ο 201042006 (wherein 'Μ denotes a species or two The above-mentioned earth-receiving metal element is generally selected from the group consisting of H pin and strontium, or two or more kinds of alkaline earth metal elements. In the case where the red light is excited by the light of the wavelength of the blue region and the red light is emitted in a vivid manner, the town is preferably a town. In addition, when = two or more alkaline earth metal elements,秘...Μ 'Bird Χ1, Χ2'』 is a positive number of + Χη=2. ... Μη activated in the acid salt is divalent to tetravalent - or both, especially in the red region In terms of high intensity of luminescence, η., the content of activated application is '°% relative to titanic acid==1 m〇1% (% of moles)~2.5 mol%, excellent; In addition to the above, the color phosphor is characterized by having the above composition below. The Si content is preferably a Si content of 24,000 PPm or less. In the case of 10 Si, Si will cause the degree of cracking to decrease, and the better the 3 is. In the present case, the Si content can be reduced to about 20 201042006 ppm. If it is the level ^, it is fully high. The red phosphor formed by the activation of Mn in the titanate represented by the general formula (1) is representative, and the inorganic material previously known as the red phosphor is usually contained in the inorganic material. Various kinds of miscellaneous materials which become metal materials of the shoulder material. However, the influence of the impurities on the performance of the red phosphor has not been reported so far. The present inventors particularly relate to the titanium represented by the general formula (1). The performance of the red phosphor formed by activation in the acid salt was studied with reference to the shellfish, and it was found that the impurity affected the light-emitting intensity. It was found that in the hybrid #, Si had a large luminous intensity. The red phosphor formed by the activation of Μ in the titanate represented by the general formula (1) (for example, the red § light body prepared by the method described in 2) contains 25GGQppm. The left and right & if it is as in the middle of the month When the amount is set to 24,000 ppm or less, the luminous intensity can be clearly improved. The Si content in the red phosphor of the present invention can be, for example, a fluorescent X-ray analyzer (zsxl〇〇e) manufactured by Rigaku Corporation. The Κα line wave bee intensity value in the range of ι 〇 8 degrees to 110 degrees is analyzed and quantified. In addition, although it is not confirmed, it is generally considered that sj 疋 is used as Si4+* in the red fluorescent body of the present invention. The red crystal of the present invention is in a solid state. The red phosphor of the present invention is a powder, and the particle shape thereof is not particularly limited. The particle shape may be amorphous, for example, in addition to a spherical shape, a polyhedral shape, a spindle shape, or a needle shape. . From the viewpoint of further improving the absorption efficiency of the excitation light and the like, it is preferably spherical. 201042006 The red phosphor of the present invention preferably has an average particle diameter of i μm to 3 μm, particularly 10 μm to 25 μm. When the average particle diameter is smaller than the average particle size, the excitation light tends to be scattered, and the absorption efficiency of the excitation light tends to decrease. When the average particle size exceeds 30 μm, the surface area of the particle becomes small, and the absorption of the excitation light is likely to be insufficient. Further, the average particle diameter described in the present invention means the average particle diameter of the secondary particles formed by the aggregation of primary particles. The average particle diameter is the median diameter. The average particle diameter (median diameter) of the secondary particles can be measured, for example, by a laser diffraction/scattering particle size distribution measuring apparatus (model LA920) manufactured by Horiba, and the refractive index of the sample is set to 丨8丨. The refractive index of the dispersion medium was set to h33 and calculated on a volume basis. The average particle diameter can be adjusted, for example, in the following manner. In other words, the calcined product obtained in the calcination step described later is subjected to pulverization treatment by an automatic grinding machine or a ball mill or the like, and grading is performed using a mesh corresponding to the target particle diameter, whereby a desired average can be obtained. Powder of particle size. 2 The red phosphor of the present invention preferably has a ΒΕΤ specific surface area of 〇〇5 m2/g to 1.0 m2/g, particularly 〇] m2/g to 〇 5 m2/g. If the area of the Μτ ratio surface is less than 0.05 m 2 /g, the absorption of the excitation light is likely to be insufficient. When the BET specific surface area exceeds L 〇 m2 / g, the average particle diameter is small as the surface area is large. Therefore, the excitation light is scattered and the absorption of the excitation light is insufficient. The BET specific surface area can be measured, for example, by using a BET method single adsorption specific surface area measuring device (FlowS〇rbII23®) manufactured by Shimadzu Corporation. The BET specific surface area can be adjusted, for example, in the following manner. In other words, the calcined product obtained in the calcination step to be described later is subjected to a pulverization treatment using an automatic mortar or a ball mill, and, as the case may be, using a 201042006 sieve of a mesh conforming to the target particle diameter to carry out classification. A powder having a BET specific surface area required. Next, a preferred method of producing the red phosphor of the present invention will be described. The method for producing a red phosphor of the present invention comprises the steps of mixing an alkaline earth metal source, a manganese source and a helium source, and calcining the obtained mixture to obtain a calcined product, followed by annealing the calcined product. That is, the method for producing a red phosphor of the present invention roughly comprises (A) a mixing step, (B) a calcining step, and (c) an annealing treatment step. (A) In the mixing step, a homogeneous mixture in which an alkaline earth metal source, a manganese source, and a titanium source are uniformly mixed is prepared. For the alkaline earth metal source of the material, for example, an oxide, a hydroxide, a carbonate, a nitrate, a sulfate, an organic acid salt or the like of an alkaline earth metal can be used. These compounds may be used alone or in combination of two or more. Among these compounds, hydroxides are preferred in terms of not leaving impurities after satin burning and high reactivity between raw materials. The alkaline earth metal source is used in a state of a solid (powder) and not a solution such as an aqueous solution. The alkaline earth metal source is preferably a material having an average particle diameter of 5 μη or less, particularly 〇 2 μπι 2 , in terms of uniform mixing. * For the manganese source of the second raw material, for example, manganese oxide, hydroxide, <acid salt', nitrate_, 琉gH organic acid salt, or the like can be used. These compounds may be used in the form of _ or two or more. Among these compounds, carbonic acid is preferred in terms of no residue remaining after calcination, and aspect and phase composition of the precursor. The seam source is also used in a solid (powder) state. In 201042006, it is preferable to use a bain having an average diameter of 10 (four) or less, particularly 1 to 9 Mm, from the viewpoint of easy (four) mixing. For the titanium source of the j3 raw material, for example, an oxide of titanium, a green hydroxide, or the like can be used. (4) The compound can be made into one kind or two kinds of in the A compound, and there is no residual impurity after calcination and Ο 〇
It方面而言’較佳的是氧化欽⑽士所使二 、、（1 2)可藉由硫酸法或氯法而獲得，另外亦可為 銳鈦礦（anatase)型或金紅石（mtile)型，可盔特別限制 地巧。另外，欽源亦是以固趙（粉體）的狀制 鈦源右使用平均粒徑為5叫以下、特別是Μ阿〜2帅 的物質’則就可容易地均勻混合的觀點而言較佳。 本發明的紅色螢光體如上所述，實質上不含Si，具體 而言，Si含量為240〇〇ppm以下。因此，於混合步驟/中， 上述各金屬源是使用該些中所含的Si量為使所得紅色螢 光體的si含量成為24_ppm以下的量之具有高純度的物 質。 本發明者們發現，Si於紅色螢光體中的混入主要來源 於原料的鈦源（例如氧化鈦）。於本發明中，所使用的鈦源 較佳的是使用Si含量為9000ppm以下、特別是6000ppm 以下、尤其是1〇〇ppm以下的高純度之物質。原料的鈦源 可使用市售品。市售品中，較佳的亦是選擇使用上述高純 度的鈦源》 關於驗土類金屬源及錳源’較佳的是與鈦源同樣地使 用Si含1低的两純度的物質。然而’驗土類金屬源及猛源 201042006 的Si含量通常低於鈦源，故於本發明中通常不成問題。鹼 土類金屬源較佳的是使用Si含量為100ppm以下的純度的 金屬源’錳源較佳的是使用Si含量為100ppm以下的純度 的金屬源。關於鹼土類金屬源及錳源，即便為通常的市售 品’亦可滿足上述Si含量。 關於驗土類金屬源及钦源的混合比例，若以驗土類金 屬，中的鹼土類金屬原子相對於鈦源中的鈦原子（Ti) 之ίϊ比（M/Ti)計為1,6〜2.5、特別是h8〜2.2，則就 獲得單晶粒子_部量子效率最優異峨㈣言較佳。 “另方面，關於猛源的混合比例，自良好地吸收激發 光而光轉換效率亦優異的觀點而言，較佳的是蚊為相對 於戶:得的敛酸鹽以Mn原子計為001 mol%〜3 mol%、特 別疋 0.1 mol%〜1.5 mol%。 最終獲得的紅色螢光體中的si含量亦受到所使用的 各金屬源的具體種_辟，但若述難純度的金 屬源及較魏合關，則通常可使紅色螢紐的 24000ppm以下。 句 將第1補〜第3補的驗域金屬源、簡及鈦源 =的方法可為濕式法及乾式法中的任—種，就可容易地 ，伸將各·均勻混合的均勻混合物的方減言，較佳的 =藉由機械機構以濕式絲進行齡。制是藉由利用作 ^可同時進行粉碎與混合的機器的介f研磨機，以满式法 進订混合處理，而可更容易地獲得均勻混合物，另外，使 用該均勻混合物麟的紅色螢光體的發光強度特別高。 12 201042006 對使用介料賴的齡處理加以進—步說明 及將混合處理基本上包括漿料製備步驟、 合L 介質研磨機中並進行混合處理的現 於漿料製備步驟中，使驗土類金屬源、 而製成漿料。分散介質可使用水及非:二 ❹ ❹ 關於漿料的固體成分濃度（鹼土類金屬源、猛源 ==濃度)，自處理規模小、操作容易的觀點而言，較 佳的疋5 wt%〜40 wt%、特別是1〇糾％〜3〇 wt〇/ :可於謝添加分跡藉由添加分散劑。，驗土類 '屬^、轉及鈦源會更均勻地分散於分散介f中。、 it獲得該些原料的均勻混合物。所使用的分散齊％ ^根據分散介質的種類來選擇適當的物f即可。當^ 質為水時，可使用各種界面活性劑、聚舰銨二 =而_賴中的分散劑的濃度，就充分的分散效ΐ :::5^ ▲ 2外’對於賴的製備巾錢的分散介f及分散劑而 :’較佳的亦是使用Si含量極少的物質，但通常，如限於 分散介質及分散劑，對紅色螢光體的發光強度有 :響的篁的Si不會來源於該些物質而混入至紅色發光體 中。另外，於本發明的製造方法中，除了漿料製備中所使 13 201042006 用的各金屬源、分散介質及分散劑以外，並不存在對红色 螢光體的發光強度有影響的程度的Si混入的要因。” 接著，將漿料製備步驟中獲得的漿料導入至介質研磨 機中並進行混合處理，獲得均勻混合物。介質研磨機可使 用珠磨機（beads mil】）、球磨機（bdl mm)、塗料振盪器 (paint shaker)、磨碎機（attrker)、砂磨機（samJ ㈤们等。 特別佳的是使用珠賴。此時，運轉條件或珠粒的種類及 大小只要根據裝置的尺寸錢理量、驗土類金屬源 、•源 及鈦源的種類等而適當墀擇即可。 就獲侍更均勻的混合物的觀點而言，利用濕式法的混 j理較佳的是進行至固體成分的平均粒徑（二次粒子的 為=粒！）達到〇.〇5卿〜】μιη、特別是〇」师〜_ 收後，自漿料中將均句混合物過濾並加以回 之前進行乾燥S混2佳的是於實施(Β)煅燒步驟 — '、处 乾燥處理例如可於8〇。(：〜20(TC下進 仃1小時〜100小時。 。 锻燒驟中獲得的均勻混合物實施⑻ 出〇。〇〜160价锻燒物。锻燒條件較佳的是锻燒溫度為 於⑽。C，則母^=是1200°c〜1350°c。若锻燒溫度小 難以固溶，另—，…曰不易以單相而獲得，另外發光離子 於粒子彼此之=面’若職溫度超過16GG°C，則存在由 時間較伟沾θ」、過73進行而難以獲得粉體的傾向。锻燒 π叹定為1小時以上、特別是3小時〜20小 201042006 =二浪燒的環境並無特別限制，可為大 境中及惰性氣體環境中的任—種。㈣化^體核 的狀是視詩轉碎輯需的純，以粉體 施後續的退火處理步驟。锻燒視需要亦可進行 成二炮^偏’為了使粉體的特性均勻，亦可暫且將锻燒而 =步驟之前’視需要亦可贱進行分級縣調整 i生。 Ο ❹ ，著’對藉由⑻锻燒步驟所得的煅燒物實施（c) =處理步驟，獲得本發_紅色螢光體。藉由進行該退 出 可顯著&回發光強度。藉由該退火處理而發光強 的理由雖不較，但—般認為，母體結晶的結構由 方sa變化為正方晶’由此將發光離子所吸㈣光能量高 效地轉換成發光。 。退火處理的條件較佳的是處理溫度為5〇〇它〜 _°c、特別是57(TC〜_t：。其理由在於：若退火處理 溫度小於50CTC，則不會引起結晶變化，另一方面，若退 火處理溫度超過細。c，财再切到立方晶的傾向。退 火處理時間較佳的是設定為1小相上、制是3小時〜 小時。退火處理的環境並無特別限制，可為氧、大氣等 氧化性環境中及惰性氣體環境中的任一種◦再者，視需要， 退火處理亦可進行數次。 退火處理後的紅色螢光體視需要亦可進行解 等直至達到所需的粒徑。 Λ 、 15 201042006 以上述方式獲得的紅色螢光體例如可用於電解發射型 顯示器（electrolysis emission display )、電漿顯示器（piasma display )、電致發光（eiectr〇iuminescence )等的顯示器件 的用途。另外，因具有接近460 nm左右的激發光譜，故 可應用於藍色LED激發用螢光體的用途。特別適合於電致 發光的顯示科的用途。另外，亦可藉由錢色激發綠色 螢光體併用的方法、與藍色LDE元件及藍色激發綠色螢光 體併用而使用的方法、或與藍色LDE元件及藍色激發黃色 發光螢光體併用而使用的方法等，而應用於白色LED。 實例 以下，藉由實例對本發明加以說明，但本發明不限定 於該些實例。 以下的實例及比較例中的Si含量、平均粒徑及BET 比表面積是分別以如下方式而測定。In terms of It, it is preferable that the oxidized chin (10) can be obtained by the sulfuric acid method or the chlorine method, or it can be an anatase type or a rutile (mtile). Type, the helmet can be specially limited. In addition, Qinyuan is also based on the shape of the solid Zhao (powder) titanium source, the average particle size is 5 or less, especially the material of the ΜA~2 handsome, then it is easy to uniformly mix. good. As described above, the red phosphor of the present invention contains substantially no Si, and specifically has a Si content of 240 〇〇 ppm or less. Therefore, in the mixing step, each of the above-mentioned metal sources is a substance having a high purity in which the amount of Si contained in the above-mentioned red phosphor is such that the Si content of the obtained red phosphor is 24 ppm or less. The inventors have found that the incorporation of Si into the red phosphor is mainly derived from a titanium source of the starting material (e.g., titanium oxide). In the present invention, the titanium source to be used is preferably a high-purity substance having a Si content of 9000 ppm or less, particularly 6000 ppm or less, particularly 1 〇〇 ppm or less. A commercially available product can be used as the titanium source of the raw material. Among the commercially available products, it is preferable to use the above-mentioned high-purity titanium source. Regarding the soil-based metal source and the manganese source, it is preferable to use a substance having a low Si content and a low purity similarly to the titanium source. However, the Si content of the soil-based metal source and the source 201042006 is generally lower than that of the titanium source, and thus is generally not a problem in the present invention. The alkaline earth metal source is preferably a metal source having a purity of 100 ppm or less. The manganese source is preferably a metal source having a purity of 100 ppm or less. Regarding the alkaline earth metal source and the manganese source, the Si content can be satisfied even if it is a normal commercial product. Regarding the mixing ratio of the soil-based metal source and the source, if the soil-based metal is used, the ratio of the alkaline earth metal atom to the titanium atom in the titanium source (M/Ti) is 1,6. ～2.5, especially h8~2.2, it is better to obtain the most excellent quantum efficiency of the single crystal particle. "On the other hand, regarding the mixing ratio of the source, from the viewpoint of good absorption of the excitation light and excellent light conversion efficiency, it is preferred that the mosquito is relative to the household: the obtained salt is 001 mol in terms of Mn atom. %~3 mol%, especially 疋0.1 mol%~1.5 mol%. The Si content in the finally obtained red phosphor is also affected by the specific species of each metal source used, but if it is a metal source of difficult purity and Compared with Weiheguan, it is usually less than 24000ppm of red fluorescent. The sentence of the first to the third complement of the domain metal source, Jane and Titanium source = can be either wet or dry method - Therefore, it is easy to stretch the square of each homogeneous mixture, preferably = by mechanical means to wet the age of the wire. The system can be simultaneously pulverized and mixed by using The machine's f-grinding machine performs the mixing process in a full-fill method, and the homogeneous mixture can be more easily obtained. In addition, the red phosphor using the uniform mixture has a particularly high luminous intensity. 12 201042006 Age processing, step-by-step instructions and mixing of treatment bases The slurry preparation step, the L medium mill and the mixing treatment are carried out in the slurry preparation step, and the soil-based metal source is used to prepare a slurry. The dispersion medium can use water and non-dioxide. Regarding the solid content concentration of the slurry (alkaline earth metal source, Mengyuan == concentration), from the viewpoint of small treatment scale and easy handling, 疋5 wt% to 40 wt%, particularly 1% correction% is preferable. ~3〇wt〇/ : You can add a dispersing agent by adding a dispersing agent. The soil testing class 'genus, turn and titanium source will be more evenly dispersed in the dispersion medium f., it obtains the uniformity of the raw materials. The mixture used may be selected according to the kind of the dispersion medium. When the quality is water, various surfactants, poly-salt ammonium Concentration, sufficient dispersion effect :::5^ ▲ 2 outside 'for the preparation of Lai's preparation of dispersing agent f and dispersing agent: 'It is also preferred to use substances with very little Si content, but usually, such as The dispersing medium and the dispersing agent have a luminous intensity for the red phosphor: the ringing Si does not originate from the Some substances are mixed into the red illuminant. Further, in the production method of the present invention, there is no red phosphor other than the metal source, dispersion medium and dispersant used in the preparation of the slurry in 13 201042006. The luminescence intensity has an influence on the degree of Si incorporation." Next, the slurry obtained in the slurry preparation step is introduced into a media mill and subjected to mixing treatment to obtain a homogeneous mixture. The media mill can use a bead mill (beads mil), a ball mill (bdl mm), a paint shaker, an attriker, a sander (samJ), etc. It is especially good to use beads. Lai. At this time, the operating conditions or the type and size of the beads can be appropriately selected according to the size of the device, the metal source of the soil, the source of the source, and the type of the titanium source. From the viewpoint of the mixture, it is preferred to carry out the mixing method by the wet method to the average particle diameter of the solid component (the secondary particle is = grain!) to reach 〇.〇5卿~]μιη, especially 〇" After the ～~, after the mixture is filtered and returned from the slurry, it is dried and S mixed. The best is to carry out the (煅) calcination step - ', the drying treatment can be, for example, 8 〇. (: ~20 (TC is simmered for 1 hour to 100 hours. The uniform mixture obtained in the calcination step is carried out (8). 〇~160 valent calcined material. The calcining condition is preferably the calcination temperature is (10). The mother ^ = is 1200 ° c ~ 1350 ° C. If the calcination temperature is too small to be solid solution, another -, ... is not easy to single phase In addition, it is obtained that the luminescent ions are in the surface of each other when the temperature exceeds 16 GG ° C, and there is a tendency that the powder is difficult to obtain the powder by the time θ θ 、 and 73. The calcination π sighs for 1 hour. Above, especially 3 hours to 20 small 201042006 = The environment of Erlang is not particularly limited, and it can be any kind in the environment and in the inert gas environment. (4) The shape of the body is determined by the poetry Pure, the powder is followed by an annealing treatment step. Forging can also be carried out as needed. In order to make the characteristics of the powder uniform, it is possible to temporarily calcine and = before the step. The classification of the county is adjusted. Ο ❹, '(c) = treatment step is performed on the calcined product obtained by the (8) calcination step to obtain the present hair red fluorescent body. By performing the withdrawal, significant & Luminous intensity. Although the reason why the luminescence is strong by the annealing treatment is not large, it is generally considered that the structure of the mother crystal is changed from the square sa to the tetragonal crystal ′, whereby the light energy absorbed by the luminescent ions is efficiently converted into luminescence. The annealing treatment condition is preferably the processing temperature 5 〇〇 it ~ _ ° c, especially 57 (TC ~ _t:. The reason is: if the annealing temperature is less than 50 CTC, it will not cause crystal change, on the other hand, if the annealing temperature exceeds fine. c, The annealing time is preferably set to 1 small phase and 3 hours to hour. The annealing treatment environment is not particularly limited, and may be inert in an oxidizing environment such as oxygen or atmosphere. In any of the gas environments, the annealing treatment may be performed several times as needed. The red phosphor after the annealing treatment may be decomposed as needed until the desired particle size is reached. Λ , 15 201042006 The red phosphor obtained in the manner can be used, for example, for a display device such as an electrolysis emission display, a piasma display, or an electroluminescence (eiectr〇iuminescence). In addition, since it has an excitation spectrum of approximately 460 nm, it can be applied to the use of a blue LED excitation phosphor. It is particularly suitable for the use of electroluminescence display. In addition, a method in which a green phosphor is excited by a luster color, a method used in combination with a blue LDE element and a blue-excited green phosphor, or a blue LDE element and a blue-excited yellow-emitting fluorescent light may be used. The method used in combination with the body is applied to a white LED. EXAMPLES Hereinafter, the invention will be illustrated by way of examples, but the invention is not limited to the examples. The Si content, the average particle diameter, and the BET specific surface area in the following examples and comparative examples were measured as follows.
Si含量：使用Rigaku公司製造的螢光χ射線分析裝 置（ZSXIOOe)’以108度〜11〇度的範圍内的Κα線波峰 強度值進行分析而定量。 平均粒徑：利用掘場製作所製造的雷射繞射/散射式粒 度分布败裝置（型號LA920)進行狀，並將樣品的折 射率設為1.8卜將分散介質的折射料為133而以體積 準計算。 BET比表面積：使用島津製作所製造的ΒΕΤ法單吸附 比表面積測定襄置（FlowSorbII2300)進行測定。 [實例1] ' 16 201042006 以鎂··鈦：錳的莫耳比為2 : 0.996 : 0.004的方式來 稱量氫氧化鎂（平均粒徑0.57 μηι)、Si含量為4676 ppm 的氧化欽（平均粒徑0.64 μπι)及碳酸猛（平均粒徑5.2 並加入至槽中。於槽中添加水及分散劑（花王（股）製造， P〇iz2100) ’製備固體成分濃度為15 wt%的漿料。分散劑 的濃度為2.0 wt%。 對漿料一邊進行攪拌一邊使用直徑2 〇 mm的氧化鍅 〇 ，進行150分鐘球磨，藉此進行利用濕式法的混合粉碎。 藉由光散射法對混合粉碎後的漿料中的原料混合物的 粒徑進行測定，為0.5 μιη。 接著 曰眾料Τ將混合物過濾並加以回收，於 下進行1〇小時乾燥而獲得乾燥紐。乾騎體的平均粒和 為 0.5μιη，靜止角（angle〇frep〇se)為衫。。The Si content was quantified by analyzing the Κα line peak intensity value in the range of 108 to 11 Torr using a fluorescent ray ray analyzer (ZSXIOOe) manufactured by Rigaku Corporation. Average particle size: using a laser diffraction/scattering particle size distribution device (model LA920) manufactured by a digger, and setting the refractive index of the sample to 1.8, and refracting the dispersion medium to 133. Calculation. BET specific surface area: The measurement was carried out using a 单 method single adsorption specific surface area measuring device (FlowSorb II 2300) manufactured by Shimadzu Corporation. [Example 1] ' 16 201042006 Weighed magnesium hydroxide (average particle size 0.57 μηι) and Si content of 4676 ppm by the molar ratio of magnesium·titanium:manganese 2: 0.996 : 0.004 (average Particle size 0.64 μπι) and carbonic acid (average particle size 5.2 and added to the tank. Add water and dispersant to the tank (made by Kao), P〇iz2100) Prepare a slurry with a solid concentration of 15 wt% The concentration of the dispersing agent was 2.0 wt%. The slurry was stirred while using a cerium oxide having a diameter of 2 mm and subjected to ball milling for 150 minutes to carry out mixing pulverization by a wet method. The particle size of the raw material mixture in the pulverized slurry was measured and found to be 0.5 μm. Next, the mixture was filtered and recovered, and dried for 1 hour to obtain a dry nucleus. It is 0.5 μm, and the angle of rest (angle〇frep〇se) is a shirt.
然後，將乾燥粉體加人至電爐中，於 下以靜置狀態煅燒5小時。桩基,.^ ^ LThen, the dry powder was placed in an electric furnace and calcined in a standing state for 5 hours. Pile foundation, .^ ^ L
G =⑽)後，: ηκ>_4+。確所传粉體為 Mg2Ti〇4:0.4 I；比較例1] pp- 除此以外，藉由與實贿比表面積6.7心> 一貫例1相同的操作及條件而獲得粉體。 201042006 ^ 上/4·丄 對所得的粉體進行與實例1相同的分析。分析結果與實例 1相同，確認到所得的粉體為Mg2Ti〇4 : 0.4 m〇1%Mn4+。 〈Si含量、平均粒徑及BET比表面積的測定〉 對只例1及比較例1令獲得的螢光體試樣進行&含 量、平均粒徑及BET比表面積的測定。測定結果示於表i 中。 〈螢光特性的評價〉 對實例1及比較例1中獲得的螢光體試樣測定激發波 長460 nm下的發光光譜的極大波長、該極大波長下的發 (The International Commission on Illumination，CIE)色度。測定結果示於表1中。另外， 極大波長下的發光強度是以耻較例i的螢錢試樣的發 光強度设為100時的相對強度值來表示。另外，圖i中示 出實例1中獲得的螢光體試樣的螢光光譜。 發光光譜及CIE色度的測定是以如下方式進行。 發光光譜：使用螢光分光光度計（日立高科技製造）， 將激發光设為460 nm’掃描430 nm至800 nm的範圍而獲 得光譜。 CIE色度·根據激發波長460 nm下的螢光光譜相對值 依照JISZ 8701求出xy表色色度座標。 [實例2] 代替實例1中使用的氧化鈦而使用Si含量為9.4 ppm 的氧化，（平均粒梭〇 64叫）’除此以外藉由與實例工 相同的操作及條件*獲得粉體。對所得的粉體進行與實例 201042006 1相同的分析。分析結果與實例1相同，確認到所得的粉 體為 Mg2Ti〇4 : 0.4 mol%Mn4+。 對於所得的粉體，與實例1同樣地進行Si含量、平均 粒徑及BET比表面積的測定以及螢光特性的評價。結果示 於表1中。 ,、 [表1]After G = (10)), ηκ>_4+. The powder was confirmed to be Mg2Ti〇4: 0.4 I; Comparative Example 1] pp- Other than this, the powder was obtained by the same operation and conditions as in Comparative Example 1 except for the specific surface area of the bribe. 201042006 ^Up/4·丄 The obtained powder was subjected to the same analysis as in Example 1. The analysis results were the same as in Example 1, and it was confirmed that the obtained powder was Mg2Ti〇4: 0.4 m〇1% Mn4+. <Measurement of Si content, average particle diameter, and BET specific surface area> The phosphor samples obtained in only Example 1 and Comparative Example 1 were subjected to measurement of & content, average particle diameter, and BET specific surface area. The results of the measurements are shown in Table i. <Evaluation of Fluorescence Characteristics> The maximum wavelength of the luminescence spectrum at an excitation wavelength of 460 nm and the emission at the maximum wavelength were measured for the phosphor samples obtained in Example 1 and Comparative Example 1 (The International Commission on Illumination, CIE) Chroma. The measurement results are shown in Table 1. Further, the luminous intensity at the maximum wavelength is expressed as a relative intensity value when the luminous intensity of the fluorescent sample of the example i is set to 100. Further, the fluorescence spectrum of the phosphor sample obtained in Example 1 is shown in Fig. i. The measurement of the luminescence spectrum and the CIE chromaticity was carried out in the following manner. Luminescence spectrum: A spectrum was obtained by using a fluorescence spectrophotometer (manufactured by Hitachi High-Technologies) to set the excitation light to a range of 460 nm' scanning from 430 nm to 800 nm. CIE Chroma · Relative value of the fluorescence spectrum at an excitation wavelength of 460 nm The xy color chromaticity coordinate is obtained in accordance with JIS Z 8701. [Example 2] Instead of the titanium oxide used in Example 1, oxidation with a Si content of 9.4 ppm, (average granules 64) was used except that the powder was obtained by the same operation and conditions* as in the example. The obtained powder was subjected to the same analysis as in Example 201042006. The analysis results were the same as in Example 1, and it was confirmed that the obtained powder was Mg2Ti〇4: 0.4 mol% Mn4+. With respect to the obtained powder, measurement of Si content, average particle diameter, and BET specific surface area, and evaluation of fluorescence characteristics were carried out in the same manner as in Example 1. The results are shown in Table 1. ,, [Table 1]
Si含量 (ppm) 平均粒 徑 (μιη) BET比表面 積 (m2/g) 發光波峰極大 波長 (nm) 相對發光強 度 (%) CIE色度座 標 X V 實例1 12300 20 0.29 659 ， 676 157 0.714 J 0.285 實例2 20 20 0.30 659 ， 676 189 0.727 0.273 比較例1 24700 20 0.32 659 ， 676 100 0.705 0.293 由表1的記載表明，Si含量對紅色螢光體的發光強度 有影響。若Si含量為24麵ppm以下，則發光強度可確認 到提升效果，若Si含量為15000 PPm以下（實例1)、特 別是100 ppm以下（實例2)，則可確認到極高的提升效果。 雖然本發明已以較佳實施例揭露如上，然其並非用以 限定本發明，任何熟習此技藝者，在不脫離本發明之精神 〇 和範圍内，當可作些許之更動與潤飾，因此本發明之保護 範圍當視後附之申請專利範圍所界定者為準。 【圖式簡單說明】 圖1是實例1中所得的紅色螢光體的螢光光譜（激發 波長 460 nm)。 【主要元件符號說明】 無 19Si content (ppm) Average particle size (μιη) BET specific surface area (m2/g) Luminescence peak maximum wavelength (nm) Relative luminous intensity (%) CIE chromaticity coordinate XV Example 1 12300 20 0.29 659 , 676 157 0.714 J 0.285 Example 2 20 20 0.30 659 , 676 189 0.727 0.273 Comparative Example 1 24700 20 0.32 659 , 676 100 0.705 0.293 It is shown in Table 1 that the Si content has an influence on the luminous intensity of the red phosphor. When the Si content is 24 ppm or less, the light-emitting intensity can be confirmed as a lifting effect. When the Si content is 15,000 ppm or less (Example 1), particularly 100 ppm or less (Example 2), an extremely high lifting effect can be confirmed. Although the present invention has been disclosed in the above preferred embodiments, it is not intended to limit the present invention, and it is to be understood that those skilled in the art can make some modifications and refinements without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a fluorescence spectrum (excitation wavelength 460 nm) of a red phosphor obtained in Example 1. [Main component symbol description] None 19