4 6 4 9 0 2 Α： _ _ β： 五、發明說明（1 ) 【發明所屬之技術領域】 本發明係有關於一種白色發光之螢光體’及使用該螢 光體之螢光顯示管。 【習知技術】 一般的榮光顯示官係具有一基本構造，即，係於使内部 呈高真空狀態之封包器（envelop)的内部收容有：為電子源 之陰極、用以控制電子之控制電極及具有螢光體之陽極等 等。陽極電壓通常是設在100V以下、數十V程度。在前 述螢光顯示管之陽極上所使用之螢光體係已知有下列記載 者。係於物質名稱後面以括號表示發光色。4 6 4 9 0 2 Α: _ _ β: V. Description of the invention (1) [Technical field to which the invention belongs] The present invention relates to a white light-emitting phosphor 'and a fluorescent display tube using the same . [Knowledge technology] The general glory display official system has a basic structure, that is, an envelope that encloses the interior in a high vacuum state. The envelope contains: a cathode for an electron source, and a control electrode for controlling electrons. And anodes with phosphors, etc. The anode voltage is usually set below 100V and about several tens of V. The fluorescent system used for the anode of the aforementioned fluorescent display tube is known as follows. The luminous color is indicated by brackets after the substance name.
ZnO:Zn (綠）ZnO: Zn (green)
ZnGa2〇4 (藍）、ZnGa2〇4:Mn (綠）ZnGa2〇4 (blue), ZnGa2〇4: Mn (green)
ZnS[Zn](藍）' ZnS:Ag,Cl (藍）、ZnS:Ag，Al (藍）ZnS [Zn] (blue) 'ZnS: Ag, Cl (blue), ZnS: Ag, Al (blue)
ZnS:Cu，Al (綠） (Zn，Cd)S:Ag系（依據Cd之含量，發光色可形成黃〜紅者) 在此’ Z:X，Y係表示掺雜有X和γ之之者，pQ[p]係 表示欠缺P(也就是與Q相比p是不足）之物質之PQ，以下 在本說明書及申請專利範圍中也同樣採用之。例如， ZnS:Cu，Cl係顯示掺雜有Ag及C1之ZnS，而ZnS[Zn]則係 表示欠缺Zn之ZnS。 在將如此具有種種發光色之螢光燈實用化中，近年 來，在使用者間有希望將螢光顯示管之主要顏色為白色之 需求逐漸高漲，但習知並沒有單獨以白色發光之螢光體。 本纸張又度適闬由國0家標牮（CNS)A4規格（210 X 297 eg ) "^'"-了···"-^·4-·-··)事項再填寫本頁)ZnS: Cu, Al (green) (Zn, Cd) S: Ag system (depending on the content of Cd, the luminous color can form yellow to red ones) Here, Z: X, Y system means those doped with X and γ In other words, pQ [p] is a PQ indicating a substance lacking P (that is, p is insufficient compared to Q), and it is also adopted in the following description and the scope of patent application. For example, ZnS: Cu, Cl shows ZnS doped with Ag and C1, while ZnS [Zn] shows ZnS lacking Zn. In the practical application of such fluorescent lamps having various luminous colors, in recent years, the demand for fluorescent white display tubes to be white has gradually increased among users, but it has not been known that fluorescent lamps emitting white light alone Light body. This paper is suitable again (CNS) A4 specification (210 X 297 eg) " ^ '" -......... "-^ · 4- · -... (This page)
- l I I l· I I I · I I----I I 經濟郭智慧財產局員工消費合作社印製 -4- --二"·5'19-'^-' :每-1-"费..--:.:: 方面可將S系 五、發明說明（，） 因此.為得到白色發光，係用以混合]、3種之其等含 名硫化物及Cd之螢光體，而得到一近似白色發光之螢光 肢-例如’ ZnS[Zn](藍色.丨和lZn.Cd)s:Ag.c](黃色丨之混 合‘ znS:Ag.Cl(藍色）和（Zn‘Cd)S:AgXh.黃色）之混合，或 ZnS系（藍色）、ZnS:Cu'A1(綠色）和（Zn，⑶s:Ag.ci(紅色）之 混合等等。 又，其他的方法則是在具有寬帶發光光譜之Zn〇:Zn 上併用粉红色濾色器‘以顯示白色發光者。 【解決課題之手段】 在用以將多種類之螢光體混合而得到白色發光螢光體 之習知形態中係以用以混合之兩方螢光體中含有硫化物之 升居多。由於該螢光體之硫碍成份（s)之分解飛散而造成 燈絲之放射特性降低.因此產生有使顯示品質劣化，且壽 命變短的問題。 且 '在用以於ZiiO : Zn螢光體上併用粉紅色濾色器之 也中’係以對應於白色發光顯示需求之顯示部份之形狀 形成濾色器，且將該濾色器以可對應於該顯示部份之形態 而定位設置於封包器上是極為煩雜。又，在該螢光顯示管 之封包器上設置濾色器之構造.係由於濾色器和發光部隔 有相當距離' 必須預先將視野角加大相當於該距離之範 圍因此.在封包器全面上設置粉紅色濾色器，就會衍生 由於該視野肖而有不願以白色顯示之部份的顔色因粉紅色 濾色器而有變化之問題. 本發叫的g的係於提伊.一種螢先體 Ϊ , --------ϊ;^*-------^ ---------'Sjf (r V·二V-..;: -W之-息^頊再域它'本頁) 46 46 經濟部智"討產局員工消費合作社印製 Λ： Β： 五、發明說明（3 ) 螢光體之使用抑制至最小限度，同時可實現長壽命及白色 發光者’特別是提供一具備有前述螢光體且以低電壓驅動 之螢光顯示管。 【解決課題之手段·】 依本發明之白色發光螢光體’其特徵在於：係用以將 藍色發光螢光想ZnGa2〇4:Li，P及黃色發光螢光體 (Zn，Cd)S:Ag，Cl相混合而形成者。 又*在依本發明之白色發光螢光體中，其中該藍色發 光螢光體ZnGa2〇4:Li,P及黃色發光營光體（ZnCd)s:AgC1 之混合比例是於約9 : 1至約7 : 3範圍内者。 又’依本發明之螢光顯示管’其特徵在於陽極係具有 用以將藍色發光螢光體ZnGa2〇4:Li，P及黃色發光榮光體 (Zn，Cd)S:Ag，Cl相混合而所形成之白色發光螢光體者D 【發明實施形態】 按本發明螢光體，係用以將藍色發光螢光體-l II l · III · I I ---- II Printed by the Consumers ’Cooperative of the Guo Guo Intellectual Property Bureau -4--2 " 5'19-'^-': Each -1- " fee. .--:. :: In the aspect, S series can be used. 5. Description of the invention (,) Therefore, in order to get white luminescence, it is used for mixing], 3 kinds of phosphors containing sulfide and Cd, and so on. An approximately white-emitting fluorescent limb-for example, 'ZnS [Zn] (blue. 丨 and lZn.Cd) s: Ag.c] (yellow 丨 mixture) znS: Ag.Cl (blue) and (Zn' Cd) S: AgXh.yellow), or ZnS (blue), ZnS: Cu'A1 (green), and (Zn, ⑶s: Ag.ci (red), etc.), and other methods It is a Zn0: Zn that has a wide-band emission spectrum and uses a pink color filter to display white light emission. [Means for solving the problem] It is used to mix various types of phosphors to obtain white light-emitting phosphors. In the conventional form, the sulfide content of the two phosphors used for mixing is mostly increased. Due to the decomposition and scattering of the sulfur hindering component (s) of the phosphor, the radiation characteristics of the filament are reduced. Therefore, the display quality is improved. Degradation and life A short problem, and 'in the case of using a pink color filter on a ZiiO: Zn phosphor' is to form a color filter in a shape corresponding to a display portion corresponding to a white light emitting display requirement, and It is extremely troublesome for the color device to be positioned and arranged on the packetizer in a form corresponding to the display portion. Moreover, the structure of setting a color filter on the packetizer of the fluorescent display tube is due to the color filter and the light-emitting part. There is a considerable distance '. The viewing angle must be increased in advance by the range corresponding to this distance. Therefore, if a pink color filter is set on the entire package, there will be parts that are unwilling to be displayed in white due to the viewing angle. The color is subject to change due to the pink filter. The g of this call is based on Ti. A kind of fluorescent precursor Ϊ, -------- ϊ; ^ * ------- ^ --------- 'Sjf (r V · 二 V-..;: -W 之-息 ^ 顼 再 域 它' this page) 46 46 Ministry of Economic Affairs " Industrial Production Bureau Staff Consumer Cooperative Cooperative Print Production Λ: Β: V. Description of the invention (3) The use of the phosphor is suppressed to a minimum, and at the same time, a long life and white light emission can be realized. Low-voltage driven fluorescent display tube. [Means to Solve the Problem ·] The white light-emitting phosphor according to the present invention is characterized in that it is used to emit blue light-emitting fluorescent light such as ZnGa204: Li, P, and yellow. The phosphor (Zn, Cd) S: Ag, Cl is mixed and formed. Also * In the white light-emitting phosphor according to the present invention, the blue light-emitting phosphor ZnGa204: Li, P and yellow The mixing ratio of ZnCds: AgC1 is within the range of about 9: 1 to about 7: 3. The 'fluorescent display tube according to the present invention' is characterized in that the anode is provided with a mixture of a blue light-emitting phosphor ZnGa204: Li, P and a yellow light-emitting phosphor (Zn, Cd) S: Ag, Cl. And the formed white light-emitting phosphor D [Inventive Embodiment] According to the present invention, the phosphor is used to convert the blue light-emitting phosphor.
ZnGa2〇4:Li，P及黃色發光螢光體（Zn，Cd)S:Ag，cl相混合， 藉發光色的混色而形成白色之螢光體。對該兩種類之螢光 體於相同電壓下比較其等發光效率，則可知道藍色發光螢 光體ZnGa2〇4:Li，P對黃色發光螢光體（Zn，Cd)s:Ag Ci之比 例為1比4左右。也就是在相同電壓下所得到的亮度，含 有Cd或S之黃色發光螢光體（Zn，Cd)s:Ag，c丨比藍色發光螢 光體ZnGa；2〇4:Li,P來得高’而可相對地減少混合的比例， 因此為佳。具體言之，在同樣的電壓下’藉用低亮度的藍 色發光螢光體ZnGa2〇4:Li，P，可以較低之比例而將含有Cd 本紙張尺度適用中國固家標革（CN_S)A4規袼（2〗[)χ 297 ) -6- 、ί ---------^-------1 ί-ν""面-fi意事項再填"本頁} 五、發明說明（4 ) 戈s的s色發光螢光體（Zn<Cd)s:Ag，cl加以混合卽可做 出白色發光螢光體。是故，可相對地減少因含有相當量之 Cd或S之螢光體之其等物質所衍生之弊害。具體言之，= 習知形態相較，可減少顯示品質之低落’ t可改善壽命的 縮減。 第1圖是顯示有關針對放射特性的時間變化.依本發 明之一實施例與習知例相比較之圖表^依本發明之白色發 光螢光體，係用以將藍色發光螢光體znGa204:L1,p及黃色 發光螢光體（211，0旬5:八8，(：1以8比2的比例混合、製造者。 習知例之白色發光螢光體，係用以將藍色發光螢光體 ZnS[Zn]和黃色發光螢光體（Zn，cd)S:Ag，Cl以6比4的比例 合、製造者。兩者都裝設在具有同一構造之螢光顯示管 之陽極上’以相同條件點燈。由所得到之資料可知：本發 明白色發光螢光體之放射殘存率較高，壽命也較長。在此， 放射殘存率係表示：將最初之放射強度設為〗00時之點燈 時間之放射強度之比率。 第2圖是用以將本發明螢光體之發光色顯示於色度圖 i chromaticity diagram )上。在第2圖中，以「_」表示 之NB是表示藍色發光螢先體ZnGa:OrLi，P '而以「匚」 表示之GY則表示黃色發光螢光體（Zn.C:d)S:Ag,Cl·在本發 明螢光顯示管中可實現白色發光螢光體之藍色發光螢光 體ZnGa:0,:L,i.P及黃色發光螢光體:Zn.Cd)S:Ag，C丨的混合 比例係自約9 : i迄至約7 : 3範圍内 在第2圏中.於NB 卜G Y間所表矛之:係表r:: 闬β將藍色發光螢先體 4 6 4 9 CK A： --- - B： 五、發明說明（5 )ZnGa204: Li, P and yellow light-emitting phosphors (Zn, Cd) S: Ag, cl are mixed to form white phosphors by mixing the emission colors. Comparing the two types of phosphors with the same luminous efficiency at the same voltage, we can know that the blue emitting phosphors ZnGa204: Li, P versus the yellow emitting phosphors (Zn, Cd) s: Ag Ci The ratio is about 1 to 4. That is, the brightness obtained under the same voltage, the yellow light-emitting phosphor (Zn, Cd) s: Ag, c 丨 containing Cd or S is higher than the blue light-emitting phosphor ZnGa; 2 04: Li, P 'It is better to reduce the mixing ratio relatively. Specifically, at the same voltage, 'borrowing low-brightness blue light-emitting phosphors ZnGa204: Li, P, can contain Cd at a lower ratio, and this paper size applies to China Gujiao Leather (CN_S) A4 Regulations (2〗 [) χ 297) -6-, ί --------- ^ ------- 1 ί-ν " " Final-fi matters and fill in " this Page} V. Description of the invention (4) The s-color light-emitting phosphor (Zn < Cd) s: Ag, cl of Gos is mixed to produce a white light-emitting phosphor. Therefore, it is possible to relatively reduce the disadvantages derived from phosphors and other substances containing a considerable amount of Cd or S. More specifically, compared with the conventional form, the decrease in display quality can be reduced 'and the life span can be reduced. Fig. 1 is a graph showing the time-dependent change in response to radiation characteristics. A chart comparing an embodiment of the present invention with a conventional example ^ The white light-emitting phosphor according to the present invention is used to convert the blue light-emitting phosphor znGa204 : L1, p and yellow light-emitting phosphor (211,0 5: 8-8, (: 1 is mixed in 8: 2 ratio, manufacturer. The white light-emitting phosphor of the conventional example is used to convert blue The luminescent phosphor ZnS [Zn] and the yellow luminescent phosphor (Zn, cd) S: Ag, Cl are combined at a ratio of 6 to 4. The two are installed in a fluorescent display tube with the same structure. The anode is lit under the same conditions. From the information obtained, it can be seen that the white light-emitting phosphor of the present invention has a high radiation residual rate and a long life. Here, the radiation residual rate indicates that the initial radiation intensity is set It is the ratio of the radiation intensity at the time of lighting at 00 o'clock. Figure 2 is used to display the luminescent color of the phosphor of the present invention on the chromaticity diagram (i chromaticity diagram). In Figure 2, "_" NB means ZnGa: OrLi, P ', which is a blue luminescent precursor, and GY, which means "匚", means yellow luminescent, (Zn.C: d) S: Ag, Cl. In the fluorescent display tube of the present invention, blue light emitting phosphors ZnGa: 0,: L, iP and yellow light emitting phosphors can be realized. : Zn.Cd) S: Ag, C 丨 The mixing ratio is in the range from about 9: i to about 7: 3. It is listed in the second section. It is shown in NB and GY: table r :: 闬 β The blue light-emitting fluorescent precursor 4 6 4 9 CK A: ----B: V. Description of the invention (5)
ZnGa2〇4:Li，P和黃色發光螢光體（Zn,Cd)S:Ag,Cl各以9 : 1、8: 2、7: 3之比例混合而製造之白色發光螢光體的色 度。 【發明的效果】 本發明係用以將2種類的螢光體相混合而得到一白色 發光螢光體者，尤其是用以將藍色發光螢光趙 ZiiGa2〇4:Li，P及黃色發光螢光體（Zn，Cd)S:Ag，Cl混合而形 成白色發光螢光體，和習知形態相比，可極力抑制為環土免 負荷物質之S及Cd之使用，結果與習知之混合製造之白 色發光螢光體相較，可明顯地實現有意義的長壽命化。 【圖面之簡單說明】 【第1圖】 係顯示各裝設有將本發明實施形態及習知例之白色# 光螢光體之螢光顯示管，其點燈時間之放射強度者。 【第2圓】 係顯示本發明之藍色和黃色發光榮光體以及用以將該 兩種混合所得到之白色發光螢光體之色度圖。 智 .¾ 產 局 消 費 合 社 (乂-^-^-之·1急事項再填、穷本頁) · I I I Γ I I I ^ --- ------Chroma of white light-emitting phosphors produced by mixing ZnGa2 04: Li, P and yellow light-emitting phosphors (Zn, Cd) S: Ag, Cl at a ratio of 9: 1, 8: 2, 7: 3, respectively . [Effect of the invention] The present invention is used for mixing two kinds of phosphors to obtain a white light-emitting phosphor, especially for blue light-emitting phosphors. ZiiGa204: Li, P, and yellow. The phosphor (Zn, Cd) S: Ag, Cl is mixed to form a white light-emitting phosphor. Compared with the conventional form, the use of S and Cd which is an unloaded substance in the earth can be greatly suppressed. The result is mixed with the conventional one. Compared with the manufactured white light-emitting phosphor, it is possible to significantly realize a meaningful long life. [Brief description of the drawing] [Figure 1] Shows the radiation intensity of the fluorescent display tubes each equipped with a white # light fluorescent body according to the embodiment and the conventional example of the present invention, and its lighting time. [Second Circle] A chromaticity diagram showing the blue and yellow light-emitting phosphors of the present invention and the white light-emitting phosphor obtained by mixing the two. Wisdom .¾ Industry Bureau Consumer Corporation (产-^-^-之 · 1 urgent refill, poor page) · I I I Γ I I I ^ --- ------