200828392 九、發明說明： 【發明所屬之技術領域】 本發明係關於照明用光源或在個人電腦之監視器、液 晶電視、汽車導航系統用之液晶顯示器等的背光等中所用 的冷陰極螢光燈，特別是有關於適合的冷陰極螢光燈用電 極。 【先前技術】 冷陰極螢光燈係如第1圖所示，在玻璃管1內，成爲 配置以端子2連接於外部的電極3於兩端的構造，於該玻 璃管1的內面塗布螢光體4，同時密封由稀有氣體與微量 水銀所構成的密封氣體5而構成。在該兩端的電極3施加 高電場而在低壓的水銀蒸氣中產生輝光放電，以該放電所 激發的水銀產生紫外線，同時藉由該紫外線激發玻璃管1 內面的螢光體4而發光。其中所用的電極係於近年正被使 用形成得到中空陰極效果的有底圓筒狀者。在該情況下， 端子2係以焊接等接著於有底圓筒狀電極3的底部。 該等構造的冷陰極燈係近年來已被用作爲液晶顯示器 的背光用光源，又，最近亦適用於液晶電視或汽車導航系 統的液晶顯示器等，其需要正愈來愈擴大。再者，在使用 於1製品之冷陰極螢燈支數或1 5吋以下的液晶顯示器等中 雖然槪略爲1支，但在大型螢幕或電視用中因不能得到必 要的輝度而使用複數支的冷陰極螢光燈。因此需要的擴大 則正激烈的進行中。 雖然是在冷陰極螢光燈中如上述需要正在擴大，但在 200828392 液晶顯示器等的性能提升要求中，對於冷陰極螢光燈及用 於其中之電極，則要求下述的事項。 (1) 由於製品薄型化及輕量化的要求，即使對冷陰極螢光燈 亦要求小徑化’同時，伴隨而來對於電極已有更上一層的 小型化之要求，並要求造形性優異。 (2) 在液晶顯示器等之中則要求低消耗電力化，並要求冷陰 極營光燈的高效率化。除了燈的輝度從與燈內徑約略成反 r- 比而增加進展到小型化之外，對於電極，則要求電子釋放 性較高的材料，即，功率函數低且陰極下降電壓低之材料 的適用。 (3 )在液晶顯示器等中變得需要1台連接於1支燈管的反相 - 器（inveter)。因此，若使冷陰極螢光燈高輝度化則可減低每 1台液晶顯示器的燈管使用數，同時可降低成本。由此觀200828392 IX. EMBODIMENT OF THE INVENTION: TECHNICAL FIELD The present invention relates to a cold cathode fluorescent lamp used for a light source for illumination or a backlight of a personal computer, a liquid crystal television, a liquid crystal display for a car navigation system, or the like. In particular, there are suitable electrodes for cold cathode fluorescent lamps. [Prior Art] As shown in Fig. 1, the cold cathode fluorescent lamp has a structure in which the electrode 3 connected to the outside by the terminal 2 is disposed at both ends in the glass tube 1, and the inner surface of the glass tube 1 is coated with fluorescent light. The body 4 is simultaneously sealed with a sealing gas 5 composed of a rare gas and a trace amount of mercury. A high electric field is applied to the electrodes 3 at both ends to generate a glow discharge in the low-pressure mercury vapor, and ultraviolet rays are generated by the mercury excited by the discharge, and the ultraviolet light is excited by the ultraviolet light on the inner surface of the glass tube 1. The electrode used therein has been used in recent years to form a bottomed cylindrical shape which has a hollow cathode effect. In this case, the terminal 2 is attached to the bottom of the bottomed cylindrical electrode 3 by welding or the like. The cold cathode lamp of these structures has been used as a backlight source for liquid crystal displays in recent years, and has recently been applied to liquid crystal displays of liquid crystal televisions or car navigation systems, and the like, and the demand thereof is increasing. In addition, although the number of the cold cathode fluorescent lamp counts used for one product or the liquid crystal display of 15 or less is less than one, in the case of a large screen or a television, a plurality of branches are used because the necessary luminance cannot be obtained. Cold cathode fluorescent lamp. Therefore, the expansion required is in progress. Although the above-mentioned needs are expanding in the cold cathode fluorescent lamp, in the performance improvement requirements of the liquid crystal display such as 200828392, the following matters are required for the cold cathode fluorescent lamp and the electrodes used therein. (1) Due to the demand for thinner and lighter products, it is required to have a smaller diameter for cold-cathode fluorescent lamps. At the same time, there has been a demand for further miniaturization of electrodes, and it is required to have excellent formability. (2) Low-power consumption is required for liquid crystal displays and the like, and high efficiency of cold cathode lamp is required. In addition to the fact that the luminance of the lamp is increased from the inverse of the inner diameter of the lamp to an approximately r-ratio, the material is required to have a higher electron emission property, that is, a material having a low power function and a low cathode drop voltage. Be applicable. (3) In a liquid crystal display or the like, one inverter is required to be connected to one lamp. Therefore, if the cold cathode fluorescent lamp is made highly bright, the number of lamps used per liquid crystal display can be reduced, and the cost can be reduced. View from this
V 點’亦對於冷陰極螢光燈要求高輝度化，對於電極則要求 陰極效果電壓低之材料的適用。 I , (4)由於液晶顯不器的製品聶命係以冷陰極營光燈壽命爲 主要因素，在冷陰極螢光燈方面則要求更進一步長的壽命 。因此電極方面則希望難以噴濺之材料的適用。 (5)在液晶顯示器等之中，由於各製造公司的競爭激烈，即 使滿足上述（1)〜（4)特性，若爲高成本亦不能成爲製品，故 希望盡可能廉價。 冷陰極螢光燈用的電極材料方面，以往，雖可使用加 工容易且廉價的鎳，但在鎳電極中，增加用來高輝度化的 電子釋放量而使放電電流上升時’鎳電極因管內的氣體離 200828392 子而噴濺，有所謂電極消耗激烈而壽命變短的問題。又， 放電電流的上升招致消耗電力的增加，因而改變成鎳，亦 要求對於陰極下降電壓較低之材料電極的適用。 又，提案有在有底圓筒狀鎳電極的內周面，設置比鎳 之功率函數低的物質層，而增加電子釋放量（例如，參照特 開平1 0- 1 44255號公報及特開2002-289 1 3 8號公報）。但是 ，在該等電極中，必須有被覆功率函數低之物質層的步驟 ，又，由於電極基材爲鎳而容易損耗，最近雖出現以加大 底層厚度而進行製品化，但未完全滿足上述的要求事項。 再者，亦嘗試適用鉬或鎢作爲功率函數低、且難以被 噴濺之高熔點的金屬於電極材料。具體而言，適用鉬作爲 電極材料的冷陰極螢光燈用電極，係藉由從鉬的壓延板鑽 孔、深撐壓而造形成有底圓筒狀，由於比鎳高熔點且放電 特性優異，而滿足上述（1)〜（4)的要求。 然而，由於鉬的壓延板容易出現各向異性或缺乏延展 性，故塑性加工困難，再者由於材料良率差，故變得高成 本，針對上述（5)則難以滿足要求。又，由於造形法的限制 而均只能得到圓筒部與底部之厚度比1 : 2者，對於形狀的 設計自由度有限制。又，對於鎢電極的適用係因鎢爲硬質 且缺乏延展性，故不可能深撐壓加工，在現實上達不到量 産。 但是，在測試試樣階段中藉由上述鉬或鎢壓延板製作 一端開口的有底圓筒形狀電極以進行放電試驗時，在一部 分的電極中看見在底部顯示被認爲是因噴濺導致之大的破 200828392 壞孔。硏究其原因時，鉬或鎢雖爲高熔點金屬，但 開口之有底圓筒形狀的電極中，難以使水銀蒸氣到 底部’而成爲稀有氣體放電而加諸電極高溫的熱履 由該高溫的熱歷程而發生所謂二次再結晶化之結晶 大化，又，在呈現該等粗大化後之結晶粒的電極中 電流上升時，判斷不論使用高熔點金屬與否，均容 因噴濺導致之材料的飛散而產生上述的破壞。 【發明内容】 因此，本發明係以提供即使在施加高溫熱歷程 下，亦防止所謂二次再結晶化之結晶粒的粗大化， 用於高輝度化或低消耗電力化的放電特性及製品壽 底圓筒狀的冷陰極螢光燈用電極爲目的。 本發明的冷陰極螢光燈用電極的特徵係以全體 Μ 〇 : 5〜8 3質量％ 、及剩餘部份爲不可避免之不純物 呈現由含有W之Mo合金相與含有Mo之W合金相 的斑狀組織，同時密度比爲8 0〜9 6 % 。 又，在本發明的冷陰極螢光燈用電極中，較佳 組成進一步包含超過0且5質量％以下的Ni，再者 組織較佳爲平均結晶粒徑爲3〜1 0 // m，最大結晶粒: // m以下。 根據本發明的冷陰極螢光燈用電極，藉由使用 的鉬及鎢，當然放電特性優異之外，成爲鉬與鎢不 金化的狀態，藉由形成細微之由含有W之Mo合金 有Mo之W合金相所構成的斑狀組織，即使在施加 在一端 達電極 歷，藉 粒的粗 ，放電 易發生 的環境 並提升 命之有 組成爲 與W， 所構成 爲全體 ，斑狀 塵爲20 高熔點 完全合 相與含 高溫熱 200828392 履歷的環境下亦抑制所謂二次再結晶化之結晶粒的粗大化 ，可防止伴隨著放電電流上升之噴濺的發生’因而可提升 電極的製品壽命。 【實施方式】 在本發明的冷陰極螢光燈用電極中，藉由使用功率函 數低且難以被噴濺之高熔點的鉬或鎢以形成不同組成的斑 狀組織，在不損及電極全體的功率函數之下，由於防止因 高溫熱歷程所致之各相的二次再結晶化，藉由燒結如下述 ί :: 的原料，形成密度比爲80〜96% 、平均結晶粒徑爲3〜10 // m 、最大結晶粒徑爲20 // m以下之細微的由含有W之Mo合 金相與含有Μ◦之W合金相所構成的斑狀組織。 . 本發明之冷陰極螢光燈用電極的全體組成爲Mo: 5〜83 質量％ 、及剩餘部份爲不可避免之不純物與W，在成爲由 耆 含有W之Mo合金相與含有Mo之W合金相所構成的斑狀 組織中，使用鉬粉末及鎢粉末作爲原料，可使用添加5〜8 3 ^ 質量％鉬粉末於鎢粉末中的原料粉末來燒結而得。此時， 在Mo量未滿5質量％的情況下，w合金相變得過多，缺乏 藉由Mo合金相之W結晶粒之粗大化抑制的效果。另外， Mo量超過83質量％的情況下，Mo合金相變得過多而缺乏 藉由W合金相之Mo結晶粒之粗大化抑制的效果。 在平均結晶粒徑超過10 // m、最大結晶粒徑超過2〇 # m 的情況下’由於各相容易普遍存在而容易發生結晶粒的二 次再結晶。該等細微結晶粒係可使用在原料方面所使用之 銷粉末及鶴粉末的粒徑爲1 〇 # m以下者而得。然而由於以 200828392 粒徑未滿1 // m者作爲原料粉末變得容易掉入模具的間隙 ’故原料粉末方面較佳爲l//m以上的粉末。在該情況下燒 結後所得的平均結晶粒徑成爲3 // m左右。如此一來平均結 晶松方面較佳爲3〜10// in的範圍。 本發明的冷陰極螢光燈用電極係可藉由燒結原料粉末 而得’在該情況下，變爲具有因原料爲金屬粉末而來的氣 孔與凹凸的表面，比較於以從壓延板之鑽孔及深撐壓所造 ^ t 形者而使表面積變大的結果，使電離效果變大。又，由於 殘留於基底中之氣孔因針栓效果抑制結晶粒的粗大化，亦 得到防止各相之二次再結晶化的效果。但是，密度比超過 9 6%時則缺乏殘留於燒結體的氣孔，而且因獨立氣孔增加 . 而缺乏導致之電離效果提升的效果，同時缺乏防止因氣孔 導致之各相的二次再結晶化的效果，而接近以從壓延板之 鑽孔及深撐壓所造形者。另外，密度比未滿80%的情況下 ，電極的機械強度顯著變弱，在之後的燈製造步驟中的處 { 理時容易發生破損。如此一來冷陰極螢光燈用電極方面， 則希望密度爲8 0〜9 6 % 。 在本發明中，藉由少量含有低熔點的鎳，並未特別降 低電極壽命與電極放電特性，並可降低燒結溫度而較佳。 鎳係以鎳粉末的形態添加於鉬粉末及/或鎢粉末而簡便。即 ，以鎳粉末的形態所添加的Ni係因較Mo或W的熔點低， 在燒結時熔融而浸潤鉬粉末及鎢粉末表面而使表面活性化 ，並促進粉末間縮徑（neck)的形成、成長。愈增加鎳粉末的 添加量則變得愈可在低溫下燒結，藉由〇. 4質量％左右的 -10- 200828392 添加’即使降低燒結溫度至145(rc左右亦變成得到密度比 80%以上的電極’可削減在燒結步驟所消耗的熱能，同時 亦可抑制高溫爐的損耗。然而，冷陰極螢光燈用電極中的 Ni量超過5質量％時，則變成Ni濃度高的部分（Ni富含相 )出現在電極表面，鉬及鎢的面積減少而降低電子釋出性。 因此’冷陰極螢光燈用電極中的Ni量必須超過〇且在5質 量％以下。 又’本發明的冷陰極螢光燈用電極雖可藉由習知公認 的方法製造’但可適當地藉由例如使用賦予以通常的壓花 凸模法所賦予於原料粉末之以上多量黏著劑等的原料來壓 花凸模成形的方法製造。以下，具體說明藉由該方法的製 造步驟。 在如上述的製造方法中，使用微小的模具，由於要求 在該模具之隙間流動由鉬粉末及鎢粉末所構成的金屬粉末 ，故較佳爲添加混練輕敲（tap)金屬粉末時之空隙率以上的 黏著劑。黏著劑的添加量方面，較佳爲40體積％以上。黏 著劑量未滿40體積％時，原料的流動性不足，變得不能進 行均勻之金屬粉末的塡充。另外，超過60體積％來添加黏 著劑時，則之後的脫黏著劑步驟變成長時間而招致製造成 本的增加。又，由於在成形體中包含過剩的黏著劑，相反 地未能進行金屬粉末的均勻塡充，同時損失在脫黏著劑步 驟及燒結步驟之形狀安定性，變得容易發生形狀不均勻。 因此，較佳爲黏結劑的添加量爲40〜60體積％ 。 該等黏結劑更佳爲由熱可塑性樹脂與蠟所構成。熱可 -11- 200828392 塑性樹脂係爲了賦予原料可塑性而被使用’可用聚苯乙烯 、聚乙烯、聚丙烯、聚乙縮醛、聚乙烯乙酸乙烯酯等。蠟 係爲了防止原料、特別是金屬粉末與模具（包含陽模及孔洞 )之間的金屬接觸而在加壓成形時實現金屬粉末的均勻流 動，同時降低脫模時的成形體與模具間的摩擦而使脫模變 容易而添加，可用石蠟、胺甲酸酯蠟、巴西棕櫚蠟等。具 有該等作用的熱可塑性樹脂與蠟係以20 : 80〜60 : 40的範 圍所構成時則成爲適當的黏著劑。 以添加混練上述黏著劑於由上述鉬粉末或/及鎢粉末 所構成的金屬粉末而得到原料Μ。藉由示於第2A〜2F圖之 模具成形該原料Μ。首先，在塡充既定量的原料Μ於模具 14之模孔14a內後（第2Α圖），如第2Β及2C圖所示，使用 形成電極形狀成形體之底部的第1陽模1 1、形成電極形狀 成形體之內徑部分的第2陽模1 2、與加壓電極形狀成形體 之開口端面的第3陽模1 3，使第1陽模1 1相對於模具14 而固定模孔1 4 a內的原料，而且押入第2陽模1 2於原料中 以加壓，同時藉由第3陽模1 3施加背壓於原料並且成形。 在脫模所得之電極形狀成形體1 5中，首先，從模具1 4上 方與電極形狀成形體15同時脫模第1陽模1 1、第2陽模 12及第3陽模13(第2D圖），其次，從電極形狀成形體15 朝向上方脫模第2陽模12(第2E圖）。其次，使第2、第3 陽模12、13上升而從電極形狀成形體15分離（第2F圖）。 還有，記載於第2B及2C圖者，雖爲藉由後方押出的成形 ，但使第1陽模1 1上升而進行前方押出亦無妨。但是，在 -12- 200828392 任何情況下均藉由第3陽模1 3施加背壓於原料並成形時， 因可均勻地成形電極形狀成形體之終端部分的高度，同時 在成形體中原料的密度變成均勻而較佳。 在上述的成形步驟中，由於必須流動原料以塡充微小 模具的間隙，原料必須加熱至在加壓前包含於黏著劑中之 熱可塑性樹脂的軟化點以上的溫度。若不加熱或即使加熱 亦未滿足熱可塑性樹脂之軟化點的溫度，則缺乏原料的流 動性，而不能均勻且緻密地塡充原料於微小模具的間隙。 又，較佳爲加熱至原料流動性爲最大之熱可塑性樹脂熔點 以上的溫度。該加熱係在模具內部設置加熱器等進行，或 在塡充原料於模具後加熱均可，亦可預先加熱以供給原料 〇 原料係以一般的壓模法處理，成爲某程度大小的造粒 粉末，亦可使用藉由飼入器（粉箱）等的粉末供給裝置的塡 充方法來供給。然而，由於用於成形作爲目標之冷陰極螢 光燈用電極的壓模的模具孔微小，難以造粒成適於一般的 壓模法中所用之粉末供給裝置的粉末大小及均勻且緻密地 塡充造粒粉末。另外，造粒粉末的粒徑變小時，則使得原 料粉末的流動性降低，難以調整成適當大小的造粒粉末。 因此原料係如第2A圖所示，較佳爲聚集相當於1次塡充量 的量作爲裝入模具孔之1個粒錠，而以粒錠單位來供給原 料。又在以粒錠單位供給原料的情況下，由於即使預先加 熱原料亦容易供給，亦因此方面而佳。 如上述所得的電極形狀成形體係因包含4 0〜6 0體積％ -13- 200828392 的黏著劑，爲了除去該黏著劑而加熱電極形狀成形體至黏 著劑成分的熱分解溫度以進行脫黏著劑步驟。黏著劑雖由 熱可塑性樹脂與蠟所構成，但由於熱可塑性樹脂及蠟之熱 分解溫度附近的升溫速度快時，則熱可塑性樹脂及蠟激烈 地氣化而膨脹，引起成形體的形狀不均勻，故至少在熱可 塑性樹脂及蠟之熱分解溫度附近的升溫必須緩慢進行。由 此觀點來看，脫黏著劑步驟較佳爲當保持於蠟升華溫度附 近時而除去黏著劑成分中的蠟成分作爲第1階段後，再次 保持於熱可塑性樹脂之熱分解溫度附近以除去熱可塑性樹 脂成分作爲第2階段，成爲2階段的加熱保持步驟。又， 由於隨著熱分解而慢慢地產生氣體，故較佳爲熱可塑性樹 脂及蠟配合熱分解溫度不同的複數種類來使用。 在進行上述黏結劑去除後的電極形狀成形體中，金屬 粉末同類間尙未擴散而爲無金屬鍵結的狀態，並極爲脆弱 。因此爲了使金屬粉末同類間金屬擴散鍵結而進行燒結。 燒結溫度係以1 500 °C以上爲適當。還有，在含有Νι的樣態 中，燒結溫度較佳爲145(TC以上。在燒結步驟中，由於使 用如上述細微且凹凸少者作爲金屬粉末，故金屬粉末的接 觸面積大，因此容易進行藉由燒結的緻密化，以上述溫度 得到密度比爲80%以上的緻密燒結體。然而，燒結溫度低 於上述溫度範圍下限時，不僅未進行藉由燒結的緻密化， 並變得不能得到低密度且強度低的燒結體。另外，燒結溫 度超過1 800°C時，由於高溫爐的損耗變激烈，故燒結溫度 上限則希望爲上述溫度。由於燒結氛圍氣體含有氧氣或碳 -14- 200828392 時，則金屬粉末表面氧化或碳化而難以進行燒結，含有氫 氣時則鉬粉末吸藏氫氣而膨脹，故必須使用不含有彼等的 非活性氣體或真空氛圍氣體（減壓氛圍氣體）。又在減壓氛 圍氣體中，在壓力爲1 MPa以上的減壓氛圍圍氣體的情況下 ，必須導入非活性氣體作爲承載氣體以避免上述不適合點 【實施例】 預備示於表1之粒徑的鉬粉末、鎢粉末及鎳粉末。又 ，預備以4 : 6之比例混合聚乙縮醛（軟化點：1 1 0 °C、熔點 :180°C )與石蠟（軟化點：39°C、熔點：61°C )者作爲黏著劑 。以示於表1之比例配合、混練彼等以調製原料，將其形 成粒錠。加熱該粒錠至200 °C並供給於預先加熱至14(TC的 模具來進行壓粉成形，冷卻至40°C後，進行脫模以製作電 極形狀壓粉體。加熱所得之壓粉體直到25(TC並保持60分 鐘後，進一步升溫而在450 °C下保持60〜120分鐘以進行脫 黏著劑。其次，在氬氣氛圍氣體中、在示於表1的溫度下 保持60分鐘以進行燒結。針對所得的電極形狀成形體，測 定藉由ΕΡΜΑ的元素分析、密度比及藉由截面光學顯微鏡 攝影的平均結晶粒徑。又，使用所得之電極形狀成形體來 組裝冷陰極螢光燈，在電極間距離：100mm、所密封之氬 氣壓力：100 torr之下，進行用於得到放電電流6mA所需 要之放電電壓的測定。再者，使用電極形狀成形體並在 0.07torr的氬氣壓力下，形成放電電壓DC 3kV、放電電流 10mA、電極間距離50mm而測量持續5小時噴濺放電賦予 -15- 200828392 於電極後的噴濺量（損耗量），以在鉬1 00%的電極情況下爲 1 00的指數來評估。還有噴濺指數愈低則愈不易被噴濺而顯 示良好的電極的指數。針對該等結果則合倂示於表1。 表1 試樣 編號 添加比^ 例質量％ 燒 結 溫 度 °C 組成質1 1% 評估 鎢粉末 粒徑 βνη 鉬粉 末 粒徑 //m tm 分末 粒徑 lim W Mo C Ni 密度 比 % 最大結晶粒徑 /zm 放電 電壓 V 噴濺 指數 01 剩餘部份 3 0.0 3 1800 剩餘部份 0.00 0.10 58 2 470 105 02 剩餘部份 3 2.7 3 1800 剩餘部份 2.73 0.10 65 3 438 85 03 剩餘部份 3 5.6 3 1800 剩餘部份 5.60 0.10 82 4 409 79 04 剩餘部份 3 11.8 3 1800 剩餘部份 11.77 0.10 87 9 404 75 05 剩餘部份 3 34.8 3 1800 剩餘部份 34.78 0.10 91 7 401 72 06 剩餘部份 3 55.5 3 1800 剩餘部份 55.42 0.10 91 7 405 75 07 剩餘部份 3 82.8 3 1800 剩餘部份 82.69 0.10 91 10 413 82 08 剩餘部份 3 91.0 3 1800 剩餘部份 90.94 0.10 92 15 430 97 09 剩餘部份 3 100.0 3 1800 剩餘部份 99.90 0.10 92 30 447 100 10 剩餘部份 1 34.8 1 1800 剩餘部份 34.78 0.10 91 6 399 72 05 剩餘部份 3 34.8 3 1800 剩餘部份 34.78 0.10 91 7 401 72 11 剩餘部份 5 34.8 5 1800 剩餘部份 34.78 0.10 91 9 403 73 12 剩餘部份 10 34.8 10 1800 剩餘部份 34.78 0.10 85 20 407 82 13 剩餘部份 15 34.8 15 1800 剩餘部份 34.78 0.10 80 23 411 90 05 剩餘部份 3 34.8 3 0.0 1800 剩餘部份 34.78 0.10 0.00 91 7 401 72 14 剩餘部份 3 34.8 3 0.5 3 1450 剩餘部份 34.60 0.10 0.50 89 7 400 72 15 剩餘部份 3 34.8 3 1.0 3 1450 剩餘部份 34.43 0.10 1.00 91 7 401 73 _16 剩餘部份 3 34.8 3 3.0 3 1450 剩餘部份 33.73 0.10 3.00 93 8 405 73 17 剩餘部份 3 34.8 3 5.0 3 1450 剩餘部份 33.04 0.10 5.00 95 10 410 80 _18 剩餘部份 3 34.8 3 6.0 3 1450 剩餘部份 32.69 0.10 6.00 97 15 460 108 19 剩餘部份 3 34.8 3 1450 剩餘部份 34.78 0.10 71 4 451 81 20 剩餘部份 3 34.8 3 1500 剩餘部份 34.78 0.10 80 4 414 75 05 剩餘部份 3 34.8 3 1800 剩餘部份 34.78 0.10 91 7 401 72 .21 剩餘部份 3 34.8 3 1900 剩餘部份 34.78 0.10 95 12 403 74 J2 剩餘部份 3 34.8 3 2200 剩餘部份 34.78 0.10 96 20 417 81 23 剩餘部份 3 34.8 3 2500 剩餘部份 34.78 0.10 98 50 435 90 再者，對於所得之電極形狀成形體的試樣編號05及 09，在贏氣氛圍氣體中、1400°C下保持60〜120分鐘以進行 結晶粒成長試驗。在第3A、3B圖及第4A、4B圖顯示彼等 截面光學顯微鏡照片。還有，第3A圖、第4A圖爲結晶粒 -16- 200828392 成長試驗前，第3 B圖、第4B圖爲結晶粒成長試驗後。 表1的試樣編號01〜09的試樣爲硏究全體組成中之Mo 含有量之影響的範例。在Mo含有量未滿5質量％的試樣編 號01及0 2的試樣中’密度比爲6 5 %以下，未形成本發明 中所規定的斑狀組織’又，放電電壓亦爲超過430V的大値 ，噴濺指數亦爲如85左右以上的高値。另外，在mo含有 量超過8 3質量％之試樣0 8及〇 9中，平均結晶粒徑成爲 1 5 // m以上，未形成本發明所規定的斑狀組織，放電電壓 亦爲超過430V的大値，噴濺指數亦爲如90左右以上的高 値。再者，相對於由第3 A、3 B圖得知，在本發明的試樣編 號05中，未見結晶粒徑的成長，由第4A、4B圖得知，在 試樣編號0 9中，觀測到結晶粒徑的成長。由該等結果確認 ，全體組成中之Μ 〇含有量爲5〜8 3質量％ ，則得到良好的 放電特性，更抑制結晶粒徑的粗大化。又，在此範圍中爲 了得到6mA之放電電流的放電電壓則顯示如4〇〇〜41〇ν左 右之低的良好値，噴濺指數亦顯示8 0左右以下的良好値。 表1之試樣編號0 5及1 0〜1 3的試樣爲硏究鉬粉末及鎢 粉末粒徑之影響的範例。相對於粒徑爲丨〇 # m以下之試樣 編號05及1 〇〜1 2的試樣中，密度比、最大結晶粒徑、放電 電壓及噴濺指數爲良好者，在粒徑超過丨〇 # m的試樣編號 1 3中’最大結晶粒徑大如23 a m，未得到細微的斑狀組織 ’放電電壓亦變成如4 1 1 V的大値，而且噴濺指數亦顯示成 爲如90的高値。由該等結果，確認鉬粉末及鎢粉末的粒徑 爲1 0 // m以下，則得到細微的斑狀組織，並發揮良好的放 -17- 200828392 電特性。又，在該範圍中顯示放電電壓爲400V左右、噴濺 指數低如8 0左右以下的良好値。 表1之試樣編號05及14〜18的試樣爲硏究全體組成中 之Ni含有量之影響的範例。相對於在Ni含有量爲5.0質 量％以下的試樣編號1 4〜1 7的試樣中，即使降低燒結溫度 至1 45 0 °C，密度比、最大結晶粒徑、放電電壓及噴濺指數 均良好’在Ni含有量超過5.0質量％之試樣編號18的試 丰永中’挖度比爲9 7 % ’最大結晶粒徑成爲1 5 // m，在斑狀 組織中形成富含鎳相，放電電壓爲460V、噴濺指數爲如108 的筒値。由該等結果確認，在全體組成中之Ni含有量超過 0而爲5 · 0質量％以下的情況下，即使降低燒結溫度，亦得 到細微的斑狀組織，並發揮良好的放電特性。又，在該範 圍中用於得到6mA之放電電流的放電電壓爲400V左右， 噴濺指數顯示如8 0左右以下之低的良好値。 表1的試樣編號05及19〜23的試樣爲硏究密度比之影 響的範例。在燒結溫度爲145(TC的試樣編號19中，密度比 爲7 1% ’放電電壓爲如450V的大値。另外，在燒結溫度 超過1 45 0 °C的試樣編號〇5、20〜22中，密度比成爲80〜96 % ’放電電壓顯示4〇〇〜420V左右的良好値而噴濺指數亦顯 示80左右以下的良好値。又在試樣編號23中，密度比爲 98% ’最大結晶粒徑粗大化成5〇//m，放電電壓爲435v、 噴灘指數爲如90的大値。由該等結果確認，在密度比爲 8 0〜96%的範圍內，發揮良好的放電特性。 【圖式簡單說明】 -18- 200828392 第1圖係顯示冷陰極螢光燈之構造的截面圖。 第2A〜2F圖係顯示適當地製造本發明之冷陰極螢光燈 用電極的塡充步驟、加壓成形步驟及脫模步驟的截面圖。 第3A及3B圖係本發明之冷陰極螢光燈用電極的截面 光學顯微鏡照片，第3A圖爲結晶粒成長試驗前，第3B圖 爲結晶粒成長試驗後。The V point ' also requires high luminance for the cold cathode fluorescent lamp, and for the electrode, the material with a low cathode effect voltage is required. I, (4) Because the product of the liquid crystal display device is based on the life of the cold cathode lamp, the cold cathode fluorescent lamp requires a longer life. Therefore, the electrode is desirable for the application of materials that are difficult to spray. (5) In a liquid crystal display or the like, since the competition among the various manufacturing companies is fierce, even if the above characteristics (1) to (4) are satisfied, the product cannot be a product at a high cost, and therefore it is desirable to be as inexpensive as possible. In the electrode material for a cold cathode fluorescent lamp, conventionally, nickel which is easy to process and inexpensive can be used. However, in the nickel electrode, the amount of electron emission for high luminance is increased and the discharge current is increased. The gas inside is splashed from 200828392, and there is a problem that the electrode consumption is intense and the life is shortened. Further, an increase in the discharge current causes an increase in power consumption, and thus it is changed to nickel, and application of a material electrode having a lower cathode drop voltage is also required. Further, it has been proposed to provide a material layer having a lower power function than nickel on the inner peripheral surface of the bottomed cylindrical nickel electrode, and to increase the amount of electron emission (for example, see Japanese Patent Laid-Open No. Hei No. Hei. -289 1 3 No. 8 bulletin). However, in these electrodes, it is necessary to have a step of coating a material layer having a low power function, and the electrode substrate is easily depleted due to nickel. Recently, productization has been carried out to increase the thickness of the underlayer, but the above is not completely satisfied. Requirements. Further, it has been attempted to apply molybdenum or tungsten as a metal material having a low melting point and a high melting point metal which is difficult to be sputtered. Specifically, an electrode for a cold cathode fluorescent lamp using molybdenum as an electrode material is formed into a bottomed cylindrical shape by drilling and deep-pressing from a rolled plate of molybdenum, and has a high melting point and excellent discharge characteristics. And meet the requirements of (1) to (4) above. However, since the rolled sheet of molybdenum is prone to anisotropy or lack of ductility, plastic working is difficult, and further, since the material yield is poor, it becomes high in cost, and it is difficult to satisfy the requirements for the above (5). Further, since the thickness ratio of the cylindrical portion to the bottom portion is only 1:2 due to the limitation of the forming method, there is a limit to the degree of freedom in designing the shape. Moreover, the application of the tungsten electrode is due to the fact that tungsten is hard and lacks ductility, so that it is impossible to carry out deep press processing, which is not practical in mass production. However, in the test sample stage, a bottomed cylindrical electrode having an opening at one end is formed by the above-mentioned molybdenum or tungsten rolled plate to perform a discharge test, and the display at the bottom of a part of the electrode is considered to be caused by the splash. Big broken 200828392 bad hole. When the reason is high, the molybdenum or tungsten is a high-melting-point metal, but in the electrode having a bottomed cylindrical shape, it is difficult to make the mercury vapor to the bottom portion, and the rare gas is discharged and the electrode is heated at a high temperature. In the thermal history, the crystallization of the so-called secondary recrystallization occurs, and when the current rises in the electrode of the crystal grain after the coarsening, it is judged whether or not the high melting point metal is used or not. The scattering of the material causes the above-mentioned damage. SUMMARY OF THE INVENTION Accordingly, the present invention provides a discharge characteristic and a product for preventing high-densification or low power consumption, in order to prevent coarsening of crystal grains of so-called secondary recrystallization even under application of a high-temperature heat history. The purpose is to use an electrode for a cylindrical cold cathode fluorescent lamp. The electrode for a cold cathode fluorescent lamp of the present invention is characterized in that the entire Μ 〇: 5 to 83% by mass, and the remaining portion is an unavoidable impurity, which is represented by a Mo alloy phase containing W and a W alloy phase containing Mo. The plaque tissue, while the density ratio is 8 0~9 6 %. Further, in the electrode for a cold cathode fluorescent lamp of the present invention, it is preferable that the composition further contains more than 0 and 5% by mass or less of Ni, and further preferably the structure has an average crystal grain size of from 3 to 10 // m, max. Crystal grain: // m or less. According to the electrode for a cold cathode fluorescent lamp of the present invention, molybdenum and tungsten are used, and of course, the discharge characteristics are excellent, and molybdenum and tungsten are not golded, and Mo is formed by a Mo alloy containing W. The plaque-like structure formed by the alloy phase of W is applied to the electrode at the one end, and the environment of the granules is thick and the discharge is easy to occur, and the composition of the composition is W and the whole is formed. In the environment where the high melting point is completely combined and the high temperature heat is included in the history of 200828392, the coarsening of the so-called secondary recrystallization crystal grains is suppressed, and the occurrence of the splash accompanying the increase of the discharge current can be prevented. . [Embodiment] In the electrode for a cold cathode fluorescent lamp of the present invention, by using a high melting point molybdenum or tungsten having a low power function and being difficult to be sputtered, a plaque structure having a different composition is formed, without impairing the entire electrode. Under the power function, by preventing the secondary recrystallization of each phase due to the high temperature thermal history, a density ratio of 80 to 96% and an average crystal grain size are formed by sintering a raw material such as the following ί :: 3 to 10 // m, a fine crystal grain having a maximum crystal grain size of 20 // m or less, and a fine structure composed of a Mo alloy phase containing W and a W alloy phase containing niobium. The overall composition of the electrode for a cold cathode fluorescent lamp of the present invention is Mo: 5 to 83% by mass, and the remainder is an unavoidable impurity and W, and is a Mo alloy phase containing W and containing Mo. In the plaque structure composed of the alloy phase, molybdenum powder and tungsten powder are used as a raw material, and it can be obtained by sintering a raw material powder in which a 5 to 8 3 % by mass of molybdenum powder is added to the tungsten powder. At this time, when the amount of Mo is less than 5% by mass, the w alloy phase becomes excessive, and the effect of suppressing the coarsening of the W crystal grains by the Mo alloy phase is lacking. When the amount of Mo exceeds 83% by mass, the Mo alloy phase becomes excessive and the effect of suppressing coarsening of Mo crystal grains by the W alloy phase is lacking. In the case where the average crystal grain size exceeds 10 // m and the maximum crystal grain size exceeds 2 〇 # m, the secondary recrystallization of the crystal grains is liable to occur because the phases are easily ubiquitous. These fine crystal grains can be obtained by using the pin powder and the crane powder used in the raw material to have a particle diameter of 1 〇 # m or less. However, since the raw material powder having a particle diameter of less than 1 // m in 200828392 is likely to fall into the gap of the mold, the raw material powder is preferably a powder of 1/m or more. In this case, the average crystal grain size obtained after sintering is about 3 // m. As a result, the average crystallinity is preferably in the range of 3 to 10//in. The electrode for a cold cathode fluorescent lamp of the present invention can be obtained by sintering a raw material powder. In this case, it is a surface having pores and irregularities due to the metal powder of the raw material, and is compared with a drill from a rolled sheet. As a result of the hole and the deep pressure build-up, the surface area is increased, and the ionization effect is increased. Further, since the pores remaining in the substrate suppress the coarsening of the crystal grains by the pinning effect, the effect of preventing secondary recrystallization of each phase is obtained. However, when the density ratio exceeds 9 6%, the pores remaining in the sintered body are lacking, and the independent pores are increased, and the effect of the ionization effect is increased, and the secondary recrystallization of the phases due to the pores is prevented. The effect is close to the shape formed by the drilling of the rolled plate and the deep pressure. Further, in the case where the density ratio is less than 80%, the mechanical strength of the electrode is remarkably weak, and it is likely to be damaged at the time of the subsequent lamp manufacturing step. As for the electrode for a cold cathode fluorescent lamp, the density is desirably 80 to 96%. In the present invention, by a small amount of nickel having a low melting point, the electrode life and electrode discharge characteristics are not particularly lowered, and the sintering temperature can be lowered, which is preferable. Nickel is easily added to the molybdenum powder and/or tungsten powder in the form of nickel powder. In other words, Ni which is added in the form of a nickel powder has a lower melting point than Mo or W, and melts during sintering to wet the surface of the molybdenum powder and the tungsten powder to activate the surface, thereby promoting the formation of a neck between the powders. ,growing up. The more the amount of the nickel powder added, the more the sintering can be performed at a low temperature, and the amount of -10-. 4% by mass is added to the -10-200828392. Even if the sintering temperature is lowered to 145 (about rc, the density ratio is 80% or more). The electrode 'can reduce the heat energy consumed in the sintering step and suppress the loss of the high-temperature furnace. However, when the amount of Ni in the electrode for the cold cathode fluorescent lamp exceeds 5% by mass, the portion having a high Ni concentration (Ni rich) The phase contains the surface of the electrode, and the area of molybdenum and tungsten is reduced to reduce the electron emission. Therefore, the amount of Ni in the electrode for cold cathode fluorescent lamps must exceed 〇 and be less than 5% by mass. The electrode for a cathode fluorescent lamp can be produced by a conventionally recognized method, but can be suitably embossed by, for example, using a raw material which imparts a large amount of the adhesive or the like imparted to the raw material powder by a usual embossing punch method. The method of forming a punch is used. Hereinafter, the manufacturing process by the method will be specifically described. In the manufacturing method as described above, a minute mold is used, since molybdenum powder and tungsten are required to flow between the gaps of the mold. The metal powder which is formed at the end is preferably an adhesive having a porosity of at least 3 times when the metal powder is tapped and kneaded. The amount of the adhesive to be added is preferably 40% by volume or more. The adhesive dose is less than 40% by volume. In the case of %, the fluidity of the raw material is insufficient, and the uniform metal powder cannot be filled. When the adhesive is added in an amount of more than 60% by volume, the subsequent debonding step becomes long and the manufacturing cost increases. Further, since the molded article contains an excessive amount of the adhesive, the uniform filling of the metal powder is not performed, and the shape stability in the debonding step and the sintering step is lost, and the shape unevenness is likely to occur. Preferably, the amount of the binder added is 40 to 60% by volume. The binder is preferably composed of a thermoplastic resin and a wax. Hot -11-200828392 Plastic resin is used to impart plasticity to the raw material. Styrene, polyethylene, polypropylene, polyacetal, polyethylene vinyl acetate, etc. Wax is used to prevent raw materials, especially metal powders and molds (including The metal contact between the mold and the hole) realizes uniform flow of the metal powder during press forming, and at the same time reduces the friction between the molded body and the mold during demolding, thereby facilitating the release of the mold, and using paraffin or uric acid. Ester wax, carnauba wax, etc. When the thermoplastic resin having such an effect and the wax system are in the range of 20:80 to 60:40, it is an appropriate adhesive. The above-mentioned adhesive is added and kneaded by the above molybdenum powder. Or a metal powder composed of tungsten powder to obtain a raw material crucible. The raw material crucible is formed by a mold shown in Figures 2A to 2F. First, after filling a predetermined amount of raw material into the die hole 14a of the mold 14, (Fig. 2), as shown in Figs. 2 and 2C, the first male mold 1 1 forming the bottom of the electrode-shaped formed body, and the second male mold 1 2 forming the inner diameter portion of the electrode-shaped formed body are used. The third male mold 13 of the open end surface of the electrode-shaped molded body is pressed, and the first male mold 11 is fixed to the raw material in the die hole 14a with respect to the mold 14, and is pushed into the second male mold 12 in the raw material. Pressurizing while applying back pressure to the raw material by the third male mold 13 shape. In the electrode-shaped molded body 15 obtained by demolding, first, the first male mold 1 1 , the second male mold 12 , and the third male mold 13 are simultaneously released from the upper side of the mold 14 and the electrode-shaped molded body 15 (second 2D) In the second embodiment, the second male mold 12 is removed from the electrode-shaped molded body 15 (Fig. 2E). Then, the second and third male molds 12 and 13 are raised and separated from the electrode-shaped molded body 15 (second F diagram). Further, in the case of the second and second embodiments, the first male mold 11 is raised and the front is pushed forward. However, in any case, when the backing material is applied to the raw material by the third male mold 13 in the case of -12-200828392, the height of the terminal portion of the electrode-shaped formed body can be uniformly formed, and the raw material in the formed body is simultaneously formed. The density becomes uniform and preferred. In the above-described forming step, since it is necessary to flow the raw material to fill the gap of the micro mold, the raw material must be heated to a temperature higher than the softening point of the thermoplastic resin contained in the adhesive before pressurization. If the temperature of the softening point of the thermoplastic resin is not satisfied even if it is not heated or heated, the flowability of the raw material is lacking, and the gap of the raw material in the minute mold cannot be uniformly and densely filled. Further, it is preferably heated to a temperature equal to or higher than the melting point of the thermoplastic resin having the largest fluidity of the raw material. The heating may be performed by providing a heater or the like inside the mold, or may be heated after the raw material is filled in the mold, or may be heated in advance to supply the raw material, and the raw material is treated by a general compression molding method to become a granulated powder of a certain size. It can also be supplied by a charging method of a powder supply device such as a feeder (powder). However, since the die hole for molding the target electrode for the cold cathode fluorescent lamp is small, it is difficult to granulate into a powder size suitable for the powder supply device used in the general compression molding method and to uniformly and densely knead. Filled with granulated powder. Further, when the particle diameter of the granulated powder is small, the fluidity of the raw material powder is lowered, and it is difficult to adjust the granulated powder of an appropriate size. Therefore, as shown in Fig. 2A, it is preferable that the raw material is aggregated in an amount equivalent to one charge to be used as one pellet to be charged into the die hole, and the raw material is supplied in units of pellets. Further, in the case where the raw material is supplied in units of pellets, it is preferable because it is easy to supply even if the raw material is heated in advance. The electrode shape forming system obtained as described above contains a binder of 40 to 60% by volume of -13 to 200828392, and heats the electrode-shaped molded body to the thermal decomposition temperature of the adhesive component to remove the adhesive to carry out the debonding step. . The adhesive is composed of a thermoplastic resin and a wax. However, when the temperature rise rate near the thermal decomposition temperature of the thermoplastic resin and the wax is fast, the thermoplastic resin and the wax are violently vaporized and expanded, causing uneven shape of the molded body. Therefore, at least the temperature rise in the vicinity of the thermal decomposition temperature of the thermoplastic resin and the wax must be slowly performed. From this point of view, the debonding step preferably removes the wax component in the adhesive component as the first stage while remaining at the wax sublimation temperature, and then remains in the vicinity of the thermal decomposition temperature of the thermoplastic resin to remove heat. The plastic resin component is a second-stage heat retention step as the second stage. Further, since the gas is slowly generated by thermal decomposition, it is preferred to use the thermoplastic resin and the wax in combination with a plurality of types having different thermal decomposition temperatures. In the electrode-shaped molded body after the removal of the above-mentioned binder, the metal powder is not diffused and is in a state of no metal bond, and is extremely weak. Therefore, sintering is performed in order to cause the metal powder to be diffusion-bonded. The sintering temperature is suitably 1 500 ° C or higher. Further, in the state in which Νι is contained, the sintering temperature is preferably 145 (TC or more. In the sintering step, since the fine particles and the unevenness are used as the metal powder, the contact area of the metal powder is large, so that it is easy to carry out. By the densification of sintering, a dense sintered body having a density ratio of 80% or more is obtained at the above temperature. However, when the sintering temperature is lower than the lower limit of the above temperature range, not only the densification by sintering but also the low density cannot be obtained. In addition, when the sintering temperature exceeds 1 800 ° C, the loss of the high-temperature furnace becomes intense, so the upper limit of the sintering temperature is desirably the above temperature. Since the sintering atmosphere contains oxygen or carbon-14-200828392 When the surface of the metal powder is oxidized or carbonized, it is difficult to perform sintering. When the hydrogen gas contains hydrogen gas, the molybdenum powder occludes hydrogen gas and swells. Therefore, it is necessary to use an inert gas or a vacuum atmosphere gas (reduced atmosphere gas) which does not contain them. In a pressurized atmosphere, in the case of a decompression atmosphere containing a pressure of 1 MPa or more, an inert gas must be introduced as a carrier gas. To avoid the above-mentioned unsuitable points [Examples] Molybdenum powder, tungsten powder and nickel powder having the particle diameters shown in Table 1 were prepared. Further, it was prepared to mix polyacetal in a ratio of 4:6 (softening point: 1 1 0 °C) , melting point: 180 ° C) and paraffin (softening point: 39 ° C, melting point: 61 ° C) as an adhesive. The ingredients shown in Table 1 were mixed and kneaded to prepare raw materials to form pellets. The pellet was heated to 200 ° C and supplied to a mold previously heated to 14 (TC) for powder molding, and after cooling to 40 ° C, demolding was performed to prepare an electrode-shaped compact. The obtained compact was heated until 25 (TC was held for 60 minutes, and further heated, and kept at 450 ° C for 60 to 120 minutes to carry out debonding agent. Secondly, it was kept in an argon atmosphere at a temperature shown in Table 1 for 60 minutes. The obtained electrode-shaped molded body was measured for elemental analysis by ruthenium, density ratio, and average crystal grain size by cross-sectional optical microscopy. Further, the obtained electrode-shaped molded body was used to assemble a cold cathode fluorescent lamp. Distance between electrodes: 100mm, sealed Argon pressure: 100 torr, the discharge voltage required for obtaining a discharge current of 6 mA was measured. Further, an electrode shape molded body was used and a discharge voltage of DC 3 kV and a discharge current were formed under an argon pressure of 0.07 torr. 10 mA, distance between electrodes is 50 mm and measurement is continued for 5 hours. Splash discharge is given to -15-200828392 The amount of splatter (loss) after the electrode is evaluated by an index of 100 Å in the case of an electrode of 100% molybdenum. The lower the splatter index, the more difficult it is to be splashed and the index of the electrode is good. For these results, it is shown in Table 1. Table 1 Sample number addition ratio ^ Example mass % Sintering temperature °C Composition 1 1% Evaluation of tungsten powder particle size βνη Molybdenum powder particle size / / m tm Partial particle size lim W Mo C Ni Density ratio % Maximum crystal grain size / zm Discharge voltage V Splash index 01 Remaining part 3 0.0 3 1800 Remaining part 0.00 0.10 58 2 470 105 02 Remaining part 3 2.7 3 1800 Remaining part 2.73 0.10 65 3 438 85 03 Remaining part 3 5.6 3 1800 Remaining part 5.60 0.10 82 4 409 79 04 Remaining part 3 11.8 3 1800 Remaining unit 11.77 0.10 87 9 404 75 05 Remaining part 3 34.8 3 1800 Remaining part 34.78 0.10 91 7 401 72 06 Remaining part 3 55.5 3 1800 Remaining part 55.42 0.10 91 7 405 75 07 Remaining part 3 82.8 3 1800 Remaining Part 82.69 0.10 91 10 413 82 08 Remaining part 3 91.0 3 1800 Remaining part 90.94 0.10 92 15 430 97 09 Remaining part 3 100.0 3 1800 Remaining part 99.90 0.10 92 30 447 100 10 Remaining part 1 34.8 1 1800 Remaining part 34.78 0.10 91 6 399 72 05 Remaining part 3 34.8 3 1800 Remaining part 34.78 0.10 91 7 401 72 11 Remaining part 5 34.8 5 1800 Remaining part 34.78 0.10 91 9 403 73 12 Remaining part 10 34.8 10 1800 Remaining part 34.78 0.10 85 20 407 82 13 Remaining part 15 34.8 15 1800 Remaining part 34.78 0.10 80 23 411 90 05 Remaining part 3 34.8 3 0.0 1800 Remaining part 34.78 0.10 0.00 91 7 401 72 14 Remaining part 3 34.8 3 0.5 3 1450 Remaining part 34.60 0.10 0.50 89 7 400 72 15 Remaining part 3 34.8 3 1.0 3 1450 Remaining part 34.43 0.10 1.00 91 7 401 73 _16 Remaining part 3 34.8 3 3 .0 3 1450 Remaining part 33.73 0.10 3.00 93 8 405 73 17 Remaining part 3 34.8 3 5.0 3 1450 Remaining part 33.04 0.10 5.00 95 10 410 80 _18 Remaining part 3 34.8 3 6.0 3 1450 Remaining part 32.69 0.10 6.00 97 15 460 108 19 Remaining part 3 34.8 3 1450 Remaining part 34.78 0.10 71 4 451 81 20 Remaining part 3 34.8 3 1500 Remaining part 34.78 0.10 80 4 414 75 05 Remaining part 3 34.8 3 1800 Remaining part 34.78 0.10 91 7 401 72 .21 Remaining part 3 34.8 3 1900 Remaining part 34.78 0.10 95 12 403 74 J2 Remaining part 3 34.8 3 2200 Remaining part 34.78 0.10 96 20 417 81 23 Remaining part 3 34.8 3 2500 Remaining part 34.78 0.10 98 50 435 90 Further, the sample numbers 05 and 09 of the obtained electrode-shaped molded body were held at 1400 ° C for 60 to 120 minutes in a winning atmosphere gas to carry out a crystal grain growth test. The cross-sectional optical micrographs are shown in Figures 3A and 3B and Figures 4A and 4B. Further, Fig. 3A and Fig. 4A show crystal grains -16 - 200828392 before the growth test, and Figs. 3B and 4B show the crystal grain growth test. The samples of sample numbers 01 to 09 in Table 1 are examples in which the influence of the Mo content in the entire composition was investigated. In the samples of sample numbers 01 and 0 2 having a Mo content of less than 5% by mass, the 'density ratio was 65 % or less, and the plaque structure defined in the present invention was not formed', and the discharge voltage was also more than 430 V. The big cockroach, the splatter index is also a sorghum like 85 or more. Further, in the samples 0 8 and 〇9 in which the mo content exceeds 83% by mass, the average crystal grain size is 1 5 // m or more, the plaque structure defined by the present invention is not formed, and the discharge voltage is more than 430 V. The big cockroach, the splatter index is also a sorghum like 90 or more. Further, as seen from the third and third graphs, in the sample No. 05 of the present invention, the growth of the crystal grain size was not observed, and it was found in the fourth and fourth graphs, in the sample No. 0 9 The growth of the crystal grain size was observed. From these results, it was confirmed that the content of ruthenium in the entire composition was 5 to 83% by mass, and good discharge characteristics were obtained, and coarsening of the crystal grain size was further suppressed. Further, in this range, in order to obtain a discharge voltage of a discharge current of 6 mA, a good enthalpy such as 4 〇〇 to 41 〇 ν is displayed, and the splatter index also shows a good enthalpy of about 80 Å or less. The sample Nos. 0 5 and 10 0 to 13 of Table 1 are examples of the influence of the particle size of the molybdenum powder and the tungsten powder. In the samples of sample No. 05 and 1 〇~1 2 having a particle diameter of 丨〇# m or less, the density ratio, the maximum crystal grain size, the discharge voltage, and the sputtering index are good, and the particle size exceeds 丨〇. #m的sample No. 1 3 'The maximum crystal grain size is as large as 23 am, no fine plaque structure is obtained. The discharge voltage also becomes a large 如 such as 4 1 1 V, and the splatter index is also shown to be 90. Sorghum. From these results, it was confirmed that the particle diameter of the molybdenum powder and the tungsten powder was 10 // m or less, and a fine punctate structure was obtained, and the electrical characteristics of the -17-200828392 were exhibited. Further, in this range, it is shown that the discharge voltage is about 400 V and the sputtering index is as low as about 80 or less. The samples of sample Nos. 05 and 14 to 18 in Table 1 are examples in which the influence of the Ni content in the entire composition was investigated. The density ratio, the maximum crystal grain size, the discharge voltage, and the splatter index are even lower than the sintering temperature to 1 450 ° C in the sample of sample Nos. 14 to 17 in which the Ni content is 5.0% by mass or less. Both of them are good in the test sample No. 18 with a Ni content exceeding 5.0% by mass. The excavation ratio is 9 7 %. The maximum crystal grain size is 1 5 // m, and nickel is formed in the plaque. Phase, the discharge voltage is 460V, and the spray index is as long as 108. From these results, when the Ni content in the entire composition exceeds 0 and is 5.0% by mass or less, even if the sintering temperature is lowered, fine punctate structure is obtained and good discharge characteristics are exhibited. Further, in this range, the discharge voltage for obtaining a discharge current of 6 mA is about 400 V, and the splatter index shows a low enthalpy as low as about 80 Å or less. The samples of sample Nos. 05 and 19 to 23 of Table 1 are examples of the effect of the density ratio. In the sintering temperature of 145 (TC sample No. 19, the density ratio was 71%), the discharge voltage was as large as 450 V. In addition, the sample number 〇5, 20~ at the sintering temperature exceeding 1 45 0 °C. In 22, the density ratio becomes 80 to 96%. 'The discharge voltage shows a good 〇〇 about 4 〇〇 to 420 V, and the splatter index also shows a good 値 of about 80 or less. Also in sample No. 23, the density ratio is 98%'. The maximum crystal grain size was coarsened to 5 〇//m, the discharge voltage was 435 volts, and the shoal index was as large as 90. From these results, it was confirmed that a good discharge was exhibited in a density ratio of 80 to 96%. [Brief Description of the Drawings] -18- 200828392 Fig. 1 is a cross-sectional view showing the structure of a cold cathode fluorescent lamp. Figs. 2A to 2F are views showing the 制造 of the electrode for cold cathode fluorescent lamp of the present invention. Sections 3A and 3B are cross-sectional optical micrographs of electrodes for cold cathode fluorescent lamps of the present invention, and FIG. 3A is before crystal grain growth test, FIG. 3B After the crystal grain growth test.
第4A及4B圖係習知之冷陰極螢光燈用電極的截面光 學顯微鏡照片，第4A圖爲結晶粒成長試驗前，第4B圖爲 結晶粒成長試驗後。 【主要元件符號說明】 1 玻璃管 2 端子 3 電極 4 螢光體 5 密封氣體 11 第1陽模 12 第2陽模 13 第3陽模 14 模具 15 電極形狀成形體 -19-Figs. 4A and 4B are cross-sectional optical micrographs of conventional electrodes for cold cathode fluorescent lamps, Fig. 4A shows the crystal grain growth test, and Fig. 4B shows the crystal grain growth test. [Description of main component symbols] 1 Glass tube 2 Terminal 3 Electrode 4 Phosphor 5 Sealing gas 11 First male mold 12 2nd male mold 13 3rd male mold 14 Mold 15 Electrode shape molded body -19-