201142917 六、發明說明： 【發明所屬之技術領域】 本發明第一方面有關用於在螢光燈中分配及配料汞之 經改良裝置，該螢光燈特別是但不專指冷陰極螢光燈（ CCFL) ° 【先前技術】 CCFL之製造需要配料精確量之汞，與需要配料足以 確保該燈正確運作及所希望之使用壽命的汞量相關之精確 度，以及減少與使用汞有關之環境衝擊的截然不同需求。 已產生各種問題及技術需求且已解決彼等以改善需要 汞規定用量之燈的製程。該領域中最早的發展其中之一與 安全顧慮有關，且如1 972年以申請人名義提出之US 3 65 7 5 8 9所述，導致TixZryHgzK合物之發展，該化合物避 免在低於500°C之溫度釋放大量汞。 解決該問題之後，下一個難關係改善汞產率以便最小 化程序廢棄物。在這方面，已發展兩種不同解決方法：第 —種方法係描述於歐洲專利EP 737995 B1之化學方法，其 設想使用特定添加劑（促進劑）：然而第二種方法係採用 供汞釋放化合物用之適當設計容器以解決該問題之機械方 法，其係如歐洲專利第E P 9 8 1 8 2 6 B I所述，此二專利均以 申請人名義提出。 已廣泛採用後一種解決方法，且現今許多汞分配器係 藉由裝載汞釋放化合物之粉末的絲狀金屬容器製成，該絲201142917 VI. Description of the Invention: [Technical Field of the Invention] A first aspect of the invention relates to an improved apparatus for dispensing and dispensing mercury in a fluorescent lamp, particularly but not exclusively for a cold cathode fluorescent lamp (CCFL) ° [Prior Art] The manufacture of CCFL requires the precise amount of mercury to be dosed, the accuracy associated with the amount of mercury needed to ensure proper operation of the lamp and the desired service life, and the reduction of environmental impact associated with the use of mercury. Very different needs. Various problems and technical needs have arisen and they have been addressed to improve the process of lamps requiring mercury. One of the earliest developments in this field is related to safety concerns, and as described in US 3,657, 579, issued in the name of the applicant in 1972, resulting in the development of the TixZryHgzK compound, which is avoided below 500°. The temperature of C releases a large amount of mercury. After solving this problem, the next difficulty is to improve mercury yields in order to minimize process waste. In this respect, two different solutions have been developed: the first method is described in the chemical method of European Patent EP 737 995 B1, which envisages the use of specific additives (accelerators): however, the second method uses mercury-releasing compounds. A mechanical method for properly designing a container to solve this problem is described in European Patent No. EP 9 8 1 8 2 6 BI, both of which are filed in the name of the applicant. The latter solution has been widely adopted, and many mercury dispensers today are made from a filamentous metal container loaded with a powder of a mercury-releasing compound.
S -3- 201142917 狀金屬容器係以機械方式裁切成所需長度。該絲狀分配器 可使用且密封於燈內，或者其可藉由諸如歐洲專利第EP 98 1 826B1號中所述之雙夾斷（double tip-off)技術僅用於 製程中，根據該專利，含有該分配器的適當玻璃質裝料容 器短暫地連接於該燈末端：在該分配器已放出汞之後，將 該容器分開且丟棄用完的分配器。 目前仍持續努力改善該產率，如以申請人名義之公告 爲WO 2006/00877 1國際專利申請案所述，其中揭示適用之 包含銅的三組分及四組分合金。對國際專利申請案 WO 2 006/008 771中所揭示該用於汞釋放的含銅化合物的最 小修飾亦已描述於隨後之韓國專利899601。 在解決該技術問題的先前嘗試中，該录化合物（通常 呈粉末形式）係與用來去除可能會干擾該釋放程序或在燈 內產生不利影響之雜質的適當吸氣劑材料倂用。 下文中，參考之術語「活性材料」係描述一或多種汞 釋放粉末化合物與隨意存在的吸氣劑材料粉末之適當混合 物。 與歐洲專利73 7995與9 8 1 8 26相似的是，係藉由互補解 決方法（化學方法對機械方法）著手解決相同問題，且可 從適當發展物理解決方法而非化學解決方法得到一些不同 或增強之技術效果。 此等嘗試其中之一有關該分配器外殼的材料與厚度， 其係描述於韓國專利896196中。 先前解決方法沒有一者著眼於新近所發生與使用較短 201142917 分配器之需求、與經改良製造程序與裝置相關之需求有關 的新問題。更明確地說，較短分配器更容易整合於燈內’ 或者在雙夾斷技術之實例中會提供諸如容許使用更小型裝 料容器之優點。 【發明內容】 本發明目的在於克服仍存在先前技術中與每單位長度 該分配器之最大汞配料需求有關的限制，其係藉由用於汞 釋放之含有呈粉末形式之活性材料的絲狀分配器進行，該 分配器兩端具有開口，其特徵在於該分配器中之粉末裝載 量係介於5與8.5 g/cm3之間。 茲參考圖式以進一步描述本發明。 【實施方式】 「絲狀分配器」目的係指具有長形結構之分配器，意 指其長度與橫向尺寸之間的比大於2，且最大橫向尺寸等 於或小於1 . 5 mm。在複雜橫斷面（諸如梯形橫斷面）之情 況中，該比係指最寬橫向尺寸。 在較佳具體實例中，該絲狀元件包括側開口，其通常 呈沿著該絲狀元件側邊存在之狹縫形式。此種較佳具體實 例係示於圖1，其圖示由適用之金屬材料11製成的絲狀分 配器10’該分配器具有在其一側形成之狹縫12及位於兩端 之兩個開口 13,13' ’且含有活性材料14之粉末。重要的是 必須強調術語活性材料係指適當之粉末混合物，該粉末混 -5- 201142917 合物包含一或多種用於汞釋放之化合物，及隨意的吸氣劑 材料粉末。 圖1所示之較佳具體實例呈現沿著該金屬結構側邊存 在之狹縫形式的側開口，該較佳具體實例具有容易釋放汞 之優點，不然的話汞只會從末端的兩個開口放出，其結果 係需要謹慎地最佳化活化程序以求有效率釋放汞以及避免 從分配器過於劇烈（在過短時間範圍內）放出氣態汞而造 成之粒子損失二者。亦參考圖1，爲了容易閱讀，通常但 不一定存在對應於該狹縫之粉末中的小凹陷未描繪出，而 是在其他圖示中顯示* 含有該活性材料之絲狀分配器的較佳具體實例之製程 通常提出在具有未定長度之平面薄片條上沉積及配料粉末 ，然後摺疊該條的側邊以製造圖1所示具有沿著側邊存在 之狹縫的金屬結構。在封閉式結構（除末端之開口以外） 之情況中，該等粉末係裝載在金屬結構（通常爲管形）內 ;更多與具有該類型結構之分配器的製造相關之資訊詳見 以申請人名義之歐洲專利EP 1 1 792 16B1。 在圖1以及其他圖示中注意到，某些元件（特別是但 非專指圖1所示具體實例沿著側邊存在之狹縫的寬度）未 顯示其正確尺寸或尺寸比，但彼等已經修改以改善該等圖 示之明確性。 術語「未定長度」本意係指製造階段結束時所獲得之 絲狀元件長度遠大於所需長度，藉由裁切操作可容易從該 未定長度絲狀元件製造單一分配器。標準裁切係藉由機械 -6 - 201142917 方式裁切進行，雖然機械方式裁切在分割操作期間之壓縮 有助於將活性材料之粉末保留在相應之裁切端，但亦可使 用其他類型之裁切，諸如雷射裁切。 該具有未定長度之絲狀元件的製造方法亦可隨意地包 括一或多種壓縮操作，在某些實例中，該等壓縮操作有助 於防止大量粉末損失。 由於損失的粒子可能導致一系列不利影響，諸如干擾 組件（特別是電極）之正確運作，或若其累積在玻璃熔融 區會削弱密封性，故高程度粉末損失對於最終裝置（即， 燈）具有相當嚴重的後果。 本發明人在經過大量努力之後已能找出在絲狀元件內 之活性材料粉末的適用裝載水準；關於損失之粉末量，以 及可導致未定長度絲狀元件之機械性質惡化的高粉末裝載 量，其造成該結構的完整性問題。例如，每單位長度之粉 末量加倍時，會產生未定長度之絲狀元件的處理問題，例 如與其撓性損失有關之問題，因此產生其於處理期間斷裂 之風險。也可能在粉末表面內形成龜裂，造成材料大量損 失。 令人意外的是，本發明人已發現藉由在窄範圍粉末裝 載量內操作可能提高每單位釋放之汞量，同時改善粉末 損失現象。 該粉末裝載量範圍係在5與8.5 g/cm3之間，且可在未 定長度絲狀元件之製程中，例如藉由選擇欲裝載之粉末量 (根據該絲狀元件之長度計算），然後藉由適用壓縮程序 201142917 將此數量「嵌入」該結構而達成及決定。 雖然在上述明確範圍內觀察到有益效果’但已發現當 以至少6 g/cm3之裝載量操作時獲得增強之效果，尤其是有 關於活化程序期間更均勻加熱的增強效果’使得燈之製程 需求較寬鬆，因此該活性材料含量之較佳範圍係介於6與 8.5 g/cm3 之間》 當將不同化合物裝載於該汞分配器時’該活性材料粉 末的較佳裝載量水準視汞釋放化合物與其他活性材料（例 如吸氣劑粉末）之間的重量比而不同。特別是，在汞化合 物與吸氣劑合金的重量比係介於9 5 : 5至8 5 : 1 5之間的情 況下，此裝載量較佳係介於5·4與8 g/cm3之間，或更佳係 介於5.4與7.4 g/cm3之間，然而在汞化合物釋放粉末的重 量比小於8 5 : 1 5之情況下，該容器內的粉末裝載量較佳係 介於5與7.6 g/cm3之間，或更佳係介於5與7 g/cm3之間。 圖2顯示圖1中所示之線的典型橫斷面，而圖3顯示本 發明分配器之另一橫斷面形狀。圖2及圖3所示之橫斷面形 狀僅爲適當形狀之實例，但本發明之槪念可應用於具有不 同橫斷面形狀之絲狀分配器。 適於進行本發明之汞釋放化合物係含有汞及鈦與其他 隨意的元素之化合物，更明確地說，係如美國專利 3 65 7 5 89所述之具有通式化合物，其中X與y的 範圍從0至13，（x + y)總和的範圍從3至13，且z爲1或2, 或是如歐洲專利EP 73 7995所述之前述TixZryHgzK合物和 銅與一或多種選自錫、銦、銀、矽或稀土族之元素的合金 -8 - 201142917 ’或如國際申請案WO 2006/00877 1所述之包含汞、鈦 '銅 以及錫、鉻與矽其中一或多者的組成物。亦同樣可使用上 述材料之組合所製成之汞釋放粉末，或包含至少75%重量 分率該等上述材料或其之組合的汞釋放粉末。 可用於與汞釋放粉末一起使用之吸氣劑材料可爲選自 錯 '鈦、釩、鈮、給或鉬之金屬，或該等元素（特別是鉻 或鈦）與一或多種選自過渡元素、稀土金屬或鋁之元素的 合金。最常用於燈之吸氣劑材料係含有約84重量％錐之鉻-鋁合金，以及含有約8 0重量％鉻、1 5重量％鈷，及5重量％ 稀土族之銷-銘-稀土合金。 本發明之第二方面係一種使用根據本發明之絲狀分配 器製造燈的方法。 在第一具體實例中，該絲狀分配器於燈密封後留在該 燈內，然而在所使用製程的第二具體實例（諸如雙夾斷技 術）中，該絲狀分配器不留在該燈內。 本發明第三方面有關一種螢光燈，其包括含有呈粉末 形式之活性材料的用於釋放汞之絲狀分配器，該分配器具 有兩個開口，其特徵在於該分配器中之粉末裝載量係介於 5與 8.5 g/cm3之間。 根據較佳具體實例實現的燈包含具有小孔的絲狀元件 ，通常呈沿著該絲狀元件之側邊存在的狹縫之形式。 亦藉由下列非限制性實例舉例說明本發明。在相同條 件下’於振動皿上在30分鐘期間測試四個不同批次之3〇〇 個絲狀分配器以測量粒子損失，其中每件絲狀分配器爲8 -9 - 201142917 mm長，具有最寬尺寸爲1 mm之梯形橫斷面，且沿著側邊 存在 0.3 mm之狹縫。 該分配器內之活性材料的組成、粉末裝載量及實驗結 果係示於表1 : 表1 _放材料 (A) 吸氣劑材料 (B) 重量比 (A:B) 粉末裝載量 粉末損失 (重量％) 樣本1 Ti-Hg Zr-Al 90 ： 10 5.42 0.25 樣本2 Ti-Hg-Cr-Cu Zr-Al 90 ： 10 6.89 0.35 樣本3 Ti-Hg Zr-Al 90 ： 10 7.69 0.15 樣本4 Ti-Hg-Cr-Cu Zr-Al 90 ： 10 7,99 0.20一 樣本5 Ti-Hg-Cr-Cu Zr-Al 90 ： 10 8.15 0.20一 對照樣本1 Ti-Hg Zr-Al 90 ： 10 4.79 0.80一 對照樣本2 Ti-Hg-Cr-Cu Zr-Al 90 ： 10 8.59 0.55一 已提及，表1中所有比均爲重量比。 從表1所示之實驗數據可能觀察到對照樣本所得之數 據顯示出粉末損失比起根據本發明條件所得之樣本明顯增 加。若與大部分市售分配器（對照樣本1所示）相較，在 申請專利範圍內實施不僅分配器之每單位長度的汞放出量 增加，且令人意外的是亦發現到粉末損失量範圍遠小於其 他做法* 【圖式簡單說明】 •圖1顯示根據本發明之絲狀元件的較佳具體實例； •圖2顯示圖1所示之絲狀元件的典型橫斷面；及 -10- 201142917 •圖3顯示適於進行本發明之絲狀元件的其他橫斷面 【主要元件符號說明】 1 〇 :絲狀分配器 1 1 :金屬材料 1 2 :狹縫 1 3，1 3 丨：開口 1 4 :活性材料 5 -11 -S -3- 201142917 Metal containers are mechanically cut to the required length. The filamentary dispenser can be used and sealed in the lamp, or it can be used only in the process by a double tip-off technique such as described in European Patent No. EP 98 1 826 B1, according to which A suitable glassy container containing the dispenser is briefly attached to the end of the lamp: after the dispenser has discharged mercury, the container is separated and the used dispenser is discarded. Efforts continue to be made to improve the yield, as described in the International Patent Application No. WO 2006/00877, the disclosure of which is incorporated herein by reference. The minimal modification of the copper-containing compound for mercury release disclosed in the international patent application WO 2 006/008 771 has also been described in the subsequent Korean Patent No. 899,601. In a previous attempt to solve this technical problem, the recorded compound (usually in powder form) was used with a suitable getter material to remove impurities that might interfere with the release procedure or have an adverse effect in the lamp. Hereinafter, the term "active material" as used herein refers to a suitable mixture of one or more mercury-releasing powder compounds and optionally present getter material powders. Similar to European patents 73 7995 and 9 8 1 8 26, the same problem is solved by a complementary solution (chemical method to mechanical method), and some differences can be obtained from the appropriate development of physical solutions rather than chemical solutions. Enhanced technical effects. One of these attempts is related to the material and thickness of the dispenser housing, which is described in Korean Patent No. 896,196. None of the previous solutions focused on new issues related to the need to use shorter 201142917 dispensers and related requirements related to improved manufacturing procedures and devices. More specifically, shorter dispensers are easier to integrate into the lamp' or in the case of double pinch-off techniques, such as the advantage of allowing the use of smaller containers. SUMMARY OF THE INVENTION It is an object of the present invention to overcome the limitations associated with the prior art maximum mercury dosing requirement per unit length of the dispenser, which is by filament distribution of the active material in powder form for mercury release. The apparatus has an opening at both ends of the dispenser, characterized in that the powder loading in the dispenser is between 5 and 8.5 g/cm3. The invention is further described with reference to the drawings. [Embodiment] The "filament dispenser" is intended to mean a dispenser having an elongated structure, meaning that the ratio between its length and the lateral dimension is greater than 2, and the maximum transverse dimension is equal to or less than 1.5 mm. In the case of a complex cross section (such as a trapezoidal cross section), the ratio refers to the widest transverse dimension. In a preferred embodiment, the filamentary element comprises a side opening that is generally in the form of a slit present along the sides of the filamentary element. A preferred embodiment of this is shown in Figure 1, which illustrates a filamentary dispenser 10' made of a suitable metallic material 11 having a slit 12 formed on one side thereof and two at both ends The opening 13, 13'' and contains a powder of the active material 14. It is important to emphasize that the term active material refers to a suitable powder mixture comprising one or more compounds for mercury release, and a random getter material powder. The preferred embodiment illustrated in Figure 1 presents a side opening in the form of a slit present along the sides of the metal structure. This preferred embodiment has the advantage of readily releasing mercury, otherwise mercury will only be released from the two openings at the end. As a result, it is necessary to carefully optimize the activation procedure in order to efficiently release mercury and to avoid both particle losses caused by the excessively intense (in too short time range) release of gaseous mercury. Referring also to Figure 1, for ease of reading, it is generally, but not necessarily, that the small depressions in the powder corresponding to the slit are not depicted, but in other figures it is preferred to have a filament dispenser containing the active material. The process of the specific example generally proposes depositing and compounding a powder on a planar strip having an undefined length, and then folding the sides of the strip to produce a metal structure having slits along the sides as shown in FIG. In the case of a closed structure (except for the opening of the end), the powders are loaded in a metal structure (usually tubular); more information relating to the manufacture of dispensers of this type is detailed in the application European patent EP 1 1 792 16B1 in the name of a person. It is noted in Figure 1 and other figures that certain elements (particularly but not exclusively the width of the slits present along the sides of the particular example shown in Figure 1) do not show their correct size or size ratio, but they It has been modified to improve the clarity of the illustrations. The term "undetermined length" is intended to mean that the length of the filamentary member obtained at the end of the manufacturing stage is much greater than the desired length, and a single dispenser can be easily fabricated from the filamentary member of the predetermined length by a cutting operation. Standard cutting is performed by mechanical -6 - 201142917, although the mechanical cutting during the splitting operation helps to retain the active material powder at the corresponding cutting end, but other types of cutting can be used. Cut, such as laser cutting. The method of making a filamentary member having an undefined length may also optionally include one or more compression operations which, in some instances, help to prevent substantial loss of powder. High levels of powder loss have a high level of powder loss for the final device (ie, the lamp) since the lost particles may cause a series of adverse effects, such as the correct operation of the interfering components (especially the electrodes), or if their accumulation in the glass melting zone weakens the seal. Quite a serious consequence. The inventors have been able, after extensive efforts, to find the appropriate loading level of the active material powder in the filamentary component; with regard to the amount of powder lost, and the high powder loading which can lead to deterioration of the mechanical properties of the filamentary component of undetermined length, It causes problems with the integrity of the structure. For example, when the amount of powder per unit length is doubled, handling problems of filamentary members of undetermined length, such as problems associated with their loss of flexibility, result in a risk of breakage during processing. It is also possible to form cracks in the surface of the powder, resulting in a large loss of material. Surprisingly, the inventors have discovered that by operating in a narrow range of powder loadings, it is possible to increase the amount of mercury released per unit while improving powder loss. The powder loading range is between 5 and 8.5 g/cm3, and can be used in the process of determining the length of the filamentary component, for example by selecting the amount of powder to be loaded (calculated according to the length of the filamentary component), and then borrowing This number is "embedded" by the applicable compression program 201142917 to achieve and determine. Although beneficial effects have been observed within the above-identified ranges, it has been found that an enhanced effect is obtained when operating at a loading of at least 6 g/cm3, especially with regard to the enhanced effect of more uniform heating during the activation procedure. It is more lenient, so the preferred range of the active material content is between 6 and 8.5 g/cm3." When loading different compounds into the mercury dispenser, the preferred loading of the active material powder is a mercury-releasing compound. It differs from the weight ratio between other active materials such as getter powder. In particular, in the case where the weight ratio of the mercury compound to the getter alloy is between 9 5 : 5 and 8 5 : 15 , the loading is preferably between 5.4 and 8 g/cm 3 . Between 5.4 and 7.4 g/cm3, however, in the case where the weight ratio of the mercury compound-releasing powder is less than 8 5 : 15 , the powder loading in the container is preferably between 5 and Between 7.6 g/cm3, or better between 5 and 7 g/cm3. Figure 2 shows a typical cross section of the line shown in Figure 1, and Figure 3 shows another cross-sectional shape of the dispenser of the present invention. The cross-sectional shape shown in Figs. 2 and 3 is only an example of a suitable shape, but the concept of the present invention can be applied to a filament dispenser having a different cross-sectional shape. A mercury-releasing compound suitable for carrying out the present invention is a compound containing mercury and titanium and other optional elements, more specifically, a compound of the formula having a range of X and y as described in U.S. Patent 3,657,589. From 0 to 13, the sum of (x + y) ranges from 3 to 13, and z is 1 or 2, or the aforementioned TixZryHgzK compound and copper and one or more selected from the group consisting of tin and indium as described in European Patent No. EP 73 7995. Alloys of silver, lanthanum or rare earth elements -8 - 201142917 ' or a composition comprising one or more of mercury, titanium 'copper and tin, chromium and niobium as described in the international application WO 2006/00877 1 . A mercury-releasing powder prepared by using a combination of the above materials, or a mercury-releasing powder comprising at least 75% by weight of the above materials or a combination thereof may also be used. The getter material useful for use with the mercury-releasing powder may be a metal selected from the group consisting of titanium, vanadium, niobium, niobium or molybdenum, or such elements (particularly chromium or titanium) and one or more selected from transitional elements. An alloy of elements of rare earth metals or aluminum. The getter material most commonly used for lamps is a chromium-aluminum alloy containing about 84% by weight of a cone, and a pin-Ming-rare earth alloy containing about 80% by weight of chromium, 15% by weight of cobalt, and 5% by weight of rare earths. . A second aspect of the invention is a method of making a lamp using a filament dispenser according to the invention. In a first embodiment, the filamentary dispenser remains in the lamp after the lamp is sealed, however in the second embodiment of the process used, such as a double pinch-off technique, the filamentary dispenser does not remain in the Inside the lamp. A third aspect of the invention relates to a fluorescent lamp comprising a filamentary dispenser for releasing mercury in an active material in powder form, the dispenser having two openings characterized by a powder loading in the dispenser The system is between 5 and 8.5 g/cm3. A lamp according to a preferred embodiment comprises a filamentary element having apertures, typically in the form of a slit present along the sides of the filamentary element. The invention is also illustrated by the following non-limiting examples. Four different filament batches of four different batches were tested on a vibrating dish under the same conditions to measure particle loss, wherein each filamentous dispenser was 8-9 - 201142917 mm long with A trapezoidal cross section with a maximum dimension of 1 mm and a 0.3 mm slit along the side. The composition, powder loading and experimental results of the active materials in the dispenser are shown in Table 1: Table 1 _ release material (A) getter material (B) weight ratio (A: B) powder loading powder loss ( % by weight) Sample 1 Ti-Hg Zr-Al 90 : 10 5.42 0.25 Sample 2 Ti-Hg-Cr-Cu Zr-Al 90 : 10 6.89 0.35 Sample 3 Ti-Hg Zr-Al 90 : 10 7.69 0.15 Sample 4 Ti- Hg-Cr-Cu Zr-Al 90 : 10 7,99 0.20 like this 5 Ti-Hg-Cr-Cu Zr-Al 90 : 10 8.15 0.20 a control sample 1 Ti-Hg Zr-Al 90 : 10 4.79 0.80 a control Sample 2 Ti-Hg-Cr-Cu Zr-Al 90 : 10 8.59 0.55 As already mentioned, all ratios in Table 1 are by weight. From the experimental data shown in Table 1, it may be observed that the data obtained for the control sample showed a significant increase in powder loss compared to the sample obtained according to the conditions of the present invention. Compared with most of the commercially available dispensers (shown in Control 1), it is not only within the scope of the patent application that not only the amount of mercury released per unit length of the dispenser is increased, but also surprisingly, the amount of powder loss is also found. Far less than other practices* [Simplified illustration of the drawings] Figure 1 shows a preferred embodiment of a filamentary member according to the present invention; Figure 2 shows a typical cross section of the filamentary member shown in Figure 1; 201142917 • Fig. 3 shows other cross sections of the filamentary element suitable for carrying out the invention [Major component symbol description] 1 〇: filament dispenser 1 1 : metal material 1 2 : slit 1 3, 1 3 丨: opening 1 4 : Active material 5 -11 -