200931748 九、發明說明 【發明所屬之技術領域】 本發明是關於用來將帶有正電或負電之帶電體的電荷 予以除電之離子發生器（除電裝置），尤其是關於低發塵 性的離子發生器。 【先前技術】 0 近年，由於技術開發的進步，積體電路的積體度明顯 提高。但是，積體電路提高基體度，電路的線寬則會變得 非常微小，故製程中容易受到外部的影響’良品率因而變 差。尤其，塵埃等的浮游粒子附著在電路上，則會發生電 路的斷線或短線。於是，LSI廠房或電子機器組裝廠房中 ，將廠房全體或該一部分設置成無塵室，以使廠房內的浮 游粒子儘可能減少。惟，爲了要抑制製品的變質並防止微 生物的繁殖，無塵室內因而保持在低濕度（40〜4 5 %RH程 〇 度），所以容易產生靜電。例如，無塵室內會因人的移動 、空氣的流動（風）等的原因而對於人、設備等產生靜電 。另外，爲了要防止發塵並提高抗藥性，使用大量塑膠等 的絕緣體，形成爲更加容易產生靜電的環境。產生靜電的 話，設有電路的晶圓帶電而會吸引無塵室內僅殘的微粒子 ，導致品質的劣化。另外，還會有因放電而破壞晶圓上的 電路的事態。進而，也會有因電磁波而導致製造裝置或電 腦的錯誤動作或因電擊衝擊而使作業者的工作效率降低之 虞。 -5- 200931748 爲了要防止這種的靜電障礙，必須除去無塵室內所產 生的靜電，首先探討除去靜電的方法，該方法爲將帶電的 物體予以接地以對於各個物體進行除去靜電。但是，該方 法只對於機材既是導電性又被固定的物體有效，對於如同 晶圓或搬運晶圓的載具要逐一搬送的複數個獨立的物體， 採取藉由接地來將電荷除電的方法則會有困難。 於是’過去以來，並不是接地來對於各個物體進行除 〇 去靜電’採取的方法是將無塵室內的空氣予以電離並予以 離子化以將靜電中和。該空氣離子化的除去靜電方法，因 未接觸到帶電的物體而可以整體將大範圍的空間予以除去 靜電’所以適用於無塵室的靜電除去。將空氣離子化的方 法已知是應用電暈放電、放射線、紫外線等，其中，電暈 放電的方法比其他的方法還要更安全又低價，所以被廣泛 利用。 過去所提案的裝置爲無塵室用離子發生器，作爲利用 Ο 這種電暈放電來進行空氣的離子化，將物體表面的靜電予 以中和之裝置。該無塵室用離子發生器則是由設置在無塵 室的頂棚之複數個離子發生電極、及將電壓施加至該離子 發生電極之裝置所構成。然後，具有這種構成之無塵室用 離子發生器係藉由將高壓電施加至離子發生電極時所造成 的電暈放電來令離子發生，藉由該離子來令靜電中和（日 本專利文獻1 )。 專利文獻1 :日本專利特開平6-3 25 894號公報 200931748 【發明內容】 <發明所欲解決之課題> 然而，離子發生電極的電極本身具有發塵性，因此， 習知的無塵室用離子發生器會有無塵室內的空氣清淨效率 降低等的問題。於是，本發明的目的是提供例如適用於無 塵室之很少發塵或不會發塵之離子發生器。 © <用以解決課題之手段> 本發明中的申請專利範圍第1項之放電電極係至少一 部分是由經過將調製含有釩酸鹽的混合物之後予以熔解和 急速冷卻而獲得之導電性釩酸鹽玻璃或是對於該玻璃進一 步施予退火處理之導電性釩酸鹽玻璃浸泡在水系液體媒體 中的步驟所獲得之導電性釩酸鹽玻璃所構成。 本發明中的申請專利範圍第2項之離子發生器係具有 空氣中施加高壓電以使進行電離，用來令離子發生之至少 © —個放電電極（例如’放電電極3)、及用來將電力供應 至前述放電電極之電源部（例如，放電電極1)，而前述 放電電極爲申請專利範圍第1項的放電電極（例如，放電 電極3 )。 此處’針對本提案書中所代表的各用語進行說明。首 先’ 「導電性玻璃」是指電導率至少爲lxl(T13S/cm (最 好是至少爲lxl(T9S/cm，更好的是至少爲ixi〇-7s/cin)的 玻璃。「導電性玻璃」例如列舉有離子傳導玻璃、電子傳 導玻璃、或前述2種傳導性共存之混合型傳導型玻璃等。 200931748 「離子傳導玻璃」並沒有特別的限定，例如列舉有含有 AgI-Ag2〇-B2〇2 ' AgI-Ag2〇-P2〇5 ' Agl-Ag20-W03 > LiCl-Li20-B203等的玻璃。「電子傳導玻璃」例如列舉有價電 子躍遷傳導玻璃、能帶隙傳導玻璃等。價電子躍遷傳導玻 璃並沒有特別的限定，列舉有含有釩酸鹽（vanadate )的 玻璃。能帶隙傳導玻璃並沒有特別的限定，列舉有〇心1^-S、Ge-Te-Se、Ge-Te-Sb 等的硫屬化物玻璃（chalcogenide 0 glass ) 。「混合型傳導型玻璃」並沒有特別的限定，列舉 有含有釩酸鹽、Agl以及Ag02的玻璃（參考日本專利特 開 2004-331416號公報）、或LixW03。這些當中，基於 高導電性的理由，含有釩酸鹽的玻璃特別理想。「放電針 」是指只要在該前端具有導電性玻璃的話，並沒有特別的 限定，例如也可以是只由導電性玻璃所組成的構件、或只 在前端具有導電性構件的複合構件、或在另外材料的表面 披覆了導電性玻璃的複合構件均可。 ❿ 〔發明效果〕 依據本發明的離子發生器，達到的效果爲將放電電極 本身的發塵壓抑在最低限度。進而，由於導電性釩酸鹽玻 璃可以利用釩酸鹽的含量或退火處理來適度調整該導電率 ，故達到很容易就能夠調節進行放電的離子量的效果。 【實施方式】 以下，根據圖面來說明本發明的實施形態。此外，本 -8- 200931748 發明的技術範圍並不侷限於本實施形態。另外，關於以一 個例子具體說明過的事項，應理解：除了並不屬該事項而 有特別記述的情況之外，也直接適用於其他的例子。 離子發生器 本發明的離子發生器係由具有空氣中施加高壓電以使 進行電離，用來令離子發生的至少一個放電電極、及用來 〇 將電力供應至前述放電電極的電源部所構成，其特徵爲： 前述放電電極爲經過將調製原料混合物之後予以熔解和急 速冷卻而獲得之導電性釩酸鹽玻璃或是對於該玻璃進一步 施予退火處理之導電性釩酸鹽玻璃浸泡在水系液體媒體中 的步驟所獲得之導電性釩酸鹽玻。此外，電源即使是利用 交流電源、直流電源的任何一種之形式皆適合應用。進而 ，電源最好是高壓電源。 以下以例子來說明被設置在無塵室內的頂棚之離子發 〇 生器，作爲本實施形態的一種構成例子。即是如第1圖所 示，由電源1、及在無塵室的頂棚C設置本體機殼2，以 至少前端突出到外部的方式設置在本體機殼2內之放電電 極3所構成。放電電極3爲將棒狀之導電性玻璃的下端加 工成圓錐形之構件，該上端連接至電源1。此外，放電電 極以外的構成，因直接應用習知的技術（例如，曰本專利 特開2004-253193號公報及日本專利特開2007-66822號公 報中所揭示的鼓風型式、日本專利特開2007-141691號公 報中的放電針型式、日本專利特開2004-3 1 93 58公報中的 200931748 噴槍型式），以下，以放電電極爲中心進行說明。 導電型玻璃 本發明的離子發生器，其特徵爲使用已施予特定處理 過的導電性釩酸鹽玻璃，作爲放電電極。即是，本發明中 ，將以通常的手法所製造的導電性釩酸鹽玻璃浸泡在水系 媒體中，本質上是使用粉體不會析出到表面之低發塵性導 〇 電性玻璃來作爲放電電極。此外，本實施形態的放電電極 最好是使用前端尖銳的放電針，至少放電電極的放電前端 部分由該導電性釩酸鹽玻璃所構成即可。此處，放電電極 的之導電性釩酸鹽玻璃以外的部分，構成上並沒有特別的 限定，例如能夠使用鎢、鈦、矽等的稀有金屬或鐵等。於 是，首先針對構成水處理前的導電性釩酸鹽玻璃（未處理 )之各成分進行說明，接著針對導電性釩酸鹽玻璃（未處 理）的性質進行說明，再接著，針對製造該導電性玻璃（ Ο 未處理）之方法進行說明。其次，針對低發塵性導電性釩 酸鹽玻璃的製造方法及其性質進行說明。以下的實施形態 中，採用以水爲例來作爲水系液體媒體予以詳述，但並不 侷限於此。 《導電性釩酸鹽玻璃（未處理）》 本實施形態之離子發生器的放電電極中，至少一部分 由導電性釩酸鹽玻璃所組成。「導電性釩酸鹽玻璃」只要 是含有釩酸鹽（vanadate )的導電性玻璃並沒有特別的限 -10- 200931748 定，基於高導電性的理由，最好是應用含有釩、鋇以及鐵 之氧化物系玻璃組成物。此處，首先釩爲用來形成氧化物 系玻璃的主骨幹之構成元素，該氧化數以2、3、4、5等 予以改變，可以提高電子躍遷的槪率。其次，鋇爲要將二 維構成之釩氧化物的玻璃骨幹予以三維化而添加之構成元 素。進而，鐵爲電導率的調整成分，可以經由改變該量來 控制導電性。 © 此處，釩酸鹽玻璃中氧化釩的含量最好是0.1〜98莫 耳％的範圍，更好的是40〜98莫耳％的範圍。釩酸鹽玻璃 中氧化鋇的含量最好是1〜40莫耳％的範圍。釩酸鹽玻璃中 氧化鐵的含量最好是1~20莫耳％的範圍。進而，氧化鋇（ B)與氧化釩（V)的莫耳比値（B : V)最好是5 : 90〜3 5 :50。另外，氧化鐵（F)與氧化釩（V)的莫耳比値（F :V )最好是 5 : 90〜15 : 50。 進而，前述導電性釩酸鹽玻璃也可以含有銶（ G rheni um )。此處，銶有優異的導電性（進而因氧化數得 以變動所以能夠提高躍遷效應），故可以更加提高釩酸鹽 玻璃的電導率。又因可以將玻璃轉移溫度或結晶化溫度設 定在特定範圍，所以退火處理也會變容易。此外，含有鍊 (rhenium)的情況，前述組成物中的量最好是1〜15莫耳 %。 進而，前述導電性釩酸鹽玻璃也可以含有其他的玻璃 成分，例如氧化鈣、氧化鈉、氧化鉀、氧化鋇、氧化砸、 氧化緦、氧化銷、氧化銀、碘化銀、氧化鋰、碘化鋰、氧 -11 - 200931748 化鉋、碘化鈉、氧化銦、氧化錫等。 這種釩酸鹽玻璃的電導率設定爲25 °C的室溫中 〜10_1S. cm — 1 ’最好是10·3〜1(T2S· cm·1的範圍。尤 基於維持半導體特性的觀點，最好是設定爲1〇-4· 以下。此處，本提案書中的電導率是指經由四端子法 定出來的體積電阻率。 此外，基於調整電導率的觀點，爲了要將導電性 © 的前述基礎組成物（釩、鋇以及氧化物系玻璃組成物 以稀釋，也可以在該組成物中添加稀釋成分〔最好是 (60〜70 莫耳 ％) 、P203 ( 1 〇〜20 莫耳％) 、Al2〇3 ( 莫耳％ ) 、ZnO ( 0〜2莫耳％ ) 、Sb203 ( 0〜2莫耳％200931748 IX. INSTRUCTIONS OF THE INVENTION [Technical Field] The present invention relates to an ion generator (elimination device) for de-energizing a charge of a positively or negatively charged charged body, in particular, for a low dusting ion generator. [Prior Art] 0 In recent years, due to advances in technology development, the integrated body of integrated circuits has been significantly improved. However, the integrated circuit increases the degree of the base, and the line width of the circuit becomes extremely small, so that the process is susceptible to external influences, and the yield is deteriorated. In particular, if floating particles such as dust adhere to the circuit, disconnection or short-circuit of the circuit occurs. Therefore, in the LSI plant or the electronic machine assembly plant, the whole plant or the part is set as a clean room, so that the floating particles in the plant are reduced as much as possible. However, in order to suppress deterioration of the product and prevent the growth of microorganisms, the clean room is kept at a low humidity (40 to 45 % RH), so static electricity is easily generated. For example, in a clean room, static electricity is generated for people, equipment, and the like due to human movement, air flow (wind), and the like. Further, in order to prevent dust generation and improve chemical resistance, an insulator such as a large amount of plastic is used to form an environment in which static electricity is more likely to be generated. When static electricity is generated, the wafer with the circuit is charged and attracts only the remaining particles in the clean room, resulting in deterioration of quality. In addition, there is a situation in which the circuit on the wafer is destroyed by the discharge. Further, there is a possibility that the malfunction of the manufacturing apparatus or the computer due to electromagnetic waves or the electric shock of the operator may cause the work efficiency of the operator to decrease. -5- 200931748 In order to prevent such static electricity, it is necessary to remove static electricity generated in the clean room. First, a method of removing static electricity is proposed. This method is to ground the charged object to remove static electricity for each object. However, this method is only effective for an object that is both electrically conductive and fixed. For a plurality of independent objects that are transported one by one like a wafer or a carrier for transporting a wafer, a method of removing the charge by grounding is performed. Difficulties. Thus, in the past, it has not been grounded to remove static electricity from various objects. The method adopted is to ionize and ionize the air in the clean room to neutralize the static electricity. This method of removing static electricity by air ionization can remove a large amount of space as a whole without coming into contact with a charged object. Therefore, it is suitable for electrostatic discharge in a clean room. The method of ionizing air is known to use corona discharge, radiation, ultraviolet light, etc., and the method of corona discharge is more safe and cheap than other methods, so it is widely used. The device proposed in the past is an ionizer for a clean room, and is a device that neutralizes the static electricity on the surface of the object by ionizing the air using such a corona discharge. The clean room ionizer is composed of a plurality of ion generating electrodes provided in a ceiling of a clean room and means for applying a voltage to the ion generating electrode. Then, the ionizer for a clean room having such a configuration generates ions by corona discharge caused by applying a high voltage electric power to the ion generating electrode, and the ion is neutralized by the ion (Japanese Patent Literature 1). [Patent Document 1] Japanese Patent Laid-Open No. Hei 6-3 25 894, No. 200931748. SUMMARY OF THE INVENTION The object of the invention is to provide dust generation. The room ion generator has problems such as a decrease in the air purification efficiency in the clean room. Accordingly, it is an object of the present invention to provide an ion generator which is, for example, suitable for use in a clean room with little or no dust. © <Means for Solving the Problem> The discharge electrode of the first aspect of the invention is at least partially a conductive vanadium obtained by melting and rapidly cooling a mixture containing vanadate. The acid salt glass is composed of a conductive vanadate glass obtained by a step of immersing the conductive vanadate glass which is further annealed in the glass in an aqueous liquid medium. The ion generator of the second aspect of the invention is characterized in that at least one discharge electrode (for example, 'discharge electrode 3) for applying ionization in the air to cause ionization is used, and Power is supplied to a power supply unit (for example, discharge electrode 1) of the discharge electrode, and the discharge electrode is a discharge electrode (for example, discharge electrode 3) of the first application of the patent scope. Here, the terms used in this proposal are described. First, 'conductive glass' means a glass having a conductivity of at least lxl (T13S/cm (preferably at least lxl (T9S/cm, more preferably at least ixi〇-7s/cin)." Conductive glass For example, an ion-conducting glass, an electron-conducting glass, or a mixed-type conductive glass in which the above two types of conductivity coexist is exemplified. 200931748 "Ion-conducting glass" is not particularly limited, and examples thereof include AgI-Ag2〇-B2〇. 2 'AgI-Ag2〇-P2〇5 ' Agl-Ag20-W03 > Glass such as LiCl-Li20-B203. Examples of "electron conductive glass" include valence electron transition conductive glass, band gap conductive glass, etc. Valence electron transition The conductive glass is not particularly limited, and a vanadium-containing glass is exemplified. The band gap conductive glass is not particularly limited, and examples thereof include a core 1^-S, a Ge-Te-Se, and a Ge-Te-. "Chalcogenide 0 glass" such as Sb. The "mixed-type conductive glass" is not particularly limited, and examples thereof include vanadate, Agl, and Ag02 (refer to Japanese Laid-Open Patent Publication No. 2004-331416). , or LixW03. Among these, based on The reason for the high conductivity is particularly preferable. The "discharge needle" is not particularly limited as long as it has a conductive glass at the tip end. For example, it may be a member composed only of conductive glass. Or a composite member having a conductive member only at the front end or a composite member having a conductive glass coated on the surface of another material. 发明 [Effect of the invention] According to the ion generator of the present invention, the effect is to discharge The dust suppression of the electrode itself is at a minimum. Further, since the conductive vanadate glass can be appropriately adjusted by the vanadium content or the annealing treatment, it is easy to adjust the amount of ions to be discharged. [Embodiment] Hereinafter, embodiments of the present invention will be described with reference to the drawings. The technical scope of the invention of the present invention is not limited to the embodiment. Understand: In addition to the case where it is not specifically mentioned, it is directly applicable to other examples. Sub-generator The ion generator of the present invention is composed of at least one discharge electrode having a high-voltage electric application in the air for ionization, and a power supply portion for supplying electric power to the discharge electrode. The discharge electrode is a conductive vanadate glass obtained by melting and rapidly cooling the mixture of the raw materials, or a conductive vanadate glass further annealed to the glass is immersed in the aqueous liquid. Conductive vanadate glass obtained by the steps in the media. In addition, the power supply is suitable for any form of AC power or DC power. Further, the power source is preferably a high voltage power source. Hereinafter, an ion generator installed in a ceiling of a clean room will be described as an example of a configuration of the present embodiment. That is, as shown in Fig. 1, the main body casing 2 is provided with the power source 1 and the ceiling C of the clean room, and the discharge electrode 3 is provided in the main body casing 2 so that at least the front end projects to the outside. The discharge electrode 3 is a member for processing the lower end of the rod-shaped conductive glass into a conical shape, and the upper end is connected to the power source 1. In addition, the configuration other than the discharge electrode is directly applied to a conventional technique (for example, the blast type disclosed in Japanese Laid-Open Patent Publication No. 2004-253193 and Japanese Patent Laid-Open No. Hei. No. 2007-66822, Japanese Patent Laid-Open The discharge needle type in the publication of the Japanese Patent Publication No. 2007-141691, and the 200931748 lance type in the Japanese Patent Publication No. 2004-3 1 9358, the following description will be focused on the discharge electrode. Conductive Glass The ionizer of the present invention is characterized in that a conductive vanadate glass to which a specific treatment has been applied is used as a discharge electrode. That is, in the present invention, the conductive vanadate glass produced by the usual method is immersed in an aqueous medium, and essentially a low-dusting conductive glass which does not precipitate on the surface of the powder is used as Discharge electrode. Further, it is preferable that the discharge electrode of the present embodiment uses a discharge needle having a sharp tip end, and at least the discharge tip end portion of the discharge electrode may be composed of the conductive vanadate glass. Here, the configuration of the portion other than the conductive vanadate glass of the discharge electrode is not particularly limited. For example, a rare metal such as tungsten, titanium or tantalum or iron or the like can be used. Therefore, first, each component constituting the conductive vanadate glass (untreated) before water treatment will be described, and then the properties of the conductive vanadate glass (untreated) will be described, and then, the conductivity is produced. The method of glass ( Ο untreated) is explained. Next, a method for producing low dusting conductive vanadate glass and its properties will be described. In the following embodiments, water is taken as an example of the water-based liquid medium, but the present invention is not limited thereto. <<Electrically conductive vanadate glass (untreated)>> At least a part of the discharge electrode of the ion generator of the present embodiment is composed of conductive vanadate glass. The "conductive vanadate glass" is not particularly limited as long as it is a vanadium-containing conductive glass. Based on the high conductivity, it is preferable to use vanadium, niobium and iron. An oxide-based glass composition. Here, first, vanadium is a constituent element of the main backbone for forming an oxide-based glass, and the oxidation number is changed by 2, 3, 4, 5, etc., and the rate of electron transition can be improved. Next, it is a constituent element to be three-dimensionally added to the glass skeleton of the two-dimensional vanadium oxide. Further, iron is an adjustment component of electrical conductivity, and conductivity can be controlled by changing the amount. © Here, the content of vanadium oxide in the vanadate glass is preferably in the range of 0.1 to 98 mol%, more preferably 40 to 98 mol%. The content of cerium oxide in the vanadate glass is preferably in the range of 1 to 40 mol%. The content of iron oxide in the vanadate glass is preferably in the range of 1 to 20 mol%. Further, the molar ratio (B: V) of cerium oxide (B) and vanadium oxide (V) is preferably 5: 90 to 3 5:50. Further, the molar ratio (F:V) of the iron oxide (F) to the vanadium oxide (V) is preferably 5:90 to 15:50. Further, the conductive vanadate glass may contain ruthenium (G rheni um ). Here, since ruthenium has excellent conductivity (and thus the transition number can be increased by the oxidation number), the electrical conductivity of the vanadate glass can be further improved. Further, since the glass transition temperature or the crystallization temperature can be set to a specific range, the annealing treatment is also easy. Further, in the case of a chain containing rhenium, the amount in the above composition is preferably from 1 to 15 mol%. Further, the conductive vanadate glass may contain other glass components such as calcium oxide, sodium oxide, potassium oxide, cerium oxide, cerium oxide, cerium oxide, oxidized pin, silver oxide, silver iodide, lithium oxide, lithium iodide. , Oxygen-11 - 200931748 Planing, sodium iodide, indium oxide, tin oxide, etc. The conductivity of the vanadate glass is set to 25 ° C at room temperature of ~ 10_1 S. cm - 1 ' is preferably 10 · 3 ~ 1 (T2S · cm · 1 range, especially based on the viewpoint of maintaining semiconductor properties, It is preferable to set it to 1〇-4·. Here, the conductivity in this proposal refers to the volume resistivity legally determined via the four terminals. In addition, based on the viewpoint of adjusting the conductivity, in order to conduct conductivity© The base composition (vanadium, niobium, and oxide-based glass composition is diluted, and a diluted component (preferably (60 to 70 mol%), P203 (1 〇 to 20 mol%) may be added to the composition. ), Al2〇3 (mole%), ZnO (0~2 mol%), Sb203 (0~2 mol%)
Ti02 ( 0~2 莫耳 ％ )〕。 此處，導電性釩酸鹽玻璃係將含有氧化釩、氧化 及氧化鐵（依情況，氧化鍊）之混合物予以熔解、急 卻而獲得該玻璃組成物之後，即使是前述玻璃組成物 © 璃轉移溫度以上，結晶化溫度以下、或結晶化溫度以 在軟化點溫度以下之退火處理的溫度下保持特定時間 夠進行製造。 例如，在白金坩堝中等將含有氧化釩5 0~9 0莫；! 氧化鋇5〜3 5莫耳％、氧化鐵5〜2 5莫耳％之混合物（ 況，該混合物100質量％中，添加氧化銶（rhenium ) 質量％)予以加熱熔解之後，經急速冷卻予以玻璃化 特定的退火處理條件下，將該玻璃化物予以熱處理。 10'4 其， cm·1 所測 玻璃 )予 Si02 2〜1 0 )' 鋇以 速冷 的玻 上， 仍能 %、 依情 1~1 0 ，在 -12- 200931748 《低發塵導電性釩酸鹽玻璃》 進而，所使用的釩酸鹽玻璃係經過將調製含有釩酸鹽 的混合物之後予以熔解和急速冷卻而獲得之導電性釩酸鹽 玻璃或是對於該玻璃進一步施予退火處理之導電性釩酸鹽 玻璃浸泡在水系液體媒體（例如，水）中的步驟所獲得之 導電性釩酸鹽玻璃。已知：一般，會有將導電性釩酸鹽玻 璃長時間浸泡在水系液體媒體（例如，水）時，因玻璃表 〇 面與水等的反應而在表面上形成游離層的情況。然後，在 導電性釩酸鹽玻璃形成該游離層的情況，明顯地降低導電 性玻璃的導電率，且該游離層會成爲產生粉塵的原因故並 不理想。然而，本發明團隊經過反覆實施，確認了不但不 會降低該導電性釩酸鹽玻璃的電導率，又可以獲得低粉塵 性導電性釩酸鹽玻璃。此處，「水系液體媒體」可以列舉 出水，例如純水、含有氯化鈉等之其他成分的水（例如， 自來水或海水）：酒精，例如乙醇、水與酒精的混合液， Ο 例如乙醇與水的混合液體。另外，「低粉塵性導電性釩酸 鹽玻璃」是指以依據JIS B 9920 : 2002爲基準的發塵性測 定法（例如，使用日本西斯美公司（Sysmex Corporation )製造的模型110)進行測定的情況，雖依用途有會所不 同’但Ιμπι以上的塵埃爲0個之玻璃（最好是〇.5μιη以上 的塵埃爲0個，更好的是0·3μιη以上的塵埃爲5個以下） 。「退火處理」不僅是玻璃轉移溫度以上結晶化溫度以下 ’即使是結晶化溫度以上，若爲軟化點溫度以下即可。 此處，更詳細地說明該水系液體媒體處理法，該方法 -13- 200931748 係由將導電性釩酸鹽玻璃（未處理）浸泡在水 組成。此外，本實施形態的步驟也可以在前述 酸鹽玻璃的製程中，於玻璃組成物熔解、急速 進行。另外，還可以於前述退火處理之後才進 也可以於加工成放電針之後才進行。其中，於 針之後才進行本步驟特別理想。依照該順來進 可以獲得發塵性更低的放電針。 Ο 具體上，將導電性釩酸鹽玻璃浸泡在水中 定在特定溫度，執行經特定時間將粉塵源成分 的處理。此處，最好是該浸泡時，對於該導電 璃，流通特定大小的電、及/或進行超音波處 合在一起，可以既有效率又短時間內執行粉塵 去。 此處，水系液體媒體的溫度最好是30 °C〜 若爲水的話，水溫最好是3 0〜1 0 0 °C，更好的是 ® 此外「沸點」是代表常壓下（1 atm )進行測 非共沸之混合液體的情況，是指成分當中最低 點，進而共沸之混合液體的情況，代表共沸點 流通的情況，電源爲交流或直流皆可，最好是 ’更好的是1〜20 mA。另外，也可以在水中電 行步驟的情況，最好是進行1~2000小時的處 是進行1〜1 500小時的處理。另外，還可以在 流一面進行該處理的情況，最好是進行1〜3 00 ，更好的是進行1~150小時的處理。另外，在 中的步驟所 的導電性釩 冷卻之後才 行。進而， 加工成放電 行本步驟， 才將水溫設 溶解在水中 性釩酸鹽玻 哩。這些組 源成分的除 沸點以下， 4 0〜70〇C。 定之沸點， 的成分之沸 。另外，電 1 〜1 0 0 m A 流不流通進 理，更好的 一面流通電 小時的處理 一面進行超 -14- 200931748 音波處理一面進行該處理的情況，超音波的頻率最好是30 kHz-4 MHz，更好的是30 kHz〜3 MHz，再更好的是30〜80 kHz。另外，超音波處理的時間最好是1~30小時，更好的 是1〜1 0小時，再更好的是1〜3小時。 此外，在進行該處理之後所獲得之低粉塵性導電性釩 酸鹽玻璃的表面附著黃色的粉末，將該附著粉末擦拭除去 ，使用所獲得之導電性釩酸鹽玻璃。 Q 進行超音波處理的情況，可以獲得超音波的氧穴效應 。該氧穴效應爲發生液體因超音波照射而劇烈搖動，發生 局部壓力較高的部分及較低的部分，因而在壓力較低的部 分，液體中產生小的真空氣泡（氧穴），該氣泡受到擠壓 而破裂因而產生衝擊波的現象。利用該氧穴效應來進行低 發塵性處理，以使該衝擊波對檢體施加衝擊，故可以有效 地除去發塵源成分。進而，防止析出在檢體表面的成分因 伴隨氧穴效應之洗淨效應而呈層狀張貼，圓滑地進行操作 以此方式所獲得之低粉塵性導電性釩酸鹽玻璃經由後 述的發塵性測定法而獲得的結果，最好是1 μιη以上的塵埃 爲〇個，更好的是〇.5μιη以上的塵埃爲0個，再更好的是 0.3 μιη以上的塵埃爲5個以下。再則，本實施形態之低粉 塵性導電性釩酸鹽玻璃的電導率，25°C中，最好是1(T13S .cm·1以上，更好的是1(T9S · cnT1以上，再更好的是 1(T7S. cm — 1 以上。 -15- 200931748 《放電針的製造方法》 其次’詳述本實施形態中由導電性玻璃所組成之放電 針的製造方法。首先’製造以釩酸鹽爲主成分之平板狀的 導電玻璃。其次，利用硏磨機來硏磨該平板狀的導電玻璃 。此時’硏磨劑最好是使用剛玉（corundum )或鋁氧粉（ alundum ;氧化鋁）、氧化铈、膠質氧化矽（c〇 11 〇idal silica )等。尤其，因剛玉的粒徑較粗，氧化铈或膠質氧 φ 化矽較細，所以最好是前者在初期階段而後者在鏡面處理 的階段使用。其次，將硏磨過之平板狀的導電性玻璃切割 成規定的大小。然後，將該四方體狀的導電玻璃固定在鑽 石硏磨機，一面繞著長軸周圍旋轉，一面用鑽石逐漸切削 成圓棒。此時，旋轉數最好是1 000〜6000 rpm。之後，用 相同的鑽石硏磨機，進行將前端部切削騍圓錐狀的操作， 可以製成放電針。 具有以上構成之本實施例的作用如以下所述。即是由 〇 電源1來對於放電電極3施加電壓。於是會從放電電極3 產生電暈放電，使放電電極周圍的空氣離子化。藉由對於 帶電的物質照射該已被離子化的空氣，除去帶電物質的靜 電。 〔實施例〕 製造例1 (導電性釩酸鹽玻璃） 作成該化學組成分別被調整成15Ba〇 · 7〇v2〇5 · 15FeO之混合物’將該混合物移至白金堪堝等，在電氣爐 -16- 200931748 中以1 000°C經過60分鐘加熱並予以熔解。該堪禍立即在 冰水中進行急速冷卻（將白金坩堝的外側、底部浸泡在冰 水中），以獲得導電性釩酸鹽玻璃（電導率：7χ10·38 . cm_1)。將該玻璃以400°C經1小時進行退火處理，製造 以下的施加低發塵性處理過之導電性飢酸鹽玻璃（電導率 :7x1 (T3S · cnT1 )。 Q 電導率的測定方法 電導率係以厚度1 m m以下的導電性釩酸鹽玻璃片經 由四端子法來求得。此處，電極則是將用熔解的金屬銦來 讓引線固定在玻璃表面。電導率（σ )係電流密度（ AcnT2)除以電場的大小之値。 A c m- 2 + V c m-1 = A / V c m-1 = S / c m -1 = S · c m 1 此外’電導率（S · cnT1 )爲比電阻（Ω · cm )的倒 數。 ❹ 發塵性的測定方法 導電性釩酸鹽玻璃本身的發塵性係用第2圖所示的測 定裝置100進行測定。測定裝置100具有10 cmx 10 cmx 10 cm的空間101、及被設置在該空間ιοί內之由細棒所組成 之Y形狀的檢體載具102、及顆粒計數器連接用孔103。 前述顆粒計數.器連接用孔103連接至顆粒計數器200 (日 本西斯美公司（Sysmex Corporation)製模型110)的空氣 吸引口。 -17- 200931748 發塵性的測定方法係依據以下的步驟（1 )〜（4 )實 施。 步驟（1 ):用脫脂棉以純水來洗淨檢體A ( 3 mm X 3 mmx40mm的長方體形狀）（10秒）之後予以充分乾燥。 步驟（2):前述步驟之後，在濕度80%和25 °C的條 件下，檢體A放置1曰。 步驟（3 ):在溫度50°C且濕度〇%的條件下，放置1 © /J、日寺° 步驟（4 ):使空間1 00成爲非常乾淨的狀態（ JIS B 9920 : 20 02的等級），將經過步驟所獲得的檢體A 擺置在載具102，進而，設置成顆粒計數器連接用孔103 與檢體A爲1 cm的距離之後，以每分鐘2.83公升的速度 ，將空間100內的空氣吸引到顆粒計數器，以JIS B 9920 :2002之粒子的個數測定方法爲基準，依照〇.1~〇.2μηι、 0.2 〜0·3μιη、0.3 ~0 · 5 μιη、0.5 ~ 1 · 0 μιη、1·0μιη 以上’實施各 〇 別測定。 此外，基本上測驗次數爲1次，不過實施過複數次時 1次都無法確認出1 μηι以上的情況，確認爲「低發塵性」 黃變性的測定方法 黃變性的測定方法係依據以下的步驟（1)〜（3)實 施。 步驟（1):用脫脂棉以純水來洗淨檢體A(3 mmx3 -18- 200931748 mm><40mrn的長方體形狀）（1〇秒）之後予以充分乾燥。 步驟（2 ):前述步驟之後’在濕度8 0 %和2 5 °C的條 件下，檢體A放置1日。 步驟（3):依照JIS Z 8701’測定L*a*b*表面色系 製造例2 (低發塵性導電性釩酸鹽玻璃） 0 將經由製造例1所獲得之低發塵性導電性釩酸鹽玻璃 ，浸泡在附蓋的樣本瓶中所備用的自來水中’室溫中大約 經過2個月，進行低發塵性處理。該結果’黃色成分溶解 在水中，水全體已染成黃色。之後’從樣本瓶中取出導電 性釩酸鹽玻璃，將表面沖洗乾淨，獲得製造例2的低發塵 性導電性釩酸鹽玻璃。再度將該低發塵性導電性釩酸鹽玻 璃浸泡在自來水中，不過之後經過2個月以上，樣本瓶中 的水並沒有溶解出黃色成分。此外，該低發塵性導電性釩 〇 酸鹽玻璃的電導率與處理前的導電性釩酸鹽玻璃比較並沒 有改變（電導率：7x l〇-3S · cm·1 )。另外，發塵測驗的結 果顯示在表1中。此外，該處理前的導電性釩酸鹽玻璃， 於前述發塵測驗的步驟（2 )前後，觀測到顏色的改變（ 改變成黃色）。一方面，該處理後的低發塵性導電性釩酸 鹽玻璃’於前述發麈測驗的步驟（2)前後，並未觀測到 顏色的改變（未改變成黃色）。 製造例3 (低發麈性導電性釩酸鹽玻璃） -19- 200931748 將經由製造例1所獲得的導電性釩酸鹽玻璃浸泡在1 5 C的水中’升溫到l〇〇C爲止，流通5〜10V、1〜5mA的電 流，經3 ~ 1 5小時進行低發塵性處理之後，擦拭附著在表 面的黃色成分並予以沖洗，獲得製造例3的低發塵性導電 性釩酸鹽玻璃（電導率：7xl(T3~lxl(T2S· cm·1)。此外 ，附著在低發塵•抗黃變性導電性釩酸鹽玻璃表面之黃色 成分經由XPS(X射線光電子能譜儀）進行分析的結果， φ 附著在表面的成分爲C: 36.7、0: 46.7、V: 8.0、N: 1.4 、S: 1.8、Fe: 1.8、Ba: 3.6 (atom%)。另外，第 3 圖 爲表示該處理前的導電性釩酸鹽玻璃之表面的樣子〔第3 (a )圖〕、及處理後的低發塵性導電性釩酸鹽玻璃之表 面的樣子〔第3(b)圖〕之圖。此外，該處理前的導電性 釩酸鹽玻璃，於前述發塵測驗的步驟（2 )前後，觀測到 顏色的改變（改變成黃色）。一方面，該處理後的低發塵 性導電性釩酸鹽玻璃，於前述發塵測驗的步驟（2 )前後 Φ ，未觀測到顏色的改變（未改變成黃色）。 製造例4 (低發塵性導電性釩酸鹽玻璃） 振盪頻率40 kHz的洗淨機（日本CITIZEN製超音波 洗淨機SW78000)中加入300 cc的水’放入經由製造例1 所製造的導電性釩酸鹽玻璃，經5分鐘進行超音波處理。 該結果，水中內發塵且改變成黃色，獲得抗發塵性導電性 釩酸鹽玻璃（電導率：7x10.3S· cm-1)。另外’發塵測驗 的結果顯示在表1中。此外，該處理前的導電性釩酸鹽玻 -20- 200931748 璃，於前述發塵測驗的步驟（2 )前後，觀測到顏色的改 變（改變成黃色）。一方面，該處理後的低發塵性導電性 釩酸鹽玻璃，於前述發塵測驗的步驟（2 )前後，未觀測 到顏色的改變（未改變成黃色）。 製造例5 (低發塵性導電性釩酸鹽玻璃） 振盪頻率72 kHz的洗淨機（Alex社製，ATSL3022) φ 中加入lOOOcc的水，放入經由製造例1所製造的導電性 釩酸鹽玻璃，經5分鐘進行超音波處理。該結果，水中內 發塵且改變成黃色，獲得抗發塵性導電性釩酸鹽玻璃（電 導率：7xl(T3S · cnT1 )。另外，發塵測驗的結果顯示在表 1中。此外，該處理前的導電性釩酸鹽玻璃，於前述發塵 測驗的步驟（2 )前後，觀測到顏色的改變（改變成黃色 )。一方面，該處理後的低發塵性導電性釩酸鹽玻璃，於 前述發塵測驗的步驟（2)前後，未觀測到顏色的改變（ ® 未改變成黃色）。 表1 粒子大小（"m) tt造例2⑴ 繾逢例2 (2> 例3 <” 轚造供3<2> S造例Mi) ft逢侧4(2) 製脚5 (1) 製造fts⑵ 0. 1 — 0. 2 7 5 68 4 1 90 82 46 23 54 6 8 4 1 93 3 1 22 9 23 3 1 0. 2~0. 3 3 7 20 2 1 0 40 32 15 B 4 2 5 2 3 1 0 2 0. 3~0. e 6 3 1 5 8 4 1 3 7 0 Ί 1 1 2 4 3 2 0. B-1. 0 7 3 0 3 1 1 2 4 0 0 0 0 0 0 0 0 1. 0- 4 2 1 2 2 1 2 4 0 0 0 0 0 0 0 0 »表中，上段爲水處理前的粒子數下段爲水處理後的粒子數置 製造例6 (放電針） -21 - 200931748 用硏磨機，將製造例2之板狀的導電性釩酸鹽玻璃構 件硏磨成平板狀的該導電玻璃。此時，使用最小# 500粒 鏡的硏磨材，再用# 1 5 00、# 2000進行階段性的硏磨（最 終的# 2000爲用膠質氧化矽的鏡面加工）。此外，實施該 硏磨係一面將硏磨劑在以水混合的狀態下滴下至旋轉中的 硏磨盤上，一面押壓板狀玻璃（兩面）。此時，時間則是 分別進行3 0分鐘，直到平面度達到±2 μηι的精度爲止持續 φ 進行鏡面加工。然後，用鑽石切刀來切割成45 mmx2.5 mrnx2.5 mm之後，將該四方體狀的導電玻璃固定在鑽石硏 磨機上，作成前端爲圓錐狀的放電針。 將以上述方式所製造的放電針安裝在第1圖所示的無 塵室用離子發生器之後，實施發塵檢查和除電檢查。該結 果，如表2所示，判定：就放電針而言，與其他材料作比 較，可以抑制在1/2以下的發塵量。此外，表中的數據爲 0.1 μιη以上之粒子的數量。另外，經由除電檢查，確認有 © 良好的除電。 表2 材料 導電玻璃 Ti W 發塵量 80 167 1667 接著，用製造例6所製造的放電針，進行該放電針之 放電特性的檢討。該結果顯示在表3中。此處則是用第1 圖所示的除電裝置，利用靜電消除監視器（charge plate m ο n i t o r ) ( 1 5 0 m m x 1 5 0 m m 2 0 p F 日本 s i s i d 〇 (音譯）靜 -22- 200931748 電社製靜電消除監視器H060 1 )，進行評估。電壓爲對於 放電針施加的電壓（kV)。施加方式爲交流（AC)或是 直流（DC) ，AC後面括弧中的數字代表AC的頻率。另 外，電流（μΑ)爲放電時流動的電流。Decay Time爲將 帶電± 1 000V的帶電體進行除電至±100V爲止所需要的時 間。另外，離子平衡爲+· -偏差量的範圍。另外，溫度 (°C )爲放電測驗時的環境溫度，濕度（％ )爲放電時的 環境相對濕度。因此，得知：實施形態的放電針即使是交 流或直流，均呈現良好的除電時間且呈現良好的離子平衡 ，故能夠當作離子發生器來使用。 表3 捆定結巣 «καν) 施加方式 電流("A) Decay Time (1，000V—100V) _子平衡 ί&*(ΐ) 濕度(》 1 2 AC 70KHz 2 +0.4sec/-0.4sec +/-2V 15.6 41 2 2-3 AC 20KHz 数 +2.4sec/-10.4sec +/-1V 21 50 3 5 DC 5 +8.7sec/-€.7sec +/-1OV 21 50 4 15-20 DC 2 *K).9sec/-1.5sec +/-5V 23 50 5 +5 〜6K-5K DC 5 +8.7sec/-6.7sec +/-1OV 21 50 使用靜電消除監視器(1 SOmm X 150mm 20pF)Ti02 (0~2 mole %)]. Here, the conductive vanadate glass is obtained by melting a mixture containing vanadium oxide, oxidation, and iron oxide (in some cases, an oxidized chain) to obtain the glass composition, and even the glass composition is transferred. Above the temperature, the crystallization temperature is lower than or the crystallization temperature is maintained at a temperature at the annealing treatment temperature below the softening point temperature for a certain period of time. For example, in the case of platinum bismuth, it will contain a mixture of vanadium oxide 50 to 90%; cerium oxide 5 to 3 5 mol%, and iron oxide 5 to 2 5 mol% (in the case where the mixture is 100% by mass, added The cerium oxide (rhenium mass %) is heated and melted, and then subjected to rapid annealing to vitrify a specific annealing treatment condition, and the glass frit is heat-treated. 10'4, cm·1 measured glass) to Si02 2~1 0 )' 钡 fast-cooled glass, still can be %, according to the situation 1~1 0, in -12- 200931748 "low dust conductivity Vanadate glass Further, the vanadate glass used is a conductive vanadate glass obtained by preparing a vanadium-containing mixture, followed by melting and rapid cooling, or further annealing the glass. Conductive vanadate glass obtained by the step of immersing conductive vanadate glass in an aqueous liquid medium (for example, water). It is known that, in general, when a conductive vanadate glass is immersed in an aqueous liquid medium (for example, water) for a long period of time, a free layer is formed on the surface due to a reaction between the surface of the glass surface and water. Then, in the case where the conductive vanadate glass forms the free layer, the conductivity of the conductive glass is remarkably lowered, and the free layer may be a cause of dust generation, which is not preferable. However, the inventors of the present invention have repeatedly demonstrated that not only the conductivity of the conductive vanadate glass is lowered, but also the low dust conductive vanadate glass can be obtained. Here, the "aqueous liquid medium" may, for example, be water, such as pure water or water containing other components such as sodium chloride (for example, tap water or sea water): alcohol, such as ethanol, a mixture of water and alcohol, Ο such as ethanol and A mixed liquid of water. In addition, the "low dust conductive vanadate glass" is measured by a dusting property measurement method based on JIS B 9920: 2002 (for example, model 110 manufactured by Sysmex Corporation). In the case of the case, the dust of the 会μπι or more is 0 glass (it is preferably 0. 5μιη or more of dust, 0, more preferably 0. 3μιη or more of dust is 5 or less). The "annealing treatment" is not limited to the glass transition temperature or higher, and the crystallization temperature is not more than the crystallization temperature, and may be equal to or lower than the softening point temperature. Here, the aqueous liquid medium treatment method will be described in more detail, and the method -13-200931748 is composed of immersing conductive vanadate glass (untreated) in water. Further, in the procedure of the present embodiment, the glass composition may be melted and rapidly formed in the process of the acid salt glass. Alternatively, it may be carried out after the annealing treatment described above or after the processing into a discharge needle. Among them, it is particularly desirable to perform this step after the needle. According to the shun, a discharge needle having a lower dusting property can be obtained. Specifically, the conductive vanadate glass is immersed in water at a specific temperature, and the treatment of the dust source component is performed for a specific period of time. Here, it is preferable that when the immersion is performed, a specific size of electricity is distributed to the conductive glass, and/or ultrasonic waves are combined to perform dust removal in an efficient and short time. Here, the temperature of the aqueous liquid medium is preferably 30 ° C. If it is water, the water temperature is preferably 3 0 to 1 0 0 ° C, more preferably, the "boiling point" is under normal pressure (1) Atm) is a case where the non-azeotropic mixed liquid is measured, which refers to the lowest point of the composition, and then the azeotropic mixed liquid, which represents the case of the aroma boiling point, and the power source is AC or DC, preferably 'better. It is 1 to 20 mA. Further, it is also possible to carry out the steps in the water, and it is preferable to carry out the treatment for 1 to 1,500 hours at 1 to 2000 hours. Further, it is also possible to carry out the treatment on the flow side, and it is preferable to carry out the treatment from 1 to 30,000, and more preferably from 1 to 150 hours. In addition, it is only after the conductive vanadium in the step is cooled. Further, it is processed into a discharge current step to dissolve the water temperature in the aqueous vanadate glass. The source components of these groups are below the boiling point, 4 0 to 70 〇C. Set the boiling point, the boiling of the ingredients. In addition, when the power is 1 to 1 0 0 m A, the flow is not circulated, and the better one is to flow the electricity hour. When the processing is performed on the super-14-200931748 sonication, the frequency of the ultrasonic wave is preferably 30 kHz. -4 MHz, more preferably 30 kHz to 3 MHz, and even better 30 to 80 kHz. In addition, the time of the ultrasonic processing is preferably 1 to 30 hours, more preferably 1 to 10 hours, and even more preferably 1 to 3 hours. Further, a yellow powder adhered to the surface of the low dust-conductive conductive vanadate glass obtained after the treatment, and the adhered powder was wiped and removed, and the obtained conductive vanadate glass was used. Q In the case of ultrasonic processing, the oxygen hole effect of the ultrasonic wave can be obtained. The oxygen pocket effect is that the liquid is vigorously shaken by the ultrasonic wave irradiation, and the portion with a higher partial pressure and the lower portion are generated, so that in the lower pressure portion, a small vacuum bubble (oxygen pocket) is generated in the liquid, and the bubble is generated. A phenomenon in which a rupture is caused by squeezing and a shock wave is generated. By using the oxygen pocket effect, the low dusting treatment is performed so that the shock wave applies an impact to the specimen, so that the dust source component can be effectively removed. Further, the low-dusting conductive vanadate glass obtained by preventing the components deposited on the surface of the sample from being deposited in a layered manner due to the washing effect accompanying the oxygen pocket effect, and smoothly performing the dusting property described later As a result of the measurement, it is preferable that the dust of 1 μm or more is one, more preferably, the dust of 〇.5 μm or more is 0, and more preferably, the dust of 0.3 μm or more is five or less. Further, the electrical conductivity of the low-dusting conductive vanadate glass of the present embodiment is preferably 1 (T13 S.cm·1 or more, more preferably 1 (T9S · cnT1 or more, furthermore) at 25 ° C. Preferably, it is 1 (T7S. cm-1 or more. -15-200931748 "Manufacturing method of discharge needle" Next, a method for producing a discharge needle composed of conductive glass in the present embodiment will be described in detail. First, 'vanadium is produced. A flat conductive glass containing salt as a main component. Secondly, the flat conductive glass is honed by a honing machine. At this time, the honing agent is preferably corundum or aluminum oxide powder (alundum; alumina). ), cerium oxide, cerium oxide cerium (c〇11 〇idal silica), etc. In particular, due to the coarser particle size of corundum, cerium oxide or colloidal oxygen φ 矽 矽 is finer, so it is better to be in the early stage and the latter in the latter The mirror-finished stage is used. Secondly, the honed flat-shaped conductive glass is cut into a predetermined size. Then, the square-shaped conductive glass is fixed to the diamond honing machine and rotates around the long axis. Gradually cut diamonds into round bars on one side. In the case of the present embodiment, the number of rotations is preferably from 1,000 to 6,000 rpm. Thereafter, the front end portion is cut into a conical shape by the same diamond honing machine, and a discharge needle can be produced. As described below, a voltage is applied to the discharge electrode 3 by the power supply 1. Thus, a corona discharge is generated from the discharge electrode 3 to ionize the air around the discharge electrode. The ionization is irradiated by the charged substance. The air is removed from the static electricity of the charged substance. [Examples] Production Example 1 (conductive vanadate glass) The mixture was adjusted to a mixture of 15Ba〇·7〇v2〇5·15FeO, respectively. Platinum can be heated and melted at 1 000 ° C for 60 minutes in the electric furnace-16- 200931748. It is immediately necessary to rapidly cool in ice water (soak the outside and bottom of the platinum crucible in ice water). Conductive vanadate glass (conductivity: 7χ10·38 cm1) was obtained. The glass was annealed at 400 ° C for 1 hour to produce the following conductive low-dusting treated conductive Phosphate glass (conductivity: 7x1 (T3S · cnT1). Q. Method for measuring conductivity. Conductivity is determined by a four-terminal method using a conductive vanadate glass sheet having a thickness of 1 mm or less. Here, the electrode is The molten metal indium is used to fix the lead to the glass surface. The conductivity (σ) is the current density (AcnT2) divided by the magnitude of the electric field. A c m- 2 + V c m-1 = A / V c M-1 = S / cm -1 = S · cm 1 In addition, the 'conductivity (S · cnT1 ) is the reciprocal of the specific resistance (Ω · cm ).测定 Measurement method of dusting property The dusting property of the conductive vanadate glass itself is measured by the measuring device 100 shown in Fig. 2 . The measuring device 100 has a space 101 of 10 cm x 10 cm x 10 cm, a sample carrier 102 of a Y shape composed of a thin rod provided in the space ιοί, and a particle counter connecting hole 103. The aforementioned particle counter connector connection hole 103 is connected to the air suction port of the particle counter 200 (model 110 manufactured by Sysmex Corporation). -17- 200931748 The dust emission measurement method is carried out in accordance with the following steps (1) to (4). Step (1): The specimen A (3 mm X 3 mm x 40 mm rectangular parallelepiped shape) (10 seconds) was washed with pure cotton with pure water and then sufficiently dried. Step (2): After the foregoing steps, the sample A was placed at a humidity of 80% and 25 °C. Step (3): Under the condition of temperature 50 ° C and humidity 〇 %, place 1 © /J, 日寺 ° Step (4): Make the space 100 very clean (JIS B 9920 : 20 02 grade The sample A obtained in the step is placed on the carrier 102, and further, the space 100 is set at a speed of 2.83 liters per minute after the particle counter connecting hole 103 and the sample A are at a distance of 1 cm. The air inside is attracted to the particle counter, based on the number of particles of JIS B 9920:2002, based on 〇.1~〇.2μηι, 0.2~0·3μιη, 0.3~0 · 5 μιη, 0.5 ~ 1 0 μιη, 1·0μιη or more 'Implementation of each discrimination test. In addition, the number of tests is basically one, but it is not possible to confirm 1 μηι or more once in a plurality of times, and it is confirmed as "low dusting". The measurement method of yellowing is based on the following methods. Steps (1) to (3) are implemented. Step (1): The specimen A (3 mm x 3 -18 - 200931748 mm >< 40 mrn rectangular shape) (1 sec) was washed with pure cotton in pure water and then sufficiently dried. Step (2): After the foregoing steps, Sample A was left for 1 day under the conditions of humidity of 80% and 25 °C. Step (3): Measurement of L*a*b* surface color system according to JIS Z 8701' Production Example 2 (low dusting conductive vanadate glass) 0 Low dusting conductivity obtained by Production Example 1 The vanadate glass was immersed in tap water which was used in a sample vial attached to the room temperature for about 2 months at room temperature for low dusting treatment. As a result, the yellow component was dissolved in water, and the entire water was dyed yellow. Thereafter, the conductive vanadate glass was taken out from the sample bottle, and the surface was rinsed off to obtain the low dusting conductive vanadate glass of Production Example 2. The low dusting conductive vanadate glass was again immersed in tap water, but after two months or more, the water in the sample bottle did not dissolve the yellow component. Further, the electrical conductivity of the low dusting conductive vanadium silicate glass was not changed as compared with the conductive vanadate glass before the treatment (conductivity: 7 x l 〇 -3 S · cm · 1 ). In addition, the results of the dust test are shown in Table 1. Further, in the conductive vanadate glass before the treatment, a change in color (changed to yellow) was observed before and after the step (2) of the aforementioned dusting test. On the one hand, the treated low dusting conductive vanadate glass was not observed to change color (not changed to yellow) before and after the step (2) of the aforementioned hairpin test. Production Example 3 (Low-curvature conductive vanadate glass) -19- 200931748 The conductive vanadate glass obtained in Production Example 1 was immersed in 15 C of water and heated to l〇〇C. 5~10V, 1~5mA current, after 3 to 15 hours of low dusting treatment, the yellow component adhering to the surface is wiped and rinsed to obtain the low dusting conductive vanadate glass of Production Example 3. (Conductivity: 7xl (T3~lxl (T2S·cm·1). In addition, the yellow component attached to the surface of the low dusting and anti-yellowing conductive vanadate glass is analyzed by XPS (X-ray photoelectron spectroscopy) As a result, the components of φ attached to the surface are C: 36.7, 0: 46.7, V: 8.0, N: 1.4, S: 1.8, Fe: 1.8, Ba: 3.6 (atom%). The appearance of the surface of the conductive vanadate glass before the treatment [Fig. 3 (a)] and the appearance of the surface of the low dusting conductive vanadate glass after the treatment [Fig. 3(b)] In addition, the conductive vanadate glass before the treatment is observed to change color before and after the step (2) of the aforementioned dust test (change) On the one hand, the treated low dusting conductive vanadate glass was Φ before and after the step (2) of the dusting test, and no change in color was observed (not changed to yellow). 4 (Low-dusting conductive vanadate glass) 300 cc of water was added to a washing machine with an oscillation frequency of 40 kHz (Japan's CITIZEN ultrasonic cleaner SW78000). The conductivity produced by the production example 1 was placed. The vanadate glass was subjected to ultrasonic treatment for 5 minutes. As a result, dust was generated in the water and changed to yellow to obtain a dust-resistant conductive vanadate glass (conductivity: 7 x 10.3 S·cm -1 ). The results of the 'dusting test' are shown in Table 1. In addition, the conductive vanadate glass before the treatment was observed, and the color change was observed before and after the step (2) of the aforementioned dusting test. Yellow). On the one hand, the treated low dusting conductive vanadate glass was not observed to have a color change (not changed to yellow) before and after the step (2) of the dusting test. Production Example 5 ( Low dusting conductive vanadate glass) In a 72 kHz washing machine (ATSL3022, manufactured by Alex Co., Ltd.), 1000 cc of water was added to φ, and the conductive vanadate glass produced in Production Example 1 was placed, and ultrasonic treatment was performed for 5 minutes. Dust and change to yellow to obtain anti-dusting conductive vanadate glass (conductivity: 7xl (T3S · cnT1). In addition, the results of the dust test are shown in Table 1. In addition, the conductivity before the treatment For the vanadate glass, a change in color (changed to yellow) was observed before and after the step (2) of the aforementioned dusting test. On the one hand, in the treated low dusting conductive vanadate glass, no change in color was observed before and after the step (2) of the aforementioned dusting test (the color was not changed to yellow). Table 1 Particle Size ("m) ttExample 2(1) Example 2 (2> Example 3 <" 供造3<2> S 造例Mi) ft 逢方4(2) Feet 5 (1) Manufacture of fts(2) 0. 1 — 0. 2 7 5 68 4 1 90 82 46 23 54 6 8 4 1 93 3 1 22 9 23 3 1 0. 2~0. 3 3 7 20 2 1 0 40 32 15 B 4 2 5 2 3 1 0 2 0. 3~0. e 6 3 1 5 8 4 1 3 7 0 Ί 1 1 2 4 3 2 0. B-1. 0 7 3 0 3 1 1 2 4 0 0 0 0 0 0 0 0 1. 0- 4 2 1 2 2 1 2 4 0 0 0 0 0 0 0 0 » In the table, the upper part is the number of particles before water treatment, and the lower part is the number of particles after water treatment. Manufacturing Example 6 (Discharge needle) -21 - 200931748 The plate-shaped conductive vanadate glass member of Production Example 2 was honed into a flat plate of the conductive glass by a honing machine. At this time, the minimum #500 mirror honing material was used, and then Staged honing with #1 5 00, #2000 (final #2000 is mirror processing with colloidal cerium oxide). In addition, the honing agent is applied while the honing agent is mixed with water to the state. On the honing disc in rotation, press the plate glass (both sides). At this time, the time is 30 minutes respectively until the flatness reaches ± The precision of 2 μη is continued until φ is mirror-finished. Then, after cutting into 45 mm x 2.5 mrnx 2.5 mm with a diamond cutter, the square-shaped conductive glass is fixed on the diamond honing machine to make a cone at the front end. The discharge needle manufactured in the above manner is attached to the clean room ion generator shown in Fig. 1, and then subjected to a dust detection and a static elimination test. As shown in Table 2, it is determined that: In the case of the discharge needle, it is possible to suppress the amount of dust generated by 1/2 or less compared with other materials. In addition, the data in the table is the number of particles of 0.1 μm or more. Table 2 Material Conductive glass Ti W Dust amount 80 167 1667 Next, the discharge characteristics of the discharge needle were examined by the discharge needle manufactured in Production Example 6. The results are shown in Table 3. Here, The static elimination device shown in Fig. 1 uses a static elimination monitor (charge plate m ο nitor) (1 50 mmx 1 5 0 mm 2 0 p F Japanese sisid 〇 (transliteration) static-22- 200931748 Supervisor Is H060 1), evaluated. The voltage is the voltage (kV) applied to the discharge needle. The application method is alternating current (AC) or direct current (DC), and the number in the back bracket of the AC represents the frequency of the AC. In addition, the current (μΑ) is the current flowing during discharge. Decay Time is the time required to de-energize a charged body with ± 1 000V to ±100V. In addition, the ion balance is a range of +·−deviation amount. Further, the temperature (°C) is the ambient temperature at the time of the discharge test, and the humidity (%) is the relative humidity at the time of discharge. Therefore, it has been found that the discharge needle of the embodiment exhibits a good static elimination time even if it is AC or DC, and exhibits a good ion balance, so that it can be used as an ion generator. Table 3 Binding knots «καν) Applying mode current ("A) Decay Time (1,000V—100V) _Sub-balance ί&*(ΐ) Humidity (》 1 2 AC 70KHz 2 +0.4sec/-0.4sec +/-2V 15.6 41 2 2-3 AC 20KHz number +2.4sec/-10.4sec +/-1V 21 50 3 5 DC 5 +8.7sec/-€.7sec +/-1OV 21 50 4 15-20 DC 2 *K).9sec/-1.5sec +/-5V 23 50 5 +5 ~6K-5K DC 5 +8.7sec/-6.7sec +/-1OV 21 50 Using a static elimination monitor (1 SOmm X 150mm 20pF)
【圖式簡單說明】 第1圖爲本發明的除電裝置之槪念圖。 第2圖爲測定裝置之槪念圖。 第3圖爲本實施型態中表示該處理前的導電性釩酸鹽 玻璃之表面的樣子〔第3 ( a )圖〕、及處理後的低發塵性 導電性釩酸鹽玻璃之表面的樣子〔第3(b)圖〕之圖。 -23- 200931748 【主要元件符號說明】 1 :電源 2 :本體機殼 3 :離子發生器電極 C :頂棚BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a conceptual view of a static elimination device of the present invention. Figure 2 is a conceptual view of the measuring device. Fig. 3 is a view showing the surface of the conductive vanadate glass before the treatment in the embodiment (Fig. 3(a)) and the surface of the low dusting conductive vanadate glass after the treatment. The picture of the picture [Fig. 3(b)]. -23- 200931748 [Explanation of main component symbols] 1 : Power supply 2 : Main body case 3 : Ion generator electrode C : Ceiling
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