201225152 六、發明說明： 【發明所屬之技術領域】 此發明係關於螢光燈，尤其是關於放射真空紫外光的 螢光燈者。 【先前技術】 先前，於進行有機質不純物之分解的水處理裝置，如 日本特開2008-260017號公報（專利文獻1)所揭示，廣泛 利用低壓水銀燈。 然而，於此種水處理中，也如同文獻1所記載，從低 壓水銀燈放射的紫外線中，尤其真空紫外光之波長1 85nm 的光線特別有效。 但是，於此低壓水銀燈中，爲了利用水銀的發光，產 生以波長2 5 4nm爲中心波長的光線，故波長1 8 5 nm的真空 紫外光係相對地其發光效率非常低。 於圖6揭示該低壓水銀燈的每一發光波長之能量比， 將具有最大峰値之波長254nm的光線之能量設爲100 %時之 其他波長的能量以相對値表示。 據此，低壓水銀燈之波長1 8 5 nm的光線之放射，係從 其全發光強度考量的話，大約爲1 0%以下的較低者。亦即 ，低壓水銀燈有相對於投入電力，波長185nm的發光效率 極低，電力的使用效率不好之問題。 如此，在從低壓水銀燈放射之光線中波長185nm的發 . 光效率較低，對於投入電力無法進行高效率的水處理。在 201225152 此種背景下，期望有高效率放射波長185nm之光線的光源 〇 又，在低壓水銀燈中，點燈時需要水銀充分蒸發，當 然，其特性係依存於水銀的蒸發之狀態者。根據使用燈之 周圍溫度條件，啓動較遲緩而發光特性不穩定，又，在高 輸入的燈中發熱會變高。於上述之水處理裝置適用高輸入 的燈的話，爲了迴避超過燈的最佳水銀蒸氣壓所致之 18 5nm的發光效率降低，需要冷卻設備而有裝置大型化之 問題。 〔先前技術文獻〕 〔專利文獻〕 〔專利文獻1〕日本特開2008-260017號公報 【發明內容】 〔發明所欲解決之課題〕 此發明欲解決之課題，係有鑒於前述先前技術的問題 點，提供於具備由石英玻璃所成，於內部封入有包含氙之 放電氣體的發光管、形成於該發光管的長邊方向，隔著介 電質而對向之一對的電極、及形成於前述發光管之內面的 螢光體層所構成的螢光燈中，可有效率地發出波長185nm 之真空紫外光，且對於被照射物，熱影響較少，放射特性 穩定的構造。 〔用以解決課題之手段〕 -6- 201225152 ' 爲了解決前述課題，關於此發明的螢光燈之特徵，係 形成於前述發光管內面之螢光體層包含利用鈸賦活的 LaP04螢光體。 又，特徵爲前述钕賦活LaP04螢光體之鈸濃度係1〜 ’ 3 %的範圍。進而，特徵爲於前述一對的電極中配置於發光 管外側的外部電極之表面上具備保護膜。 〔發明的效果〕 依據此發明的螢光燈，螢光體層包含鈸賦活LaP04螢 光體，故可有效率地放射於波長185nm附近具有峰値的真 空紫外光。 尤其，藉由將前述鈸賦活LaP04螢光體之鉸濃度設爲1 〜3 %的範圍，能以非常高的效率將投入至燈的電力轉換爲 真空紫外光。 又，如低壓水銀燈，即使使對燈的輸入成爲高輸入化 ，也不會產生燈的1 8 5 nm附近的發光效率降低之問題，也 有可使冷卻設備小型化之優點。 【實施方式】 圖1係本發明之螢光燈的剖面圖，（A)係軸方向剖面 圖，（B )係其A-A剖面圖。 於圖中，螢光燈1係於由石英玻璃所成的發光管2之外 周面上對向配置一對的外部電極3、4。此外部電極3、4係 爲延伸於管軸方向之大略帶狀的形狀，例如，由混合銀（ 201225152201225152 VI. Description of the Invention: [Technical Field of the Invention] This invention relates to a fluorescent lamp, particularly to a fluorescent lamp that emits ultraviolet light. [Prior Art] In the prior art, a low-pressure mercury lamp is widely used as disclosed in Japanese Laid-Open Patent Publication No. 2008-260017 (Patent Document 1). However, in such water treatment, as described in Document 1, light rays emitted from a low-pressure mercury lamp, particularly light having a wavelength of 1 85 nm of vacuum ultraviolet light, are particularly effective. However, in this low-pressure mercury lamp, in order to utilize the luminescence of mercury, light having a wavelength centering at 254 nm is generated, so that the vacuum ultraviolet light having a wavelength of 185 nm is relatively low in luminous efficiency. The energy ratio of each of the light-emitting wavelengths of the low-pressure mercury lamp is disclosed in Fig. 6. The energy of the other wavelengths when the energy of the light having the maximum peak wavelength of 254 nm is set to 100% is expressed as relative 値. Accordingly, the emission of light having a wavelength of 185 nm at a low-pressure mercury lamp is about the lowest of 10% or less from the viewpoint of its total luminous intensity. That is, the low-pressure mercury lamp has a problem that the luminous efficiency at a wavelength of 185 nm is extremely low and the use efficiency of electric power is not good with respect to the input electric power. As described above, in the light emitted from the low-pressure mercury lamp, the light having a wavelength of 185 nm is low in efficiency, and high-efficiency water treatment cannot be performed for the input electric power. In the background of 201225152, it is desirable to have a light source that emits light with a high efficiency of 185 nm. In a low-pressure mercury lamp, mercury is required to be sufficiently evaporated when lighting, and of course, its characteristics depend on the state of evaporation of mercury. Depending on the ambient temperature conditions of the lamp used, the start-up is slow and the illuminating characteristics are unstable, and the heat is increased in the high-input lamp. When the high-input lamp is applied to the water treatment device described above, in order to avoid the decrease in luminous efficiency of 185 nm which exceeds the optimum mercury vapor pressure of the lamp, it is necessary to cool the device and increase the size of the device. [Prior Art] [Patent Document 1] [Patent Document 1] JP-A-2008-260017 [Claim of the Invention] [Problems to be Solved by the Invention] The problem to be solved by the present invention is in view of the problems of the prior art described above. Provided in an arc tube formed of quartz glass and having a discharge gas containing xenon inside, an electrode formed in the longitudinal direction of the arc tube, facing each other with a dielectric interposed therebetween, and being formed on the electrode In the fluorescent lamp comprising the phosphor layer on the inner surface of the arc tube, vacuum ultraviolet light having a wavelength of 185 nm can be efficiently emitted, and the object to be irradiated is less affected by heat and has stable radiation characteristics. [Means for Solving the Problems] -6-201225152 In order to solve the above problems, the fluorescent lamp of the present invention is characterized in that the phosphor layer formed on the inner surface of the arc tube includes a LaP04 phosphor using an endowment activity. Further, it is characterized in that the concentration of the lanthanum of the endowment-active LaP04 phosphor is in the range of 1 to 3%. Further, it is characterized in that a protective film is provided on the surface of the external electrode disposed outside the arc tube among the pair of electrodes. [Effect of the Invention] According to the fluorescent lamp of the present invention, since the phosphor layer contains the active LaP04 phosphor, it can be efficiently emitted to the vacuum ultraviolet light having a peak 附近 near the wavelength of 185 nm. In particular, by setting the hinge concentration of the endowment-active LaP04 phosphor to a range of 1 to 3%, the electric power input to the lamp can be converted into vacuum ultraviolet light with a very high efficiency. Further, in the case of a low-pressure mercury lamp, even if the input to the lamp is made high, the problem that the luminous efficiency near the lamp of 1 8 5 nm is lowered does not occur, and the cooling device can be miniaturized. [Embodiment] Fig. 1 is a cross-sectional view of a fluorescent lamp of the present invention, (A) is a cross-sectional view in the axial direction, and (B) is a cross-sectional view taken along line A-A. In the figure, the fluorescent lamp 1 is disposed on a pair of outer electrodes 3, 4 opposed to the outer peripheral surface of the arc tube 2 made of quartz glass. The other electrodes 3, 4 are generally strip-shaped shapes extending in the direction of the tube axis, for example, by mixing silver (201225152)
Ag )與粉玻璃之銀膠、混合金（Au )與粉玻璃之金膠等 的導電膜所形成。 於前述外部電極3、4上，覆蓋有由玻璃層所成的保護 膜7、8，於該外部電極3、4分別連接導線Wl、W2，該等 連接於產生高頻電壓的電源9。 前述發光管2係由對於波長18 5nm的真空紫外光具有高 透射性的合成石英玻璃所成。進而，爲了有良好的紫外線 照射維持率，使用OH基含有量較高的合成石英玻璃，例 如，可使用信越石英公司製的F310。 然後，於該發光管2內，作爲放電氣體而封入稀有氣 體，但是，作爲稀有氣體係僅爲氙或爲氙與其他稀有氣體 的混合氣體之任一皆可。 如圖1 ( B )及圖2所詳細揭示般，於發光管2的內面， 玻璃層5以幾近擴散至全區域之方式形成，並以層積於此 玻璃層5的內表面上之方式形成螢光體層6。再者，如後述 般’於發光管與玻璃層之間，除了一部分之外，也可形成 紫外線反射膜。 前述玻璃層5係用以對於構成發光管2的石英玻璃而使 螢光體層6附著者，作爲其玻璃特性，理想爲軟化點在螢 光體的燒成溫度（400〜900 °C )範圍者。 例如，軟質玻璃及硬質玻璃，理想爲有良好耐熱衝擊 性的硬質玻璃。作爲具體的材質，硬質玻璃之狀況中’硼 矽酸玻璃（S i - B - 0系玻璃，軟化點：約8 0 0 °C )、矽酸鋁 玻璃（S i - A1 - Ο系玻璃，軟化點：約9 〇 〇 °C )、或者以該等 201225152 任一的組合爲基準’添加鹼土氧化物或鹼金屬氧化物、金 屬氧化物的玻璃爲佳。 關於此種玻璃層5，如日本特開2010-56007號公報所 記載，藉由使螢光體層6與發光管2之間中介存在玻璃層5 ，發揮可將螢光體的燒成溫度設定爲較低，可穩定地保持 螢光體層6的作用效果者。而且，成爲可抑制玻璃層5所致 之透射率的降低，可有效率地放射所期望之紫外光的燈。 構成螢光體層6的螢光體，係被照射藉由發光管內之 氙氣的準分子發光所放射之172nm等的真空紫外光，藉此 激發，於波長185ηιη具有發光峰値者，利用以下述一般式 表示之钕賦活的LaP04螢光體。 (Lai-x，Ndx ) PO4 藉由使用前述螢光體，可提供將波長185nm的發光特 性設爲最大，效率極爲良好的螢光燈。 針對此種螢光燈舉出具體的數値的話，如以下所述。 發光管的全長：約300〜2000mm，管的厚度：0.5〜 2mm。又’螢光體層的平均厚度：1〇〜20 μιη，形成於螢光 體層與發光管之間的由低軟化點玻璃所成之玻璃層的厚度 :1 〜3 0 μ m 〇 圖3係關於本發明之其他實施形態之螢光燈的剖面圖 。於在發光管2的內面形成紫外線反射膜10，切除其圓周 狀的一部份來形成光圏11，於該紫外線反射膜1 〇上，層積 . 形成玻璃層5與螢光體層6者。 • 前述紫外線反射膜10，係包含焦磷酸鈣（Ca2P207 ) -9- 201225152 、磷酸鈣（Ca3 (P〇4) 2)、焦磷酸鎂（Mg2P2〇7) &Ba-N a - S i - Ο、S i Ο 2、A丨2 Ο 3之任一者，該等總量以超過5 0 %的 範圍包含於膜中爲佳。 依據此實施形態’在發光管2內產生之紫外線係一邊 在該發光管內藉由紫外線反射膜10反射’—邊以光圏11部 份的螢光體層6、玻璃層5之順序透光’往發光管2的外部 具有指向性而放射。 以下，說明本發明的具體例。 1. 螢光體的製造方法 首先，製作銨賦活LaP04螢光體時，作爲原材料，使 用 La203，H2P04，Nd20 3 的粉末。 在此具體例中，在將一般式以（Lai-x，Ndx ) ?〇4來表 示時，以成爲χ=〇·〇1〜0.11的組成比之方式進行調製。以 成爲設定之化學計量比例之方式秤量並混合原料粉末，進 行燒成。燒成條件係在大氣中（或混入若干還原性氣體亦 可）以1 200〜1 400 °C，進行約2h程度。燒成後，以進行粉 碎，平均粒徑成爲約3〜5μιτι之方式進行分級。 2. 螢光燈的製作 依據圖1所示之構造，製作外部電極型的稀有氣體蛋 光燈1。發光管2係由透射真空紫外光的合成石英玻璃所成 。於此合成石英玻璃製之發光管2的內表面，覆蓋低溶點 玻璃的粉末’形成玻璃層5，改善與螢光體層6的附著性。 -10- 201225152 ' 在螢光體的塗佈時，將該螢光體與加有硝化纖維素的醋酸 丁酯混合，製作螢光體漿液，並塗佈於前述的螢光管內面 〇 接下來，於發光管2的外表面上，將金或混合銀與粉 玻璃的膠材作網板印刷並燒成，藉此形成外部電極3、4。 進而，於該等電極3、4上，將使Si-B-0的玻璃粉末成爲膠 狀者作網板印刷來進行印刷並燒成。如此，形成於電極上 的玻璃層係具有作爲電極表面的保護膜7、8的功能。在此 使用的玻璃材係膨脹係數爲30x1 0_1 2 3 4 5 ( 1/K )以下者爲佳。 又，於發光管2，將乂6氣體封入21.31^&(1601'〇1*〇。 1 .點燈實驗 2 將如上所製作之螢光體的組成不同的螢光燈1連接於 點燈電源9，施加VC.P=1 700V的矩形波而使其點燈，進行 放射之光線的分光光譜測定。測定使用分光器（牛尾電機 製，USR40及VUV分光器）。 3 於圖4，揭示銨的莫耳濃度χ = 0.02 ( 2莫耳％ )的分光 分布圖。 4 又，於圖5揭示銨濃度與波長185nm之放射強度的關係 。再者，在同圖中，使用钕濃度爲1·5莫耳％之螢光體的燈 表示出最大強度，故將此設爲1 〇〇%，以相對値表示其他強 度。 5 如同圖所不’可知銳濃度爲1〜3莫耳％的範圍，爲大 略7 0%以上的範圍，可爲實用範圍。 201225152 如以上所說明般，依據關於本發明的螢光燈，可藉由 設爲螢光體層包含利用鈸賦活的LaP〇4螢光體，有效率地 放射於波長185nm附近具有峰値的真空紫外光。 【圖式簡單說明】 〔圖1〕本發明之螢光燈的剖面圖。 〔圖2〕圖1之B部的放大剖面圖》 〔圖3〕揭示本發明其他實施形態之螢光燈的剖面圖 〇 〔圖4〕揭示本發明之螢光燈的發射光譜之一例的圖 〇 〔圖5〕揭示（Lai.x,Ndx ) P04螢光體的Nd濃度（X ) 與發光強度之關係的圖表。 〔圖6〕以相對値揭示先前之低壓水銀燈的每一放射 波長之光輸出的圖。 【主要元件符號說明】 1 :螢光燈 2 :發光管 3，4 :電極 5 :玻璃層 6 :螢光體層 7，8 :電極保護膜 1 〇 :紫外線反射膜 1 1 :光圈 -12-Ag) is formed by a conductive film such as silver paste of powdered glass, gold (Au), and gold glue of powdered glass. The external electrodes 3, 4 are covered with protective films 7, 8 made of a glass layer, and the external electrodes 3, 4 are connected to wires W1, W2, respectively, which are connected to a power source 9 for generating a high-frequency voltage. The arc tube 2 is made of synthetic quartz glass having high transmittance for vacuum ultraviolet light having a wavelength of 18 5 nm. Further, in order to have a good ultraviolet irradiation maintenance ratio, synthetic quartz glass having a high OH group content is used. For example, F310 manufactured by Shin-Etsu Co., Ltd. can be used. Then, a rare gas is enclosed in the arc tube 2 as a discharge gas. However, the rare gas system may be either helium or a mixed gas of helium and other rare gases. As shown in detail in FIG. 1(B) and FIG. 2, on the inner surface of the arc tube 2, the glass layer 5 is formed to be diffused to the entire area, and is laminated on the inner surface of the glass layer 5. The phosphor layer 6 is formed in a manner. Further, as will be described later, an ultraviolet reflecting film may be formed between the arc tube and the glass layer in addition to a part. The glass layer 5 is used for attaching the phosphor layer 6 to the quartz glass constituting the arc tube 2, and as the glass property, it is preferable that the softening point is in the range of the firing temperature (400 to 900 ° C) of the phosphor. . For example, soft glass and hard glass are preferably hard glass having good thermal shock resistance. As a specific material, in the case of hard glass, 'boron silicate glass (S i - B - 0 glass, softening point: about 800 ° C), aluminum silicate glass (S i - A1 - bismuth glass, Softening point: about 9 〇〇 ° C), or a glass containing an alkaline earth oxide or an alkali metal oxide or a metal oxide based on a combination of any of these 201225152. In the glass layer 5, as described in Japanese Laid-Open Patent Publication No. 2010-56007, the glass layer 5 is interposed between the phosphor layer 6 and the arc tube 2, so that the firing temperature of the phosphor can be set to Lower, the effect of the phosphor layer 6 can be stably maintained. Further, it is a lamp which can suppress a decrease in transmittance due to the glass layer 5 and can efficiently emit desired ultraviolet light. The phosphor constituting the phosphor layer 6 is excited by ultraviolet ray of 172 nm or the like which is emitted by excimer light emission of helium in the arc tube, and has a luminescence peak at a wavelength of 185 η, and is used as follows. The general formula indicates the active LaP04 phosphor. (Lai-x, Ndx) PO4 By using the above-described phosphor, it is possible to provide a fluorescent lamp having a maximum luminous efficiency of 185 nm and an extremely excellent efficiency. A specific number of such fluorescent lamps is as follows. The total length of the light-emitting tube is about 300 to 2000 mm, and the thickness of the tube is 0.5 to 2 mm. Further, the average thickness of the phosphor layer: 1 〇 20 πηη, the thickness of the glass layer formed by the low-softening point glass formed between the phosphor layer and the arc tube: 1 to 3 0 μ m 〇 Figure 3 is about A cross-sectional view of a fluorescent lamp according to another embodiment of the present invention. An ultraviolet reflecting film 10 is formed on the inner surface of the arc tube 2, and a portion of the circumference is cut away to form a diaphragm 11 which is laminated on the ultraviolet reflecting film 1 .. The glass layer 5 and the phosphor layer 6 are formed. . • The ultraviolet reflecting film 10 includes calcium pyrophosphate (Ca2P207)-9-201225152, calcium phosphate (Ca3(P〇4) 2), magnesium pyrophosphate (Mg2P2〇7) &Ba-N a - S i - In any of Ο, S i Ο 2, A 丨 2 Ο 3, it is preferred that the total amount is included in the film in a range of more than 50%. According to this embodiment, the ultraviolet ray generated in the arc tube 2 is reflected by the ultraviolet ray reflection film 10 in the illuminating tube, and is transmitted in the order of the phosphor layer 6 and the glass layer 5 of the pupil 11 portion. It is directed to the outside of the arc tube 2 and is emitted. Hereinafter, a specific example of the present invention will be described. 1. Method for producing a phosphor First, when an ammonium-activated LaP04 phosphor is produced, a powder of La203, H2P04, and Nd20 3 is used as a raw material. In this specific example, when the general formula is expressed by (Lai - x, Ndx ) ? 4, the modulation is performed so as to have a composition ratio of χ = 〇 · 〇 1 to 0.11. The raw material powder is weighed and mixed in such a manner as to be a stoichiometric ratio, and is fired. The firing conditions are carried out in the atmosphere (or a plurality of reducing gases may be mixed) at about 1 200 to 1 400 ° C for about 2 hours. After the calcination, the powder was pulverized, and the average particle diameter was about 3 to 5 μm. 2. Production of fluorescent lamp According to the structure shown in Fig. 1, an external electrode type rare gas egg light lamp 1 was produced. The arc tube 2 is made of synthetic quartz glass that transmits vacuum ultraviolet light. Here, the inner surface of the arc tube 2 made of quartz glass is synthesized, and the powder covering the low-melting point glass is formed to form the glass layer 5, thereby improving the adhesion to the phosphor layer 6. -10- 201225152 ' At the time of coating the phosphor, the phosphor is mixed with butyl acetate added with nitrocellulose to prepare a phosphor slurry, which is applied to the inner surface of the fluorescent tube. Next, on the outer surface of the arc tube 2, gold or a mixed material of mixed silver and powder glass is screen-printed and fired, whereby the external electrodes 3, 4 are formed. Further, on the electrodes 3 and 4, the glass powder of Si-B-0 was gel-coated, and screen printing was performed to carry out printing and baking. Thus, the glass layer formed on the electrode functions as the protective films 7, 8 as the electrode surface. The glass material used here has a coefficient of expansion of 30x1 0_1 2 3 4 5 (1/K) or less. Further, in the arc tube 2, 乂6 gas was sealed in 21.31^& (1601'〇1*〇. 1. Lighting experiment 2. The fluorescent lamp 1 having a different composition of the phosphors produced as above was connected to the lighting. The power supply 9 was applied with a rectangular wave of VC.P = 1 700 V to illuminate the spectroscopic spectrum of the emitted light. The measurement was performed using a spectroscope (oxtail mechanism, USR40 and VUV spectroscope). 3 The spectroscopic distribution of ammonium molar concentration χ = 0.02 (2 mol%). 4 Further, the relationship between the ammonium concentration and the radiation intensity at a wavelength of 185 nm is shown in Fig. 5. Furthermore, in the same figure, the radon concentration is 1 · The lamp of 5 mol% phosphor shows the maximum intensity, so this is set to 1 〇〇%, and the other intensity is expressed relative to 値. 5 As the figure does not, the sharp concentration is 1~3 mol%. The range is approximately 70% or more, which is a practical range. 201225152 As described above, according to the fluorescent lamp of the present invention, it is possible to include the LaP〇4 fluorescent light using the endowment activity by using the phosphor layer as the phosphor layer. The body is efficiently radiated to the vacuum ultraviolet light having a peak 附近 near the wavelength of 185 nm. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] A cross-sectional view of a fluorescent lamp of the present invention. Fig. 2 is an enlarged cross-sectional view of a portion B of Fig. 1. Fig. 3 is a cross-sectional view showing a fluorescent lamp according to another embodiment of the present invention. 4] A diagram showing an example of an emission spectrum of a fluorescent lamp of the present invention (Fig. 5) reveals a graph of the relationship between the Nd concentration (X) of the (Lai.x, Ndx) P04 phosphor and the luminescence intensity. 〕 A diagram showing the light output of each of the radiation wavelengths of the previous low-pressure mercury lamp in a relative manner. [Main component symbol description] 1 : Fluorescent lamp 2 : Illuminating tube 3, 4: Electrode 5: Glass layer 6: Phosphor layer 7 , 8 : Electrode protective film 1 〇: Ultraviolet reflective film 1 1 : Aperture-12-