201201247 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種作為例如面向液晶面板之製造，用以 對製造中途之面板（被處理基板）照射以紫外線之紫外線照 射裝置、紫外線照射方法及製造此種紫外線照射裝置之方 法。 【先前技術】 作為面向液晶面板的製造之紫外線照射裝置，存在具有 紫外線燈、以及位於該紫外線燈的外側而在内部設置有紫 外區域透射濾光片之水冷套管之構成者。紫外區域透射濾 光片係可使被照射物所必需之特定波長範圍之紫外線透射 之分光濾光片。此種分光濾光片由於會因來自紫外線燈之 紫外線而於其自身產生紫外線透射特性之劣化，因此在該 紫外線照射裝置中，會需要在來自紫外線燈之紫外線到達 至分光濾光片之前，預先截斷較上述特定的波長範圍更短 波長之紫外線之機構（例如’參照jPH6_267509(KOKAI))。 利用此種機構，作為紫外線照射裝置可改善紫外線輸出働 程特性，且可謀求其長壽命化β 上述專利文獻之紫外線截斷機構係對玻璃或石英素材施 以預先添加或是在表面蒸鍍可抑制更短波長的紫外線之金 屬氧化物等之加工而獲得之紫外線截斷濾光片。在上述專 利文獻中，係令此種紫外線截斷濾光片在空間上位於相較 於紫外區域透射滤光片更靠紫外線燈之側。此種紫外線截 斷濾光片會在製造上花費工夫且較昂貴。 15352l.doc 201201247 作為面向液晶面板之製造之紫外線照射裝置，除如上述 之構成以外’亦可考慮的是，為使因被照射物所必需之特 疋的波長範圍（例如自320 nm至380 nm為止）之紫外線透 射’而將短波長側之紫外線截斷濾光片與長波長側之光截 斷濾光片在空間上縱列配置之構成者。即使在此種構成 中，作為短波長側之紫外線截斷濾光片，亦可使用藉由朝 如上述專利文獻中所揭示之金屬氧化物的玻璃中添加或是 朝玻璃表面蒸鍍所形成者。在該情形下，在製造大型液晶 面板之設備中，雖可採用將紫外線截斷濾光片覆滿特定之 較大面積之構成，但在其構成中，會有在其對接面產生漏 光或由熱所引起的膨脹收縮而導致產生應力之可能性。 【發明内容】 本發明之目的在於提供一種紫外線照射裝置、紫外線照 射方法及紫外線照射裝置之製造方法，其係作為例如面向 液晶面板之製造，用以對製造中途之面板（被處理基板）照 射以紫外線之紫外線照射裝置、紫外線照射方法及製造此 種紫㈣照射裝置之方法，且具㈣_必要的紫外線之 效果尚且低成本的紫外線截斷濾光片。 為解決上述之問題 ，本發明一態様之紫外線處理裝置之 特徵為’、#.具有筒狀石英玻璃素材的發光管之金屬鹵素 U重：，其具備設置在以筒狀包圍前述金屬函素燈的201201247 VI. [Technical Field] The present invention relates to an ultraviolet ray irradiation device, an ultraviolet ray irradiation method, and the like, which are used for manufacturing a liquid crystal panel, for example, for irradiating a panel (substrate to be processed) in the middle of manufacturing with ultraviolet rays. A method of manufacturing such an ultraviolet irradiation device. [Prior Art] As an ultraviolet irradiation device for manufacturing a liquid crystal panel, there is a structure including an ultraviolet lamp and a water-cooling jacket which is located outside the ultraviolet lamp and is provided with a violet-region transmission filter inside. The ultraviolet region transmission filter is a spectral filter that transmits ultraviolet light of a specific wavelength range necessary for the object to be irradiated. Such a spectroscopic filter has a deterioration in ultraviolet light transmission characteristics due to ultraviolet rays from the ultraviolet lamp. Therefore, in the ultraviolet irradiation device, it is necessary to advance the ultraviolet light from the ultraviolet lamp to the spectroscopic filter. A mechanism for cutting off ultraviolet rays having a shorter wavelength than the above specific wavelength range (for example, 'refer to jPH6_267509 (KOKAI)). According to such a mechanism, the ultraviolet light irradiation device can improve the ultraviolet output process characteristics and can achieve a long life. The ultraviolet cut mechanism of the above patent document applies pre-addition to glass or quartz material or can be suppressed by surface evaporation. An ultraviolet cut filter obtained by processing a metal oxide such as a shorter wavelength ultraviolet ray. In the above patent document, such an ultraviolet cut filter is spatially located closer to the side of the ultraviolet lamp than the ultraviolet filter of the ultraviolet region. Such UV cut filters can be labor intensive and expensive to manufacture. 15352l.doc 201201247 As an ultraviolet irradiation device for the manufacture of a liquid crystal panel, in addition to the above-described configuration, it is also conceivable that the wavelength range necessary for the object to be irradiated (for example, from 320 nm to 380 nm) In the ultraviolet light transmission of the above, the ultraviolet cut filter on the short wavelength side and the light cut filter on the long wavelength side are arranged in a space. In such a configuration, the ultraviolet cut filter on the short-wavelength side may be formed by adding it to the glass of the metal oxide as disclosed in the above patent document or by vapor deposition on the glass surface. In this case, in the apparatus for manufacturing a large liquid crystal panel, although the ultraviolet cut filter may be covered with a specific large area, in the configuration, light leakage or heat may occur on the mating surface. The resulting expansion shrinkage leads to the possibility of stress. SUMMARY OF THE INVENTION An object of the present invention is to provide an ultraviolet irradiation device, an ultraviolet irradiation method, and a method for producing an ultraviolet irradiation device, which are used, for example, to manufacture a liquid crystal panel for irradiating a panel (substrate to be processed) in the middle of manufacturing. Ultraviolet ultraviolet irradiation device, ultraviolet irradiation method, and method for producing such a violet (four) irradiation device, and having a low-cost ultraviolet cut filter which has the effect of (4) necessary ultraviolet rays. In order to solve the above problems, the ultraviolet processing apparatus of the present invention is characterized by ', #. the metal halide U weight of the light-emitting tube having the cylindrical quartz glass material: it is provided to surround the metal element lamp in a cylindrical shape of
的第2管之外管， 、巴闽战円管之位置之筒狀石英玻璃素材 且以可在前述第1管與前述第2管之間的 153521.doc 201201247 空間使流體流動之方式使該第1管與該第2管之間的前述空 間為封閉空間；及形設在前述雙層管之前述外管之外面 上、或是前述雙層管之前述内管的對向於前述金屬齒素燈 之面上之膜厚為0.3 μιη以上、1.3 pm以下之含有鈦之氧化 膜。 根據本發明，可提供一種具有截斷非必要的紫外線之效 果高且低成本的紫外線截斷濾光片之紫外線照射裝置、紫 外線照射方法及此種紫外線照射裝置之製造方法。 【實施方式】 (實施例之説明） 本發明之實施例雖參照圖面進行了記述，但該等圖面僅 是用作圖解之目的而予以提供，在任何情況下皆不限定發 明。 以下，茲就用以實施本發明之形態，一面參照圖面一面 進行詳細地説明。 圖1係顯示本發明一實施形態之紫外線照射裝置的構成 之縱剖面圖，圖2係圖i中所示iA_Aa位置之箭頭角度方向 的剖面圖。 如圖1 ' w2所示，該紫外線照射裝置係由金屬鹵素燈 0以及冷却單元2〇〇構成。金屬鹵素燈丨⑽與冷却單元 〇(其雙層管）之間係藉由安裝在金屬_素燈⑽的插座 51 352上之固持器m、112而設定為特定之間隔。 兹參照圖3及圖4，就金屬齒素燈1〇〇進行説明。圖3係顯 不圖1中所不之金屬鹵素燈的構成之縱剖面圖，圖4係顯示 15352 丨.doc 201201247 將圖3的圖示一部分放大之縱剖面圖。 如圖3、圖4所示，金屬鹵素燈100具備有紫外線透射性 之由例如石英玻璃形成放電空間3〇之發光管3丨。發光管3工 具有筒狀形狀’在其長度方向兩端之内部配置有例如鶴製 之電極321、322。 電極321、322係分別介以内引腳33 i、332而焊接在例如 鉬製之金屬箔341、342的一端。在金屬箔341、342的另一 端焊接有未圖示之外引腳的一端。金屬箔341、342的一部 分係加熱且密封内引腳331、332與外引腳之間之發光管31 者。在發光管31的内部除稀有氣體以外，還封入有例如 汞、鐵、錫及破化汞。 金屬箔341、3 42只要為接近形成發光管31之石英玻璃的 熱膨脹率之材料即可，作為適於該條件者，係使用鉬。在 一端分別與金屬箔341、342連接之外引腳的另一端，電性 連接有絕緣密封在例如陶瓷製之插座35 1、352内之供電用 的導線361、362，且導線121、122係與未圖示之電源電路 連接。 如上述般構成之金屬鹵素燈100可作為例如外徑為27 f mm，發光長為1000 „1111的長電弧對應者。圖5係顯示圖叉中 所示之金屬函素燈放射之光的分光分佈之例的特性圖。更 具體而言，係顯示使燈電壓為1310 v、燈電流為1〇3 A、 燈功率為12 kW進行點燈之情形之分光分佈。 再者，參照圖1、圖2，冷却單元2〇〇具有雙層管，該雙 層管具備與金屬鹵素燈1〇〇之發光管31具有同樣之紫外線 153521.doc -6 - 201201247 透射性之石英玻璃製的内管12(内徑為32 mm、外役為36 mm)、及設置在内管丨2的外側之具有與發光管3丨同様的紫 外線透射性之石英玻璃製的外管13(内徑為64 mm、外徑為 70 mm)»内管12係設置在以筒狀包圍發光管31之位置，外 管13係設置在以筒狀包圍内管12之位置。内管12與外管13 之間成為以可使流體流動之方式封閉之空間，通過該空 間’可使冷卻用媒體之水等之水溫為25°C左右之冷却水丄5 自設置在外周端部之連接管141朝連接管142自外部循環。 更具體而言，係使溫度較低之冷却水15自連接管14 1注 水，自連接管142使進行金屬鹵素燈1〇〇之冷却後而被加溫 之冷却水15出水。以使經加溫之冷却水15再次冷却且再次 自連接管141注水之方式，使冷却單元2〇〇整體成為循環構 造。 外管13係由例如至少包含Si〇2為5〇%以上之石英玻璃製 形成’進而，在外管13之外面上形成有以Ti為主要成份之 氧化膜16 ^氧化膜16係利用浸潰等之方法塗佈成為原料之 氧化物溶液’而後以例如ll〇〇t左右之高溫進行加熱處理 (熔接、培燒），使其同樣定著、覆蓋在外管13的外面上 者。 利用浸潰之溶液的塗佈係以使冷却單元2〇〇的雙層管在 長度方向上改變其朝向，並複數次自收容有氧化物的溶液 之槽内拉起之方式進行之。藉此，經塗佈之膜厚變得相 同’而有與氧化膜16同樣之形成。 氧化膜16可將自金屬鹵素燈1〇〇予以放射之光中波長未 153521.doc 201201247 達320⑽之非必要紫外線截斷。其分光特性係例如圖6所 在V却單元200之雙層管的ia之區域、比之區域變為大 致相同之分光透射率。其可叔姑你备 再了根據與氧化膜16相同之形成膜 厚（圖6所示之情形之名稱㈣成膜厚為0.7㈣。 圖7A、B、C係作為非必要紫外線截斷滤光片形成在其 外面上之比較例之水冷套管之觀察與其軸向不同之各區域 的表面狀態之顯微鏡照片。浸潰雖係、比較廉價的膜形成方 法仁右使膜厚形成為薄，則截斷未達特定波長（例 如320 的紫外線之效果會變得不充分，反之若形成為厚則 會易於產生裂縫等機械性特性之困難。若產生裂縫，則會 由於自此處茂漏非必要紫外線’而使截斷非必要紫外線之 效果變得不充分。將此種裂縫產生之例作為比較例，參照 圖7A、B、C、圖8進行説明。該财之非必要紫外線截斷 濾光片係在水冷套管的外側之面上浸潰特定的溶液（溶媒 與溶質）’而後加熱處理其等而形成之;慮光片。為觀察膜 厚與裂縫產生之關係、’在浸潰中，會故意在水冷套管的轴 向上改變利用浸潰之膜的厚度。 圖7A、B、C之（II)、（III)、（IV)係分別顯示使此種非必 要紫外線截斷濾光片形成在其外面上之與水冷套管的轴向 不同之各區域的表面狀態。各區域係顯示與圖8之圖橫向 對應。雖紫外線截斷濾光片之膜厚係自（11)朝向（ιν)依序 為厚，但如圖7A、B、C所示，在與其相同之（11)至（ιν)之 方向上裂縫產生顯著。且’如圖8之圖所示，非必要紫外 線截斷之特性會劣化至（IV)側之程度。圖8係測定非必要 153521.doc 201201247 兔外線截斷濾光片之分光透射率之圖，（II)、（III)、（IV)之 各自之複數個圖係對應於在各區域内不同之位置的測定結 果。 圖1、圖2中所示之氧化膜16 一般會根據成膜原料之比 率、溶液之塗佈厚度條件及其加熱處理條件等，使其紫外 線截斷特性變動。利用其等，可獲得雖在某種程度之範圍 内但具有所期望之紫外線截斷特性之分光濾光片。為獲得 所期望之紫外線截斷特性，在需要將氧化膜16之膜厚形成 為厚之情形下，亦可將原料溶液之塗佈次數次數增多。 又，為提高形成為較厚之膜厚之氧化膜16的機械性強度， 作為成膜原料添加Ta係有效者（後述）。 作為特性例，在原料溶液中之重量比為si〇yTi〇2: 2〇5 45.45.1〇之情形下形成之氧化膜16中，可設為波長 在350 nm附近透射率為5〇%左右，波長在32〇 近透射 率為5%以下之分光濾光片。 圖9係顯示圖6所示之特性根據氧化膜16之厚度如何變化 特陡比較圖。自圖示之A朝向D，顯示在膜厚較厚之情 形下的特性。如圖9所示，#由改變氧化膜16的膜厚，可 使紫外線截斷特性具有控制性而變動。 將上述之紫外線照射裝置設為1個單元，且利用複數個 (=5個單①）其等可構成液晶面板製造裝置。該液晶面板 製^裝置可使在液晶面板製造步驟中為必要的具有例如如 、生所τ之刀光分佈之光予以放射。藉此，在液晶面板製 b驟中’可—面抑制對液晶面板之不良影響，—面放射 153521.doc 201201247 適合於該步驟之紫外光。圖11係顯示將圖10所示之圖示中 的波長為360 nm以下之部分放大顯示之特性圖。另，圖10 及圖11係使用減光濾光片（使光強度減少之測定用濾光片） 測定之結果。 圖12 A、B係顯示圖1所示之紫外線照射裝置放射之紫外 線的強度測定之結果例的表。茲參照圖12A、B，就該紫 外線照射裝置之對製造中途之液晶面板有不良影響之波長 區域的紫外線強度進行説明。該圖係未通過減光濾光片測 定之結果。 圖12A係由在波長340 nm〜400 nm中具有感度峰值之例 如奥克（OAK)公司製的強度計「UV-35」、或是USHIO電機 公司製的強度計「UVD-S365」所測定之結果。圖12B係由 在波長300 nm~320 nm中具有感度峰值之例如奥克公司製 之強度計「UV-3 1」所測定之結果。可觀察到，對製造中 途之液晶面板帶來劣化損傷之紫外線的波長未達320 nm。 另一方面，製造中途之液晶面板所必需之紫外線的波長為 例如320 nm〜380 nm。因而，在將圖12A所示之測定結果 設為100%之情形下’圖12B所示之測定結果較小為佳，具 體而言，在5 °/〇以下為佳。更佳的是在1 %以下。 於圖12A中，作為利用在波長34〇 nm~400 nm中具有感 度峰值之強度計所得之結果，光之強度最大為9〇 mW/cm2，最小為 77·2 mW/cm2，平均為 85 6 mW/cm2。 又’同圖B中，作為利用在波長3〇〇 nm〜320 nm中具有感度 峰值之強度計所得之結果’光之強度最大為〇118 153521.doc •10- 201201247 mW/cm2。最小為 0,09 mW/cm2，平均為 〇 1〇5 mW/cm2。 因而，比較最大値彼此為約〇13%，比較最小値彼此為 約0.12%，比較平均値彼此為約〇12%。該等相較於非常佳 之1%為小。因此，根據該紫外線照射裝置，可一面抑制 對製造中途之液晶面板的劣化損傷，一面對其等照射以所 期望波長之紫外線。 接著，圖13係顯示與圖5不同之圖1中所示之金屬齒素燈 放射之光的分光分佈之例的特性圖。該情形之金屬自素燈 1〇〇除稀有氣體以外，還封入有汞、碘化鉈（T1I)。其點燈 之條件係燈電壓為1.31 kV，燈電流為1〇 3 a ,燈功率為12 kW。 圖14係顯示與圖10不同之圖i所示之紫外線照射裝置放 射之光的分光分佈之例的特性圖，具體而言係使用在圖13 中顯不特性之金屬鹵素燈100之紫外線照射裝置之情形 者。在此種分光分佈之紫外線放射中，亦可一面抑制對製 造中途的液晶面板之不良影響，一面進行適於其步驟之紫 外線照射。另，圖15係顯示將圖丨4所示之圖示中之波長為 360 nm以下放大之特性圖。圖14、圖15與圖1〇、圖u所示 之情形相同，係使用減光濾光片進行測定之結果。 圖16A、B係顯示與圖12A、B所示者不同之，所示之紫 外線照射I置放射之紫外、線的強度測定之結果例的表。兹 參照圖16A、B，就該紫外線照射裝置之對製造中途的液 晶面板有不良影響之波長區域的紫外線強度進行説明。圖 16A、B係未通過減光濾光片進行測定之結果。另，在圖 153521.doc 201201247 16A、B中，關於其使用之強度計、其看法或評估係與在 圖12A、B中之説明相同。 圖16A係顯示作為利用波長為34〇 nm〜4〇〇 中具有感 度峰值之強度計之結果，光之強度最大為83 3 ， 最小為71 mW/Cm2 ’平均為78 4 mW/cm2。又，圖i6B係顯 示作為利用波長為3〇〇 nm〜320 nm中具有感度峰值之強度 計之結果’光之強度最大為〇 〇93 mW/cm2，最小為〇 〇77 mW/cm2，平均為 0.086 mw/Cm2。 因而，比較最大値彼此為約〇.112%，比較最小値彼此為 約0.108%，比較平均値彼此為約〇11〇%。該等相較於非常 佳之10/〇以下為小。因此，即使作為使用封入有碘化鉈之 金屬函素燈之紫外線照射裝置，亦可一面抑制對製造中途 之液晶面板的劣化損傷，一面對其照射以所期望波長的紫 外線》 接著，茲就製造中途的液晶面板所需要之紫外線的波長 進行説明。其可作為使在製造液晶面板之時令使用之紫外 線硬化型樹脂開始硬化之光起始劑的吸收波長頻帶予以規 定’例如為320 nm〜380 nm。作為此種光起始劑。可舉的 是’ 2,2-二曱氧基-2-苯基。將該光起始劑之光吸收特性顯 示在圖17中。在圖17中，「0.0020%」、「0.0011%」係表示 樹脂中之濃度。在圖17中，在波長為200 nm台座中雖顯示 有較大吸收特性，但藉由實際照射之紫外線的波長為320 nm〜3 80 nm之紫外線吸收，可使上述物質作為光起始劑發 揮功能。 153521.doc -12· 201201247 在以上實施形態中，由於利用氧化物16之非必要紫外線 截斷濾光片係形成在雙層管之外管13的外面上，因此可抑 制在照射較大面積之時自成為問題之對接面之漏光、或由 熱所引起的膨脹收縮導致濾光片彼此之碰撞而引起破損等 之問題。X ’由於可使非必要紫外線截斷遽光片藉由對各 種形狀之物件的表面塗布原料溶液並加熱處理而形成，因 此有形成之自由度高且廉價之優點。形成的自由度較高係 意味著亦可使利用氧化物16之非必要紫外線截斷濾光片形 設在對向於雙層管之内管12的金屬函素燈1〇〇之面上。 在該實施形態中，可施加如以下般之變形。氧化膜16雖 說明了形設在外管13的外面上之情形，但如已説明般，亦 可形設在對向於雙層管之内管12的金屬齒素燈1〇〇之面 上’再者’亦可形設其等兩者。加之，亦可考慮的是，將 氧化膜16形設在面向内管12、外管13之冷却液之表面上。 在該It形下，作為氧化膜i 6之形成方法，亦可採用以浸潰 原料溶液等之方法進行塗佈，而後進行加熱處理使其定著 之方法。 原料溶液之浸潰雖如已説明般，可將冷却單元200之雙 層目在長度方向上改變其朝向’並以複數次自收容氧化物 的/谷液之槽内拉起之方式進行，但亦可採用如以下之方 法。亦即，並非一次性對外管13的長度方向整體塗佈，亦 可對例如每一半進行塗佈。更具體而言，第丨次是塗佈到 卜e 13的中間附近，第2次是自相反側塗佈到其中間附 近此時，由於可避免浸潰區域不足而導致紫外線之截斷 153521.doc 201201247 特性變得不全之區域產生，因此較佳的是，在外管η之長 度方向的中央以-部分膜重疊之方式浸潰，據此點，在 更長之外管13之情形下’亦可以整體進行同樣之膜厚的浸 潰。為實現更均勾之膜厚，亦可將上述第卜欠、第2次之操 作再進行一次（亦即合計4次之塗佈）。 接著’圖18係顯示本發明其他實施形態之紫外線照射裝 置的構成之縱剖面圖，圖19係圖18中所示之B_Ba位置之箭 頭角度方向的剖面圖。餅| 4 — m對與已说明之實施形態相同之構成 部分標注以同一符號，而省略其説明。 該實施形態係在冷却單元之雙層管的外面上未形成 氧化膜’而是與冷却單元200之外管13_，並在對向配 置之紫外線透射性的玻璃板i 6 2之面上形設以T i為主成分 之氧化膜161者。氧化膜161可利用例如印刷等之手法，作 為具有所期望之分光透射特性之膜厚者予以形成。 氧膜161係如圖示般除形成在對向於玻璃板⑹之冷却 單元_之⑽面）上以夕卜’亦可形成在玻璃板162的背面 上。再者’亦可形成在兩面上。 在違貫施形態之情形下’由於可在紫外線透射性之玻璃 板162上印刷原料溶液等之後進行加熱處理會形成氧化膜 161，因此在印刷之時點會易於進行其膜厚之調整。藉 此’作為氧化膜161亦會易於獲得所期望之分光透㈣ - …叫1 不又茱外踝照射j 進-步附加熱線吸收濾光片之方式予以構成。藉由附) 15352I.doc 201201247 為一種光學濾光片之熱線吸收濾光片而設置，可進一步確 實地截斷被照射物無需之例如400 nm以上之光。此種熱線 吸收渡光片可設置在圖18中所示之冷却單元2〇〇之雙層管 内。更具體而言’在雙層管之内管12與外管13之間的空間 内可以筒狀包圍内管12之方式予以定位。藉由在雙層管内 設置’可抑制該熱線吸收濾光片由熱線而過熱。 又’作為其他變形例’可在玻璃板162上設置氧化膜161 之光學濾光片，且以進一步具備熱線反射濾光片之方式予 以構成。該情形亦可藉由附加性設置作為一種光學濾光片 之熱線反射濾光片，而進一步確實地截斷被照射物無需之 例如400 nmw上之光。關於熱線反射濾光片，可利用由後 述之實施形態（圖22)説明般之構成者。 又，作為在金屬齒素燈1〇〇中封入之發光金屬，只要是 可使波長為例如320 nm〜380 nm之紫外線發光之金屬即可 採用〇 接著，茲就上述説明之紫外線照射裝置之氧化膜16(或 是即使氧化膜161亦相同。以下相同）針對其膜厚及其製造 步驟進行補充性之下述説明。雖已說明了藉由改變氧化膜 16之膜厚可使紫外線截斷特性具有控制性而變動，但首先 就其較佳之膜厚的範圍進行更具體的説明。 ..........、咏狀抓哀置具有之氧化 (非必要紫外線截斷濾光片）的分光透射率之、The outer tube of the second tube, the cylindrical quartz glass material at the position of the scorpion scorpion tube, and the fluid is flowed in a space of 153521.doc 201201247 between the first tube and the second tube. The space between the first pipe and the second pipe is a closed space; and the outer surface of the outer pipe of the double pipe or the inner pipe of the double pipe is opposite to the metal tooth An oxide film containing titanium having a film thickness of 0.3 μm or more and 1.3 pm or less on the surface of the lamp. According to the present invention, it is possible to provide an ultraviolet irradiation device, an ultraviolet irradiation method, and a method for producing such an ultraviolet irradiation device, which have a high-efficiency and low-cost ultraviolet cut filter which cuts off unnecessary ultraviolet rays. [Embodiment] (Description of Embodiments) The embodiments of the present invention have been described with reference to the drawings, but the drawings are provided for the purpose of illustration only, and the invention is not limited in any way. Hereinafter, the form for carrying out the invention will be described in detail with reference to the drawings. Fig. 1 is a longitudinal cross-sectional view showing the configuration of an ultraviolet irradiation apparatus according to an embodiment of the present invention, and Fig. 2 is a cross-sectional view taken along the line an angle of the iA_Aa position shown in Fig. i. As shown in Fig. 1 'w2, the ultraviolet irradiation device is composed of a metal halide lamp 0 and a cooling unit 2A. The metal halide lamp (10) and the cooling unit 〇 (the double pipe) are set to a specific interval by the holders m and 112 mounted on the socket 51 352 of the metal lamp lamp (10). Referring to Fig. 3 and Fig. 4, a metal gutta lamp 1 〇〇 will be described. Fig. 3 is a longitudinal sectional view showing the configuration of a metal halide lamp which is not shown in Fig. 1, and Fig. 4 is a longitudinal sectional view showing a part of Fig. 3 in an enlarged view of 15352 丨.doc 201201247. As shown in Figs. 3 and 4, the metal halide lamp 100 is provided with an ultraviolet light-transmitting light-emitting tube 3A having a discharge space of 3 Å, for example, quartz glass. The arc tube 3 has a cylindrical shape. Electrodes 321, 322 made of, for example, cranes are disposed inside the both ends in the longitudinal direction. The electrodes 321 and 322 are welded to one ends of, for example, metal foils 341 and 342 made of molybdenum via internal leads 33 i and 332, respectively. One end of a pin other than the one shown in the figure is welded to the other end of the metal foils 341 and 342. A portion of the metal foils 341, 342 heats and seals the arc tube 31 between the inner leads 331, 332 and the outer leads. In addition to the rare gas inside the arc tube 31, for example, mercury, iron, tin, and decarburized mercury are sealed. The metal foils 341 and 3 42 may be any material that is close to the thermal expansion coefficient of the quartz glass forming the arc tube 31, and molybdenum is used as a suitable condition. The other end of the pin, which is connected to the metal foils 341 and 342 at one end, is electrically connected to the wires 361 and 362 for insulating power supply, for example, in the ceramic sockets 35 1 and 352, and the wires 121 and 122 are connected. Connected to a power supply circuit not shown. The metal halide lamp 100 constructed as described above can be used as, for example, a long arc counterpart having an outer diameter of 27 f mm and an emission length of 1000 -1111. Fig. 5 is a view showing the splitting of the light emitted by the metal element lamp shown in the fork. The characteristic map of the example of the distribution. More specifically, the spectral distribution is shown in the case where the lamp voltage is 1310 v, the lamp current is 1 〇 3 A, and the lamp power is 12 kW for lighting. 2, the cooling unit 2A has a double tube having the same ultraviolet ray 153521.doc -6 - 201201247 transmissive quartz glass inner tube 12 as the light-emitting tube 31 of the metal halide lamp. (32 mm in inner diameter and 36 mm in external service), and an outer tube 13 made of quartz glass having an ultraviolet-transmitting property similar to that of the arc tube 3 disposed outside the inner tube 2 (inner diameter: 64 mm, The outer diameter is 70 mm)»the inner tube 12 is disposed at a position surrounding the arc tube 31 in a cylindrical shape, and the outer tube 13 is disposed at a position surrounding the inner tube 12 in a cylindrical shape. The inner tube 12 and the outer tube 13 become a space that allows the fluid to flow in a manner that allows the water of the cooling medium to be warmed by the space The cooling water enthalpy 5 of about 25 ° C is circulated from the outside to the connecting pipe 142 from the connecting pipe 141 at the outer peripheral end. More specifically, the cooling water 15 having a lower temperature is injected from the connecting pipe 14 1 and self-connected. The tube 142 discharges the cooling water 15 heated by the cooling of the metal halide lamp, so that the cooled cooling water 15 is cooled again and the water is again injected from the connection pipe 141 to cause the cooling unit 2 to be cooled. The outer tube 13 is formed of, for example, quartz glass containing at least 5 % by mass of Si 2 , and further, an oxide film 16 containing an oxide film as a main component is formed on the outer surface of the outer tube 13 . The oxide solution as a raw material is applied by a method such as dipping, and then heat-treated (welded, fired) at a high temperature of, for example, about 11 〇〇t, and is fixed to the outside of the outer tube 13 as well. The coating of the impregnated solution is performed such that the double tube of the cooling unit 2 turns its orientation in the longitudinal direction and is pulled up from the groove of the solution containing the oxide several times. Thus, the coated film thickness becomes The same pattern is formed as the oxide film 16. The oxide film 16 can cut off the unnecessary ultraviolet light having a wavelength of 153521.doc 201201247 up to 320 (10) from the light emitted from the metal halide lamp. The spectral characteristics are as shown in Fig. 6 The region of the ia of the double tube of the V unit 200 is substantially the same as the spectral transmittance of the region. It can be prepared by the same film thickness as the oxide film 16 (shown in Fig. 6). The name of the case (4) film thickness is 0.7 (four). Fig. 7A, B, and C are the surface states of the water-cooled sleeve of the comparative example formed on the outer surface of the non-essential ultraviolet cut filter, which are different from the axial direction thereof. Microscope photo. Although the film formation method of the impregnation is relatively inexpensive, the thickness of the film is thin, and the cutoff does not reach a specific wavelength (for example, the effect of ultraviolet rays of 320 is insufficient, and if it is formed thick, cracks are likely to occur. Difficulties in mechanical properties. If cracks are generated, the effect of cutting off unnecessary ultraviolet rays is insufficient due to leakage of unnecessary ultraviolet rays from here. An example of such crack generation is described as a comparative example, see FIG. 7A. B, C, and Fig. 8. The non-essential ultraviolet cut filter is formed by dipping a specific solution (solvent and solute) on the outer surface of the water-cooled sleeve and then heat-treating it; In order to observe the relationship between the film thickness and the crack, 'in the impregnation, the thickness of the film using the impregnation is intentionally changed in the axial direction of the water-cooled casing. Figure 7A, B, C (II), ( III) and (IV) respectively show the surface states of the regions different from the axial direction of the water-cooling sleeve formed on the outer surface of the non-essential ultraviolet cut filter. The respective regions are displayed transversely to the graph of Fig. 8. Corresponding. Although UV The film thickness of the cut filter is thick from (11) toward (ι), but as shown in Figs. 7A, B, and C, cracks are remarkable in the direction of (11) to (ι) which are the same. And, as shown in the graph of Fig. 8, the characteristics of the unnecessary ultraviolet cutoff will deteriorate to the extent of the (IV) side. Fig. 8 is a graph for measuring the spectral transmittance of the non-essential 153521.doc 201201247 rabbit external cut-off filter, ( The plurality of graphs of each of II), (III), and (IV) correspond to the measurement results at different positions in the respective regions. The oxide film 16 shown in Figs. 1 and 2 is generally based on the ratio of the film forming material. The coating thickness conditions of the solution, the heat treatment conditions, and the like change the ultraviolet cutoff characteristics, and a spectroscopic filter having a desired ultraviolet cutoff characteristic within a certain range can be obtained by using. When the desired ultraviolet cutoff characteristic is obtained, when the film thickness of the oxide film 16 needs to be formed thick, the number of times of application of the raw material solution can be increased. Further, in order to increase the thickness of the oxide film formed into a thick film thickness Mechanical strength of 16 as a film former It is effective to add a Ta system (described later). As a characteristic example, in the oxide film 16 formed in the case where the weight ratio of the raw material solution is si〇yTi〇2: 2〇5 45.45.1〇, the wavelength can be set to 350. A spectroscopic filter having a transmittance of about 5% in the vicinity of nm and a transmittance of 5% or less at a wavelength of 32 Å. Fig. 9 is a graph showing a comparison of the characteristics of the oxide film 16 according to the thickness of the oxide film 16. The characteristic shown in the case where A is thicker than D is shown in Fig. 9. As shown in Fig. 9, by changing the film thickness of the oxide film 16, the ultraviolet cut characteristic can be controlled and fluctuated. The ultraviolet irradiation device is one unit, and a plurality of (= five single ones) can be used to constitute a liquid crystal panel manufacturing apparatus. The liquid crystal panel manufacturing apparatus can radiate light having a light distribution of, for example, a knife τ which is necessary in the liquid crystal panel manufacturing step. Thereby, the adverse effect on the liquid crystal panel is suppressed in the liquid crystal panel manufacturing process, and the surface radiation 153521.doc 201201247 is suitable for the ultraviolet light of this step. Fig. 11 is a characteristic diagram showing an enlarged view of a portion having a wavelength of 360 nm or less in the diagram shown in Fig. 10. In addition, FIG. 10 and FIG. 11 are the results of measurement using a light-reducing filter (filter for measuring light intensity reduction). Fig. 12 is a table showing the results of the measurement of the intensity of the ultraviolet rays emitted by the ultraviolet irradiation device shown in Fig. 1. Referring to Figs. 12A and 12B, the ultraviolet light intensity of the wavelength region in which the ultraviolet ray irradiation device adversely affects the liquid crystal panel in the middle of manufacture will be described. This figure is the result of not being measured by the dimming filter. Fig. 12A is measured by a strength meter "UV-35" manufactured by OAK Co., Ltd., or a strength meter "UVD-S365" manufactured by USHIO Electric Co., Ltd., which has a sensitivity peak at a wavelength of 340 nm to 400 nm. result. Fig. 12B is a result measured by, for example, a strength meter "UV-3 1" manufactured by Oak Corporation at a wavelength of 300 nm to 320 nm. It can be observed that the wavelength of ultraviolet rays which cause deterioration damage to the liquid crystal panel in the middle of manufacturing is less than 320 nm. On the other hand, the wavelength of ultraviolet rays necessary for manufacturing a liquid crystal panel in the middle is, for example, 320 nm to 380 nm. Therefore, in the case where the measurement result shown in Fig. 12A is set to 100%, the measurement result shown in Fig. 12B is preferably small, and specifically, 5 ° / 〇 or less is preferable. More preferably, it is below 1%. In Fig. 12A, as a result of using an intensity meter having a sensitivity peak at a wavelength of 34 〇 nm to 400 nm, the intensity of light is at most 9 〇 mW/cm 2 , the minimum is 77·2 mW/cm 2 , and the average is 85 6 . mW/cm2. Further, in the same figure B, as a result of using an intensity meter having a sensitivity peak at a wavelength of 3 〇〇 nm to 320 nm, the intensity of light is 〇118 153521.doc •10-201201247 mW/cm2 at the maximum. The minimum is 0,09 mW/cm2 and the average is 〇 1〇5 mW/cm2. Thus, the maximum enthalpy is about 13% for each other, and the minimum 値 is about 0.12% for each other, and the average 値 is about 12% for each other. These are smaller than the very good 1%. Therefore, according to the ultraviolet irradiation device, ultraviolet rays of a desired wavelength can be irradiated while suppressing deterioration of the liquid crystal panel in the middle of production. Next, Fig. 13 is a characteristic diagram showing an example of the spectral distribution of light emitted by the metal guillo lamp shown in Fig. 1 different from Fig. 5. In this case, the metal-based lamp 1 is sealed with mercury and cesium iodide (T1I) in addition to the rare gas. The condition of the lighting is 1.31 kV, the lamp current is 1 〇 3 a, and the lamp power is 12 kW. Fig. 14 is a characteristic diagram showing an example of a spectral distribution of light emitted from the ultraviolet irradiation device shown in Fig. 10 different from Fig. 10, specifically, an ultraviolet irradiation device using the metal halide lamp 100 of the characteristic which is not shown in Fig. 13. The situation. In the ultraviolet radiation of such a spectral distribution, it is also possible to perform ultraviolet irradiation suitable for the steps while suppressing the adverse effect on the liquid crystal panel in the middle of production. Further, Fig. 15 is a characteristic diagram showing that the wavelength in the diagram shown in Fig. 4 is enlarged to 360 nm or less. Fig. 14 and Fig. 15 are the same as those shown in Fig. 1 and Fig. u, and are measured by using a dimming filter. Figs. 16A and 16B are views showing examples of the results of measurement of the intensity of ultraviolet rays and rays of the ultraviolet radiation I emitted as shown in Figs. 12A and 12B. Referring to Figs. 16A and 16B, the ultraviolet light intensity in the wavelength region in which the ultraviolet irradiation device adversely affects the liquid crystal panel in the middle of production will be described. Fig. 16A and Fig. B show the results of measurement without passing through a light-reducing filter. In addition, in Fig. 153521.doc 201201247 16A, B, the intensity meter used for its use, its opinion or evaluation is the same as that described in Figs. 12A and B. Fig. 16A shows the results of an intensity meter having a sensitivity peak in a wavelength of 34 〇 nm to 4 ,, the intensity of light being at most 83 3 and the minimum being 71 mW/cm 2 'an average of 78 4 mW/cm 2 . Further, Fig. i6B shows that as a result of using an intensity meter having a sensitivity peak in a wavelength of 3 〇〇 nm to 320 nm, the intensity of light is at most 〇〇93 mW/cm2, and the minimum is 〇〇77 mW/cm2, and the average is 0.086 mw/cm2. Thus, the maximum enthalpy is about 112112%, the minimum 値 is about 0.108%, and the average 値 is about 〇11〇%. These are smaller than the very good 10/〇. Therefore, even if it is an ultraviolet irradiation apparatus using a metal element lamp in which a cesium iodide lamp is enclosed, it is possible to suppress ultraviolet rays of a desired wavelength while suppressing deterioration of the liquid crystal panel in the middle of manufacturing. The wavelength of the ultraviolet rays required for the liquid crystal panel in the middle of manufacture will be described. The absorption wavelength band of the photoinitiator which starts to harden the ultraviolet curable resin used in the manufacture of the liquid crystal panel can be specified, for example, from 320 nm to 380 nm. As such a photoinitiator. It is exemplified by ' 2,2-dimethoxy-2-phenyl. The light absorption characteristics of the photoinitiator are shown in Fig. 17. In Fig. 17, "0.0020%" and "0.0011%" indicate the concentrations in the resin. In Fig. 17, although a large absorption characteristic is shown in a pedestal having a wavelength of 200 nm, the above-mentioned substance can be used as a photoinitiator by ultraviolet ray having a wavelength of ultraviolet light of 320 nm to 3 80 nm which is actually irradiated. Features. 153521.doc -12· 201201247 In the above embodiment, since the unnecessary ultraviolet cut filter using the oxide 16 is formed on the outer surface of the tube 13 outside the double tube, it is possible to suppress the irradiation of a large area. Light leakage from the abutting surface of the problem or expansion and contraction caused by heat causes a problem that the filters collide with each other to cause breakage or the like. Since X ′ can be formed by applying a raw material solution to the surface of each shape of the object and heat-treating the non-essential ultraviolet light-cutting calender sheet, there is an advantage that the degree of freedom of formation is high and the cost is low. The higher degree of freedom of formation means that an unnecessary ultraviolet cut filter using the oxide 16 can also be formed on the face of the metal element lamp facing the inner tube 12 of the double tube. In this embodiment, deformation as described below can be applied. Although the oxide film 16 is described as being formed on the outer surface of the outer tube 13, as described above, it may be formed on the surface of the metal guillo lamp facing the inner tube 12 of the double tube. Furthermore, 'they can also be shaped. Further, it is also conceivable to form the oxide film 16 on the surface of the coolant facing the inner tube 12 and the outer tube 13. In the It shape, as a method of forming the oxide film i 6 , a method of coating by a method such as dipping a raw material solution or the like may be employed, followed by heat treatment to fix it. Although the impregnation of the raw material solution can be carried out, the bilayer of the cooling unit 200 can be changed in the longitudinal direction by the direction of the double layer of the cooling unit 200 and pulled up in the groove of the oxide/valley liquid for a plurality of times, but The following methods can also be used. That is, it is not possible to apply the entire outer tube 13 in the longitudinal direction, and it is also possible to coat, for example, each half. More specifically, the second time is applied near the middle of the cloth, and the second time is applied from the opposite side to the middle thereof. At this time, the ultraviolet light is cut off because the insufficient area of the impregnation can be avoided. 201201247 The region in which the characteristics become incomplete is generated. Therefore, it is preferable that the center portion of the outer tube η is immersed in a manner in which the partial film overlaps, and accordingly, in the case of the tube 13 longer than the longer one, The same film thickness is impregnated as a whole. In order to achieve a more uniform film thickness, the above-mentioned second and second operations may be performed again (i.e., a total of four coatings). Fig. 18 is a longitudinal sectional view showing the configuration of an ultraviolet ray irradiation apparatus according to another embodiment of the present invention, and Fig. 19 is a cross-sectional view showing the arrow angle direction of the B_Ba position shown in Fig. 18. The same components as those of the embodiment described above are denoted by the same reference numerals, and the description thereof will be omitted. In this embodiment, the oxide film is not formed on the outer surface of the double tube of the cooling unit, but is formed on the surface of the oppositely disposed ultraviolet light transmissive glass plate i 6 2 with the outer tube 13_ of the cooling unit 200. The oxide film 161 having T i as a main component. The oxide film 161 can be formed by a method such as printing or the like as a film thickness having a desired spectral transmission characteristic. The oxygen film 161 may be formed on the back surface of the glass plate 162 in addition to the (10) surface of the cooling unit _ opposed to the glass plate (6) as shown. Furthermore, ' can also be formed on both sides. In the case of the sterilized form, the oxide film 161 is formed by heat-treating the raw material solution or the like after printing the ultraviolet ray-transmissive glass plate 162. Therefore, the film thickness can be easily adjusted at the time of printing. By this, as the oxide film 161, it is also easy to obtain the desired partial light transmission (4) - which is constituted by the method of adding the heat-absorbing filter to the step-by-step. By providing 15352I.doc 201201247 as a heat absorbing filter for an optical filter, it is possible to further reliably cut off light of, for example, 400 nm or more that is unnecessary for the object to be irradiated. Such a heat ray absorbing louver can be disposed in the double tube of the cooling unit 2 所示 shown in Fig. 18. More specifically, the inner tube 12 can be positioned in a cylindrical shape in the space between the inner tube 12 and the outer tube 13 of the double tube. The hot wire absorbing filter can be suppressed from being overheated by the hot wire by being disposed in the double tube. Further, as another modification, an optical filter of an oxide film 161 may be provided on the glass plate 162, and further configured to include a heat ray reflection filter. In this case, it is also possible to additionally set the heat-ray reflection filter as an optical filter, and further surely cut off the light on the object to be irradiated, for example, at 400 nmw. The heat reflecting filter can be configured as described in the embodiment (Fig. 22) to be described later. Further, as the luminescent metal enclosed in the metal gurogen lamp 1 即可, any metal which can emit ultraviolet light having a wavelength of, for example, 320 nm to 380 nm can be used, and the oxidation of the ultraviolet ray irradiation device described above is used. The film 16 (or the same as the oxide film 161. The same applies hereinafter) will be described below with respect to the film thickness and the manufacturing steps thereof. Although it has been described that the ultraviolet cut-off characteristics are controlled by changing the film thickness of the oxide film 16, the range of the film thickness is preferably more specifically described. .........., the spectroscopy of the oxidized (non-essential UV cut-off filter)
IK ^ M. w ^ /、形成 J 厚之差異h比較之特性圖。作為試料係準備 0·1 帥、〇·3 μπι、0.5 μηι、！·〇 μιη、！ 3 · μ J.5 Pm之 q 153521.doc •15- 201201247 類型之氧化膜而進行測定。另，在由圖6等顯示透射特性 之氧化膜16之情形下，其膜厚如已敘述般係為〇·7 μιη，其 成膜原料係使Si〇2:Ti〇2:Ta2〇5=45:45:l〇之比的重量。/D之溶 質溶解在特定的溶液中者。又，所形成之該等氧化膜之膜 厚可使用例如透過型電子顯微鏡（TEM)進行測定。 如觀察圖20所知般，相較於膜厚為〇」μιη之情形之紫外 線截斷特性，隨著膜厚增加至1.5 μιη ,可順次使其紫外線 截斷之特性在長波長側偏移。若實際斟酌必要之分光特 性，則在膜厚為0.3 μπι至ι·3 μηΐ2情形下，可考慮的是， 成為使必要的紫外線（波長為320 nm至380 nm)透射而截斷 非必要之紫外線（波長未達到320 nm)之特性為佳。 亦即，可觀察到的是，若膜厚未達0.3 μηι，則無法充分 截斷非必要之紫外線。另一方面，在膜厚超過i3 之情 形下，會損傷使必要之紫外線充分透射之功能❶ 關於氧化膜16之較佳之膜厚，亦需要考量其機械性之牢 固丨生（不易使裂縫產生之程度）。因此，雖已敘述了作為氧 化膜16之成膜原料添加^係有效者，但觀察以下参照之圖 21亦有顯示。另，若考量氧化膜16之非必要紫外線戴斷特 性及機械性特性’則發明人等可獲得在實用上將膜厚設為 〇.5 μιη以上，1.〇 μιη以下更佳之觸感。 圖21係顯示針對在變更氧化膜16之成膜原料的重量％之 時所獲得之各種氧化膜16，評估其分光特性（非必要紫外 線的截斷特性、必要紫外線的透射特性）及裂縫的產生之 、。果的表。作為成膜原料，係使用包含改變Ti〇2、Ta2〇5 153521.doc • 16 - 201201247 之各自的重量％之溶質之溶液’而形成氧化膜16。重量％ 之殘留係為si〇2。另，形成膜厚係g07pm。 在圖2i中，「X」係表示判斷為無法使用(不可)者，「〇」 係表示判斷為能夠使用（可）者，「◎」係表示判斷為特別優 異（良）者。 就結論而言，可將圖21所示之結果評估為：在Ti〇2係為 3〇重量。/。至50重量。/。，且Ta2〇5係為i重量5%至15重量％之 情形下，由於分光特性並無不可，即使裂縫產生亦無不 可，因此综合其等亦無不可.又，可考慮的是，在耵〇2係 為40重量％至50重量5，且^山5係為5重量％至15重量％之 情形下更佳。另，裂縫之產生大致相同，係Ta2〇5之含有 愈多其裂縫愈少，且顯示有將Τ&2〇5添加在成膜原料中之 效果。 接著，茲就上述説明之紫外線照射裝置之製造進行說明 其概略的過程。 首先’準備具有如圖1中所示之内管12與外管13之雙層 管°接著’在雙層管之外管13的外面上、或是在並非面向 又層s之内管12所封閉之空間之側的側面上，藉由例如浸 潰塗佈含有作為氧化膜16的成膜原料之溶質之溶液。溶質 係選自由參照圖21而説明之較佳（〇以上）之原料比者之 中。 接著’加熱處理塗佈有溶液之雙層管，並覆蓋在雙層管 之面上’將氧化膜16形成（熔接）為特定膜厚《該特定膜厚 係參照圖20而説明之較佳之膜厚。説明雖有前後，但會以 153521.doc •17· 201201247 形成在此種較佳之膜厚上之方式，在上述之浸潰中控制其 溶液的塗佈膜厚。在藉由加熱處理而獲得之氧化膜16中， Ti、Si雖會殘留，但Ta僅殘留有少量。可考慮的是，這是 因為藉由加熱處理會使仏擴散至氣體中。惟，在加熱處理 中’藉由Ta存在’會有助於不易產生裂縫之相同性較高之 膜之形成。其寄予之點亦可參照圖21所示。 在雙層管上形成氧化膜16之後，接著，在其雙層管之内 管12的内側配置筒狀之具有石英玻璃素材的發光管31之金 屬鹵素燈100。基於以上，可製造圖1所示之紫外線照射裝 置。 ’ 接著，茲參照圖22、圖23就進一步之其他實施形態進行 説明。圖22係顯示本發明進一步之其他實施形態之紫外線 照射裝置的構成之縱剖面圖，圖23係圖22中所示之c_Ca位 置之箭頭角度方向的剖面圖。在圖22、圖23中，對已説明 之構成要素標注以同一符號，只要是無附加之事項，即可 省略其説明。 在該實施形態之發光管31内，為使燈之啟動性安定，除 封入充分之量之1.3 kPa的稀有氣體（氬）以外，還封入有果 為 0.9 mg/cm3，碘化汞為〇.〇8 mg/cm3，鐵為 〇 〇1 mg/cm3， 锡為 0.005 mg/cm3。 作為金屬鹵素燈100之封入物，亦可添加碘化鉈（T⑴或 是代替鐵而封入。根據此點，如圖u所示，可重新使波長 為352 nm、378 nm之紫外線的強度提高，且可增加必要之 紫外線區域之強度。圖11雖是已説明之圖， 一 —疋顯不圖 153521.doc -18· 201201247 2 2中所示之金屬鹵素燈放射之光的分光分佈之例的特性 圖。 關於圖22中所示之氧化膜16之分光透射率特性會根據其 厚度如何變化，可參照已説明之圖7。如圖7所示，藉由改 變氧化膜16之臈厚，可使紫外線截斷特性具有控制性變 動。 了將上述之紫外線照射裝置作為1個單元，而使用其複 數個（例如5個單元）構成液晶面板製造裝置。該液晶面板製 裝置"T使在液晶面板製造步驟中為必要的具有如已説明 之圖10所示之分光分佈之光予以放射。藉此，在液晶面板 製造步驟中，可一面抑制對液晶面板之不良影響，一面放 射適合其步驟之紫外光。 關於圖22所示之紫外線照射裝置放射之紫外線的強度測 定之結果例，可參照已説明之圖12A、B。關於圖l2A、 B’其使用之強度計、其看法或評估係如已説明般。 再者，參照圖22及圖23，符號17係配置在冷却單元2〇〇 與作為被照射體之液晶面板丨8之間的一種光學遽光片的熱 線反射遽光片。熱線反射濾光片17係包含例如Si〇2與IK ^ M. w ^ /, a characteristic map comparing the difference in J thickness h. Prepared as a sample system 0·1 handsome, 〇·3 μπι, 0.5 μηι,! ·〇 μιη,! 3 · μ J.5 Pm q 153521.doc •15- 201201247 Type oxide film for measurement. Further, in the case of the oxide film 16 having the transmission characteristics shown in Fig. 6, etc., the film thickness thereof is 〇·7 μηη as described above, and the film forming raw material is Si〇2:Ti〇2:Ta2〇5= 45:45: The weight of the ratio of l〇. The solute of /D is dissolved in a specific solution. Further, the film thickness of the oxide film formed can be measured by, for example, a transmission electron microscope (TEM). As is apparent from the observation of Fig. 20, the ultraviolet cutoff characteristic of the case where the film thickness is 〇"μηη, as the film thickness is increased to 1.5 μm, the characteristics of the ultraviolet cutoff are sequentially shifted on the long wavelength side. If the necessary spectral characteristics are actually considered, in the case of a film thickness of 0.3 μπι to ι·3 μηΐ2, it is conceivable that the necessary ultraviolet rays (wavelengths from 320 nm to 380 nm) are transmitted to intercept unnecessary ultraviolet rays ( The characteristics of the wavelength not reaching 320 nm are preferred. That is, it can be observed that if the film thickness is less than 0.3 μm, the unnecessary ultraviolet rays cannot be sufficiently cut off. On the other hand, in the case where the film thickness exceeds i3, the function of sufficiently transmitting the necessary ultraviolet rays is impaired. Regarding the preferable film thickness of the oxide film 16, it is also necessary to consider the mechanically strong twinning (not easy to cause cracks). degree). Therefore, it has been described that the film forming raw material of the oxide film 16 is effective, but it is also observed in Fig. 21 which will be referred to below. In addition, the inventors of the present invention can obtain a touch with a film thickness of 〇.5 μm or more and 1. 〇 μηη or less, in consideration of the unnecessary ultraviolet ray breaking property and mechanical properties of the oxide film 16 . Fig. 21 shows the various oxidation films 16 obtained when the weight % of the film-forming raw material of the oxide film 16 is changed, and the spectral characteristics (the cut-off characteristics of unnecessary ultraviolet rays, the transmission characteristics of necessary ultraviolet rays) and the generation of cracks are evaluated. ,. Fruit table. As the film forming raw material, the oxide film 16 is formed by using a solution ～ which changes the respective solute weight % of Ti〇2, Ta2〇5 153521.doc • 16 - 201201247. The residual weight % is si〇2. Further, a film thickness system g07pm was formed. In Fig. 2i, "X" indicates that it is judged to be unusable (not available), "〇" indicates that it is determined to be usable, and "◎" indicates that it is determined to be particularly excellent (good). In conclusion, the results shown in Fig. 21 can be evaluated as: 3 〇 weight in the Ti〇2 system. /. Up to 50 weight. /. And when the Ta2〇5 system is 5% by weight to 15% by weight of i, since the spectral characteristics are not impossible, even if cracks are generated, it is impossible to integrate them. Further, it is considered that The 〇2 is preferably from 40% by weight to 50% by weight, and more preferably from 5% by weight to 15% by weight. Further, the occurrence of cracks is substantially the same, and the more the content of Ta2〇5 is, the less the cracks are, and the effect of adding Τ&2〇5 to the film-forming raw material is exhibited. Next, the outline of the process of manufacturing the ultraviolet irradiation device described above will be described. First, 'prepare the double tube with the inner tube 12 and the outer tube 13 as shown in Fig. 1 and then 'on the outside of the tube 13 outside the double tube, or in the tube 12 not facing the layer s On the side of the side of the closed space, a solution containing a solute as a film forming raw material of the oxide film 16 is applied by, for example, dipping. The solute is selected from the preferred ratios of the materials described above with reference to Fig. 21. Then, 'heat-treating the double-layer tube coated with the solution and covering the surface of the double-layer tube', the oxide film 16 is formed (fused) to a specific film thickness. The specific film thickness is preferably a film described with reference to FIG. thick. Although there are before and after, the coating film thickness of the solution is controlled in the above-mentioned impregnation manner by forming 153521.doc •17·201201247 on such a preferable film thickness. In the oxide film 16 obtained by the heat treatment, Ti and Si remain, but only a small amount remains in Ta. It is conceivable that this is because the heat treatment causes the helium to diffuse into the gas. However, the presence of 'Ta by' in the heat treatment contributes to the formation of a film having higher uniformity which is less likely to cause cracks. The point of its submission can also be seen in Figure 21. After the oxide film 16 is formed on the double tube, next, a metal halogen lamp 100 having a tubular arc tube 31 having a quartz glass material is disposed inside the inner tube 12 of the double tube. Based on the above, the ultraviolet irradiation device shown in Fig. 1 can be manufactured. Next, other embodiments will be described with reference to Figs. 22 and 23 . Fig. 22 is a longitudinal sectional view showing the configuration of an ultraviolet irradiation apparatus according to still another embodiment of the present invention, and Fig. 23 is a sectional view showing the c_Ca position shown in Fig. 22 in the direction of an arrow angle. In Fig. 22 and Fig. 23, the same components are denoted by the same reference numerals, and the description thereof may be omitted as long as there is no additional matter. In the arc tube 31 of this embodiment, in order to stabilize the startability of the lamp, in addition to sealing a sufficient amount of 1.3 kPa of rare gas (argon), the fruit is sealed at 0.9 mg/cm3, and the mercury iodide is ruthenium. 〇 8 mg/cm3, iron is 〇〇1 mg/cm3, and tin is 0.005 mg/cm3. As an enclosure of the metal halide lamp 100, cesium iodide (T(1) or iron may be added instead of iron. According to this point, as shown in Fig. u, the intensity of ultraviolet rays having a wavelength of 352 nm and 378 nm can be re-increased. Moreover, the intensity of the necessary ultraviolet region can be increased. Although FIG. 11 is an explanatory view, an example of the spectral distribution of the light emitted by the metal halide lamp shown in Fig. 153521.doc -18·201201247 2 2 The characteristic map of the oxide film 16 shown in Fig. 22 varies depending on the thickness thereof, and can be referred to Fig. 7. As shown in Fig. 7, by changing the thickness of the oxide film 16, The ultraviolet light-shielding characteristic is controlled to change. The above-mentioned ultraviolet irradiation device is used as one unit, and a plurality of (for example, five units) are used to constitute a liquid crystal panel manufacturing apparatus. The liquid crystal panel manufacturing apparatus <T enables liquid crystal panel The light having the spectral distribution as shown in FIG. 10 which is necessary in the manufacturing step is radiated, whereby the adverse effect on the liquid crystal panel can be suppressed while the liquid crystal panel is manufactured. The ultraviolet light suitable for the step is irradiated. For an example of the result of measuring the intensity of the ultraviolet light emitted by the ultraviolet irradiation device shown in Fig. 22, reference may be made to Figs. 12A and B. The intensity meter used in Fig. 12A and B' is used. The view or evaluation is as described. Further, referring to Fig. 22 and Fig. 23, reference numeral 17 is a heat line reflection of an optical calender between the cooling unit 2A and the liquid crystal panel 8 as an object to be irradiated. A calender sheet. The heat line reflection filter 17 includes, for example, Si〇2 and
Zr〇2，或是包含以…與Si〇2之膜（亦可為多層），且可形成 在例如玻璃板上。 藉由》又置熱線反射遽光片17，可防止自金屬鹵素燈1〇〇 放射之不需要光的波長400 nm左右以上之可視光及紅外光 (熱線）到達至被照射體。該熱線反射濾光片丨7相較於具有 如圖24所示之分光透射特性之目前存在之熱線吸收濾光 153521.doc •19- 201201247 片’係如圖25所示，可使波長為360 nm至380 nm之波長區 域之透射率提高。因而，根據具有熱線反射渡光片17之紫 外線照射裝置，可使包含在必要之波長區域的波長為360 nm〜380 nm之紫外線強度提高。 圖26係表示組合氧化膜16與熱線吸收濾光片（配置於雙 層管内）之情形之照射光的分光分佈之例》圖2 7係表示組 合氧化膜16與熱線反射濾光片17之情形之照射光的分光分 佈之例。如比較該等圖所知般，在使用熱線反射濾光片17 之組合中，波長為340〜380 nm之累計能量會顯著提高。 藉由如此設置熱線反射遽光片17，會有在維持防止熱線 之效果方面’且可易於將其配置在金屬鹵素燈1〇〇與被照 射體之間之較為廣闊之區域内之優點。因此，可使在接近 金屬鹵素燈100之區域的構成負擔減輕，且可設置例如反 射器等而有效利用紫外線。 另’兹就在參照圖26之説明中所提及之熱線吸收濾光片 進行補充。此種熱線吸收濾光片亦可如上述以接觸之方 式’設置在圖22中所示之冷却單元2〇〇的雙層管内。更具 體而言’可以筒狀包圍内管12之方式位於雙層管之内管12 與外管13之間的空間内^藉由設置在雙層管内，可抑制該 熱線吸收濾光月因熱線而過熱。 接著’茲就在上述説明之各實施形態中所使用之具有金 屬鹵素燈100之封入物，以下說明其變形例。藉由變更封 入物，可增加必要的例如波長為32〇 〇111至波長為38〇 nm2 紫外線的放射強度。 153521.doc •20- 201201247 首先，作為金屬鹵素燈100内的封入物，說明除稀有氣 體（氬）以外，封入有汞（Hg)、鐵（Fe)、碘化鉈（T1I)、錫 (Sn)、碘化鋅（Znl2)及碘化汞（Hgl2)之情形。 此種金屬自素燈作為在紫外線區域具有發光特性之金 屬’會具有Fe、Ή、Sn、Zn、Hg。利用該金屬鹵素燈之紫 外線當然對紫外線硬化性之樹脂組成物係有效者，且可使 推動在該樹脂組成物中含有之光起始劑之樹脂的重合開 始。 作為例’準備直徑φ為27.5 mm，肉厚m為1.5 mm，發光 長L為1000 mm之金屬鹵素燈ι〇〇(容積為490 cm3)。其中之 一作為比較例’係設為在發光管3 1内將Fe為9 mg、Sn為2 mg、Hgl 2為45 mg之各種量微量添加封入，加上Hg為1 .〇4 mg/cm3之封入量之金屬函素燈，作為另外一個更佳之例， 係设為在發光管3 1内將Fe為9 mg，Sn為2 mg、Hgl2為40 mg、T1I為5 mg、ZnIA 12 mg之各種量微量添加封入，加 上Hg為1.00 mg/cm3之封入量之金屬鹵素燈。 將比較例與較佳之例之比較顯示在圖28中。圖28係顯示 比較變更封入在金屬_素燈中之金屬種類之時之發光的波 長分佈之特性圖。在該特性圖中，對金屬函素燈之輸入功 率係為1200 W。 如圖28所示’可知較佳之例之金屬鹵素燈相較於比較例 之金屬素燈’可在波長為320〜380 nm之頻帶放射累計強 度較強之紫外線。 圖29係顯示將例如氯仿之溶媒中之2,2-二甲氧基-i，2-二 153521.doc -21- 201201247 苯基乙烷-1-酮之光起始劑的濃度設為0.1%、0.01%、 0.001 %之情形的吸光度之特性圖。如同圖所示，在相對於 溶媒之光起始劑的濃度為0.1%之情形下，在波長為 320〜3 80 nm之範圍内有較高之吸光度。 是以，圖30係顯示比較藉由比較例之金屬鹵素燈作用於 上述光起始劑之情形、與藉由更佳之例之金屬函素燈作用 於上述光起始劑之情形之樹脂硬化的比率之表。 亦即，在將以Fe、Sn、Hgl2、Hg為封入物之由對利用比 較例之金屬齒素燈之光起始劑之照射而完成之樹脂硬化之 比率設為100之情形下，以Fe、Sn、Hgl2、Til、Znl2、Hg 為封入物之由對利用更佳之例之金屬鹵素燈之起始劑之照 射所完成之樹脂硬化的比率係為121。因而，根據更佳之 例之金屬函素燈’可提高紫外線硬化性樹脂之硬化速度， 且可有助於液晶面板等之生產性提高。 接著’作為更佳之其他例，準備在發光管3丨内將以為9 mg、Sn為 2 mg、11812為25 mg、T1I為 3 mg、乙1112為0 mg(典 型值）之各種量微量添加封入’加上Hg為1.00 mg/cm3之封 入量之金屬鹵素燈1〇〇(容積490 cm3)。以下，針對其進行 説明。 圖3 1係顯示比較使此種金屬鹵素燈之Zn的封入量（惟， 換算成碘化鋅之量）變化之時之在必要紫外線區域的發光 之分光分佈的圖。另，如上述般，將ZnI2封入6 mg之情形 係相g於約12.2 pg/cm3之濃度。圖32係顯示基於圖3 1之結 果算出之特定波長區域的累計紫外線強度之表。如圖32所 15352 丨.doc •22- 201201247 不’在包含在必要之紫外線波長區域之波長為320 nm至波 長為340 nm、波長為320 nm至波長為360 nm、波長為320 nm至波長為380 nm任一者中進行評估，皆Zn的封入量愈 多，其波長區域之紫外線強度愈高。 圖33係顯示使上述之金屬鹵素燈之以的封入量（唯，換 异成破化鋅之量）變化之時之波長為32〇 nm至波長為340 nm的累s十紫外線強度之變化的圖。基於圖3 3所示之結果， 可知在s亥波長區域之累計紫外線強度若是Zn超過25 Kg/cm3則會達到頂點，不會見到在其以上之增加。因而， 用以增加必要之波長的紫外線強度之Zn的添加量可將自有 資料之最小値之2 gg/cm3至達到頂點之25 pg/cm3之範圍作 為暫時推薦値。雖即使超過25 gg/cm3在其意義上亦有效 果’但Zn之量在發光管31内若變得濃度較大，則亦會有不 良影響，濃度增加至其以上為不佳。亦即，若Zn增加，則 在發光管31内會使Zn的蒸發不易充分產生，而有導致分離 發光荨之不安定發光之可能性。 另’圖3 4係顯示比較由使Zn的封入量變化之金屬函素燈 作用於光起始劑之情形之樹脂硬化的比率之表。該表當然 會與圖32所示之波長為320 nm至波長為380 nm之結果一致 (·波長為320 nm〜380 nm係必要紫外線區域）。 參照以上之圖31至圖34説明之更佳之其他金屬鹵素燈之 例作為封入物係包含T1(鉈）。關於用以獲得zn之添加較佳 之效果之與τι的添加濃度之關係’進行以下補充。若使Zn 的添加濃度增加’則如圖3 1所示，針對利用τΐ之發光波長 153521.doc •23- 201201247 之352 nm或378 nm之紫外線可使其強度減弱。相較於未添 加Zn之情形’在添加Zn(惟，換算成项化鋅）為15 μβ/(；ιη3之 情形下’其等之波長的強度會減少約2〇〇/0。 除在必要之波長區域之累計強度以外，在封入有T1之金 屬鹵素燈中，在此種觀點下亦可考慮較佳之Zn與η之濃度 比。如已敘述般，在將Zn(換算成碘化鋅之量，以下同）之 添加量設為2 μιη/cm3至25 μιη/cm3之情形下，在發光管31 内設為3 mg之Ή(換算成碘化鉈之量）之添加量若以Zn的添 加量為基準來看，則可算出為其〇· 24倍至3倍。 本發明作為並不限定於在此處圖解所述之特定態様者， 然而可理解為，其係全部包含進行如在以下請求範圍般之 變形者。 【圖式簡單說明】 圖1係顯示本發明一實施形態之紫外線照射裝置的構成 之縱剖面圖。 圖2係圖1中所示之A_Aa位置之箭頭角度方向的剖面圖。 圖3係顯示圖1中所示之金屬鹵素燈的構成之縱剖面圖。 圖4係顯示將圖3之圖示一部分放大之縱剖面圖。 圖5係顯示圖丨中所示之金屬齒素燈放射之光的分光分佈 之例的特性圖。 圖6係顯示圖丨中所示之紫外線照射裝置所具有之氧化膜 (非必要紫外線截斷濾光片）的分光透射率之例的特性圖。 圖7A ' B、C係使非必要紫外線截斷濾光片形成在其外 面上之作為比較例之水冷套管之觀察與其軸向不同之各區 153521.doc •24· 201201247 域的表面狀態之顯微鏡照片。 圖8係顯示使非必要紫外線截斷據光片形成在其外面上 之作為比較例之水冷套管之在與其軸向不同之各區域中的 分光透射率之例的特性圖。 圖9係顯示圖6所示之特性椒姑备& 竹f生根據氧化膜之厚度如何變化之 特性比較圖。 圖10係顯Μ丨所^之紫外線照射裝置放射之光的分光 分佈之例的特性圖。 圖11係顯示將圖1 〇所示夕顆_ + 闽汀不之圖不中的波長在360 nm以下之 部分放大之特性圖。 圖12A、B係顯示圖i所示之紫外線照射裝置放射之紫外 線的強度測定之結果例之表。 圖13係顯示與圖5不同之圖1中所示之金屬㈣燈放射之 光的分光分佈之例的特性圖。 圖14係顯示與圖10不同之圖1所示之紫外線照射裝置放 射之光的分光分佈之例的特性圖。 圖15係將圖14所示之圖示中的波長在36〇 nm以下放大之 特性圖。 圖16A、B係顯示與圖12八、B所示者不同之圖丨所示之紫 外線照射裝置放射之紫外線的強度測定之結果例的表。 圖17係顯示由利用圖i所示之紫外線照射裝置之紫外線 照射而進行良好地硬化之樹脂組成物所必需的光起始劑之 例示的分光吸收率之特性圖。 圖18係顯示本發明其他實施形態之紫外線照射裝置的構 153521.doc -25· 201201247 成之縱剖面圖。Zr〇2, or a film comprising (in addition to a plurality of layers) of Si〇2, may be formed on, for example, a glass plate. By reflecting the light-receiving sheet 17 by the hot line, it is possible to prevent visible light and infrared light (hot line) having a wavelength of about 400 nm which is not required to be radiated from the metal halide lamp from reaching the object to be irradiated. The hot line reflection filter 丨7 is compared with the existing hot line absorption filter having a spectral transmission characteristic as shown in FIG. 24, 153521.doc • 19-201201247, which is shown in Fig. 25, and has a wavelength of 360. The transmittance in the wavelength region from nm to 380 nm is increased. Therefore, according to the ultraviolet irradiation device having the hot-line reflection light-passing sheet 17, the ultraviolet light intensity of the wavelength included in the necessary wavelength region of 360 nm to 380 nm can be improved. Fig. 26 is a view showing an example of the spectral distribution of the irradiation light in the case where the oxide film 16 and the heat ray absorbing filter (disposed in the double tube) are combined. Fig. 27 shows the case where the oxide film 16 and the heat ray reflection filter 17 are combined. An example of the spectral distribution of the illuminating light. As is known from the comparison of the figures, in the combination using the hot line reflection filter 17, the cumulative energy having a wavelength of 340 to 380 nm is remarkably improved. By providing the heat ray reflection sheet 17 in this way, there is an advantage that the effect of preventing the heat ray is maintained, and it can be easily disposed in a relatively wide area between the metal halide lamp 1 〇〇 and the object to be irradiated. Therefore, the structural load in the region close to the metal halide lamp 100 can be reduced, and ultraviolet rays can be effectively utilized by, for example, a reflector. Further, it is supplemented by the heat absorbing filter mentioned in the description with reference to Fig. 26. Such a heat absorbing filter may also be disposed in the double tube of the cooling unit 2''' shown in Fig. 22 as described above in a contact manner. More specifically, the manner in which the inner tube 12 can be surrounded by the tube is located in the space between the inner tube 12 and the outer tube 13 of the double tube. By being disposed in the double tube, the heat absorbing filter can be suppressed. And overheated. Next, the enclosure having the metal halide lamp 100 used in each of the embodiments described above will be described below, and a modification thereof will be described below. By changing the encapsulant, it is possible to increase the necessary radiation intensity such as a wavelength of 32 〇 〇 111 to a wavelength of 38 〇 nm 2 . 153521.doc •20- 201201247 First, as an enclosure in the metal halide lamp 100, mercury (Hg), iron (Fe), cesium iodide (T1I), and tin (Sn) are enclosed in addition to a rare gas (argon). ), zinc iodide (Znl2) and mercury iodide (Hgl2). Such a metal self-priming lamp has Fe, yttrium, Sn, Zn, and Hg as a metal having luminescent properties in an ultraviolet region. The ultraviolet rays of the metal halide lamp are of course effective for the ultraviolet curable resin composition, and the superposition of the resin for pushing the photoinitiator contained in the resin composition can be started. As an example, a metal halide lamp ι (volume of 490 cm3) having a diameter φ of 27.5 mm, a meat thickness m of 1.5 mm, and an emission length L of 1000 mm was prepared. One of them was used as a comparative example, and it was set to contain a total amount of Fe of 9 mg, 2 mg of Sn, and 45 mg of Hgl 2 in the arc tube 3 1 , and Hg was 1. 4 mg/cm 3 . As a further preferred example, the enclosed metal element lamp is set to have 9 mg of Fe, 2 mg of Sn, 40 mg of Hgl2, 5 mg of T1I, and 12 mg of ZnIA in the arc tube 31. Various amounts of micro-addition were added, and a metal halide lamp having an Hg of 1.00 mg/cm 3 was added. A comparison of the comparative example with the preferred example is shown in FIG. Fig. 28 is a characteristic diagram showing the distribution of the wavelength of the light emitted when the metal type enclosed in the metal-based lamp is changed. In this characteristic diagram, the input power to the metal element lamp is 1200 W. As shown in Fig. 28, it is understood that the metal halide lamp of a preferred example can emit ultraviolet light having a relatively strong cumulative intensity in a wavelength band of 320 to 380 nm as compared with the metal lamp of the comparative example. Figure 29 is a graph showing the concentration of a photoinitiator of 2,2-dimethoxy-i,2-di 153521.doc -21 - 201201247 phenylethan-1-one in a solvent such as chloroform is set to 0.1. Characteristic chart of absorbance in the case of %, 0.01%, and 0.001%. As shown in the figure, in the case where the concentration of the photoinitiator relative to the solvent is 0.1%, there is a high absorbance in the wavelength range of 320 to 3 80 nm. Therefore, FIG. 30 shows a resin hardening in the case where the metal halide lamp of the comparative example is applied to the photoinitiator and the photoinitiator is acted upon by the metallocene lamp of a better example. The table of ratios. That is, in the case where the ratio of the resin hardening by the irradiation of the photoinitiator of the metal dentate lamp of the comparative example using Fe, Sn, Hgl2, and Hg as the enclosure is set to 100, Fe is used. The ratio of resin hardening by Sn, Hgl2, Til, Znl2, and Hg which are encapsulated by the irradiation of the initiator of the metal halide lamp of a better example is 121. Therefore, according to a metallurgical lamp of a better example, the curing speed of the ultraviolet curable resin can be increased, and the productivity of the liquid crystal panel or the like can be improved. Then, as a better example, it is prepared to add a small amount of 9 mg, Sn 2 mg, 11812 25 mg, T1I 3 mg, and B 1112 to 0 mg (typical) in the arc tube 3丨. 'A metal halide lamp with a Hg of 1.00 mg/cm3 is enclosed in a volume of 490 cm3. The following is explained. Fig. 3 is a view showing a spectral distribution of light emission in a necessary ultraviolet region when the amount of Zn enclosed in the metal halide lamp (in terms of the amount converted to zinc iodide) is changed. Further, as described above, when ZnI2 was enclosed in 6 mg, the phase g was at a concentration of about 12.2 pg/cm3. Fig. 32 is a table showing the cumulative ultraviolet light intensity in a specific wavelength region calculated based on the result of Fig. 31. As shown in Figure 32, 15352 丨.doc •22- 201201247 does not 'in the wavelength range of 320 nm to 340 nm, wavelength 320 nm to wavelength 360 nm, wavelength 320 nm to wavelength in the necessary ultraviolet wavelength region In any of the 380 nm evaluations, the more the Zn is enclosed, the higher the UV intensity in the wavelength region. Figure 33 is a graph showing changes in the intensity of the tens of ultraviolet light at a wavelength of 32 〇 nm to a wavelength of 340 nm when the amount of the metal halide lamp described above is changed (only the amount of zinc sulfide is changed). Figure. Based on the results shown in Fig. 3, it can be seen that if the cumulative ultraviolet light intensity in the s-wavelength region exceeds 25 Kg/cm3, the apex will be reached, and an increase above it will not be seen. Therefore, the addition amount of Zn for increasing the ultraviolet intensity of the necessary wavelength can be made as a temporary recommendation from the range of 2 gg/cm 3 of the minimum data of the own data to 25 pg/cm 3 of the peak. Even if it exceeds 25 gg/cm3, it is effective in the sense of ', but if the amount of Zn becomes large in the arc tube 31, it will have an adverse effect, and it is not preferable that the concentration is increased above. That is, if Zn is increased, evaporation of Zn is less likely to occur in the arc tube 31, and there is a possibility of causing unstable luminescence of the separated luminescence. Further, Fig. 3 is a table showing the ratio of hardening of the resin in the case where a metal element lamp which changes the amount of encapsulation of Zn acts on the photoinitiator. The table will of course be identical to the result of a wavelength of 320 nm to a wavelength of 380 nm as shown in Fig. 32 (a wavelength of 320 nm to 380 nm is necessary for the ultraviolet region). Further examples of other metal halide lamps described with reference to Figs. 31 to 34 above include T1 (铊) as an enclosure. The following is added with respect to the relationship between the additive concentration of τι and the effect of obtaining the better effect of adding zn. If the concentration of Zn is increased by ', as shown in Fig. 31, the intensity of the 352 nm or 378 nm ultraviolet light using the τ ΐ emission wavelength of 153521.doc • 23 - 201201247 can be weakened. Compared with the case where Zn is not added, 'the intensity of the wavelength of Zn (only, converted to zinc) is 15 μβ/(;ιη3), and the intensity of the wavelength is reduced by about 2 〇〇/0. In addition to the cumulative intensity of the wavelength region, in the metal halide lamp in which T1 is enclosed, a preferable concentration ratio of Zn to η can be considered from this viewpoint. As described above, Zn is converted into zinc iodide. When the amount of addition is the same as the amount of 2 μιη/cm3 to 25 μηη/cm3, the amount of addition of 3 mg (in terms of the amount of cesium iodide) in the arc tube 31 is Zn. The amount of addition can be calculated as a basis of 24 to 3 times. The present invention is not limited to the specific state described herein, but it can be understood that all of them are included in the process. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a longitudinal sectional view showing the configuration of an ultraviolet irradiation device according to an embodiment of the present invention. Fig. 2 is an arrow angular direction of the A_Aa position shown in Fig. 1. Fig. 3 is a longitudinal section showing the structure of the metal halide lamp shown in Fig. 1. Fig. 4 is a longitudinal cross-sectional view showing a part of the illustration of Fig. 3. Fig. 5 is a characteristic diagram showing an example of the spectral distribution of light emitted by the metal dentate lamp shown in Fig. 6. Fig. 6 is a diagram showing A characteristic diagram of an example of the spectral transmittance of an oxide film (non-essential ultraviolet cut filter) included in the ultraviolet irradiation device shown in Fig. 7. Fig. 7A 'B, C system in which an unnecessary ultraviolet cut filter is formed The outer surface of the water-cooled casing as a comparative example is observed in a different area from the axial direction of the 153521.doc •24·201201247 domain. The microscopic photograph of the surface state. Figure 8 shows the formation of non-essential ultraviolet light intercepting the light sheet outside. The characteristic diagram of the example of the spectral transmittance of the water-cooled sleeve of the comparative example in the respective regions different from the axial direction thereof. Fig. 9 is a view showing the characteristic pepper prepared in Fig. 6 and the bamboo based on the oxide film. A comparison chart of the characteristics of how the thickness changes. Fig. 10 is a characteristic diagram showing an example of the spectral distribution of the light emitted by the ultraviolet irradiation device. Fig. 11 is a diagram showing that the figure 1 _ _ 不 不The wavelength of the picture is not at 360 Fig. 12A and Fig. 2B are diagrams showing an example of the results of measuring the intensity of ultraviolet rays emitted by the ultraviolet irradiation device shown in Fig. i. Fig. 13 is a view similar to Fig. 5 shown in Fig. 1. FIG. 14 is a characteristic diagram showing an example of a spectral distribution of light emitted by the ultraviolet irradiation device shown in FIG. 1 different from that of FIG. 10. FIG. 15 is a view of FIG. The characteristic diagram in which the wavelength in the figure shown is enlarged at 36 〇 nm or less. Figs. 16A and 16B show the measurement of the intensity of ultraviolet rays emitted by the ultraviolet ray irradiation device shown in Fig. 12 and B. Table of the results. Fig. 17 is a characteristic diagram showing the spectral absorptivity of an example of a photoinitiator necessary for a resin composition which is well cured by ultraviolet irradiation by the ultraviolet irradiation apparatus shown in Fig. i. Fig. 18 is a longitudinal sectional view showing the structure of an ultraviolet irradiation apparatus according to another embodiment of the present invention, 153521.doc -25·201201247.
圖19係顯示圖18十所示之B_Ba位置之箭頭角度 面圖。 J 圖2〇係顯示將圖1所示之紫外線照射裝置所具有之氧化 膜（非必要紫外線截斷濾光片）的分光透射率之例由其形成 膜厚之差異予以比較之特性圖。 圖、係顯示針對在變更氧化膜丨6之成膜原料的重量％之 時所獲得之各種氧化膜16，評估其分光特性（非必要紫外 線的截斷特性 '必要紫外線的透射特性）及裂縫的產生之 結果的表。 圖22係顯不本發明進一步之其他實施形態之紫外線照射 裝置的構成之縱剖面圖。 圖23係圓22中所示之c_Ca位置之箭頭角度方向的剖面 圖。 圖24係顯不® 22中所示之熱線反㈣光片的分光透射率 之例的特性圖。 圖25係顯不目前存在之熱線吸收濾光片的分光透射率之 例的特性圖。 圖26係顯不作為圖22所示之紫外線照射裝置的變形例之 i外線照射裝置放射之紫外線的分光分佈之例的特性圖。 SI 27#’ _ π g 22所*之紫外線照射裝置放射之紫外線的 分光分佈之例的特性圖。 圖28係顯示比較變更封入在金屬函素燈中之金属種類之 時之發光的波長分佈之特性圖。 153521.doc • 26 - 201201247 圖29係顯示將例如氣仿之溶媒中之^^_二甲氧基 一笨基乙烧-1 -酮之光起始劑的濃度設為〇丨％、〇. 〇丨％、 0.001 %之情形的吸光度之特性圖。 圖3 0係顯示比較藉由比較例之金屬鹵素燈作用於上述光 起始劑之情形、與藉由更佳之例之金屬自素燈作用於上述 光起始劑之情形之樹脂硬化的比率之表。 圖3 1係顯示比較使金屬鹵素燈之Zn的封入量（惟，換算 成蛾化鋅之量）變化之時之在必要紫外線區域的發光之分 光分佈的圖。 圖3 2係顯示基於圖3 1之結果所算出之特定波長區域的累 計紫外線強度之表。 圖33係顯示使金屬鹵素燈之Zn的封入量（只是換算成峨 化鋅之量）變化之時之波長為320 nm至波長為340 nm的累 計紫外線強度之變化的圖。 圖34係顯示比較由使zn的封入量變化之金屬鹵素燈作用 於光起始劑之情形之樹脂硬化的比率之表。 【主要元件符號說明】 12 内管 13 外管 15 冷却水 16 氧化膜 17 熱線反射濾光片 30 放電空間 31 發光管 153521.doc •27· 201201247 100 金屬_素燈 111 固持器 112 固持器 141 連接管 142 連接管 161 氧化膜 162 玻璃板 200 冷却單元 321 電極 322 電極 331 内引腳 332 内引腳 341 金屬箔 342 金屬箔 351 插座 352 插座 361 導線 362 導線 153521.doc -28 ·Fig. 19 is a perspective view showing the arrow angle of the B_Ba position shown in Fig. 18; Fig. 2 is a characteristic diagram showing an example of the difference in film thickness between the examples of the spectral transmittance of the oxide film (non-essential ultraviolet cut filter) of the ultraviolet irradiation device shown in Fig. 1 . In the figure, the various oxide films 16 obtained when the weight % of the film-forming raw material of the oxide film 6 is changed are evaluated, and the spectral characteristics (the intercepting characteristics of the unnecessary ultraviolet rays, the transmission characteristics of the necessary ultraviolet rays) and the generation of cracks are evaluated. The table of results. Fig. 22 is a longitudinal sectional view showing the configuration of an ultraviolet irradiation apparatus according to still another embodiment of the present invention. Figure 23 is a cross-sectional view of the arrow angle direction of the c_Ca position shown in the circle 22. Fig. 24 is a characteristic diagram showing an example of the spectral transmittance of the hot-line (four) light sheet shown in Fig. 22 . Fig. 25 is a characteristic diagram showing an example of the spectral transmittance of a heat absorbing filter which is not currently present. Fig. 26 is a characteristic diagram showing an example of the spectral distribution of ultraviolet rays emitted by the external beam irradiation device which is not a modification of the ultraviolet irradiation device shown in Fig. 22 . A characteristic diagram of an example of the spectral distribution of ultraviolet rays emitted by the ultraviolet irradiation device of SI 27#' _ π g 22*. Fig. 28 is a characteristic diagram showing the wavelength distribution of the luminescence when the type of the metal enclosed in the metal element lamp is changed. 153521.doc • 26 - 201201247 Figure 29 shows the concentration of the photoinitiator of ^^_dimethoxy-p-ethylidene-1-ketone in a solvent such as a gas-like solution, 〇丨%, 〇. Characteristic chart of absorbance at 〇丨%, 0.001%. Fig. 30 shows the ratio of the hardening of the resin in the case where the metal halide lamp of the comparative example is applied to the above photoinitiator and the case where the metal photoinitiator is applied to the photoinitiator by a better example. table. Fig. 3 is a view showing a spectral distribution of light emission in a necessary ultraviolet region when the amount of Zn enclosed in the metal halide lamp (in terms of the amount of zinc molybdenum) is changed. Fig. 3 2 is a table showing the cumulative ultraviolet intensity of a specific wavelength region calculated based on the result of Fig. 31. Fig. 33 is a graph showing changes in the cumulative ultraviolet intensity at a wavelength of 320 nm to a wavelength of 340 nm when the amount of Zn enclosed in the metal halide lamp (only the amount converted to zinc telluride) is changed. Fig. 34 is a table showing the ratio of hardening of the resin in the case where the metal halide lamp which changes the amount of encapsulation of zn acts on the photoinitiator. [Main component symbol description] 12 Inner tube 13 Outer tube 15 Cooling water 16 Oxide film 17 Heat line reflection filter 30 Discharge space 31 Illumination tube 153521.doc •27· 201201247 100 Metal _ element lamp 111 Holder 112 Holder 141 Connection Tube 142 Connection tube 161 Oxide film 162 Glass plate 200 Cooling unit 321 Electrode 322 Electrode 331 Inner pin 332 Inner pin 341 Metal foil 342 Metal foil 351 Socket 352 Socket 361 Conductor 362 Conductor 153521.doc -28 ·