201132688 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種對連續之薄膜進行表面處理之裝置， 尤其係關於一種適用於例如提高偏光板之保護薄膜的接著 性之處理等的薄膜表面處理裝置。 【先前技術】 例如，液晶顯示裝置中組裝有偏光板。偏光板係利用接 著劑將保護薄膜接著於偏光薄膜上而成者。一般而言偏 光薄膜係由包含聚乙烯醇（PVA)作為主成分之樹脂薄膜（以 下稱作「PVA薄膜」）而構成。保護薄膜係由包含三乙酸纖 維素（TAC)作為主成分之樹脂薄膜（以下稱作「tac薄膜」） 而構成。作為接著劑，可使用聚乙烯醇系或聚醚系等之水 系接著劑° PVA薄膜與該等接著劑之接著性良好，而tac 薄膜之接著性並不良好。作為提高TAC薄膜之接著性之方 法’ -般採用皂化處理。皂化處理係將TAc薄膜浸潰於高 溫、高濃度之驗性溶液中。因此，存在作業性或廢液處理 之問題。 =為替代技術’專利文⑴中記載有如下技術：於上述 接著步驟之刖’對保護薄膜之表面披覆聚合性單體且照射 =氣壓電聚。大氣壓電漿之照射裝置中，於密閉容器内收 有個親子電極，沿著該輥子電極之外周隔著間隔而排 列有複數個平板電極。將披覆有上述聚合性單體之保護薄 膜繞掛於輥子電極上。並且，將氮氣等放電氣體導入至密 閉容器内’於輥子電極與各平板電極之間進行電聚化處 154529.doc 201132688 理。藉此，使上述聚合性單體聚合，提高保護薄膜之親水 性’水系接著劑容易與保護薄膜相容。 專利文獻2、3中之電漿處理裝置中，具有—對輥子電 極、及處理氣體之喷出喷嘴。喷出噴嘴係面向輥子電極之 間的空隙。將連續之薄膜捲繞於一對輥子電極上，於輥子 電極之間的空隙内進行電漿處理。一對輥子電極相互同步 旋轉’藉此搬送連續之薄膜。 [先行技術文獻] [專利文獻] [專利文獻1]日本專利特開2009-25604號公報 [專利文獻2]國際公開WO 2009/008284號（圖5) [專利文獻3]曰本專利特開2009-035724號公報 【發明内容】 [發明所欲解決之問題] 上述專利文獻1中，電漿照射裝置之輥子電極係由保護 薄膜覆蓋，而平板電極或氣體喷嘴係直接暴露於電漿下。 因此，平板電極或氣體喷嘴上容易附著包含聚合性單體之 聚合物等的污垢》該污垢成分會形成微粒，從而導致良率 下降。因此’難以長期穩定地運轉。 對此’只要使用專利文獻2、3之具有一對輥子電極之電 聚處理裝置’則因被處理薄膜覆蓋於兩個輥子電極，故 而，電極之污垢較少。並且，自面向放電空間之喷出喷嘴 喷出含聚合性單體之氣體，藉此’可使聚合性單體進行電 漿聚合。然而，聚合性單體自喷出喷嘴直接喷出至放電空 154529.doc 201132688 間’故而’喷出之同時產生聚合反康 交 + j町厓王不〇汉應今易不附著於被處 理薄膜之表面，而過度穿過放電空間而排出。因此認為， 聚合性單體之損耗較大，無法獲得充分之處理效果（接著 力）。 本發明係鑒於上述情況而研製，其目的在於當將聚合性 單體作為反應成分而對偏光板用保護薄膜等被處理薄膜進 行電漿處理時，能夠防止電極等之污濁，且提高接著性等 處理效果。 [解決問題之技術手段] 為了解決上述問題，本發明之特徵在於，其係一種使聚 合性單體接觸於連續之被處理薄膜、且使上述被處理薄膜 經過壓力接近大氣壓之放電空間而進行表面處理之裝置， 且包括： 第1輥子電極，其繞掛有上述被處理薄膜，且圍繞自身 之轴線旋轉從而搬送上述被處理薄膜； 第2輕子電極，其平行於上述第1輥子電極而配置且在 其與上述第1輥子電極之間形成上述放電空間，上述被處 理薄臈之較上述第1輥子電極更靠近搬送方向之下游側的 部分穿過上述放電空間之後折回而繞掛於該第2輥子電極 上且3玄第2輥子電極上圍繞自身之軸線而向與上述第1輥 子電極相同的方向旋轉，從而搬送上述被處理薄膜； 反應氣體喷嘴’其配置成沿著上述第1輥子電極之圓周 方向自上述放電空間往上述第1輥子電極之旋轉方向之上 轉相丨離開’且與上述第1輥子電極之捲繞有上述被處理薄 154529.doc 201132688 膜的部分相向，嘴出合右 有上述聚合性單體之反應氣體；及 放電生成氣體喷嘴，其配置於上述第1、第2輕子電極彼 此之間的上述被處理薄膜之折回部分之内側，將不含有上 述聚合性單體之放電生成氣體喷向上述放電空間。 因被處理薄膜覆蓋於第！親子電極及第2輕子電極上，故 能防止或抑制第1、第2輥子電極上附著有污垢。反應氣體 喷嘴係與放電空間相離而配置，因此，能防止或抑制該反 應氣體喷嘴上附著有污垢。藉此，能防止或抑制微粒之產 生’且可提高良率。因此，能使裝置長期穩定地運轉。 一藉由上述第1輥子電極及第2輥子電極之旋轉，將被處理 薄膜自第1輥子電極搬送至第2輥子電極。 自反應氣體喷嘴噴出反應氣體。反應氣體自放電空間喷 附於搬送方向上游側之第！輥子電極之周面上的被處理薄 膜上。該反應氣體之至少一部分於被處理薄膜之表面上沿 著被處理薄膜之搬送方向流向放電空間，該過程中，反應 氣體中之聚合性單體能接觸於被處理薄膜。因此，能使聚 合性單體以未聚合之狀態在被處理薄膜上凝結，從而附著 於被處理薄膜上。 於隔著放電空間而流來上述反應氣體之側的相反側自 放電生成氣體喷嘴喷出放電生成氣體。放電生成氣體係向 與上述反應氣體之流向相向的方向流動，穿過放電空間而 電漿化（包括激發、活化、自由基化、離子化等），並且與 上述反應氣體相遇。藉此，使反應氣體滯留，能增加未聚 合之聚合性單體接觸於被處理薄膜之機會，且能增大聚合 154529.doc 201132688 性單體對於被處理薄膜之附著量。 被處理薄訂之附著有聚合性單體之部分隨即被導入至 放電空間。藉此，上述附著之聚合性單體產生聚合反應而 成為聚合物，並且與被虛王里蒱描Λ 士 板處理4膜之表面分子鍵結（接枝聚 合)。因此’能於被處理薄膜之表面切實地形成聚合性單 體之聚合膜。結果，能提高被處理薄膜之處理效果。 較佳為’進而具有遮蔽構件，其係以自上述反應氣體喷 嘴向上述放電空間覆蓋上述第1輥子電 伸，於上述第i輥子電極之周面與上述遮蔽構件之間形成 有與上述放電空間相連之遮蔽空間。 藉由遮蔽構件將反應氣體封鎖於遮蔽空間内，能防止反 應氣體擴散至外部環境中。反應氣體與逆向流來之放電生 成氣體相遇之後’能使反應氣體切實地滯留於被處理薄膜 之表面上。因此’能切實地增加反應氣體中之聚合性單體 接觸於被處理薄膜的機會’且能進一步切實地增大聚人性 單體對於被處理薄膜之附著量。並且’能將反應氣體:實 地導入至放電空間。另外，藉由遮蔽構件，能防止或抑制 外部環境中之氧等阻礙反應成分進入遮蔽空間甚至是放電 空間。藉此’能切實地提高處理效果。進而’藉由遮蔽構 件旎確保氣流之均勻性，甚至能提高處理之均勻性。 上述反應氣體噴嘴配置成沿著上述第丨輥子電極之圓周 方向自上述放電空間往上述旋轉方向之上游側離開，較2 為約45。〜180。’更加為約9〇。即約四分之一周。 藉此，能切實地防止反應氣體喷嘴上附著污垢。而且 154529.doc 201132688 能使反應氣體沿著第1輥子電極之圓周方向切實地流向放 電空間。若增長自喷附直至到達放電空間為止的距離，能 確保聚合性單體對於被處理薄膜之附著量。 較佳為’進而具有堵塞構件，其係以隔著上述放電空間 而與上述放電生成氣體喷嘴相向之方式配置，上述遮蔽空 間經由上述第1輥子電極之周面與上述堵塞構件之間所形 成的第1間隙而與上述放電空間相連，且於上述堵塞構件 與上述第2輥子電極之周面之間形成有第2間隙。 藉由堵塞構件，能以某種程度將放電空間之放電生成氣 體喷嘴側的相反側之端部堵塞。藉由放電生成氣體喷嘴及 堵塞構件，旎以某種程度將放電空間之電極軸線方向及與 電極相向方向正交的方向之兩端部堵塞。能將放電生成氣 體之一部分經由第丨間隙而切實地導入至遮蔽空間。因 此使放電生成氣體與反應氣體切實地於遮蔽空間内相 遇，且能切實地增大聚合性單體對於被處理薄膜之附著 量。放電生成氣體之另一部分則經過第2間隙而排出至外 部。藉此，㉟切實地防止外部環境中之氧等阻礙反應成分 進入放電空間。 較佳為，上述放電生成氣體之溫度低於上述反應氣體之 溫度。詳細而言’較佳為’上述放電生成氣體之自上述放 電生成氣㈣対㈣之溫度低於上述反應氣體之自上述 反應氣體噴嘴喷㈣之溫度。而且較佳為，上述放電生成 氣體之喷出溫度較上述反應氣體之喷出溫度低 2〇°C〜7Gt。更佳為，上述放電生成氣體之㈣溫度低於 I54529.doc 201132688 上述反應氣體中之聚合性單體蒸汽之凝結溫度。 藉此，當放電生成氣體與反應氣體相遇且混合時，能使 反應氣體冷卻。因此，能促進反應氣體中之聚合性單體的 凝結而使其切實地附著於被處理薄膜上。藉此，能切實地 提高處理效果。 較佳為，上述表面處理於壓力接近大氣壓下實施。此 處，所謂壓力接近大氣壓係指h之 範圍，若考慮到壓力調整之容易化或裝置構成之簡便化， 較佳為 1.333X104 〜1〇.664x104 Pa ，更佳為 9.331xl〇4〜l〇.397xl〇4pa。 本發明適合於難接著性光學樹脂薄膜之處理，當將該難 接著性之光學樹脂薄膜接著於易接著性光學樹脂薄膜時， 適合於提高難接著性之光學樹脂薄膜的接著性。 作為上述難接著性光學樹脂薄膜之主成分，可列舉例如 二乙酸纖維素（TAC)、聚丙烯（pp)、聚乙烯（pE)、環烯烴 聚合物（cop)、環烯烴共聚物（coc)、聚對苯二甲酸乙二 酯（PET)、聚甲基丙烯酸甲酯（pMMA) '聚醯亞胺等。 作為上述易接著性光學樹脂薄膜之主成分，可列舉例如 聚乙烯醇（PVA)、乙烯-乙酸乙烯酯共聚物（EVA)等。 在用於提高上述難接著性光學樹脂薄膜之接著性的表面 處理等中，作為上述反應成分，較佳為使用聚合性單體。 作為上述聚合性單體，可列舉具有不飽和鍵及規定之官 能基的單體。作為規定之官能基，較佳為自羥基、羧基、 乙醯基、縮水甘油基、環氧基' 碳數為卜⑺之酯基、碾 J54529.doc 201132688 基、路基中選擇’尤佳為羧基或羥基等親水基。 作為具有不飽和鍵及羥基之單體，可列舉子基丙烯酸乙 二醇s旨、稀丙醇、甲基丙稀酸經乙醋等。 作為具有不飽和鍵及羧基之單體，可列舉丙烯酸、甲基 丙烯酸、衣康酸、順丁烯二酸、2_f基丙烯醯基丙酸等。 作為具有不飽和鍵及乙醯基之單體，可列舉乙酸乙烯酯 等。 作為具有不飽和鍵及縮水甘油基之單體，可列舉甲基丙 烯酸縮水甘油酯等。 作為具有不飽和鍵及酯基之單體，可列舉丙烯酸甲酯、 丙烯Sa乙酯、丙烯酸丁酯、丙烯酸第三丁酯丙烯酸_2乙 基己酯、丙烯酸辛酯、甲基丙烯酸甲酯、甲基丙烯酸乙 Sa、曱基丙烯酸丁酯、甲基丙烯酸第三丁酯、甲基丙烯酸 異丙酯、曱基丙烯酸_2_乙酯等。 作為具有不飽和鍵及醛基之單體，可列舉丙烯醛、巴豆 醛等。 較佳為’上述聚合性單體係具有乙烯性不飽和雙鍵及羧 基之單體。作為該單體，可列舉丙烯酸（CH2 = CHC〇〇H)、 甲基丙烯酸（CH2=C(CH3)C00H)。上述聚合性單體較佳 為，丙烯酸或者曱基丙烯酸。藉此，能切實地提高難接著 性樹月a薄膜之接著性。上述聚合性單體較佳為丙稀酸。 上述聚合性單體可藉由載體氣體而搬送。載體氣體較佳 為可自氮氣、氬氣、氦氣等惰性氣體中選擇。自經濟性 之觀點考慮，作為載體氣趙，較佳使用氮氣。 154529.doc 201132688 下=稀 料等大多數聚合性單體，於常溫常壓 下為液相。此種聚合性單體於惰性氣體等載體氣體中氣化 即可。作為使聚合性單體於載體氣體中氣化之方法，可 舉：利用載體氣體將聚合性單體液之液面上之飽和基汽擠 出之方法、使載體氣體於聚合性單體液中起泡之方 聚合性單體液加熱而促進蒸發之方法等。亦可併用擠出與 加熱、或者起泡與加熱。 當進行加熱使其氣化之情形時，考慮到加熱器之負擔， 聚合性單體較佳為選擇彿點為30(rc以下者。而且，聚人 性單體較佳為選擇加熱時不會分解（化學變化）者。 。 [發明之效果] 根據本發明，當將聚合性單體作為反應成分來對偏光板 用保護薄膜等被處理薄膜進行電漿處理時，能防止電極等 之污濁’且能提高處理效果。 【實施方式】 以下，根據圖式，說明本發明之一實施形態。 如圖1所示，被處理薄膜9成為連續之片狀。此處，作為 被處理薄膜9，可使用偏光板之保護薄膜。保護薄膜9係由 含有二乙酸纖維素（TAC)作為主成分之TAC薄膜而構成。 而且，薄膜9之成分並不限於TAC，可為聚丙烯（pp)、聚乙 烯（PE)、環烯烴聚合物（c〇p)、環稀烴共聚物（c〇c)、聚對 苯二曱酸乙二醋（PET)、聚曱基丙烯酸甲酯（pmma)、聚醯 亞胺（PI)等《薄膜9之厚度例如為10〇pm左右。 利用接著劑將上述保護薄膜貼合於偏光薄膜上，藉此構 154529.doc 201132688 成偏光板。偏光_包含PVA薄膜。作為接著劑，可使用 V Jc ♦液等水系接著劑。於接著步驟之前，藉由薄膜表 面處理裝置1對保護薄膜進行表面處理，《高保護薄膜之 接著性》 如圖1及圖2所不’薄膜表面處理裝置1具有處理部1〇。 處理部H)包括-對電極u、12、放電生成氣體喷嘴Η、及 反應氣體喷嘴3 1。 電極11、12成為輥子狀(圓筒形狀)。輥子電極u、12各 自之軸線沿著與圖1之紙面正交的水平方向相互平行地配 置。以下’將沿電極U、12之轴線之方向（圖1之紙面正交 方向）適當地稱作「處理寬度方向」（參照圖2)β 01中，左 侧之第1輥子電極丨丨連接於電源2。圖丨中，右側之第2輥子 電極12電性接地。電源2將例如脈衝波狀之高頻電力供給 至電極11。藉此，於電極"、12之間，在壓力接近大氣壓 之壓力下生成電漿放電。輥子電極u、12相互相向之部分 彼此的空間成為壓力接近大氣壓之放電空間Μ。具體而 言，輥子電極11、12彼此之間的最狭窄之部位及其上下附 近之空間成為放電空間14。電源2亦可連接於第2輥子電極 12，且第丨電極丨丨亦可電性接地。 被處理薄膜9之寬度方向沿著上述處理寬度方向（圖1之 紙面正交方向）而組裝於薄膜表面處理裝置〗中。第丨輥子 電極U之上侧之周面上，以半周之程.度繞掛有被處理薄膜 9。被處理薄膜9沿著第1輥子電極η之周面而穿過放電空 間14’且自放電空間14下垂。進而，被處理薄膜9藉由導 154529.doc 12 201132688 輥16'㈣向上折回’且沿著第2輥子電㈣之周面而穿 過放電空間H。藉此，被處理薄膜9之於報子電極η』 彼此之間且較放電空間14更下側之部分形成折回部分％。 自處理寬度方向觀察時’折回部分9a成為三角形狀。而 且’被處理薄膜9係以半周之程度而繞掛於第2輥子電極12 之上側之周面上。雙方之輕子電極u、12之包含區分出放 電空間M之部分在内的約半周部分由被處理薄膜9覆蓋。 雖省略圖式’但各輥子電極u、12係與旋轉機構連結。 旋轉機構包括馬達等驅動部、及將該驅動部之驅動力傳輸 至輥子電極11、12之軸的傳輸機構。傳輸機構係'例如由皮 帶輪（beh pulley)機構或齒輪行構成。如圖【中之空心圓旅 狀箭頭所示’#由旋轉機構，使輥子電極n、_繞各自 之轴線、且相互同步地向相同之方向（圖丨中為順時針）旋 轉。藉此，被處理薄膜9自第】輥子電極丨丨搬送至第2輥子 電極12。 各輥子電極11、12中組裝有調溫機構（省略圖式）。調溫 機構係例如由輥子電極n、12内所形成之調溫路徑而構 成。調溫路徑上流動經調溫之水等媒體，藉此能對親子電 極11、12進行調溫。進而，可對輥子電極u、12之周面上 之被處理薄膜9進行調溫。 於較放電空間14更下側之輥子電極u、12彼此之間，配 置有上述放電生成氣體喷嘴21。放電生成氣體供給源2〇經 由氣體供給路22而與噴嘴21相連。喷嘴21係配置於被處理 薄膜9之二角形狀之折回部分9a之内側。喷嘴21係於處理 I54529.doc •13· 201132688 寬度方向上較長地延伸，且與其延伸方向正交之剖面向上 方變細。喷嘴21之上端（前端）之喷出口面向放電空間14。 放電空間14之下端部藉由喷嘴21而受到某種程度之堵塞。 喷嘴之下端部設有整流部（省略圖式），使放電生成氣體 於處理寬度方向上變得均勻且導入至喷嘴21。該放電生成 氣體自喷嘴21之喷出口向放電空間14喷出。該放電生成氣 體之喷出氣流成為均勻地分佈於處理寬度方向上之氣流。 作為放電生成氣體，可使用惰性氣體。作為放電生成氣 體用之惰性氣體，可列舉氮氣（Νζ),但並不限於此，亦可 使用Ar、He等稀有氣體。 雖省略圖示，但喷嘴21之内部組裝有放電生成氣體調溫 機構。調溫機構係例如由形成於喷嘴2丨内之調溫路徑而構 成。調溫路徑上流動經調溫之水等媒體，藉此，能對喷嘴 21進行調溫，進而對放電生成氣體之喷出溫度進行調節。 放電生成氣體之喷出溫度係較反應氣體之噴出溫度更低 溫，較佳為較反應氣體中之丙烯酸（聚合性單體）之凝結溫 度更低溫。例如·’放電生成氣體之喷出溫度成為 l〇〇c 〜50〇c。 於較放電空間14更上側之輥子電極丨丨、〗2彼此之間，配 置有堵塞構件50 ^堵塞構件5〇係隔著放電空間14而與放電 生成氣體喷嘴21相向。堵塞構件5〇係於處理寬度方向上較 長地延伸，且與其延伸方向正交之剖面向下方變細。堵塞 構件50之下端（前端）面向放電空間14。於堵塞構件50與第1 輥子電極11之周面之間形成有第i間隙5丨。於堵塞構件5〇 154529.doc 14 201132688 與第2輥子電極12之周面之間形成有第2間隙52。放電空間 14經由第2間隙52而與外部相連。作為堵塞構件5〇，可使 用構造與放電生成氣體喷嘴21相同之喷嘴，且將其設置成 與放電生成氣體噴嘴21上下對調。 於第1親子電極11之上方，以與電極Η相向之方式而配 置有上述反應氣體喷嘴31。反應氣體喷嘴31沿著第丨輥子 電極11之圓周方向自放電空間14往電極旋轉方向進而是薄 膜搬送方向之上游側離開約四分之一周。反應氣體喷嘴3 ι 朝向較放電空間14更靠近搬送方向之上游側的電極U上之 被處理薄膜9。反應氣體喷嘴31係於處理寬度方向上較長 地延伸，且於第1輥子電極丨丨之圓周方向（圖1之左右）上具 有某種程度之寬度。省略詳細之圖式，但反應氣體喷嘴31 中組裝有整流部。於反應氣體噴嘴31之下表面上設有喷出 口。噴出口形成為分佈於喷嘴31之下表面上的較廣之範圍 (處理寬度方向及電極圓周方向）。 反應氣體供給源30經由供給線32而連接於喷嘴31。來自 供給源30之反應氣體被供給至喷嘴31。該反應氣體於上述 整流部變得均勻’自噴嘴31之下表面之噴出口喷出。該反 應氣體之喷出氣流成為於處理寬度方向上均勻分佈之氣 流。 反應氣體中含有聚合性單體作為反應成分。作為聚合性 單體，此處可使用丙烯酸ΑΑ。丙烯酸具有如乙酸之臭 味’且亦具有爆炸性等，故而需要妥善管理。作為聚合性 單體’並不限於丙烯酸，亦可為甲基丙婦酸、衣康酸、順 154529.doc 15 201132688 丁婦二酸等。反應氣體中除了反應成分（聚合性單體）之 外，進而包含載體氣體。作為載體氣體，可使用惰性氣 體。此處，作為載體氣體用之惰性氣體，可使用氮氣 (n2)，但並不限於此，亦可為Ar、He等稀有氣體。 乳 反應氣體供給源30包含汽化器。汽化器内，作為聚合性 單體，丙烯酸AA以液體之狀態蓄積。作為載體氣體:氮 氣(N2)被導入至汽化器内。丙烯酸氣化且與該載體氣體 (N2)混合，從而生成反應氣體（丙烯酸AA+N2)。載體氣體 可導入至較邝化器内之液體丙烯酸之液面更上側，亦可導 入至液體丙烯酸之内部而起泡。亦可將載體氣體之一部分 導入至汽化器，而使剩餘部分不經過汽化器，使載體氣體 之上述一部分與剩餘部分於汽化器之下游側匯合。可根據 汽化器之溫度或載體氣體之上述一部分與剩餘部分之分配 率來調節反應氣體中之丙烯酸濃度。 反應氣體供給線32及喷嘴3 1係由反應氣體溫度調節機構 (省略圖式）而調溫。反應氣體供給線32之溫度調節機構係 例如由電熱帶（ribbon heater)而構成。喷嘴3丨内之溫度調 節機構係例如由穿過經調溫之水等媒體的調溫路徑而構 成。反應氣體之溫度係調節成高於丙烯酸之凝結溫度。例 如’反應氣體之溫度調節為30°C~80°C » 於反應氣體喷嘴31之底部設有遮蔽構件4〇。遮蔽構件4〇 係於處理寬度方向上以與電極11大致相同的長度延伸，且 與其延伸方向正交的剖面成為沿第1輥子電極丨丨之上表面 之圓周方向呈圓弧狀的彎曲板狀。遮蔽構件40以某種程度 154529.doc -16 · 201132688 覆盍於第1報子電極11之上側之周面。反應氣體喷嘴Η連 結於遮蔽構件40之圓弧方向（圖1中為左右）的中央部。遮蔽 構件40之圓弧方向（圖1中為左右）之兩端部較噴嘴31更向電 極11之圓周方向伸出》圖1中’遮蔽構件4〇之右側之端部 抵接且連結於堵塞構件50之側部。 於遮蔽構件40與第1輥子電極丨丨之周面之間，形成有遮 蔽空間41。遮蔽空間41成為沿第1觀子電極丨丨之上側之周 面且剖面呈圓弧狀之空間。遮蔽空間41係，於上述圓弧方 向（圖1中為左右）之中央部狹窄，隨著朝向圓弧方向之兩端 部而逐漸變寬。反應氣體噴嘴31之下表面之喷出口貫穿於 遮蔽構件40而與遮蔽空間41連通。圖，遮蔽空間“之 右側之端部經由第！間隙51而與放電空間14相連。圖i中’ 遮蔽空間41之左側（堵塞構件5〇之才目反側）之端部向外部開 放。 遮蔽構件40之上述圓弧方向上之周長例如為24〇〜3〇〇 _左右。遮蔽空間41之厚度較佳為1 _〜10 mm左右。遮 蔽空間41之最窄部位之厚度較佳為例如1 mm左右。遮蔽空 間41之最寬部位之厚度較佳為例如1G _左右。遮蔽空間 之厚度亦可為整體上固定。遮蔽構件可隔著喷嘴Η而 ”輥子電極11之旋轉方向之上游側的部分及下游側的部分 相離，亦可騎嘴31之底面直接面向遮蔽空間41。 、下對於藉由以上述方式構成之薄膜表面處理裝置i 對被處理薄膜9進行表面處理的方法、進而是偏光板之製 造方法進行說明。 154529.doc 201132688 將包含TAC薄膜之被處理薄膜9繞掛於輥子電極丨丨、12 上。 圖1中使輥子電極11、12順時針旋轉，且使被處理薄膜9 自第1輥子電極11向第2輥子電極12(圖1中為大致右方向）搬 送。 藉由來自電源2之電力供給，向輥子電極U、〗2之間施 加電場，使電極之間的空間14内生成大氣壓電漿放電。 將反應氣體（丙烯酸+N2)自供給源30導入至喷嘴31，且 自喷嘴31喷出至遮蔽空間41。反應氣體被喷附至第i輥子 電極11之上側之周面、即較放電空間14更靠近搬送方向上 游側之被處理薄膜9。該反應氣體中之丙烯酸（反應成分）凝 結’且附著於被處理薄膜9上。 大部分反應氣體係於被處理薄膜9之表面上沿著該被處 理薄膜9之搬送方向流動。可藉由遮蔽構件40將反應氣體 封鎖於遮蔽空間41内，從而能防止或者抑制反應氣體洩漏 至外部環境中。因此，能增加反應氣體中之丙烯酸接觸於 被處理薄膜9之機會，且能確保丙烯酸對於被處理薄膜9之 附著量。進而，藉由遮蔽構件4〇能確保氣流之處理寬度方 向之均勻性。反應氣體自遮蔽空間4〗經過第1間隙5丨而流 向放電空間14。 進而’藉由遮蔽構件40 ’能防止外部之空氣等含有氧之 環境氣體進入遮蔽空間41，且能防止氧混入反應氣體中。 於隔著放電空間14而流來上述反應氣體之側的相反側 (下側）’自放電生成氣體噴嘴21喷出放電生成氣體（n2)。 154529.doc •18· 201132688 放電生成氣體之喷出溫度低於反應氣體之喷出溫度。該放 電生成氣體向與上述反應氣體之流動相向之方向（上方）流 動，且導入至放電空間14。穿過放電空間14之放電生成氣 體^:到堵塞構件50之作用而分流至第！間隙5丨及第2間隙 52。進入第！間隙51之放電生成氣體進而被導入至遮蔽空 間41。因此，於遮蔽空間41及第i間隙51内，反應氣體與 放電生成氣體相遇且混合。藉此，使反應氣體滯留，能進 一步增加丙烯酸接觸於被處理薄膜9之機會。而且，藉由 低溫之放電生成氣體，使反應氣體冷卻。因此，能促進反 應氣體中之丙烯酸之凝結且使其切實地附著於被處理薄膜 9上。因此，能切實地增大丙烯酸對於被處理薄膜9之附著 量 0 分流至第2間隙52之放電生成氣體經過第2間隙52而排出 至外部。藉由該排出流，能阻止外部環境進入第2間隙 52。 'BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a device for surface treating a continuous film, and more particularly to a film surface suitable for use in, for example, a process for improving the adhesion of a protective film of a polarizing plate. Processing device. [Prior Art] For example, a polarizing plate is incorporated in a liquid crystal display device. The polarizing plate is formed by adhering a protective film to a polarizing film using an adhesive. In general, a polarizing film is composed of a resin film (hereinafter referred to as "PVA film") containing polyvinyl alcohol (PVA) as a main component. The protective film is composed of a resin film (hereinafter referred to as "tac film") containing cellulose triacetate (TAC) as a main component. As the adhesive, a water-based adhesive such as a polyvinyl alcohol-based or polyether-based adhesive can be used. The PVA film has good adhesion to the adhesive, and the adhesion of the tac film is not good. As a method of improving the adhesion of the TAC film, a saponification treatment is generally employed. In the saponification treatment, the TAc film is immersed in a high temperature, high concentration test solution. Therefore, there is a problem of workability or waste liquid disposal. = is an alternative technique. The patent (1) describes a technique in which the surface of the protective film is coated with a polymerizable monomer and irradiated with a gas pressure electropolymerization. In an atmospheric piezoelectric slurry irradiation apparatus, a parent electrode is housed in a sealed container, and a plurality of plate electrodes are arranged along the circumference of the roller electrode. A protective film coated with the above polymerizable monomer is wound around the roller electrode. Further, a discharge gas such as nitrogen gas is introduced into the closed container, and electropolymerization is performed between the roller electrode and each of the plate electrodes. 154529.doc 201132688. Thereby, the polymerizable monomer is polymerized to improve the hydrophilicity of the protective film. The aqueous binder is easily compatible with the protective film. The plasma processing apparatus of Patent Documents 2 and 3 has a pair of roller electrodes and a discharge nozzle for processing gas. The discharge nozzle faces the gap between the roller electrodes. A continuous film was wound around a pair of roller electrodes and subjected to a plasma treatment in the gap between the roller electrodes. A pair of roller electrodes are rotated in synchronization with each other to thereby carry a continuous film. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-25604 (Patent Document 2) International Publication No. WO 2009/008284 (Fig. 5) [Patent Document 3] [Problem to be Solved by the Invention] In the above Patent Document 1, the roller electrode of the plasma irradiation device is covered with a protective film, and the plate electrode or the gas nozzle is directly exposed to the plasma. Therefore, dirt such as a polymer containing a polymerizable monomer easily adheres to the plate electrode or the gas nozzle. The dirt component forms fine particles, resulting in a decrease in yield. Therefore, it is difficult to operate stably for a long time. As long as the electropolymerization apparatus having a pair of roller electrodes of Patent Documents 2 and 3 is used, since the film to be treated covers the two roller electrodes, the dirt of the electrode is small. Further, a gas containing a polymerizable monomer is ejected from a discharge nozzle facing the discharge space, whereby the polymerizable monomer can be subjected to plasma polymerization. However, the polymerizable monomer is directly ejected from the ejection nozzle to the discharge space 154529.doc 201132688 'There is a spurting out of the same time to produce a polymerization anti-Kangjiao + j choi ya 〇 〇 应 应 应 应 易 易 易 易 易 易 易 易 易 易The surface is excessively discharged through the discharge space. Therefore, it is considered that the loss of the polymerizable monomer is large, and a sufficient treatment effect (adhesion force) cannot be obtained. The present invention has been developed in view of the above-mentioned circumstances, and it is an object of the present invention to prevent contamination of electrodes and the like, and to improve adhesion, etc., when a film to be treated such as a protective film for a polarizing plate is subjected to plasma treatment using a polymerizable monomer as a reaction component. Processing effect. [Means for Solving the Problems] In order to solve the above problems, the present invention is characterized in that a surface of a polymerizable monomer is brought into contact with a continuous film to be processed, and the film to be treated is subjected to a pressure close to atmospheric pressure to carry out a surface. The apparatus for processing, comprising: a first roller electrode wound around the processed film and rotating around the axis of the film to transport the processed film; and a second lepton electrode parallel to the first roller electrode Arranging the discharge space between the first roller electrode and the first roller electrode, and the portion of the processed thin film that is closer to the downstream side in the transport direction than the first roller electrode passes through the discharge space and then folds back and wraps around The second roller electrode is rotated in the same direction as the first roller electrode around the axis of the first roller electrode to transfer the processed film; the reaction gas nozzle is disposed along the first roller The circumferential direction of the electrode is rotated from the discharge space to the rotation direction of the first roller electrode, and is separated from the above The first roller electrode is wound around the portion of the film to be processed 154529.doc 201132688, and the reaction gas of the polymerizable monomer is disposed on the right side of the nozzle; and the discharge generating gas nozzle is disposed on the first and second light portions. Inside the folded-back portion of the processed film between the sub-electrodes, a discharge generating gas not containing the polymerizable monomer is sprayed toward the discharge space. Covered by the treated film! Since the parent electrode and the second lepton electrode are disposed, it is possible to prevent or suppress the adhesion of dirt to the first and second roller electrodes. Since the reaction gas nozzle is disposed apart from the discharge space, it is possible to prevent or suppress the adhesion of the reaction gas nozzle to the dirt. Thereby, the generation of fine particles can be prevented or suppressed, and the yield can be improved. Therefore, the device can be operated stably for a long period of time. The film to be processed is transferred from the first roller electrode to the second roller electrode by the rotation of the first roller electrode and the second roller electrode. The reaction gas is ejected from the reaction gas nozzle. The reaction gas is ejected from the discharge space to the upstream side in the transport direction! On the treated film on the circumferential surface of the roller electrode. At least a part of the reaction gas flows onto the surface of the film to be treated in the direction in which the film to be processed is transported to the discharge space, and the polymerizable monomer in the reaction gas can contact the film to be processed. Therefore, the polymerizable monomer can be condensed on the film to be treated in an unpolymerized state to adhere to the film to be treated. The discharge generating gas is ejected from the discharge forming gas nozzle on the side opposite to the side on which the reaction gas flows through the discharge space. The discharge generating gas system flows in a direction opposite to the flow direction of the above reaction gas, passes through the discharge space to be plasma (including excitation, activation, radicalization, ionization, etc.), and meets the above reaction gas. Thereby, the reaction gas is retained, and the opportunity for the unpolymerized polymerizable monomer to contact the film to be treated can be increased, and the amount of polymerization of the monomer to be treated can be increased. The portion to which the polymerizable monomer is attached is processed and introduced into the discharge space. Thereby, the above-mentioned attached polymerizable monomer is polymerized to form a polymer, and is bonded to the surface of the film treated by the virgin scorpion (graft polymerization). Therefore, a polymer film of a polymerizable monomer can be reliably formed on the surface of the film to be treated. As a result, the treatment effect of the treated film can be improved. Preferably, the present invention further includes a shielding member that electrically extends from the reaction gas nozzle to the discharge space to cover the first roller, and forms a discharge space between the peripheral surface of the ith roller electrode and the shielding member. Connected shelter space. By blocking the reaction gas in the shielding space by the shielding member, it is possible to prevent the reaction gas from diffusing into the external environment. After the reaction gas encounters the discharge generating gas from the reverse flow, the reaction gas can be reliably retained on the surface of the film to be treated. Therefore, it is possible to reliably increase the chance that the polymerizable monomer in the reaction gas contacts the film to be processed, and the amount of adhesion of the polyvalent monomer to the film to be processed can be further reliably increased. And 'the reaction gas: can be introduced into the discharge space in the field. Further, by the shielding member, it is possible to prevent or suppress oxygen or the like in the external environment from obstructing the reaction component from entering the shielding space or even the discharge space. This can effectively improve the processing effect. Furthermore, the uniformity of the airflow can be ensured by the shielding member, and the uniformity of the treatment can be improved. The reaction gas nozzle is disposed to extend away from the discharge space to the upstream side in the rotation direction along the circumferential direction of the second roller electrode, which is about 45. ~180. It’s about 9 miles. That is about a quarter of a week. Thereby, it is possible to reliably prevent the dirt from adhering to the reaction gas nozzle. Further, 154529.doc 201132688 enables the reaction gas to reliably flow to the discharge space along the circumferential direction of the first roller electrode. If the distance from the spraying to the discharge space is increased, the amount of the polymerizable monomer attached to the film to be treated can be ensured. Preferably, the method further includes a clogging member disposed to face the discharge generating gas nozzle via the discharge space, wherein the shielding space is formed between a peripheral surface of the first roller electrode and the clogging member The first gap is connected to the discharge space, and a second gap is formed between the clogging member and the circumferential surface of the second roller electrode. By blocking the member, the discharge portion of the discharge space can be blocked to some extent on the opposite side of the gas nozzle side. By the discharge generating gas nozzle and the clogging member, the enthalpy is blocked to some extent by both the electrode axis direction of the discharge space and the direction orthogonal to the direction in which the electrodes face. A part of the discharge generating gas can be reliably introduced into the shielding space via the second gap. Therefore, the discharge generating gas and the reaction gas are surely encountered in the shielding space, and the amount of deposition of the polymerizable monomer on the film to be processed can be reliably increased. The other portion of the discharge generating gas is discharged to the outside through the second gap. Thereby, 35 is surely prevented from obstructing the reaction component into the discharge space by oxygen or the like in the external environment. Preferably, the temperature of the discharge generating gas is lower than the temperature of the reaction gas. Specifically, it is preferable that the temperature of the discharge generating gas from the discharge generating gas (4) 対 (4) is lower than the temperature of the reaction gas from the reaction gas nozzle spray (4). Further preferably, the discharge temperature of the discharge generating gas is lower than the discharge temperature of the reaction gas by 2 ° C to 7 Gt. More preferably, the (four) temperature of the above-mentioned discharge generating gas is lower than the condensation temperature of the polymerizable monomer vapor in the above reaction gas in I54529.doc 201132688. Thereby, when the discharge generating gas meets and mixes with the reaction gas, the reaction gas can be cooled. Therefore, the polymerization of the polymerizable monomer in the reaction gas can be promoted and adhered to the film to be treated. Thereby, the processing effect can be effectively improved. Preferably, the surface treatment is carried out at a pressure close to atmospheric pressure. Here, the pressure close to the atmospheric pressure means the range of h, and in consideration of the ease of pressure adjustment or the simplification of the device configuration, it is preferably 1.333X104 to 1〇.664x104 Pa, more preferably 9.331xl〇4~l〇. .397xl〇4pa. The present invention is suitable for the treatment of a difficult-to-adhere optical resin film, and is suitable for improving the adhesion of an optical resin film having poor adhesion when the difficult-to-adhere optical resin film is attached to an easily-adhesive optical resin film. Examples of the main component of the above-mentioned difficult-to-adhere optical resin film include cellulose diacetate (TAC), polypropylene (pp), polyethylene (pE), cycloolefin polymer (cop), and cyclic olefin copolymer (coc). , polyethylene terephthalate (PET), polymethyl methacrylate (pMMA) 'polyimine and the like. The main component of the above-mentioned easy-adhesive optical resin film may, for example, be polyvinyl alcohol (PVA) or ethylene-vinyl acetate copolymer (EVA). In the surface treatment or the like for improving the adhesion of the above-mentioned difficult-to-adhere optical resin film, a polymerizable monomer is preferably used as the reaction component. The polymerizable monomer may, for example, be a monomer having an unsaturated bond and a predetermined functional group. As a predetermined functional group, it is preferably selected from the group consisting of a hydroxyl group, a carboxyl group, an ethyl fluorenyl group, a glycidyl group, an epoxy group having an epoxy group having a carbon number of (7), a J54529.doc 201132688 group, and a subgrade selected as a carboxyl group. Or a hydrophilic group such as a hydroxyl group. Examples of the monomer having an unsaturated bond and a hydroxyl group include a sub-group of ethylene glycol s, a dilute propanol, and a methyl acrylate acid, and the like. Examples of the monomer having an unsaturated bond and a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, and 2_f-based acrylonitrile propionic acid. Examples of the monomer having an unsaturated bond and an acetyl group include vinyl acetate and the like. Examples of the monomer having an unsaturated bond and a glycidyl group include glycidyl methacrylate and the like. Examples of the monomer having an unsaturated bond and an ester group include methyl acrylate, propylene Sa ethyl ester, butyl acrylate, t-butyl acrylate 2-ethylhexyl acrylate, octyl acrylate, and methyl methacrylate. Ethylene methacrylate, butyl methacrylate, tert-butyl methacrylate, isopropyl methacrylate, 2-ethyl methacrylate, and the like. Examples of the monomer having an unsaturated bond and an aldehyde group include acrolein and crotonaldehyde. Preferably, the above polymerizable single system has a monomer having an ethylenically unsaturated double bond and a carboxyl group. Examples of the monomer include acrylic acid (CH2 = CHC〇〇H) and methacrylic acid (CH2=C(CH3)C00H). The above polymerizable monomer is preferably acrylic acid or methacrylic acid. Thereby, it is possible to reliably improve the adhesion of the film which is difficult to bond. The above polymerizable monomer is preferably acrylic acid. The above polymerizable monomer can be carried by a carrier gas. The carrier gas is preferably selected from inert gases such as nitrogen, argon and helium. From the viewpoint of economy, nitrogen gas is preferably used as the carrier gas. 154529.doc 201132688 Under = most of the polymerizable monomers, such as thinner, are in the liquid phase at normal temperature and pressure. Such a polymerizable monomer may be vaporized in a carrier gas such as an inert gas. As a method of vaporizing a polymerizable monomer in a carrier gas, a method of extruding a saturated group on a liquid surface of a polymerizable monomer liquid by a carrier gas, and a carrier gas in a polymerizable monomer liquid may be mentioned. A method in which a foaming side polymerizable monomer liquid is heated to promote evaporation. Extrusion and heating, or foaming and heating may also be used in combination. When heating is performed to vaporize it, the polymerizable monomer is preferably selected to have a point of 30 or less in consideration of the burden of the heater. Moreover, the polyvalent monomer is preferably not decomposed when heated. (Chemical change) According to the present invention, when a film to be treated such as a protective film for a polarizing plate is subjected to plasma treatment using a polymerizable monomer as a reaction component, contamination of an electrode or the like can be prevented. [Embodiment] Hereinafter, an embodiment of the present invention will be described with reference to the drawings. As shown in Fig. 1, the film to be processed 9 is in the form of a continuous sheet. Here, as the film to be processed 9, it can be used. A protective film for a polarizing plate. The protective film 9 is composed of a TAC film containing cellulose diacetate (TAC) as a main component. Further, the composition of the film 9 is not limited to TAC, and may be polypropylene (pp) or polyethylene ( PE), cycloolefin polymer (c〇p), cycloaliphatic copolymer (c〇c), polyethylene terephthalate (PET), polymethyl methacrylate (pmma), polypyrene Amine (PI), etc. "The thickness of the film 9 is, for example, 10 pm. The protective film is bonded to the polarizing film by an adhesive to form a polarizing plate, and the polarizing film contains a PVA film. As the adhesive, a water-based adhesive such as V Jc ♦ liquid can be used. Before the step, the protective film is surface-treated by the film surface treatment apparatus 1. "Adhesion of high-protection film" As shown in FIGS. 1 and 2, the film surface treatment apparatus 1 has a treatment portion 1A. The treatment portion H) includes - Counter electrodes u, 12, a discharge generating gas nozzle Η, and a reaction gas nozzle 31. The electrodes 11 and 12 have a roller shape (cylindrical shape). The respective axes of the roller electrodes u, 12 are arranged in parallel with each other in the horizontal direction orthogonal to the plane of the paper of Fig. 1. Hereinafter, the direction along the axis of the electrodes U and 12 (the direction perpendicular to the plane of the drawing of Fig. 1) is appropriately referred to as the "processing width direction" (refer to Fig. 2) β 01, and the first roller electrode 丨丨 of the left side is connected. For power supply 2. In the figure, the second roller electrode 12 on the right side is electrically grounded. The power source 2 supplies, for example, a pulse wave of high frequency power to the electrode 11. Thereby, a plasma discharge is generated between the electrodes ", 12 at a pressure close to atmospheric pressure. The space where the roller electrodes u and 12 face each other becomes a discharge space 压力 whose pressure is close to atmospheric pressure. Specifically, the narrowest portion between the roller electrodes 11, 12 and the space in the vicinity thereof are the discharge spaces 14. The power source 2 can also be connected to the second roller electrode 12, and the second electrode electrode can also be electrically grounded. The width direction of the film to be processed 9 is assembled in the film surface treatment apparatus along the processing width direction (the direction perpendicular to the plane of the drawing of Fig. 1). On the circumferential surface of the upper side of the second roller electrode U, the film to be processed 9 is wound around a half cycle. The film to be processed 9 passes through the discharge space 14' along the circumferential surface of the first roller electrode η and hangs down from the discharge space 14. Further, the film to be processed 9 is folded back by the roller 16' (four) by the guide 154529.doc 12 201132688 and passes through the discharge space H along the circumferential surface of the second roller (four). Thereby, the portion of the film to be processed 9 to the lower side of the discharge space 14 between the reporter electrodes η ′′ forms a folded-back portion %. When viewed from the processing width direction, the folded-back portion 9a has a triangular shape. Further, the film to be processed 9 is wound around the circumferential surface of the upper side of the second roller electrode 12 by a half cycle. The portion of the lepton electrodes u, 12 which are separated from each other by the portion of the discharge space M is covered by the film to be processed 9. Although the drawings are omitted, the roller electrodes u and 12 are coupled to the rotating mechanism. The rotating mechanism includes a driving portion such as a motor, and a transmission mechanism that transmits the driving force of the driving portion to the axes of the roller electrodes 11, 12. The transmission mechanism is constituted, for example, by a beh pulley mechanism or a gear row. As shown by the hollow circular arrow in the figure, the roller electrodes n and _ are rotated about the respective axes and in the same direction (clockwise in the figure) in synchronization with each other. Thereby, the film to be processed 9 is transferred from the first roller electrode 至 to the second roller electrode 12. A temperature adjustment mechanism (not shown) is incorporated in each of the roller electrodes 11 and 12. The temperature control mechanism is constituted by, for example, a temperature regulation path formed in the roller electrodes n and 12. The medium such as the temperature-controlled water flows through the temperature regulation path, whereby the parental electrodes 11, 12 can be tempered. Further, the film 9 to be processed on the circumferential surface of the roller electrodes u and 12 can be tempered. The discharge generating gas nozzle 21 is disposed between the roller electrodes u and 12 on the lower side of the discharge space 14. The discharge generating gas supply source 2 is connected to the nozzle 21 via the gas supply path 22. The nozzle 21 is disposed inside the folded-back portion 9a of the two-corner shape of the film to be processed 9. The nozzle 21 is elongated in the width direction in the process of I54529.doc •13·201132688, and the section orthogonal to the extending direction is tapered upward. The discharge port of the upper end (front end) of the nozzle 21 faces the discharge space 14. The lower end of the discharge space 14 is blocked to some extent by the nozzle 21. A rectifying portion (omitted from the drawing) is provided at the lower end portion of the nozzle to make the discharge generating gas uniform in the processing width direction and introduced into the nozzle 21. This discharge generating gas is ejected from the discharge port of the nozzle 21 to the discharge space 14. The discharge gas stream of the discharge generating gas becomes a gas stream uniformly distributed in the processing width direction. As the discharge generating gas, an inert gas can be used. Examples of the inert gas for the gas for generating a discharge include nitrogen gas. However, the gas is not limited thereto, and a rare gas such as Ar or He may be used. Although not shown in the drawings, a discharge generating gas temperature adjusting mechanism is incorporated in the inside of the nozzle 21. The temperature adjustment mechanism is constituted by, for example, a temperature regulation path formed in the nozzle 2A. The medium such as the temperature-controlled water flows through the temperature adjustment path, whereby the nozzle 21 can be tempered, and the discharge temperature of the discharge generating gas can be adjusted. The discharge temperature of the discharge generating gas is lower than the discharge temperature of the reaction gas, and is preferably lower than the condensation temperature of the acrylic acid (polymerizable monomer) in the reaction gas. For example, the discharge temperature of the discharge generating gas is l〇〇c 〜50〇c. The clogging member 50 is disposed between the roller electrodes 〗 and 〖2 on the upper side of the discharge space 14, and the clogging member 5 is opposed to the discharge generating gas nozzle 21 via the discharge space 14. The clogging member 5 is elongated in the processing width direction, and the cross section orthogonal to the extending direction thereof is tapered downward. The lower end (front end) of the blocking member 50 faces the discharge space 14. An i-th gap 5丨 is formed between the clogging member 50 and the circumferential surface of the first roller electrode 11. A second gap 52 is formed between the clogging member 5 〇 154529.doc 14 201132688 and the circumferential surface of the second roller electrode 12 . The discharge space 14 is connected to the outside via the second gap 52. As the clogging member 5, a nozzle having the same configuration as that of the discharge generating gas nozzle 21 can be used, and it is disposed to be vertically aligned with the discharge generating gas nozzle 21. The reaction gas nozzle 31 is disposed above the first parent electrode 11 so as to face the electrode Η. The reaction gas nozzle 31 is separated from the discharge space 14 in the circumferential direction of the second roller electrode 11 by about a quarter of a turn from the discharge direction of the electrode to the upstream side in the film transport direction. The reaction gas nozzle 3 is directed closer to the treated film 9 on the electrode U on the upstream side in the transport direction than the discharge space 14. The reaction gas nozzle 31 extends long in the processing width direction and has a certain width in the circumferential direction of the first roller electrode (left and right in Fig. 1). The detailed drawing is omitted, but the rectifying portion is incorporated in the reaction gas nozzle 31. A discharge port is provided on the lower surface of the reaction gas nozzle 31. The discharge port is formed to be distributed over a wide range (process width direction and electrode circumferential direction) distributed on the lower surface of the nozzle 31. The reaction gas supply source 30 is connected to the nozzle 31 via the supply line 32. The reaction gas from the supply source 30 is supplied to the nozzle 31. The reaction gas is uniformly distributed in the rectifying portion, and is ejected from the discharge port on the lower surface of the nozzle 31. The discharge gas of the reaction gas becomes a gas flow uniformly distributed in the processing width direction. The reaction gas contains a polymerizable monomer as a reaction component. As the polymerizable monomer, yttrium acrylate can be used herein. Acrylic acid has an odor such as acetic acid, and is also explosive, and therefore needs to be properly managed. The polymerizable monomer 'is not limited to acrylic acid, and may be methyl acetoacetic acid, itaconic acid, cis 154529.doc 15 201132688 dibutoic acid or the like. The reaction gas contains a carrier gas in addition to the reaction component (polymerizable monomer). As the carrier gas, an inert gas can be used. Here, as the inert gas for the carrier gas, nitrogen gas (n2) may be used, but it is not limited thereto, and may be a rare gas such as Ar or He. The milk reactive gas supply source 30 contains a vaporizer. In the vaporizer, acrylic acid AA is accumulated as a polymerizable monomer in a liquid state. As a carrier gas: nitrogen gas (N2) is introduced into the vaporizer. Acrylic acid is vaporized and mixed with the carrier gas (N2) to form a reaction gas (acrylic acid AA + N2). The carrier gas can be introduced to the upper side of the liquid acrylic acid in the vaporizer, or can be introduced into the interior of the liquid acrylic to be foamed. It is also possible to introduce a part of the carrier gas to the vaporizer so that the remaining portion does not pass through the vaporizer, so that the above portion of the carrier gas and the remaining portion meet at the downstream side of the vaporizer. The concentration of acrylic acid in the reaction gas can be adjusted depending on the temperature of the vaporizer or the distribution of the above portion of the carrier gas and the remainder. The reaction gas supply line 32 and the nozzle 31 are temperature-controlled by a reaction gas temperature adjustment mechanism (not shown). The temperature adjustment mechanism of the reaction gas supply line 32 is constituted by, for example, a ribbon heater. The temperature adjustment mechanism in the nozzle 3 is constituted, for example, by a temperature regulation path that passes through a medium such as temperature-controlled water. The temperature of the reaction gas is adjusted to be higher than the condensation temperature of acrylic acid. For example, the temperature of the reaction gas is adjusted to 30 ° C to 80 ° C. A shielding member 4 is provided at the bottom of the reaction gas nozzle 31. The shielding member 4 is extended in the processing width direction to have substantially the same length as the electrode 11, and a cross section orthogonal to the extending direction thereof is a curved plate shape which is arcuate in the circumferential direction of the upper surface of the first roller electrode . The shielding member 40 is covered on the circumferential surface of the upper side of the first newspaper sub-electrode 11 by a certain degree 154529.doc -16 · 201132688. The reaction gas nozzle is connected to a central portion of the shielding member 40 in the arc direction (left and right in Fig. 1). Both end portions of the shielding member 40 in the arc direction (left and right in FIG. 1) project more toward the circumferential direction of the electrode 11 than the nozzle 31. The end portion of the right side of the shielding member 4A in FIG. 1 abuts and is connected to the blockage. The side of the member 50. A shielding space 41 is formed between the shielding member 40 and the circumferential surface of the first roller electrode. The shielding space 41 has a space along the circumferential surface of the upper side of the first observation electrode 且 and has an arcuate cross section. The shielding space 41 is narrow in the center portion of the circular arc direction (left and right in Fig. 1), and gradually widens toward both end portions in the arc direction. The discharge port on the lower surface of the reaction gas nozzle 31 penetrates the shield member 40 to communicate with the shield space 41. The end portion of the right side of the shielding space is connected to the discharge space 14 via the first gap 51. The end of the left side of the shielding space 41 (the opposite side of the blocking member 5) is opened to the outside. The circumferential length of the member 40 in the circular arc direction is, for example, about 24 〇 to 3 〇〇 _. The thickness of the shielding space 41 is preferably about 1 to 10 mm. The thickness of the narrowest portion of the shielding space 41 is preferably, for example. The thickness of the widest portion of the shielding space 41 is preferably, for example, about 1 G. The thickness of the shielding space may be fixed as a whole. The shielding member may be separated from the nozzle ” "the upstream side of the rotation direction of the roller electrode 11" The portion and the downstream portion are separated from each other, and the bottom surface of the riding nozzle 31 may directly face the shielding space 41. Next, a method of surface-treating the film to be processed 9 by the film surface processing apparatus i configured as described above, and a method of manufacturing a polarizing plate will be described. 154529.doc 201132688 The treated film 9 containing the TAC film is wound around the roller electrodes 丨丨, 12. In Fig. 1, the roller electrodes 11, 12 are rotated clockwise, and the film to be processed 9 is transported from the first roller electrode 11 to the second roller electrode 12 (toward the right direction in Fig. 1). An electric field is applied between the roller electrodes U and θ2 by the supply of electric power from the power source 2, and an atmospheric piezoelectric slurry is generated in the space 14 between the electrodes. The reaction gas (acrylic acid + N2) is introduced from the supply source 30 to the nozzle 31, and is ejected from the nozzle 31 to the shielding space 41. The reaction gas is sprayed onto the peripheral surface of the upper side of the i-th roller electrode 11, that is, the film to be processed 9 which is closer to the upstream side in the transport direction than the discharge space 14. The acrylic acid (reaction component) in the reaction gas is condensed' and adheres to the film 9 to be treated. Most of the reaction gas system flows on the surface of the film to be treated 9 in the conveying direction of the treated film 9. The reaction gas can be blocked in the shielding space 41 by the shielding member 40, so that leakage of the reaction gas into the external environment can be prevented or suppressed. Therefore, the chance that the acrylic acid in the reaction gas contacts the film to be processed 9 can be increased, and the amount of adhesion of the acrylic acid to the film to be processed 9 can be ensured. Further, the uniformity of the processing width direction of the airflow can be ensured by the shielding member 4?. The reaction gas flows into the discharge space 14 from the shadow space 4 through the first gap 5丨. Further, by the shielding member 40', it is possible to prevent ambient gas containing oxygen such as outside air from entering the shielding space 41, and to prevent oxygen from being mixed into the reaction gas. The discharge generating gas (n2) is ejected from the discharge generation gas nozzle 21 on the opposite side (lower side) from the side where the reaction gas flows through the discharge space 14. 154529.doc •18· 201132688 The discharge temperature of the discharge generating gas is lower than the discharge temperature of the reaction gas. The discharge generating gas flows in a direction (upward) toward the flow direction of the reaction gas, and is introduced into the discharge space 14. The discharge generating gas passing through the discharge space 14 is shunted to the first by the action of the blocking member 50! The gap 5 丨 and the second gap 52. Enter the first! The discharge generating gas of the gap 51 is further introduced into the shielding space 41. Therefore, in the shielding space 41 and the i-th gap 51, the reaction gas meets and mixes with the discharge generating gas. Thereby, the reaction gas is retained, and the chance of the acrylic acid contacting the film to be processed 9 can be further increased. Further, the gas is generated by the discharge at a low temperature to cool the reaction gas. Therefore, it is possible to promote the coagulation of acrylic acid in the reaction gas and to reliably adhere to the film 9 to be treated. Therefore, the amount of adhesion of acrylic acid to the film to be processed 9 can be surely increased. 0 The discharge generating gas which is branched to the second gap 52 is discharged to the outside through the second gap 52. By this discharge flow, the external environment can be prevented from entering the second gap 52. '
隨著被處理薄膜9之搬送，被處理薄膜9之附著有上述丙 烯酸之部分隨即被導入至放電空間14。藉由該放電空間Μ 之電漿，被處理薄膜9之表面之丙烯酸被活化，產生雙鍵 之斷鍵1 口等。並且，放電生成氣體及反應氣體中之氮 氣電梁化’從而產生氮電漿。該氮電漿或電漿光照射至被 處理薄膜9，將被處理薄膜9之表面分子之C c、c_〇、C H 等鍵切斷。認為於該鍵結斷開部，鍵結（接枝聚合）有丙烯 酸之聚合物，或者鍵結有自丙婦酸分解之c〇〇h基等。藉 此，於被處理薄膜9之表面形成接著性促進層。被處㈣ 154529.doc 201132688 膜9上’於導入至放電空間14之前，充分附著有丙稀酸， 因此’可於放電空間14切實地形成接著性促進層。藉由遮 蔽構件41，能確保氣流之處理寬度方向上之均勾性，故 而，能確保放電空間14内之處理之均勻性，且能獲得均質 之接著性促進層》並且，藉由遮蔽構件40，能防止或者抑 制外部環境氣體進入放電空間14。進而，藉由來自第2間 隙52之放電生成氣體之排出流，亦能防止或者抑制外部環 境氣體進入放電空間14。因此’能充分地防止或者抑制外 部環境中之氧等阻礙反應成分阻礙放電空間14内之反應。 因此，能切實地提高處理效果。 被處理薄膜9係以接觸於第1輥子電極11之狀態穿過放電 空間I4’且由導親16折回，以接觸於第2報子電極12之狀 態再次穿過放電空間14。因此’被處理薄膜9於放電空間 14内2次受到處理。 被處理薄膜9覆蓋於第1輥子電極11及第2輥子電極12之 至少區分放電空間14之部分，藉此，能防止或者抑制污垢 附著於電極11、12上。並且，反應氣體噴嘴31係與放電空 間14相離而配置’並且遮蔽空間41内之丙烯酸為幾乎未聚 合之狀態。因此’能防止或者抑制丙稀酸之聚合物等污垢 附著於喷嘴31之喷出口或遮蔽構件40上。故而，能防止或 者抑制微粒之產生，從而可提高良率。因此，能使表面處 理裝置1長期穩定地運轉。 將表面處理後之TAC薄膜9經由PVA水溶液等水系接著劑 而接著於PVA偏光薄膜’以此製作偏光板^ TAC薄膜9上充 154529.doc •20· 201132688 分地且均質地形成有接著性促進層，故而，能獲得具有良 好之接著強度之偏光板。 繼而’對本發明之另一實施形態進行說明。以下之實施 形態中，對於與已說明之形態重複的構成，於圖式中標註 相同符號’且簡化說明。 圖3及圖4中表示本發明之第2實施形態。第2實施形態之 薄膜表面處理裝置1A具有3個輥子電極11% 12、13。藉由 該等3個輥子電極丨丨〜13，構成2段處理部1〇A、1〇B。前段 處理部10A係包含輥子電極11、12、及喷嘴21、31作為構 成要素，且與第1實施形態之處理部1〇相對應。後段處理 部10B係輥子電極12、13、及喷嘴23、33作為構成要素。 3個輥子電極11、12、13依序且平行地排列。左側之輥 子電極11構成前段處理部1〇A之第1輥子電極。中央之輥子 電極12兼作前段處理部1〇A之第2輥子電極、及後段處理部 1〇Β之第1輥子電極。右側之輥子電極13構成後段處理部 10B之第2輥子電極。 雖省略圖式，但例如中央之輥子電極12連接於電源2(參 照圖1) ’且左右之輥子電極丨丨、13電性接地。取而代之， • 亦可為，左右之輥子電極11、13分別連接於電源，且中央 . 之輥子電極12電性接地。藉由來自電源之電力供給，於左 側之輥子電極11與中央之輥子電極12之間形成前段處理部 10A的放電空間14。於中央之輥子電極12與右側之輥子電 極13之間’形成後段處理部1〇B之放電空間15。 被處理薄膜9繞掛於3個輥子電極u、12、13之上側之周 154529.doc 21 201132688 面上。於輥子電極u、12之間的下側形成有被處理薄膜9 之折回部分9a，該方面係與第}實施形態相同。於輥子電 極12、13之間的下側，形成有被處理薄膜9之折回部分 9b。折回部分9b繞掛於導輥17、17上，且自與圖3正交之 處理寬度方向觀察時呈三角形狀。3個輥子電極u、12、 13相互同步地、且圖中為順時針地旋轉。藉此，被處理薄 膜9向大致右方向搬送。 於前段處理部1 〇A，在折回部分9b之内側配置有放電生 成氣體喷嘴21，在輥子電極n之上側配置有反應氣體喷嘴 3 1及遮蔽構件40，於輥子電極丨丨、12彼此之間的上側部分 配置有堵塞構件50，該等方面係與第i實施形態之處理部 10 » 於後段處理部10B ’在折回部分9b之内側配置有後段處 理部10B之放電生成氣體喷嘴23。放電生成氣體喷嘴23之 構造係與放電生成氣體喷嘴21相同，其前端部朝上且面向 放電空間15。放電生成氣體供給路22產生分支，從而，分 別與前段之放電生成氣體喷嘴21及後段之放電生成氣體喷 嘴23相連。 於輥子電極12之上側配置有後段處理部10B之反應氣體 喷嘴33。反應氣體喷嘴33之構造係與反應氣體喷嘴31相 同，且與輥子電極1 2之上側之周面相向。反應氣體供給線 32產生分支，從而連接於前段之反應氣體喷嘴31及後段之 反應氣體喷嘴33。 於反應氣體喷嘴33之底部，設有構造與遮蔽構件40大致 154529.doc •22· 201132688 相同且剖面呈《狀之遮蔽構件43。遮蔽構件43之圓弧方 向（沿電極12之周面之方向）之周長例如為24〇〜3〇〇爪⑺左 右。 於遮蔽構件43與輥子電極12上側之周面之間，形成有遮 •㉟空間44。反應氣體喷嘴33之噴出口貫穿於遮蔽構件“而 • 與遮蔽空間44相連通。遮蔽空間44成為沿槪子電極12之上 側之周面且剖面呈圓弧狀之空間。遮蔽空間44係於上述圓 弧方向（圖3中為左右）之中央部狹窄，且隨著朝向圓弧方向 之兩端部而逐漸變寬。遮蔽空間44之厚度較佳為i mm〜i〇 mm左右。遮蔽空間44之最窄部位之厚度較佳為例如}爪爪 左右。遮蔽空間44之最寬部位之厚度較佳為例如1〇 mm左 右。遮蔽空間44之厚度亦可為整體上固定。遮蔽構件44可 隔著喷嘴33而與輥子電極12之旋轉方向之上游側之部分及 下游側之部分相離，亦可為喷嘴33之底面直接面向遮蔽空 間44 〇 於輥子電極12、13之間的上側部分，配置有構造與堵塞 構件50大致相同之堵塞構件53。於堵塞構件53與輥子電極 12之間，形成有第2處理部1〇B之第i間隙M。於堵塞構件 53與親子電極丨3之間，形成有第2處理部丨〇B之第2間隙 55 〇 圖3中’遮蔽構件43之左端部抵接或者接近於堵塞構件 5〇。遮蔽空間44之左端部與第1處理部丨〇A之第2間隙52之 上端部相連。並且，圖3中，遮蔽構件43之右端部抵接或 者接近於堵塞構件5 3。遮蔽空間44之右端部與第2處理部 154529.doc -23- 201132688 1 〇B之第1間隙54相連，進而是經由第1間隙54而與放電空 間15相連。第2處理部10B之第2間隙55與輥子電極13之上 側之外部空間相連。 利用薄膜表面處理裝置1A ’自前段處理部i〇A之反應氣 體喷嘴31將丙烯酸喷附至被處理薄膜9上。接著，於放電 空間14内，將氮電漿照射至被處理薄膜9。之後，進而， 利用後段處理部10 B之反應氣體喷嘴3 3將丙稀酸喷附至被 處理薄膜9上。然後，於放電空間15内，將氮電聚照射至 被處理薄膜9。因此’可2次執行丙稀酸之電毁聚合膜之形 成處理。故而’可提高丙稀酸之聚合度，且可增大聚合膜 之厚度。結果，可切實地提高被處理薄膜9之接著性。 於前段處理部10A’來自反應氣體喷嘴31之含丙烯酸之 氣體與自放電生成氣體喷嘴21進入至第1間隙51的氮氣相 遇且滞留，從而促進丙烯酸附著於被處理薄膜9,該方面 與第1實施形態相同。 於後段處理部10B，來自反應氣體喷嘴33之含丙烯酸之 氣體由遮蔽構件43導引，於圖3中係分流至遮蔽空間44之 左側部及右側部。分流至左側之含丙烯酸之氣體與自前段 處理部10A之放電生成氣體喷嘴21進入第2間隙52的氮氣相 遇且滯留。分流至右側之含丙烯酸之氣體係與自後段處理 部10B之放電生成氣體喷嘴23進入第1間隙54之氮氣相遇且 滯留。藉此，於後段處理部10B，亦能促進丙烯酸附著於 被處理薄膜9之表面。自後段處理部10B之放電生成氣體喷 嘴23流入至第2間隙55之氮氣排出至外部環境中。藉由該 154529.doc •24- 201132688 排出流，能防止外部環境氣體（空氣）自第2間隙55進入放電 空間15。 本發明並不限於上述實施形態，可於不脫離其宗旨之範 圍内進行多種變更。 例如’於第1實施形態（圖丨）之處理部1〇及第2實施形態 (圖3)之前段處理部1〇A，反應氣體喷嘴3 1可沿第1輥子電 極Π之捲繞有被處理薄膜9之部分的圓周方向自放電空間 14往電極旋轉方向之上游側離開。反應氣體喷嘴3丨可以與 較電極11之上端部更靠近放電空間丨4側之周面相向的方式 傾斜地配置’亦可以與較電極丨丨之上端部更靠近放電空間 14之相反側之周面相向的方式傾斜地配置。以上方面對 於第2實施形態（圖3)之後段處理部1〇B之反應氣體喷嘴32 而言亦相同。 於第1實施形態（圖1)之處理部1〇及第2實施形態（圖3)之 前段處理部10A中，遮蔽構件4〇可自反應氣體喷嘴31至少 向放電空間14延伸，亦可自反應氣體喷嘴3丨不向放電空間 14側之相反側延伸。亦可縮小遮蔽空間41之放電空間⑷則 之相反側之端部的開π。以上方面，對於第2實施形態（圖 3)之後段處理部l〇B之遮蔽構件43而言亦相同。 亦可不設置遮蔽構件4〇、43。 作為堵塞構件50、53，可利用構造與放電生成氣體喷嘴 21、23上下對調之喷嘴而構成，亦可自該堵塞構件兼喷嘴 5〇、53放電生成氣體喷向放電空間14、15。 亦可不設置堵塞構件50、53。 154529.doc -25- 201132688 薄膜表面處理裝置之輥子電極之數量並不限於2個或者3 個’亦可為4個以上。薄膜表面處理裝置之處理部之段數 並不限於1段（圖1)或者2段（圖3)，亦可為3段以上。 本發明並不限於應用於偏光板用保護薄膜之表面處理， 亦可應用於在各種樹脂薄膜上形成聚合性單體之聚合膜的 處理。 [實施例1] 以下對實施例進行說明’但本發明並不限定於以下之實 施例。 使用圖1及圖2所示之薄膜表面處理裝置1，對薄膜9進行 表面處理。 裝置1之尺寸構成係如下所述。 輥子電極11、12之處理寬度方向之軸長：39〇 mm 輥子電極11、12之直徑：320 mm 反應氣體喷嘴31之處理寬度方向之外尺寸：39〇mm 反應氣體喷嘴31之喷出寬度：300 mm 遮蔽構件40之圓弧方向之周長：275 mm 遮蔽空間41之厚度：整體為5 mm(固定） 輥子電極11、12之間的空隙：1 mm 作為被處理薄膜9，係使用TAC薄膜。TAC薄膜9之寬度 為 325 mm。 TAC薄膜9之搬送速度係設為15 m/min。 電極11、12之溫度、進而是TAC薄膜9之溫度係設定為 25°C。 154529.doc •26· 201132688 反應氣體之聚合性單體係使用丙烯酸，載體氣體係使用 氮氣（n2)。 汽化器30内之液體丙烯酸之溫度係設為120°C。 載體氣體（NO之流量、進而是反應氣體（丙烯酸+n2)之流 量係設為30 slm。 反應氣體中之丙烯酸濃度係4.5 g/min。 反應氣體喷嘴3 1之溫度（反應氣體之喷出溫度）係設定為 55。(：。 放電生成氣體係使用氮氣（N2)。來自下側噴嘴21之放電 生成氣體（N2)之喷出流量係設為1〇 sim。 下側喷嘴21之溫度（放電生成氣體之噴出溫度）係設定為 15〇C。 而且，實施例1中所使用之裝置1之堵塞構件50係構造與 下側噴嘴21上下對調之氣體噴嘴。來自放電生成氣體供給 源2 0之氣體供給管產生分支，從而分別連接於下側喷嘴21 及上側喷嘴50。來自上側喷嘴50之放電生成氣體（N2)之喷 出流置係設為〇 slm。 電源2中，將270 V、6· 1 A之直流電轉換成交流電。供給 至電極11、12之電力為1647 W，電極u、12之間的施加電 壓為 17.3 kV。 確認表面處理後之噴嘴21、31之噴出口等處有無污垢， 未發現有堆積物。 將表面處理後之被處理TAC薄膜9貼合於PVA薄膜之一個 面上°作為接著劑，係使用（A)聚合度為500之PVA之5 154529.doc • 27- 201132688As the film to be processed 9 is conveyed, the portion of the film to be treated 9 to which the above acrylic acid adheres is introduced into the discharge space 14. By the plasma in the discharge space 丙烯酸, the acrylic acid on the surface of the film to be processed 9 is activated to generate a double bond or the like. Further, the discharge generating gas and the nitrogen in the reaction gas are electrically beamed to generate nitrogen plasma. The nitrogen plasma or the plasma light is irradiated onto the film to be processed 9, and the bonds of C c, c_〇, and CH such as the surface molecules of the film 9 to be processed are cut. It is considered that the bond-breaking portion is bonded (graft-polymerized) with a polymer of acrylic acid or bonded with a c〇〇h group derived from the decomposition of pro-glycolic acid. Thereby, an adhesion promoting layer is formed on the surface of the film 9 to be processed. (4) 154529.doc 201132688 The film 9 is sufficiently adhered to the discharge space 14 before the introduction into the discharge space 14, so that the adhesion promoting layer can be reliably formed in the discharge space 14. By the shielding member 41, the uniformity in the processing width direction of the airflow can be ensured, so that the uniformity of the processing in the discharge space 14 can be ensured, and the homogeneous adhesion promoting layer can be obtained and by the shielding member 40. It can prevent or inhibit the external environment gas from entering the discharge space 14. Further, it is possible to prevent or suppress the entry of the external environment gas into the discharge space 14 by the discharge flow of the discharge generating gas from the second gap 52. Therefore, it is possible to sufficiently prevent or suppress oxygen or the like in the external environment from hindering the reaction component from hindering the reaction in the discharge space 14. Therefore, the processing effect can be effectively improved. The film to be processed 9 passes through the discharge space I4' in a state of coming into contact with the first roller electrode 11, and is folded back by the guide 16 to pass through the discharge space 14 again in contact with the second reporter electrode 12. Therefore, the film to be processed 9 is treated twice in the discharge space 14. The film to be processed 9 covers at least the portion of the first roller electrode 11 and the second roller electrode 12 that distinguishes the discharge space 14, whereby the adhesion of dirt to the electrodes 11 and 12 can be prevented or suppressed. Further, the reaction gas nozzle 31 is disposed apart from the discharge space 14 and the acrylic acid in the shielding space 41 is in a state of being almost unpolymerized. Therefore, dirt such as a polymer of acrylic acid can be prevented or suppressed from adhering to the discharge port or the shielding member 40 of the nozzle 31. Therefore, it is possible to prevent or suppress the generation of fine particles, thereby improving the yield. Therefore, the surface treatment apparatus 1 can be stably operated for a long period of time. The surface-treated TAC film 9 is passed through a water-based adhesive such as a PVA aqueous solution and then to a PVA polarizing film ′ to prepare a polarizing plate. The TAC film 9 is filled with 154529.doc • 20·201132688 and is uniformly formed with adhesion promoting. The layer, therefore, can obtain a polarizing plate having a good bonding strength. Next, another embodiment of the present invention will be described. In the following embodiments, the same configurations as those of the above-described embodiments are denoted by the same reference numerals and the description will be simplified. 3 and 4 show a second embodiment of the present invention. The film surface treatment apparatus 1A of the second embodiment has three roller electrodes 11% 12 and 13. The three-stage processing units 1A and 1B are formed by the three roller electrodes 丨丨 to 13. The front stage processing unit 10A includes the roller electrodes 11 and 12 and the nozzles 21 and 31 as constituent elements, and corresponds to the processing unit 1A of the first embodiment. The rear stage processing unit 10B is a constituent element of the roller electrodes 12 and 13 and the nozzles 23 and 33. The three roller electrodes 11, 12, 13 are arranged in sequence and in parallel. The roller electrode 11 on the left side constitutes the first roller electrode of the front stage processing unit 1A. The center roller electrode 12 also serves as the second roller electrode of the front stage processing unit 1A and the first roller electrode of the rear stage processing unit. The roller electrode 13 on the right side constitutes the second roller electrode of the rear stage processing unit 10B. Although the drawings are omitted, for example, the center roller electrode 12 is connected to the power source 2 (refer to Fig. 1) and the left and right roller electrodes 丨丨, 13 are electrically grounded. Alternatively, it is also possible that the left and right roller electrodes 11, 13 are respectively connected to the power source, and the roller electrode 12 of the center is electrically grounded. The discharge space 14 of the front-stage processing portion 10A is formed between the roller electrode 11 on the left side and the roller electrode 12 on the center by power supply from the power source. The discharge space 15 of the rear stage processing unit 1B is formed between the center roller electrode 12 and the right side roller electrode 13. The film to be treated 9 is wound around the circumference 154529.doc 21 201132688 on the upper side of the three roller electrodes u, 12, 13. The folded portion 9a of the film to be processed 9 is formed on the lower side between the roller electrodes u and 12, and this aspect is the same as that of the first embodiment. On the lower side between the roller electrodes 12, 13, a folded-back portion 9b of the film 9 to be processed is formed. The folded-back portion 9b is wound around the guide rolls 17, 17, and has a triangular shape when viewed in the processing width direction orthogonal to Fig. 3. The three roller electrodes u, 12, 13 are rotated in synchronization with each other and in the figure. Thereby, the processed film 9 is conveyed in the substantially right direction. In the front stage processing unit 1A, the discharge generating gas nozzle 21 is disposed inside the folded portion 9b, and the reaction gas nozzle 31 and the shielding member 40 are disposed above the roller electrode n, and between the roller electrodes 丨丨 and 12 The upper side portion is provided with the clogging member 50, and the processing unit 10 of the i-th embodiment is disposed in the rear-stage processing unit 10B'. The discharge-generating gas nozzle 23 of the rear-stage processing unit 10B is disposed inside the folded-back portion 9b. The discharge generating gas nozzle 23 has the same structure as the discharge generating gas nozzle 21, and its front end portion faces upward and faces the discharge space 15. The discharge generating gas supply path 22 is branched, and is connected to the discharge generating gas nozzle 21 of the preceding stage and the discharge generating gas nozzle 23 of the subsequent stage, respectively. The reaction gas nozzle 33 of the rear stage processing unit 10B is disposed on the upper side of the roller electrode 12. The structure of the reaction gas nozzle 33 is the same as that of the reaction gas nozzle 31, and faces the circumferential surface of the upper side of the roller electrode 12. The reaction gas supply line 32 is branched to be connected to the reaction gas nozzle 31 of the preceding stage and the reaction gas nozzle 33 of the subsequent stage. At the bottom of the reaction gas nozzle 33, a shielding member 43 having a structure similar to that of the shielding member 40 and having a cross section of a shape is provided. The circumference of the arcuate direction of the shielding member 43 (in the direction of the circumferential surface of the electrode 12) is, for example, 24 〇 to 3 〇〇 claws (7). A cover space 44 is formed between the shield member 43 and the peripheral surface of the upper side of the roller electrode 12. The discharge port of the reaction gas nozzle 33 penetrates through the shielding member and communicates with the shielding space 44. The shielding space 44 has a space along the circumferential surface of the upper side of the die electrode 12 and has an arcuate cross section. The shielding space 44 is attached to the above. The central portion of the arc direction (left and right in Fig. 3) is narrow and gradually widens toward both end portions in the arc direction. The thickness of the shielding space 44 is preferably about i mm to i 〇 mm. The thickness of the narrowest portion is preferably, for example, about the claws. The thickness of the widest portion of the shielding space 44 is preferably, for example, about 1 mm. The thickness of the shielding space 44 may be integrally fixed. The shielding member 44 may be separated. The nozzle 33 is spaced apart from the upstream side and the downstream side of the roller electrode 12, and the bottom surface of the nozzle 33 may directly face the shielding space 44 between the roller electrodes 12 and 13, and may be disposed. The clogging member 53 having substantially the same structure as the clogging member 50 is formed between the clogging member 53 and the roller electrode 12, and the i-th gap M of the second processing portion 1B is formed between the blocking member 53 and the parent electrode 丨3. Formed with 2The second gap 55 of the processing unit 丨〇B 〇In FIG. 3, the left end portion of the shielding member 43 abuts or approaches the clogging member 5A. The left end of the shielding space 44 and the second gap of the first processing unit 丨〇A The upper end portion of the shielding member 43 is abutted or close to the blocking member 53. The right end portion of the shielding space 44 and the second processing portion 154529.doc -23-201132688 1 〇B The first gap 54 is connected to each other and further connected to the discharge space 15 via the first gap 54. The second gap 55 of the second processing unit 10B is connected to the outer space on the upper side of the roller electrode 13. The film surface treatment apparatus 1A' is used from the front stage. The reaction gas nozzle 31 of the processing unit i〇A sprays acrylic acid onto the film to be processed 9. Next, the nitrogen plasma is irradiated to the film to be processed 9 in the discharge space 14. Thereafter, the post-processing unit 10B is used. The reaction gas nozzle 3 3 sprays acrylic acid onto the film to be treated 9. Then, in the discharge space 15, nitrogen is electropolymerized and irradiated to the film 9 to be processed. Therefore, the electric destruction of the acrylic acid can be performed twice. The formation of a polymeric film. Therefore, 'can improve C The degree of polymerization of the acid increases the thickness of the polymer film. As a result, the adhesion of the film to be processed 9 can be surely improved. The acrylic acid-containing gas and the self-discharge generating gas nozzle from the reaction gas nozzle 31 in the front-stage processing portion 10A'. 21, the nitrogen gas which has entered the first gap 51 meets and stays, and promotes the adhesion of the acrylic acid to the film to be processed 9. This is the same as in the first embodiment. In the latter stage processing portion 10B, the acrylic acid-containing gas from the reaction gas nozzle 33 is shielded. The member 43 is guided and branched to the left side portion and the right side portion of the shielding space 44 in Fig. 3. The acrylic acid-containing gas branched to the left side meets the nitrogen gas entering the second gap 52 from the discharge generating gas nozzle 21 of the preceding stage processing portion 10A. And staying. The acrylic acid-containing gas system branched to the right side and the nitrogen gas entering the first gap 54 from the discharge generating gas nozzle 23 of the subsequent stage processing portion 10B meet and remain. Thereby, it is also possible to promote adhesion of acrylic acid to the surface of the film to be processed 9 in the subsequent stage treating portion 10B. The nitrogen gas which has flowed into the second gap 55 from the discharge generating gas nozzle 23 of the subsequent stage processing unit 10B is discharged to the external environment. By the 154529.doc •24-201132688 exhaust flow, external ambient gas (air) can be prevented from entering the discharge space 15 from the second gap 55. The present invention is not limited to the above embodiments, and various modifications can be made without departing from the spirit and scope of the invention. For example, in the processing unit 1A of the first embodiment (Fig. 3) and the previous processing unit 1A of the second embodiment (Fig. 3), the reaction gas nozzle 31 can be wound along the first roller electrode The circumferential direction of a portion of the treatment film 9 is separated from the discharge space 14 toward the upstream side in the direction of rotation of the electrode. The reaction gas nozzle 3A may be disposed obliquely so as to face the peripheral surface of the upper surface of the electrode 11 closer to the discharge space 丨4 side, or may be disposed closer to the opposite side of the discharge space 14 than the upper end of the electrode 丨丨. The way to the direction is obliquely configured. The above is also the same for the reaction gas nozzle 32 of the subsequent stage processing unit 1A in the second embodiment (Fig. 3). In the processing unit 1A of the first embodiment (FIG. 1) and the previous processing unit 10A of the second embodiment (FIG. 3), the shielding member 4A can extend from the reaction gas nozzle 31 at least to the discharge space 14, or The reaction gas nozzle 3 does not extend to the opposite side of the discharge space 14 side. It is also possible to reduce the opening π of the end portion on the opposite side of the discharge space (4) of the shield space 41. The above is also the same for the shielding member 43 of the subsequent processing unit 10B in the second embodiment (Fig. 3). It is also possible not to provide the shielding members 4, 43. The clogging members 50 and 53 can be configured by nozzles whose structures are vertically aligned with the discharge generating gas nozzles 21 and 23, and can be discharged from the clogging member/nozzles 5?, 53 to the discharge spaces 14 and 15. It is also possible not to provide the blocking members 50, 53. 154529.doc -25- 201132688 The number of roller electrodes of the film surface treatment apparatus is not limited to two or three, and may be four or more. The number of stages of the treatment portion of the film surface treatment apparatus is not limited to one stage (Fig. 1) or two stages (Fig. 3), and may be three or more stages. The present invention is not limited to the surface treatment applied to the protective film for a polarizing plate, and can be applied to the treatment of forming a polymer film of a polymerizable monomer on various resin films. [Example 1] Hereinafter, examples will be described, but the present invention is not limited to the following examples. The film 9 was subjected to surface treatment using the film surface treating apparatus 1 shown in Figs. 1 and 2 . The size configuration of the device 1 is as follows. The axial length of the roller electrodes 11, 12 in the processing width direction: 39 〇 mm The diameter of the roller electrodes 11, 12: 320 mm The outside of the processing width direction of the reaction gas nozzle 31 Size: 39 〇 mm The ejection width of the reaction gas nozzle 31: The circumference of the circular direction of the 300 mm shielding member 40: 275 mm The thickness of the shielding space 41: 5 mm in total (fixed) The gap between the roller electrodes 11, 12: 1 mm As the film to be treated 9, a TAC film is used . The width of the TAC film 9 is 325 mm. The transport speed of the TAC film 9 was set to 15 m/min. The temperature of the electrodes 11, 12 and further the temperature of the TAC film 9 were set to 25 °C. 154529.doc •26· 201132688 Acetate is used as the polymerizable single system of the reaction gas, and nitrogen (n2) is used as the carrier gas system. The temperature of the liquid acrylic acid in the vaporizer 30 was set to 120 °C. The carrier gas (the flow rate of NO, and further the flow rate of the reaction gas (acrylic acid + n2) is 30 slm. The concentration of acrylic acid in the reaction gas is 4.5 g/min. The temperature of the reaction gas nozzle 31 (the discharge temperature of the reaction gas) The system is set to 55. (: The nitrogen gas (N2) is used for the discharge generating gas system. The discharge flow rate of the discharge generating gas (N2) from the lower nozzle 21 is set to 1 〇 sim. The temperature of the lower nozzle 21 (discharge) The discharge temperature of the generated gas is set to 15 〇 C. Further, the clogging member 50 of the apparatus 1 used in the first embodiment is a gas nozzle whose structure is vertically adjusted to the lower nozzle 21. The discharge generating gas supply source 20 The gas supply pipe is branched and connected to the lower nozzle 21 and the upper nozzle 50. The discharge flow of the discharge generating gas (N2) from the upper nozzle 50 is set to 〇slm. In the power supply 2, 270 V, 6 The direct current of 1 A is converted into alternating current, and the electric power supplied to the electrodes 11 and 12 is 1647 W, and the applied voltage between the electrodes u and 12 is 17.3 kV. It is confirmed that there is no dirt at the discharge ports of the nozzles 21 and 31 after the surface treatment. , not Existing deposits would be processed after the surface-treated TAC film bonded to a surface of 9 [deg.] PVA film as the adhesive, based using (A) a degree of polymerization of PVA 500. 5 154529.doc • 27- 201132688
Wt%水溶液、與（B)羥甲基纖維素鈉之2 wt%水溶液混合後 所得的水溶液。（A)及（B)之混合比係設為（A):(B)=20:1。接 著劑之乾燥條件係設為80°C、5分鐘。PVA薄膜之相反側 之面上，利用與上述相同之接著劑貼合有經過皂化處理之 TAC薄膜。藉此，製作3層構造之偏光板樣本。偏光板樣 本之寬度係設為25 mm。自被處理薄膜9之寬度方向之5個 部位切出樣本片，製作5個上述偏光板樣本。 接著劑硬化之後，利用浮輥法（jIS K6854)測定各樣本之 被處理TAC薄膜9與PVA薄膜的接著強度。 5個樣本之平均接著強度係7.5 N/25 mm。 利用下式1計算5個樣本之接著強度之偏差度（均勻性）， 結果為3.8 %。 偏差度（％)={(最大值-最小值）/平均值/2}χ1〇〇 (式丄） [實施例2] 實施例2中，於裝置！中，將放電生成氣體（N2)之流量設 為20 slm »並且，將供給電力設為18〇9 w(27〇 v、6 7 A)’將施加電壓設為17.6 kv。除此以外之處理條件與實 施例1設為相同。表面處理後之喷嘴21、31之喷出口等處 未發現有堆積物。 表面處理後’按照與實施例i相同之順序製作偏光板樣 本’測定接著強度。 測定之後，可知，平均接著強度為9 9 N/25龍。偏差 度為4.2%。 [實施例3] 154529.doc •28- 201132688An aqueous solution obtained by mixing a Wt% aqueous solution with a 2 wt% aqueous solution of (B) sodium carboxymethylcellulose. The mixing ratio of (A) and (B) is set to (A): (B) = 20:1. The drying conditions of the adhesive were set to 80 ° C for 5 minutes. On the opposite side of the PVA film, a saponified TAC film was bonded to the same adhesive as described above. Thereby, a sample of a polarizing plate having a three-layer structure was produced. The width of the polarizing plate sample is set to 25 mm. Sample pieces were cut out from five portions in the width direction of the film 9 to be processed, and five samples of the above polarizing plates were produced. After the subsequent hardening, the adhesion strength of the treated TAC film 9 and the PVA film of each sample was measured by a floating roll method (jIS K6854). The average adhesion strength of the five samples was 7.5 N/25 mm. The degree of deviation (uniformity) of the subsequent strengths of the five samples was calculated by the following formula 1, and the result was 3.8%. Degree of deviation (%) = {(maximum - minimum value) / average / 2} χ 1 〇〇 (Formula 丄) [Embodiment 2] In Example 2, in the device! In the middle, the flow rate of the discharge generating gas (N2) was set to 20 slm » and the supplied electric power was set to 18 〇 9 w (27 〇 v, 6 7 A)', and the applied voltage was set to 17.6 kv. The processing conditions other than this are the same as in the first embodiment. No deposits were found at the discharge ports of the nozzles 21, 31 after the surface treatment. After the surface treatment, a polarizing plate sample was prepared in the same order as in Example i. After the measurement, it was found that the average bonding strength was 9 9 N/25 dragons. The degree of deviation is 4.2%. [Example 3] 154529.doc •28- 201132688
未發現有堆積物。 ，將放電生成氣體（n2)之流量設 W(270 V、 將供給電力設為1944 W(270 V、7.；2 %17.8 kV。除此以外之處理條件與實 面處理後之喷嘴21、31之喷出口等處 表面處理後’按照與實施例i相同之順序製作偏光板樣 本’測定接著強度。 測定之後，可知， mm。偏差 平均接著強度為9.3 N/25 度為6.5 %。 [比較例1] 比較例1中，作為構件5〇，係使用構造與下側喷嘴21相 同且與下側喷嘴21上下對調之喷嘴，將來自汽化器3〇之反 應氣體供給線32連接於喷嘴5〇而非喷嘴31。汽化器3〇之氣 化條件與實施例1相同，將組成及流量均與實施例丨相同之 反應氣體自上側喷嘴50之下端之喷出口喷向放電空間μ。 將上側喷嘴50之溫度調節至55它。下側喷嘴21之氣體噴出 流量係設為0 slm。並且，將供給電力設為1〇8〇 w(27〇 v、 4 A) ’將施加電壓設為15.7 kV。除此以外之處理條件與實 施例1設為相同。 比較例1中，表面處理後之噴嘴50之噴出口等處未發現 有堆積物。 表面處理後，按照與實施例1相同之順序製作偏光板樣 本，測定接著強度，可知，平均接著強度為4.9 N/25 mm，偏差度為60%。 154529.doc •29. 201132688 [比較例2] 比較例2中’於與實施例1相同之裝置1中，作為構件 50 ’係使用構造與下側喷嘴21相同且與下側喷嘴2丨上下對 調之喷嘴’將放電生成氣體供給路22連接於上側喷嘴5〇。 將上側喷嘴50之放電生成氣體（No之喷出流量設為1〇 slm。將下側喷嘴21之喷出流量設為〇 sim。並且，將供給 電力设為1377 W(270 V、5.1 A)，將施加電壓設為16.7 kV ^除此以外之處理條件與實施例丨設為相同。表面處理 後之喷嘴31之喷出口等處未發現有堆積物。 表面處理之後，按照與實施例1相同之順序製作偏光板 樣本，測定接著強度，可知，平均接著強度為3 9 N/25 ’偏差度為3.7%。 自以上之結果可確認，根據本發明，能獲得充分之處理 效果（接著性）’且可提高處理寬度方向之均勻性。 [產業上之可利用性] 本發明可適於製造例如平板顯示器（FPD)之偏光板。 【圖式簡單說明】 圖1係表示本發明之第i實施形態之薄膜表面處理裝置的 概略構成之側面講解圖。 圖2係上述薄膜表面處理裝置之處理部之立體圖。 圖3係表示本發明之第2實施形態之薄膜表面處理裝置的 概略構成之側面講解圖。 圖4係上述第2實施形態之薄膜表面處理裝置之2段處理 部的立體圖。 J54529.doc -30- 201132688 【主要元件符號說明】 1、1A 薄膜表面處理裝置 2 電源 9 被處理薄膜 9a ' 9b 折回部分 10 處理部 10A 前段處理部 10B 後段處理部 11 、 12 、 13 輥子電極 14、15 放電空間 16、17 導輥 20 放電生成氣體供給源 21 ' 23 放電生成氣體噴嘴 22 放電生成氣體供給路 30 反應氣體供給源（汽化器） 31、33 反應氣體喷嘴 32 反應氣體供給線 40 ' 43 遮蔽構件 41、44 遮蔽空間 50 ' 53 堵塞構件 51、54 第1間隙 52 > 55 第2間隙 154529.doc •31 ·No deposits were found. The flow rate of the discharge generating gas (n2) is set to W (270 V, and the supplied electric power is set to 1944 W (270 V, 7.; 2 % 17.8 kV. Other processing conditions and the nozzle 21 after the solid surface treatment, After the surface treatment of the discharge port of 31, etc., 'the polarizing plate sample was prepared in the same order as in Example i', the subsequent strength was measured. After the measurement, it was found that the average deviation strength of mm was 9.3 N/25 degrees and 6.5%. [Example 1] In the comparative example 1, a nozzle having the same structure as that of the lower nozzle 21 and being aligned with the lower nozzle 21 is used, and the reaction gas supply line 32 from the vaporizer 3 is connected to the nozzle 5 The non-nozzle 31. The vaporization conditions of the vaporizer 3 are the same as in the first embodiment, and the reaction gas having the same composition and flow rate as that of the embodiment is sprayed from the discharge port at the lower end of the upper nozzle 50 toward the discharge space μ. The temperature was adjusted to 55. The gas discharge flow rate of the lower nozzle 21 was set to 0 slm, and the supplied electric power was set to 1 〇 8 〇 w (27 〇 v, 4 A) 'The applied voltage was set to 15.7 kV. The processing conditions other than this are the same as those in the first embodiment. In Comparative Example 1, no deposit was observed in the discharge port of the nozzle 50 after the surface treatment. After the surface treatment, a polarizing plate sample was prepared in the same manner as in Example 1, and the subsequent strength was measured, and it was found that the average bonding strength was 4.9. N/25 mm, the degree of deviation is 60%. 154529.doc • 29. 201132688 [Comparative Example 2] In Comparative Example 2, in the same apparatus 1 as in the first embodiment, the structure and the lower nozzle are used as the member 50'. The nozzle which is the same as 21 and which is up-and-down with the lower nozzle 2A connects the discharge-generating gas supply path 22 to the upper nozzle 5A. The discharge-forming gas of the upper nozzle 50 (No discharge flow rate is 1 〇slm. The discharge flow rate of the side nozzles 21 is 〇sim, and the supply electric power is 1377 W (270 V, 5.1 A), and the applied voltage is 16.7 kV ^. The other processing conditions are the same as in the embodiment 丨. No deposit was observed at the discharge port of the nozzle 31 after the surface treatment. After the surface treatment, a polarizing plate sample was prepared in the same manner as in Example 1, and the subsequent strength was measured. It was found that the average bonding strength was 3 9 N/25. 'The degree of deviation is 3. From the above results, it has been confirmed that according to the present invention, a sufficient treatment effect (adhesiveness) can be obtained and the uniformity in the processing width direction can be improved. [Industrial Applicability] The present invention can be suitably used for manufacturing, for example. Fig. 1 is a side view showing a schematic configuration of a film surface treatment apparatus according to an i-th embodiment of the present invention. Fig. 2 is a processing unit of the film surface treatment apparatus. Fig. 3 is a side view showing a schematic configuration of a film surface treatment apparatus according to a second embodiment of the present invention. Fig. 4 is a perspective view showing a two-stage processing unit of the film surface processing apparatus according to the second embodiment. J54529.doc -30- 201132688 [Description of main component symbols] 1. 1A film surface treatment device 2 power supply 9 processed film 9a ' 9b folded back portion 10 processing portion 10A front processing portion 10B rear processing portion 11 , 12 , 13 roller electrode 14 15 discharge space 16, 17 guide roller 20 discharge generation gas supply source 21 ' 23 discharge generation gas nozzle 22 discharge generation gas supply path 30 reaction gas supply source (vaporizer) 31, 33 reaction gas nozzle 32 reaction gas supply line 40 ' 43 Shading member 41, 44 shielding space 50' 53 blocking member 51, 54 first gap 52 > 55 second gap 154529.doc • 31 ·