200927264 九、發明說明 【發明所屬之技術領域】 本發明係關於剝離液廢液之剝離液之再生方法和再生 裝置。 '【先前技術】 從液晶的製造過程（液晶顯示器的陣列基板單元製造 φ 過程）排出之含有光阻的剝離液廢液中，除了光阻以外， 還含有：水、重金屬類和各種微粒子等的非揮發性成分、 低沸點成分、高沸點成分。習知之專利文獻1至3揭示 出，用來回收從光阻剝離液廢液精製出的溶劑（精製剝離 液）的方法和裝置。依據專利文獻1所記載之溶劑再生回 收裝置，是使用降膜式蒸發器作爲前述高沸點成分的除去 手段’將前述蒸發器所產生的包含溶劑及低沸點污染成分 的蒸氣經由油霧分離機供應至精餾塔，將精餾塔的餾分之 〇 低沸點成分予以分離，並將精餾塔的餾出液中的高沸點成 分作爲側流成分，藉此獲得精製剝離液。 . 此外’依據專利文獻2的溶劑回收裝置，作爲從剝離 液廢液中除去光阻成分並將溶劑予以再生回收之手段是使 用··旋轉體內面刮取式的降膜機構所構成之蒸發濃縮手 段、用來除去剝離液廢液中所含的低沸點雜質之第1蒸餾 塔、用來高精度地分離精製出高沸點物質之第2蒸餾塔， 藉此精製出剝離液廢液而進行再生回收。 另一方面’在專利文獻3提出的技術，是使用主成分 -5- 200927264 包含單乙醇胺之光阻剝離液來進行光阻的剝離除去後的剝 離液廢液之再生回收用的方法及裝置，其具備：在剝離液 廢液中添加氫氧化鹼，將剝離液廢液中的碳酸成分以碳酸 鹼的狀態予以固定之鹼添加步驟；以及，將碳酸成分以碳 酸鹼的狀態予以固定後的剝離液廢液藉由蒸餾來回收剝離 液之蒸餾回收步驟。前述氫氧化鹼的添加量設定爲，爲了 將前述碳酸成分以碳酸鹼的狀態予以固定所必須的理論量 ❹ 的1〜1.5倍的範圍。在專利文獻3，是基於除去光阻剝離 液中的碳酸成分的目的來添加鹸成分，其添加量比本發明 的鹼添加量多1位數。因此，由於剝離液廢液中通常碳酸 成分的含量爲〇.5~2質量％，若剝離液廢液中所含的碳酸 成分爲0.5質量％，則使用氫氧化鈉作爲鹼來使用時之氫 氧化鈉的添加量爲 0.5 (碳酸濃度）+44 (二氧化碳分子量）X40 (氫氧 〇 化鈉分子量）=0.45質量％ 而必須使用大量的鹼。如此般專利文獻3的技術，純粹是 用來固定剝離液廢液中的碳酸，並不是用來處理剝離液廢 液的光阻，又關於對光阻實施鹼處理之技術思想，在專利 文獻3中完全沒有記載，且連暗示也沒有。 然而，在剝離液廢液中，除了光阻以外，還混入水、 重金屬類和微粒子等的非揮發性成分、高沸點成分，在上 述習知的剝離液廢液再生裝置之實際運轉狀況，隨著剝離 -6- 200927264 液廢液之濃縮，剝離液中光阻的溶解度降低（到達剝離液 可溶解光阻的限度以上）’因此若光阻濃縮至一定限度以 上，光阻會析出而附著、固著於裝置內面。特別是在光阻 濃度變濃之高沸點成分、非揮發性成分之除去步驟’光阻 成分的附著、固著變多，在專利文獻2’在旋轉體內面刮 '取式的降膜機構所構成之蒸發濃縮手段的旋轉體部、刮取 面上會附著、固著光阻成分，而使裝置之正常運轉變困 Q 難。同樣的，在專利文獻1、3也是，在降膜式的蒸發 器，光阻成分會附著、固著於用來賦予蒸發所必須的熱的 面上，而使蒸發器本身的功能變差。總之，由於光阻會附 著、固著於裝置，因此必須定期實施裝置的洗淨。此外， 光阻之附著、固著於裝置上，不僅會使裝置的運轉率降 低，且暗示精製剝離液的回收率的界限。和濃縮後的光阻 在一起的剝離液，會成爲損失，而必須購買新的剝離液來 進行補充，爲了取得高價的剝離液會造成成本上昇。 〇 另外’在固接後的光阻中，洗淨性差的非揮發性成分 完全不會剝落，因此就算實施洗淨步驟，其裝置的功能仍 會隨著時間經過而變差。 〔專利文獻1〕日本特開2003- 1 4480 1號公報 〔專利文獻2〕日本特開2005-288329號公報 〔專利文獻3〕日本特開2002-131923號公報 【發明內容】 本發明是有鑑於上述問題而開發完成者，其課題是爲 -7- 200927264 了減少液晶和半導體製造的光阻剝離步驟所使用的全新的 剝離液的補充而提供出，能從前述光阻剝離步驟所排出的 剝離液廢液以比以往更高的回收率來進行精製剝離液的再 生之新穎的剝離液之再生方法以及再生裝置。 例如，在半導體製造工廠和液晶顯示面板的製程之陣 '列基板製造過程，是在母玻璃基板上形成金屬膜並實施洗 淨，在其上方塗布可用紫外線感光之光阻原料（光阻塗布 Φ 步驟），爲了讓該光阻原料中的溶劑蒸發而進行高溫處理 (預供烤步驟），接著在其上方放置光罩並照射紫外線 (露光步驟），再用顯影液進行顯影（顯影步驟）。結 果，由於光罩上有圖案的部分未受紫外線的照射，光阻不 會產生變化而無法溶解於顯影液中，但在沒有圖案的部 分，受紫外線照射而進行感光之光阻，會溶解於顯影液中 而被除去。然後，再度進行高溫處理（後烘烤），接著爲 了除去不需要的金屬膜而進行蝕刻，最後將形成圖案用的 〇 光阻利用剝離液來除去。 本發明的目的，是爲了提供從如此般產生的剝離液廢 液（該剝離液廢液含有0.1〜3質量％的光阻）進行剝離液 的再生之方法及裝置。 本發明人等，爲了達成上述目的而進行深入探討的結 果發現，在從液晶顯示面板的製造過程排出之光阻剝離液 廢液將其中所含的正型光阻予以分離除去而再生剝離液之 方法中，相對於前述剝離液廢液中的光阻質量添加0.0 1〜 〇·2倍質量的鹼性化合物，藉此能從前述剝離液廢液以高 -8- 200927264 回收率再生出精製剝離液，如是到達本發明的完成。 亦即，本發明的第1觀點，是在從液晶顯示面板 造過程排出之光阻剝離液廢液將其中所含的正型光阻 分離除去而再生剝離液之方法，其特徵在於：將相對 述剝離液廢液所含的光阻質量爲0.01~0.2倍質量的鹼 合物，添加於該剝離液廢液中。 作爲第2觀點，在是第1觀點所記載之剝離液之 φ 方法中，前述鹼性化合物是以水溶液的形態來添加。 作爲第3觀點’在是第1觀點所記載之剝離液之 方法中，在添加前述鹼性化合物之同時或其添加前， 述剝離液廢液以光阻曝光用的波長範圍的光線進行曝 理。 作爲第4觀點，在第1觀點所記載之剝離液之再 法，係具有從前述剝離液廢液分離其中的高沸點成分 驟，藉由該分離來除去光阻的方法，而前述鹼性化合 〇 在該分離步驟之前添加。 作爲第5觀點，在是第1觀點所記載之剝離液之 方法中’係具有：從前述剝離液廢液分離除去其中的 點成分的步驟、分離除去其中的高沸點成分的步驟、 從剩餘的液體中將精製剝離液予以分離回收的步驟。 作爲第6觀點，是在從液晶顯示面板的製造過程 之光阻剝離液廢液將其中所含的正型光阻予以分離除 再生剝離液之裝置，其特徵在於：係具備： 從前述剝離液廢液分離除去其中的低沸點成分之 的製 予以 於前 性化 再生 再生 將前 光處 生方 的步 物是 再生 低沸 接著 排出 去而 低沸 -9- 200927264 點物除去塔、從該剝離液廢液分離除去其中的高沸點成分 之薄膜式蒸發器、以及從剩餘的液體中分離回收精製剝離 液之剝離液精製塔； 而且具備：讓前述剝離液廢液流過該低沸點物除去 塔、該薄膜式蒸發器以及該剝離液精製塔之間，而以精製 剝離液的狀態進行回收的配管系統； 在前述薄膜式蒸發器及/或比其更上游側的配管系 0 統，係具備用來將鹼性化合物添加於該剝離液廢液之鹼添 加手段。 作爲第7觀點，在是第6觀點所記載之剝離液之再生 裝置中，係具備：讓前述剝離液廢液依前述低沸點物除去 塔、前述薄膜式蒸發器、前述剝離液精製塔的順序流過其 等之間，而以精製剝離液的狀態進行回收的配管系統； 在前述薄膜式蒸發器及/或比其更上游側的配管系 統，具備前述鹼添加手段。 〇 作爲第8觀點，在是第6觀點所記載之剝離液之再生 裝置中，係具備：讓前述剝離液廢液依前述薄膜式蒸發 •器、前述低沸點物除去塔、前述剝離液精製塔的順序流過 其等之間，而以精製剝離液的狀態進行回收的配管系統； 在前述薄膜式蒸發器及/或比其更上游側的配管系 統，具備前述鹼添加手段。 作爲第9觀點，在是第6觀點至第8觀點中任一者所 記載之剝離液之再生裝置中，係在前述鹼添加手段之配置 部位，或是比該配置部位更上游側的部位，具備用來將前 -10- 200927264 述剝離液廢液以光阻曝光用的波長範圍的光線進行曝光處 理之曝光手段。 作爲第10觀點，在是第6觀點至第8觀點中任一者 所記載之剝離液之再生裝置中，前述鹼添加手段，是能將 相對於前述剝離液廢液所含的光阻質量爲0.01〜0.2倍質量 的鹼性化合物添加於該剝離液廢液中的手段。 作爲第11觀點，在是第6觀點至第8觀點中任一者 〇 所記載之剝離液之再生裝置中，進一步在前述低沸點物除 去塔及/或前述薄膜式蒸發器連接：使從其內部排出的氣 體液化後送回該內部之冷凝器。 作爲第12觀點，在是第6觀點至第8觀點中任一者 所記載之剝離液之再生裝置中，進一步在前述低沸點物除 去塔及/或前述剝離液精製塔連接：使來自其內部的液體 加熱沸騰後送回該內部之再沸器。 第1 3觀點是關於一種剝離液之再生裝置，是在從液 〇 晶顯示面板的製造過程排出之光阻剝離液廢液將其中所含 的正型光阻予以分離除去而再生剝離液之裝置，其特徵在 於：係具備：低沸點物除去塔、連接於低沸點物除去塔的 底部且用來使塔內的液體氣化後送回之第1再沸器、連接 於低沸點物除去塔且用來使從塔上部排出的氣體液化而讓 除去低沸點成分後的液體送回塔內部之第1冷凝器、剝離 液精製塔、連接於剝離液精製塔的底部且用來使塔內的液 體氣化後送回之第2再沸器、用來將除去低沸點成分後的 剝離液廢液從低沸點物除去塔供應至第2再沸器之配管、 -11 - 200927264 薄膜式蒸發器、用來將從剝離液精製塔的下部排出之除去 低沸點成分後的液體供應至薄膜式蒸發器的上部之配管、 用來將從薄膜式蒸發器的下部排出之處理液以含有光阻的 高沸點成分的狀態回收並送回薄膜式蒸發器的上部之配 管、用來將分離光阻後的剝離液從薄膜式蒸發器的上部供 應至剝離液精製塔之配管、連接於剝離液精製塔且用來使 從塔上部排出的氣體液化而將產生的精製剝離液予以回收 〇 之第2冷凝器；在前述薄膜式蒸發器或比其更上游的配管 或是裝置上設置：相對於剝離液廢液中的光阻質量添加 0.0 1〜0 · 2倍質量的鹼性化合物之鹼添加手段。 依據本發明，在剝離液廢液的管線之最佳部位，相對 於剝離液廢液的非揮發性成分（光阻）添加0.01〜0.2倍的 水溶性鹼，以及按照需要來對剝離液廢液全體利用螢光燈 等的光線來進行曝光，藉此可防止光阻析出，而提昇精製 剝離液的回收率，進一步可防止裝置壁面之光阻附著，結 © 果可減輕裝置之定期洗淨及保養的負擔。 又依據本發明，能以精製剝離液的回收率比使用習知 . 再生裝置的情況下之精製剝離液的回收率（与90% )提昇 5%的狀態進行再生。結果，可減少光阻剝離步驟中之高價 剝離液的補充量，除具有經濟價値外，藉由減輕洗淨及保 養的負擔可進行更穩定的裝置運轉而發揮極大的效果。 【實施方式】 依據本發明，藉由在剝離液廢液中添加鹼性化合物， -12- 200927264 可增加剝離液中光阻的溶解度，而減少光阻析出以及 上光阻的附著，藉此可提昇剝離液的回收率。 又較佳爲，除了添加前述鹼性化合物以外，對剝 廢液全體用螢光燈等具有紫外線（波長l(T9m)-光-紅外線（波長1 (T4m )的波長的光進行曝光。藉 讓未反應的光阻進行反應而使光阻變化成更容易溶解 中的狀態，藉此減少光阻析出以及裝置上光阻的附著 φ 能提昇剝離液的回收率。 在本發明的剝離液廢液中含有光阻剝離步驟所使 各種的溶劑，例如含有：用來除去光阻的剝離液、用 淨基板之稀釋劑（thinner )等。本發明的剝離液廢液 含有基板洗淨液。作爲光阻的剝離液，是對光阻具有 解度的溶液，例如包括：單乙醇胺（MEA)、二乙二 丁醚（BDG)、二甲亞碾（DMSO)、丙二醇單甲醚 酯（以下也稱PGMEA )等的1種或數種的混合物。 〇 光阻的剝離液中經常採用者，是將MEA和DMSO、 MEA和BDG以既定比例混合而成者，又作爲基板洗 的稀釋劑，其代表性的物質，例如是P G Μ E A和丙二 甲醚（PGME)所混合成的溶劑等。 添加於前述剝離液廢液中的鹼性化合物，可列舉 氧化鈉、氫氧化鉀、碳酸鈉等的無機鹼性化合物；氫 四甲銨等的有機鹼性化合物等。其添加量換算成鈉時 對於剝離液廢液的非揮發性成分（光阻）爲0 · 0 1 ~ 0.2 質量。 裝置 離液 可見 此， 於鹼 ，而 用之 來洗 中也 高溶 醇單 醋酸 前述 或是 淨用 醇單 :氣 氧化 ，相 倍的 -13- 200927264 鹼性化合物的添加手段，可將溶解於水中的鹼性化合 物連續定量地供應，也能分批定量地添加於裝置內貯留部 中。鹼性化合物，能以固體或液體等任意的形式配合水， 在鹼調整槽內用攪拌機均一混合來進行調整。在投入氫氧 化鈉等的固體鹼性化合物的情況下的調整，是使用鹼濃度 檢測器來檢測鹼濃度，接著調整補給水的量而調整成一定 的濃度。或者是，也能使用濃度事先調整好的具有任意濃 φ 度之鹼性化合物。鹼性化合物的添加量，是按照調整後的 鹼濃度、剝離液廢液中的光阻濃度來決定。 對前述剝離液廢液全體利用螢光燈等具有紫外線（波 長icr9m)-可見光-紅外線（波長l(T4m)的波長的光進 行曝光的時間，在從液深1 0mm的上面進行曝光的情況下 是1〜6000秒，較佳爲300〜1200秒。 此外，作爲將系統曝光之具體手段，可在所期望的部 位例如設置透明的派熱司（pyrex，註冊商標）玻璃管或 〇 曝光裝置（包含觀察窗等的採光部），對通過其內部的剝 離液廢液以具有前述波長的光線進行曝光。曝光強度（光 束）爲800流明（lumen)以上，較佳爲1000流明以上。 本發明之剝離液廢液所含的低沸點成分，是指沸點比 剝離液成分更低的成分，其典型是剝離液廢液所含之水、 溶解於剝離液之二氧化碳。又本發明之剝離液廢液所含之 高沸點成分，是指沸點比剝離液成分更高的成分，具體例 爲光阻。 以下參照圖式來詳細說明本發明。 -14- 200927264 第ι〇圖係顯示，未添加本發明的特徵之鹼性化合物 的情況下之光阻剝離液廢液的再生裝置之代表性流程圖的 一例之槪略圖。剝離液廢液供應至低沸點物除去塔（Τι ) 的中 間部’ 將餾出 物之水 、二氧 化碳等 的低沸 點成分 予以除去。從塔底部，是將排出物之剝離液、光阻、金 屬、微粒子排出。該排出物供應至再沸器（RB-2 )的下 部’在使一部分的剝離液蒸發下從塔下部藉由泵送往薄膜 〇 式蒸發器（FD·1 )而使大部分的剝離液蒸發，光阻、金 屬、微粒子是屬於非揮發性成分，故不會蒸發而和少量的 剝離液一起以高沸點成分的狀態排出系統外。在剝離液精 製塔（Τ-2 ) ’由於能將前述高沸點成分和剝離液實施精 密地精餾分離’而能從塔頂餾出可再生回收的剝離液。τι 代表 內部具 備塡充 物之進 行減壓 操作的 低沸點 物除去 塔’ Τ-2代表內部具備塡充物之進行減壓操作的連續精餾 塔’藉此容易將剝離液和低沸點成分進行分離。在壁面刮 © 取式降膜式蒸發器（FD-1)，可高效率地從高沸點成分中 將剝離液予以分離蒸發。 • 然而’在第1 〇圖之習知的方式，受到蒸氣的加熱溫 度、滞留時間等的影響，會析出高沸點成分而附著於裝置 壁面。所附著的場所包括：處理液滯留的場所、在光阻高 度濃縮的場所且溫度變高（1 25 °C以上）的場所。具體而 Η，在第10圖中，特別是在再沸器（RB-2)、薄膜式蒸 發器（FD-1)的裝置壁面。因此，在習知的裝置，會造成 處理能力變差，而必須實施定期洗淨、保養。 -15- 200927264 本發明人等針對此問題進行深入硏究，發現出以下的 手段可減少光阻析出以及壁面上之光阻附著。亦即，在剝 離液廢液管線之最佳部位’採用添加手段，來將氫氧化 鈉、氫氧化鉀、碳酸鈉等的無機鹼性化合物、或氫氧化四 甲銨等的有機鹼性化合物的水溶液，添加相當於剝離液廢 液中的非揮發性成分（光阻）的0.01〜0.2倍質量的量。又 除了此手段以外可倂用：對剝離液廢液全體用螢光燈等具 Q 有紫外線-可見光-紅外線（波長1 (T9m〜l 0_4m )進行曝 光的手段。 藉此，可防止光阻析出以及光阻附著於壁面，能提昇 精製剝離液的回收率，又能減輕定期洗淨及保養的負擔。 第2圖至第5圖係顯示本發明的基本實施態樣。圖中 標示〔1〕爲添加鹼性水溶液之1個具體部位，標示〔2〕 爲用螢光燈等的光線進行曝光之1個具體部位。 在第2圖，是依低沸點物除去塔、薄膜式蒸發器以及 〇 剝離液精製塔的順序進行排列，鹼性水溶液是在（A )剝 離液廢液進入低沸點物除去塔或薄膜式蒸發器之前的階段 添加，或（B)在薄膜式蒸發器循環的步驟中添加。又按 照需要來進行的曝光，在前述（A )的情況下是在鹼性水 溶液添加前的階段，在前述（B)的情況下是在薄膜式蒸 發器內部的壁面進行。 在第3圖至第5圖的情況下，是依薄膜式蒸發器、低 沸點物除去塔及剝離液精製塔的順序排列，鹼性水溶液是 在（A )剝離液廢液進入低沸點物除去塔之前的階段添 -16- 200927264 加，或（B)在離開薄膜式蒸發器而進入低沸點物除 之前的階段添加。又按照需要來進行的曝光，在 (A )的情況下是在鹼性水溶液添加前的階段，在 (B)的情況下是在薄膜式蒸發器內部的壁面、或是 膜式蒸發器和低沸點物除去塔之間進行鹼性化合物的 之前的階段實施光照射。 第1圖係顯示本發明的代表性流程圖。圖中 D 〔 1〕爲添加鹼性水溶液之1個具體部位，標示〔2〕 螢光燈等的光線進行曝光之1個具體部位。此外，爲 連結裝置與裝置之配管部分進行曝光，可在配管之期 位設置讓光線透過的部分。在薄膜式蒸發器（FD-1 ) 裝置，也能透過該裝置所具備之觀察窗等光線可透過 位來進行曝光照射。 接著簡單說明處理液的流動情形，使用後的剝離 液是從剝離液廢液管線送往低沸點物除去塔（T-1 〇 水、二氧化碳等的低沸點成分是經由管線（a )從低 物除去塔（T-1)的上方排出，另一方面，以高沸點 爲主成分之剝離液是經由管線（b )而由低沸點物除 (T-1)的下方排出。所排出之以高沸點成分爲主成 剝離液，經由第2再沸器（RB-2)送往剝離液精製塔 2 )。在此，一部分的主成分會被精製，在第2冷 (C-2 )液化後經由管線（c )以精製剝離液的狀態 收。從剝離液精製塔（T-2 )的下部回收之含有光阻 離液廢液，通過管線（d)而送往薄膜式蒸發器（ 去塔 前述 前述 在薄 添加 標示 爲用 了在 望部 等的 的部 液廢 )， 沸點 成分 去塔 分之 (T-凝器 被回 的剝 FD- -17- 200927264 1 )。在薄膜式蒸發器（FD-l )，藉由刮 構使光阻成分變成薄膜，和光阻分離後的 而從薄膜式蒸發器（FD-1)的上部通過1 至剝離液精製塔（T_2 )的中段，在此被 冷凝器（C-2)進行液化後，從管線（^) 狀態被回收。含有不需要的光阻之廢液， (FD-1 )的下部通過管線（f)排出。 〇 如此般’含有低沸點物除去塔（T-1 塔（T-2)以及薄膜式蒸發器（FD-1)( 光阻儘可能分離）這3種不同的裝置之剝 例如可在〔I〕〜〔V〕所示的部位添加鹼 照需要來進行光照射。 在薄膜式蒸發器（FD-1)，是利用藉 刮除器（wiper )，使從薄膜式蒸發器（ 應之剝離液廢液中的光阻在二層管的表面 〇 剝離液廢液中的低沸點成分高效率地氣化 分從底部排出。 第1圖之添加鹼性化合物的場所的具 1 :剝離液廢液供應至低沸點物除去3 任意場所 2:從第1冷凝器（C-1)的下部透過 除去塔（T-1 )的上部之供應管線（低沸 流管線）之任意場所 3 :從低沸點物除去塔（T-1 )連通 取式薄膜蒸發機 剝離液會蒸發， f線（e )而供應 精製然後在第2 以精製剝離液的 從薄膜式蒸發器 )、剝離液精製 用來將剝離液和 丨離液再生裝置， 性化合物，以按 由旋轉軸旋轉之 F D -1 )的上部供 形成薄膜狀，使 ，且使高沸點成 體例 答（T-1 )以前的 !栗送往低沸點物 點物除去塔的gj [至第2再沸器 -18- 200927264 (RB-2)的管線的任意場所 4:從剝離液精製塔（T-2)的下部送往薄膜式蒸發器 (FD-1)的上部之供應管線的任意場所 5:從薄膜式蒸發器（FD·1)的下部朝薄膜式蒸發器 (FD-1)的上部進行再循環之管線的任意場所 第1圖之光線照射場所的具體例 0 1 :剝離液廢液供應至低沸點物除去塔（T-1 )以前的 任意場所 2:從第1冷凝器（C-1)的下部透過泵送往低沸點物 除去塔（T-1)的上部之供應管線（低沸點物除去塔的回 流管線）的任意場所 3:從低沸點物除去塔（T-1)連通至第2再沸器 (RB-2 )的管線之任意場所 4 :從剝離液精製塔（T-2 )的下部送往薄膜式蒸發器 〇 ( FD-1 )的上部之供應管線的任意場所 5 :薄膜式蒸發器（FD-1)內部壁面 〔實施例〕 以下用實施例來更具體地說明本發明，但本發明並不 受這些實施例的限定。 比較例1 第9圖係用來驗證實際裝置中光阻的析出、附著情形 -19- 200927264 之試驗裝置。在用油浴加熱成一定溫度之燒杯內的剝離液 廢液中投入試驗片（SUS316，15mm寬x3mm厚xl50mm 長）’觀察附著於試驗片上的光阻量及其附著狀態。事先 用旋轉蒸發器來濃縮剝離液廢液而將其光阻濃度調整爲約 1 7質量％ (在剝離液廢液中含有2質量％光阻時之剝離液 回收率90質量％的情況）。在此實驗中，當然對處理液有 室內光的照射。 〇 使用前述第9圖的實驗裝置，將剝離液廢液溫度分別 保持於120、130、140 °C，測定隨著時間經過之單位面積 的附著量。其數値如下述表1所示。從表1可看出，在 1 4 0 °C，從3小時後開始發生附著；在1 3 0 °C，從6小時後 開始發生附著；在120 °C，從9小時後開始發生附著。附 著物爲褐色，呈硬且炭化的狀態，即使實施水洗淨、再生 前之剝離液廢液洗淨，仍不容易將其除去。又得知，剝離 液廢液的光阻受加熱溫度的影響很大，而必須儘量進行低 〇 溫加熱。此乃基於’若剝離液滯留於裝置內，光阻受熱的 影響會發生固化、炭化。如此般’本發明人等可掌握實際 裝置中的附著狀態。 -20- 200927264 表1附著試驗(非揮發性成分17質量％ ) 濃縮之剝離麵液的溫_ 120°C 130°C 140°C 時間 單位面積的附著量 單位面積的附著量 單位面積的附著量 〔hr〕 〔mg/cm2〕 C mg/cm2 ] [mg/cm2) 3 0.92 2.24 2.58 6 2.24 4.88 4.94 9 4.21 5.27 6.14 18 5.39 5.61 6.00 剝離液廢液洗淨後 4.86 5.08 5.10 水洗淨後 4.46 4.92 4.98 實施例1 於是，本發明人等，針對用來解決上述問題的手段’ 根據以下的實施例而解明出··在析出光阻前的階段添加鹼 性化合物’或除此外更進行光照射是有效的。 表2顯示出，使用和第9圖的試驗器相同的試驗器 (由於使用燒杯，故屬於倂用光照射的例子），在剝離液 © 廢液的原液中添加0.05質量％ (48質量％ NaOH水溶液的 狀態下的添加比例）的氫氧化鈉水溶液，用旋轉蒸發器濃 縮成光阻濃度約1 7質量％，進行和前述同樣的試驗的結 果。在140°C從24小時開始發生附著，在130°C從34小 時開始發生附著，在1 2 0 °C從4 8小時開始發生附著。附著 物爲淡褐色的泥狀物，看不出炭化的狀態，藉由實施水洗 淨、再生前的剝離液廢液洗淨很容易就能除去。在發生附 著的時間以及附著量雙方，都比比較例1的試驗結果（表 1的資料）獲得更良好的結果。 -21 - 200927264 表2附著試驗（非揮發性成分17質量％，添加NaOH水溶液) 濃縮之剝離液廢液的溫度 120°C 130°C 140°C 時間 單位面積的附著量 單位面積的附著量 單位面積的附著量 〔hr〕 〔mg/cm2〕 [mg/cm2) 〔mg/cm2〕 24 0.13 0.31 1.11 36 0.74 1.64 —---- 2.58 48 1.07 3.52 4.46 剝離液廢液洗淨後 0.54 1.53 1.88 水洗淨後 0.11 0.31 0.56 此外，爲了提昇精製剝離液的回收率，將同樣添加有 氫氧化鈉水溶液的剝離液廢液用旋轉蒸發器濃縮成光阻濃 度約31質量％，藉由和實施例1同樣的方法進行試驗。結 果顯示於表3。在目視觀察下，在140 °C從18小時開始發 生附著，在130 °C從23小時開始發生附著，在120 °C從32 小時開始發生附著。附著物呈褐色泥狀，雖看得出有若干 炭化狀態，但藉由實施水洗淨、再生前的剝離液廢液洗淨 可將其除去。如此般確認出，即使光阻濃度提高，仍能獲 得比比較例1的表1所示的結果更良好的結果，因此鹼性 化合物的添加效果相當顯著。 又表1~表3之附著量資料，並不是根據目視，而是定 量測定的結果。 -22- 200927264 表3附著纖（非揮發性成分31質量％，添加NaOH 7Jc^) 濃縮之剝離液廢液的溫摩 120°C 130°C 140°C 時間 [hr] 單位面積的附著量 [mg/cm2 ] 單位面積的附著量 [mg/cm2 ] 單位面積的附著量 [mg/cm2 ] 24 0.53 1.11 1.39 36 0.73 2.31 3.08 48 1.57 3.92 5.12 剝離液廢液洗淨後 1.12 1.28 2.81 水洗淨後 0.42 0.52 0.82 ❹ 實施例2、比較例2 本發明人等發現，從剝離液廢液貯槽供應至第1圖的 再生裝置之剝離液廢液中的光阻，是混合有在液晶製造過 程等中進行曝光的光阻和未進行曝光的光阻，而該差異可 能會影響光阻之析出、附著。於是，本實驗裝置，是接續 於未圖示的剝離液廢液貯槽，而使用由不鏽鋼構成且幾乎 完全遮光（僅從局部的觀察孔等可進行曝光）的狀態之再 〇 生裝置。前述比較例1及實施例1，是在室內進行燒杯試 驗，因此剝離液是進行曝光。 • 本試驗，兩個例子都是，首先用旋轉蒸發器將剝離液 廢液濃縮至光阻濃度約1 5質量％。接著，將所得的濃縮剝 離液廢液進行以下的處理。 (1 )比較例2 :未添加氫氧化鈉也不進行曝光。 (2)實施例2-1 :換算成剝離液廢液是添加0.05質 量％的氫氧化鈉，但不進行曝光。 實施例2-2 :換算成剝離液廢液是添加0.05質量％的 -23- 200927264 氫氧化鈉，且進行曝光ι〇分鐘。 然後，在用140 °C的油浴加熱之含濃縮剝離液的容器 中分別投入試驗片，保持48小時。這些試驗都是在暗室 中進行。 表4顯示前述比較例1、實施例2-1及實施例2-2的 結果。比較例1的附著量爲8.35 g/cm2，實施例2 -1的附 著量爲4.46g/cm2，實施例2-2的附著量爲4.02g/cm2。由 Q 此結果可知，藉由進行曝光可減少光阻之析出、附著。此 外’在實施水洗淨、剝離液洗淨方面，比起未添加氫氧化 鈉的情況，添加氫氧化鈉的情況更容易除去附著物。 表4附著試驗 試驗條件（濃縮之剝離液廢液的溫度140〇C ) 比較例1 實施例2-1 實施例2-2 時間 單位面積的附著量 單位面積的附著量 單位面積的附著量 〔hr〕 [mg/cm2) [mg/cm2 ] [mg/cm2 ] 48 8.35 4.46 4.02 剝離液廢液洗淨後 5.37 1.88 1.34 水洗淨後 5.30 0.56 0.03 實施例3 第6圖顯示水溶性無機鹼性化合物添加裝置的1個實 施例。鹼性化合物是使用氫氧化鈉水溶液，在鹼調整槽用 攪拌機進行均一混合。氫氧化鈉的情況之濃度調整，是用 鹼濃度檢測器來檢測鹼濃度，藉由調整補給水的量來調整 成一定濃度。氫氧化鈉的添加量，是依據調整後的氫氧化 -24- 200927264 鈉的濃度、剝離液廢液中的光阻濃度來決定。剝離液廢液 中鹼性化合物的供應，是使用定量泵，在第1圖所示的 〔1〕部位〔從供應管線至精製剝離液管線之最佳部位〕 的配管管線供應。在供應位置的後方，具備靜態混合器等 之用來混合氫氧化鈉水溶液和剝離液廢液的機構。第6圖 顯示1個實施例，只要能供應調整成一定濃度的氫氧化鈉 水溶液，則只需定量泵，而能省略鹼調整槽。 ❹ 實施例4 第7圖及第8圖係顯示曝光裝置的2個實施例。第7 圖是在配管管線中插入曝光裝置的1個實施例，是將配管 中途變更成光線可透過之派熱司（pyrex，註冊商標）玻 璃等的配管，從該配管的兩面用螢光燈等之具有紫外線 (波長l(T9m)-可見光-紅外線（波長l〇_4m)的波長的 光進行曝光，以使未反應光阻進行反應的裝置。本例的裝 〇 置，爲了使用螢光燈而至少進行5分鐘曝光，根據廢液的 流速，將光線可透過之配管部分的長度設定爲約8m長。 第8圖係利用第1圖所示的薄膜式蒸發器（FD-1)的觀察 窗來進行紫外線曝光的裝置，在上下觀察窗的4個部位設 置該裝置。具備攪拌機之降膜式蒸發裝置（FD-1)，可藉 由安裝於攪拌機之撞葉（flapper)將剝離液以1mm左右 的膜厚均一分散在蒸發器壁面，且不會因液深而造成曝光 的衰減，即使光量較少仍能進行均一曝光。 -25- 200927264 實施例5 將實施例3及實施例4的鹼性化合物添加裝置和曝光 裝置安裝於第1圖所示的實際裝置，和安裝前進行比較實 驗。將鹼性化合物添加裝置插入第1圖之〔II〕所示的配 管中途。曝光裝置，是利用設置於攪拌機之降膜式蒸發裝 置（FD-1)的φ 150觀察窗，在上下2個部位（合計4個 部位）設置水銀燈，而以1 000流明進行曝光。 Q 本剝離液再生裝置之既定處理量爲540kg/h，其組成 分析値爲：剝離液廢液476kg/h、光阻等的高沸點成分1 〇 kg/h、水等的低沸點成分54kg/h。48質量％的氫氧化鈉以 5 40x0.0 00 5 = 0.27kg/h的添加量進行定量供應。 對各條件下的精製再生量進行比較。 •鹼性化合物的添加以及曝光皆未進行之習知方法 精製剝離液之平均回收率約88質量％、4 1 9kg/h，在 〇 FD-1的壁面及FD-1的下部的貯液部發生光阻的析出、附 著，必須實施定期（1次/3天的自動水洗，1次/年的拆解 洗淨）保養。 •本發明之添加鹼性化合物的改善效果（無曝光） 精製剝離液之平均回收率約90質量％、428kg/h，可 在定量且穩定的狀態下進行剝離液的再生。FD-1壁面上 的光阻附著以及FD-1下部的貯液部的光阻析出、附著幾 乎看不到，但必須進行定期（1次/3天的自動水洗）洗 -26- 200927264 淨。亦即，藉由添加鹼性化合物，能增加光阻對剝離液的 溶解度，而減少光阻之析出、附著，因此能提高剝離液的 回收率。 •本發明之添加鹼性化合物及進行曝光的改善效果 精製剝離液之平均回收率約95質量％、425kg/h，可 在定量且穩定的狀態下進行剝離液的再生。FD-1壁面上 Q 的光阻附著以及FD-1下部的貯液部的光阻析出、附著幾 乎看不到，藉由進行定期（1次/3天的自動水洗）洗淨可 避免發生最糟的情況。 【圖式簡單說明】 第1圖係顯示本發明的實施例之具體的剝離液再生裝 置的流程一例。 第2圖係顯示本發明的基本的剝離液再生裝置的流程 —例。 第3圖係顯示本發明的基本的剝離液再生裝置的流程 另一例。 第4圖係顯示本發明的基本的剝離液再生裝置的流程 另一例。 第5圖係顯示本發明的基本的剝離液再生裝置的流程 另一例。 第6圖係顯示鹼定量添加裝置。 第7圖係顯示配管管線曝光裝置，（a)爲前視圖， -27- 200927264 (b )爲側視圖。 第8圖係顯示安裝於薄膜式蒸發器的曝光裝置。 第9圖係顯示附著試驗用的實驗裝置。 第10圖係顯示習知的剝離液再生裝置的流程。 【主要元件符號說明】 FD-1 :薄膜式蒸發器 Q T-1 :低沸點物除去塔 T-2 :剝離液精製塔 RB :再沸器 C :冷凝器 P :泵 (a ):連結低沸點物除去塔上部和第1冷凝器的配 管 (b ):連結低沸點物除去塔底部和第2再沸器的配 ❹ 管 (c ):用來回收精製剝離液的配管 (d) :連結剝離液精製塔底部和薄膜式蒸發器上部 的配管 (e) :連結薄膜式蒸發器上部和剝離液精製塔中段 的配管 -28-BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and a regeneration apparatus for a stripping liquid for a stripping liquid waste liquid. '[Prior Art] In addition to photoresist, water, heavy metals, and various fine particles are included in the liquid waste-removing liquid waste liquid discharged from the liquid crystal manufacturing process (the φ process of the liquid crystal display array substrate unit). Non-volatile components, low boiling components, high boiling components. Patent Documents 1 to 3 disclose a method and apparatus for recovering a solvent (purified stripping liquid) purified from a photoresist stripping liquid. According to the solvent recovery and recovery apparatus described in Patent Document 1, a falling film evaporator is used as a means for removing the high-boiling point component, and a solvent containing a solvent and a low-boiling point pollutant component generated by the evaporator is supplied via an oil mist separator. In the rectification column, the low boiling point component of the fraction of the rectification column is separated, and the high boiling component in the distillate of the rectification column is used as a side stream component, thereby obtaining a purified stripping liquid. . Further, according to the solvent recovery device of Patent Document 2, the means for removing the photoresist component from the waste liquid of the peeling liquid and recovering and recovering the solvent is a method of evaporating and concentrating using a falling film falling mechanism of the inner surface scraping type. The first distillation column for removing low-boiling impurities contained in the waste liquid of the stripping liquid, and the second distillation column for separating and purifying the high-boiling substance with high precision, thereby purifying the waste liquid of the stripping liquid and recovering and recycling . On the other hand, the technique proposed in Patent Document 3 is a method and an apparatus for recycling and recovering a peeling liquid waste liquid after peeling off the photoresist using the main component-5-200927264, which comprises a photoresist stripping liquid of monoethanolamine. The alkali addition step of adding the alkali hydroxide to the waste liquid waste liquid, and fixing the carbonic acid component in the waste liquid waste liquid in the form of a carbonate base; and peeling off the carbonic acid component in a state of being carbonated The liquid waste liquid is subjected to a distillation recovery step of recovering the stripping liquid by distillation. The amount of the alkali hydroxide added is set to be 1 to 1 of the theoretical amount necessary for fixing the carbonic acid component in the state of carbonate. 5 times the range. In Patent Document 3, a bismuth component is added for the purpose of removing a carbonic acid component in the resist release liquid, and the amount thereof is added by one digit more than the alkali addition amount of the present invention. Therefore, the content of carbonic acid in the stripping liquid waste is usually 〇. 5~2% by mass, if the carbonic acid component contained in the stripping liquid waste liquid is 0. 5 mass%, when sodium hydroxide is used as a base, the amount of sodium hydroxide added is 0. 5 (carbonic acid concentration) +44 (carbon dioxide molecular weight) X40 (hydrogen oxyhydroxide molecular weight) = 0. 45 mass% and a large amount of alkali must be used. The technique of Patent Document 3 is purely for fixing the carbonic acid in the waste liquid of the stripping liquid, not the photoresist for treating the waste liquid of the stripping liquid, and the technical idea of performing alkali treatment on the photoresist, in Patent Document 3 There is no record at all, and there is no hint. However, in the stripping liquid waste liquid, in addition to the photoresist, non-volatile components such as water, heavy metals, and fine particles, and high-boiling components are mixed, and the actual operating state of the above-described conventional stripping liquid waste regeneration device is Stripping-6-200927264 Concentration of liquid waste liquid, the solubility of the photoresist in the stripping solution is reduced (above the limit of the photoresist that can dissolve the stripping solution)" Therefore, if the photoresist is concentrated to a certain limit or more, the photoresist will precipitate and adhere. Fixed to the inside of the device. In particular, in the step of removing the high-boiling component and the non-volatile component in which the photoresist concentration is increased, the adhesion and fixation of the photoresist component are increased, and in Patent Document 2, the falling film mechanism of the rotating body surface is scraped. It is difficult to make the normal operation of the device difficult to accumulate and fix the photoresist component on the rotating body portion and the scraping surface of the evaporation concentration means. Similarly, in Patent Documents 1 and 3, in the falling film type evaporator, the photoresist component adheres to and adheres to the surface for imparting heat necessary for evaporation, and the function of the evaporator itself is deteriorated. In short, since the photoresist is attached and fixed to the device, it is necessary to periodically clean the device. Further, the adhesion of the photoresist to the device not only lowers the operation rate of the device, but also implies the limit of the recovery rate of the purified stripper. The stripping solution with the concentrated photoresist is a loss, and a new stripping solution must be purchased for replenishment, which increases the cost in order to obtain a high-priced stripping solution. 〇 In addition, in the photoresist after the fixation, the non-volatile components with poor detergency do not peel off at all, so even if the cleaning step is carried out, the function of the device will deteriorate with time. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. 2005-288329 (Patent Document 3). The problem was solved by the above-mentioned problem, and it is provided for the replenishment of a new stripping liquid used for the photoresist stripping step for reducing liquid crystal and semiconductor manufacturing, which can be peeled off from the photoresist stripping step. A method and a regeneration apparatus for regenerating a novel stripping liquid in which a liquid waste liquid is recovered at a higher recovery rate than in the prior art. For example, in the manufacturing process of a semiconductor manufacturing factory and a liquid crystal display panel, a column substrate is formed by forming a metal film on a mother glass substrate and performing cleaning thereon, and coating a photoresist material with ultraviolet light sensitivity thereon (photoresist coating Φ) Step), in order to evaporate the solvent in the photoresist raw material, high temperature treatment (pre-bake step), followed by placing a photomask thereon and irradiating ultraviolet rays (exposure step), and then developing with a developing solution (developing step). As a result, since the patterned portion of the photomask is not irradiated with ultraviolet rays, the photoresist does not change and cannot be dissolved in the developer, but in the portion where there is no pattern, the photoresist which is exposed to ultraviolet light and is photosensitive is dissolved. It is removed in the developer. Then, high-temperature treatment (post-baking) is performed again, followed by etching to remove the unnecessary metal film, and finally the photoresist for pattern formation is removed by the stripping liquid. SUMMARY OF THE INVENTION The object of the present invention is to provide a stripping liquid waste which is produced in such a manner (the stripping liquid waste liquid contains 0. A method and apparatus for regenerating a stripping liquid in a photoresist of 1 to 3 mass%. As a result of intensive investigation to achieve the above object, the present inventors have found that the photoresist of the photoresist stripping liquid discharged from the manufacturing process of the liquid crystal display panel separates and removes the positive photoresist contained therein to regenerate the stripping liquid. In the method, the mass of the photoresist in the stripping liquid waste liquid is added to 0. 0 1 to 2·2 times the mass of the basic compound, whereby the refined stripping liquid can be regenerated from the stripping liquid waste liquid at a recovery rate of -8-200927264, as it is at the completion of the present invention. In other words, the first aspect of the present invention is a method for separating and removing a positive-type photoresist contained in a photoresist release liquid discharged from a liquid crystal display panel to regenerate a peeling liquid, which is characterized in that: The photo-resistance of the stripping liquid waste liquid is 0. 01~0. A 2-fold mass of the alkali compound was added to the stripping liquid waste liquid. According to a second aspect, in the method of φ of the peeling liquid described in the first aspect, the basic compound is added in the form of an aqueous solution. According to a third aspect of the invention, in the method of the peeling liquid described in the first aspect, the stripping liquid waste liquid is exposed to light in a wavelength range for resist exposure while the basic compound is added or before the addition thereof. . According to a fourth aspect of the present invention, in the method of resolving the peeling liquid described in the first aspect, the high-boiling component separated from the peeling liquid waste liquid is removed, and the photoresist is removed by the separation, and the alkaline compound is removed.添加 Add before this separation step. In the method of the peeling liquid described in the first aspect, the method of separating and removing the point component from the peeling liquid waste liquid, the step of separating and removing the high boiling point component thereof, and the remaining The step of separating and recovering the purified stripping liquid in the liquid. According to a sixth aspect of the invention, there is provided a device for separating a positive-type photoresist contained in a photoresist liquid waste liquid from a process for producing a liquid crystal display panel, which comprises: a stripping liquid from the foregoing The waste liquid is separated and removed from the low-boiling component, and the precursor is regenerated and regenerated. The step of the front light is recycled, low boiling, and then discharged, and the low boiling -9-200927264 point removal tower, from which the strip is removed a thin film evaporator in which a liquid waste liquid is separated and removed, and a stripping liquid refining tower for separating and recovering the purified stripping liquid from the remaining liquid; and further comprising: allowing the stripping liquid waste liquid to flow through the low boiling point removal tower a piping system that recovers between the film evaporator and the stripping liquid refining tower in a state in which the stripping liquid is purified; and the membrane evaporator and/or the piping system upstream of the thin film evaporator are provided. A base addition means for adding a basic compound to the stripping liquid waste liquid. According to a seventh aspect of the invention, in the apparatus for regenerating a stripping liquid according to the sixth aspect, the apparatus for allowing the stripping liquid waste liquid to pass through the low-boiling point removal tower, the thin film evaporator, and the stripping liquid refining tower A piping system that recovers in a state in which the stripping liquid is purified, and a piping system in which the thin film evaporator and/or the upstream side thereof are provided with the alkali addition means. According to a sixth aspect of the invention, in the apparatus for regenerating a peeling liquid according to the sixth aspect, the peeling liquid waste liquid is provided in the thin film evaporation apparatus, the low boiling point removal tower, and the peeling liquid refining tower. In the piping system in which the stripping liquid is in a state of being purified, the piping system is recovered; and the membrane evaporator system and/or the piping system on the upstream side thereof are provided with the alkali addition means. According to a ninth aspect of the present invention, in the apparatus for regenerating the peeling liquid according to any one of the sixth aspect to the eighth aspect, the portion to be placed in the alkali addition means or the portion on the upstream side of the arrangement portion is An exposure means for exposing the light of the wavelength range of the peeling liquid waste liquid of the above-mentioned -10-200927264 for exposure exposure is provided. According to a tenth aspect of the present invention, in the apparatus for regenerating a peeling liquid according to any one of the sixth aspect to the eighth aspect, the alkali addition means is capable of providing a photoresist mass contained in the waste liquid of the peeling liquid 0. 01~0. A means of adding 2 times the mass of the basic compound to the stripping liquid waste. According to a seventh aspect of the present invention, in the apparatus for regenerating the peeling liquid described in any one of the sixth aspect to the eighth aspect, the low-boiling substance removing tower and/or the thin film evaporator are further connected: The internally discharged gas is liquefied and sent back to the internal condenser. According to a second aspect of the present invention, in the apparatus for regenerating a stripping liquid according to any one of the sixth aspect to the eighth aspect, the low-boiling point removal column and/or the stripping liquid refining tower are further connected from the inside The liquid is heated to boil and returned to the internal reboiler. The first aspect is a device for regenerating a stripping liquid, which is a device for separating and removing a positive photoresist contained in a photoresist stripping liquid discharged from a liquid crystal display panel during a manufacturing process. It is characterized in that it comprises a low-boiling substance removal column, a first reboiler connected to the bottom of the low-boiling substance removal column, and used to vaporize the liquid in the column, and is connected to the low-boiling substance removal tower. And liquefying the gas discharged from the upper portion of the column, and returning the liquid from which the low-boiling point component is removed to the first condenser, the stripping liquid refining tower, and the bottom of the stripping liquid refining tower, and used to make the inside of the column The second reboiler that is returned after the liquid is vaporized, and the waste liquid for removing the low-boiling component from the low-boiling substance removal tower to the second reboiler, -11 - 200927264 thin film evaporator a liquid for removing a liquid having a low boiling point component discharged from a lower portion of the stripping liquid refining column and supplying it to an upper portion of the thin film evaporator, and a treatment liquid for discharging the lower portion of the thin film evaporator to contain a photoresist. High boiling point The state of the component is recovered and sent back to the piping of the upper portion of the film evaporator, and the stripping liquid after separating the photoresist is supplied from the upper portion of the thin film evaporator to the piping of the stripping liquid refining tower, and is connected to the stripping liquid refining tower. a second condenser that liquefies the gas discharged from the upper portion of the tower to recover the produced purified stripping liquid; and is disposed on the thin film evaporator or a pipe or device upstream thereof: with respect to the stripping liquid The photoresist quality in the addition adds 0. 0 1~0 · 2 times the mass of the basic compound to add a base. According to the present invention, the optimum portion of the stripping liquid waste liquid is added with respect to the non-volatile component (photoresist) of the stripping liquid waste liquid. 01~0. The water-soluble alkali is twice as large as possible, and the entire waste liquid waste liquid is exposed to light such as a fluorescent lamp as needed, thereby preventing the precipitation of the photoresist, thereby improving the recovery rate of the purified peeling liquid and further preventing the wall surface of the device. The photoresist is attached, which can reduce the burden of periodic cleaning and maintenance of the device. According to the present invention, it is also possible to use a recovery ratio of the purified stripping solution. In the case of the regeneration apparatus, the recovery rate (90%) of the purified stripping liquid was increased by 5%. As a result, it is possible to reduce the amount of replenishment of the high-priced peeling liquid in the resist stripping step, and in addition to having an economical price, it is possible to perform a more stable operation of the apparatus by reducing the burden of washing and maintenance. [Embodiment] According to the present invention, by adding a basic compound to the waste liquid of the stripping liquid, -12-200927264 can increase the solubility of the photoresist in the stripping solution, thereby reducing the precipitation of the photoresist and the adhesion of the upper photoresist. Improve the recovery rate of the stripper. In addition, it is preferable to expose light having a wavelength of ultraviolet (wavelength l (T9m)-light-infrared (wavelength 1 (T4m)) to a whole waste liquid, such as a fluorescent lamp, in addition to the above-mentioned basic compound. The unreacted photoresist reacts to change the photoresist to a state in which it is more soluble, thereby reducing the precipitation of the photoresist and the adhesion of the photoresist on the device, which can improve the recovery rate of the stripper. The solvent contained in the photoresist stripping step includes, for example, a stripping liquid for removing photoresist, a thinner for using a clean substrate, and the like. The stripping liquid waste liquid of the present invention contains a substrate cleaning liquid. The resist stripping solution is a solution having a solution to the photoresist, and includes, for example, monoethanolamine (MEA), diethylene dibutyl ether (BDG), dimethyl sulfite (DMSO), and propylene glycol monomethyl ether ester (hereinafter also referred to as Mixture of one or more kinds of PGMEA), etc. It is often used in the stripping solution of bismuth photoresist, which is a mixture of MEA and DMSO, MEA and BDG in a predetermined ratio, and is used as a diluent for substrate washing. Sexual substance, such as PG Μ EA A solvent to be mixed with propylene glycol (PGME), etc. The basic compound added to the waste liquid of the stripping liquid may, for example, be an inorganic basic compound such as sodium oxide, potassium hydroxide or sodium carbonate; The organic basic compound, etc., when the amount of addition is converted to sodium, the non-volatile component (photoresist) of the stripping liquid waste liquid is 0 · 0 1 ~ 0. 2 quality. The device can be seen from the liquid, in the case of alkali, and is also used to wash the high-alcohol monoacetic acid or the net alcohol alone: gas oxidation, phase-doubling -13-200927264 basic compound addition means can be dissolved in The alkaline compound in the water is supplied continuously and quantitatively, and can also be quantitatively added to the storage portion in the apparatus in batches. The basic compound can be blended in any form such as a solid or a liquid, and uniformly adjusted by a mixer in an alkali adjusting tank. In the case of adding a solid basic compound such as sodium hydroxide, the alkali concentration detector is used to detect the alkali concentration, and then the amount of the makeup water is adjusted to adjust to a constant concentration. Alternatively, an alkaline compound having an arbitrary concentration of φ can be used in advance. The amount of the basic compound to be added is determined in accordance with the adjusted alkali concentration and the resist concentration in the stripping liquid. In the case where the entire stripping liquid waste liquid is exposed to light having a wavelength of ultraviolet light (wavelength icr9m)-visible light-infrared light (wavelength l (T4m), such as a fluorescent lamp, when exposure is performed from the upper surface of the liquid depth of 10 mm It is 1 to 6000 seconds, preferably 300 to 1200 seconds. Further, as a specific means for exposing the system, a transparent Pyrex (registered trademark) glass tube or a krypton exposure device may be provided at a desired portion (for example). The lighting unit including the observation window or the like exposes the light having the above-described wavelength to the liquid waste liquid passing through the inside. The exposure intensity (light beam) is 800 lumens or more, preferably 1000 lumens or more. The low-boiling point component contained in the stripping liquid waste liquid is a component having a boiling point lower than that of the stripping liquid component, and is typically water contained in the stripping liquid waste liquid and carbon dioxide dissolved in the stripping liquid. Further, the stripping liquid waste liquid of the present invention The high-boiling point component is a component having a higher boiling point than the component of the stripping liquid, and is specifically a photoresist. The present invention will be described in detail below with reference to the drawings. -14- 200927264 A schematic diagram of an example of a representative flow chart of a regenerating apparatus for a photoresist stripping liquid waste liquid in which a basic compound of the present invention is not added. The stripping liquid waste liquid is supplied to a low-boiling substance removing tower (Τι) The middle portion of the distillate removes the low-boiling components such as water or carbon dioxide from the distillate. From the bottom of the column, the discharge liquid, the photoresist, the metal, and the fine particles are discharged. The discharge is supplied to the reboiler (RB). The lower part of -2 ) evaporates a part of the stripping liquid from the lower part of the tower by pumping it to the thin film evaporator (FD·1) to evaporate most of the stripping liquid. The photoresist, metal, and fine particles are non- The volatile component is not evaporated and is discharged to the outside of the system together with a small amount of the stripping liquid in a state of high boiling point component. In the stripping liquid refining tower (Τ-2), the high boiling point component and the stripping liquid can be precisely refined. Distillation separation can be used to distill the recyclable recyclable liquid from the top. τι represents a low-boiling substance removal tower that has a decompression operation inside the enthalpy. Τ-2 represents the inside of the retentate. The continuous rectification column operated under reduced pressure 'is easy to separate the stripping liquid and the low-boiling point component. The wall-surface scraping type falling film evaporator (FD-1) can efficiently peel off from the high-boiling point component. The liquid is separated and evaporated. However, the method known in the first drawing is affected by the heating temperature and residence time of the vapor, and precipitates high-boiling components and adheres to the wall surface of the device. The place where it stays, where the temperature is high, and the temperature becomes high (above 1 25 °C). Specifically, in Figure 10, especially in the reboiler (RB-2), thin film evaporation The device wall of the device (FD-1). Therefore, in the conventional device, the processing capability is deteriorated, and regular cleaning and maintenance must be performed. -15-200927264 The inventors of the present invention conducted intensive studies on this problem and found that the following means can reduce the precipitation of photoresist and the adhesion of photoresist on the wall surface. That is, an inorganic basic compound such as sodium hydroxide, potassium hydroxide or sodium carbonate or an organic basic compound such as tetramethylammonium hydroxide is used in the optimum portion of the stripping liquid waste liquid line. The aqueous solution is added to the non-volatile component (photoresist) in the waste liquid of the stripping liquid. 01~0. 2 times the amount of mass. In addition to this means, it is possible to use a UV-visible-infrared light (wavelength 1 (T9m to l_4m)) for exposure of the entire liquid of the stripping liquid waste liquid to prevent the precipitation of the photoresist. And the photoresist adheres to the wall surface, which can improve the recovery rate of the refined stripping liquid, and can reduce the burden of regular washing and maintenance. Fig. 2 to Fig. 5 show the basic embodiment of the present invention. In order to add a specific portion of the alkaline aqueous solution, the indication [2] is a specific portion exposed by light such as a fluorescent lamp. In the second drawing, the low-boiling substance removal tower, the thin film evaporator, and the crucible are used. The order of the stripping liquid refining tower is arranged, and the alkaline aqueous solution is added at a stage before (A) the stripping liquid waste liquid enters the low boiling point removal tower or the thin film evaporator, or (B) in the step of circulating the membrane evaporator In addition, in the case of the above (A), the exposure is performed before the alkaline aqueous solution is added, and in the case of the above (B), it is performed on the wall surface inside the thin film evaporator. Figure to the 5th In the case of a membrane evaporator, a low-boiling point removal tower, and a stripping liquid refining tower, the alkaline aqueous solution is added at the stage before the (A) stripping liquid waste liquid enters the low-boiling point removal tower. 200927264 Add, or (B) add at the stage before leaving the thin film evaporator and entering the low boiling point. The exposure is carried out as needed, in the case of (A), before the addition of the alkaline aqueous solution, In the case of (B), light irradiation is performed on the wall surface inside the film evaporator or in the stage before the basic compound is carried out between the membrane evaporator and the low-boiling substance removal tower. Fig. 1 shows the present invention. A representative flow chart. In the figure, D [1] is a specific portion to which an alkaline aqueous solution is added, and a specific portion where [2] a light such as a fluorescent lamp is exposed, and a piping portion for connecting the device and the device is indicated. In the exposure, the portion through which the light is transmitted can be set in the position of the pipe. In the film evaporator (FD-1) device, the light can be transmitted through the observation window such as the observation window of the device. The flow of the treatment liquid is briefly described. The stripping liquid after use is sent from the stripping liquid waste line to the low-boiling substance removal tower (T-1 water, low-boiling components such as carbon dioxide, etc. are from the low-level substance via the line (a) The upper side of the removal tower (T-1) is discharged, and on the other hand, the stripping liquid having a high boiling point as a main component is discharged from the lower side of the low boiling point product (T-1) via the line (b). The boiling point component is mainly a stripping liquid, and is sent to the stripping liquid refining tower 2 via the second reboiler (RB-2). Here, some of the main components are purified, and after the second cold (C-2) is liquefied The product is collected in the state of the purified stripping liquid via the line (c). The photoresist liquid containing waste liquid recovered from the lower portion of the stripping liquid refining column (T-2) is sent to the thin film evaporator through the line (d) (de-tower) In the above-mentioned thin addition, it is indicated that the liquid portion of the liquid used in the observation portion is used, and the boiling point component is desubdivided (T-condenser is peeled off FD--17-200927264 1). In the thin film evaporator (FD-1), the photoresist component is changed into a thin film by scraping, and the photoresist is separated from the upper portion of the thin film evaporator (FD-1) through 1 to the stripping liquid refining tower (T_2). The middle section is liquefied here by the condenser (C-2) and is recovered from the line (^) state. The waste liquid containing the unnecessary photoresist, the lower portion of (FD-1) is discharged through the line (f).剥 Such a stripping of three different devices containing a low-boiling substance removal column (T-1 column (T-2) and a thin film evaporator (FD-1) (the photoresist is separated as much as possible), for example, ～~[V] is added to the part to be irradiated with light as needed. In the film evaporator (FD-1), the film evaporator is used to remove the liquid from the film evaporator. The photoresist in the waste liquid is discharged from the bottom at a low-boiling point in the waste liquid of the stripping liquid in the surface of the second-layer tube. The first part of the place where the basic compound is added: the peeling liquid waste liquid Supply to low-boiling point removal 3 Any place 2: Any place where the lower part of the first condenser (C-1) is passed through the upper supply line (low boiling flow line) of the removal tower (T-1) 3: from a low boiling point The material removal tower (T-1) is connected to the stripping membrane evaporator to evaporate, the f line (e) is supplied and refined, and then the second stripping liquid is purified from the thin film evaporator), and the stripping liquid is refined for stripping. Liquid and helium chaotropic regenerative device, the compound is formed by the upper part of FD -1 rotated by the rotating shaft Membrane-like, so that the high-boiling adult form (T-1) is sent to the low-boiling point removal tower gj [to the second reboiler-18-200927264 (RB-2) pipeline Any place 4: Any place 5 from the lower portion of the stripping liquid refining tower (T-2) to the upper supply line of the membrane evaporator (FD-1) 5: from the lower part of the membrane evaporator (FD·1) Any place in the line where the upper portion of the thin film evaporator (FD-1) is recirculated. Specific example of the light irradiation place in Fig. 1 1 : Before the stripping liquid waste liquid is supplied to the low boiler removal tower (T-1) Any place 2: Any place where the lower part of the first condenser (C-1) is pumped to the upper supply line of the low-boiling substance removal tower (T-1) (return line of the low-boiling substance removal tower) 3 : Any place 4 from the line connecting the low boiler removal tower (T-1) to the second reboiler (RB-2): from the lower portion of the stripping refining tower (T-2) to the membrane evaporator Any place 5 of the upper supply line of (FD-1): inner wall surface of the film evaporator (FD-1) [Embodiment] Hereinafter, the present invention will be more specifically described by way of examples. The present invention is not limited to these embodiments. Comparative Example 1 Fig. 9 is a test apparatus for verifying the precipitation and adhesion of photoresist in an actual device -19-200927264. A test piece (SUS316, 15 mm wide x 3 mm thick x l50 mm long) was placed in a waste liquid of a peeling liquid in a beaker heated to a certain temperature in an oil bath. The amount of light adhered to the test piece and the state of adhesion thereof were observed. The stripping liquid waste liquid was concentrated by a rotary evaporator in advance to adjust the photoresist concentration to about 17% by mass (when the peeling liquid recovery rate was 90% by mass in the case where the peeling liquid waste liquid contained 2% by mass of the photoresist). In this experiment, of course, the treatment liquid was irradiated with room light. 〇 Using the experimental apparatus of the above-mentioned Fig. 9, the temperature of the stripping liquid waste liquid was maintained at 120, 130, and 140 ° C, respectively, and the amount of adhesion per unit area with time was measured. The number is shown in Table 1 below. As can be seen from Table 1, at 140 ° C, adhesion occurred from 3 hours later; at 130 ° C, adhesion occurred from 6 hours later; at 120 ° C, adhesion occurred from 9 hours later. The appendage is brown, hard and charred, and it is not easy to remove it even after washing with water and washing the stripping liquid before regeneration. It is also known that the photoresist of the stripping liquid waste liquid is greatly affected by the heating temperature, and it is necessary to perform heating at a low temperature as much as possible. This is based on the fact that if the stripping solution is retained in the device, the photoresist will be solidified and charred by the influence of heat. Thus, the inventors of the present invention can grasp the state of adhesion in the actual device. -20- 200927264 Table 1 adhesion test (non-volatile component 17% by mass) Concentrated peeling surface liquid temperature _ 120 ° C 130 ° C 140 ° C time unit area adhesion amount per unit area adhesion amount per unit area adhesion amount [hr] [mg/cm2] C mg/cm2 ] [mg/cm2) 3 0. 92 2. 24 2. 58 6 2. 24 4. 88 4. 94 9 4. 21 5. 27 6. 14 18 5. 39 5. 61 6. 00 After the stripping liquid waste is washed 4. 86 5. 08 5. 10 After washing with water 4. 46 4. 92 4. 98. First, the inventors of the present invention have been directed to the means for solving the above problems. According to the following examples, it is explained that the addition of the basic compound at the stage before the precipitation of the photoresist is performed or Effective. Table 2 shows that the same tester as the tester of Fig. 9 is used (for the case of using a beaker, it is an example of light irradiation), and 0 is added to the stock solution of the peeling liquid © waste liquid. The sodium hydroxide aqueous solution of 05 mass% (addition ratio in the state of 48 mass% NaOH aqueous solution) was concentrated by a rotary evaporator to a resist concentration of about 17% by mass, and the results of the same tests as described above were carried out. Adhesion occurred from 24 hours at 140 ° C, adhesion occurred at 34 ° C from 34 hours, and adhesion occurred at 48 ° C from 48 hours. The adherend was a pale brown mud, and the carbonized state was not observed. It was easily removed by washing with water and washing the stripping liquid before regeneration. Both the time of attachment and the amount of adhesion were obtained better than the test results of Comparative Example 1 (data of Table 1). -21 - 200927264 Table 2 adhesion test (non-volatile component 17% by mass, adding NaOH aqueous solution) Concentrated stripping liquid waste liquid temperature 120 °C 130 °C 140 °C time unit area adhesion amount unit area adhesion unit Area adhesion amount [hr] [mg/cm2] [mg/cm2) [mg/cm2] 24 0. 13 0. 31 1. 11 36 0. 74 1. 64 —---- 2. 58 48 1. 07 3. 52 4. 46 After the stripping liquid waste is washed, 0. 54 1. 53 1. 88 After washing, 0. 11 0. 31 0. In order to increase the recovery rate of the purified stripping solution, the stripping liquid waste liquid to which the sodium hydroxide aqueous solution was added in the same manner was concentrated by a rotary evaporator to have a photoresist concentration of about 31% by mass, and the test was carried out in the same manner as in Example 1. . The results are shown in Table 3. Under visual observation, adhesion occurred at 18 °C from 140 °C, adhesion occurred from 23 hours at 130 °C, and adhesion occurred at 32 °C from 32 hours. The deposit was brownish mud, and although it was found to have a certain carbonization state, it could be removed by washing with a stripping liquid before washing with water and before regeneration. As a result, it was confirmed that even if the resist concentration was increased, a better result than the results shown in Table 1 of Comparative Example 1 was obtained, and therefore the effect of adding a basic compound was remarkable. The amount of adhesion data in Tables 1 to 3 is not based on visual observation, but is the result of quantitative measurement. -22- 200927264 Table 3 Attached fiber (non-volatile component 31% by mass, NaOH 7Jc^ added) Concentrated stripping liquid waste liquid 120°C 130°C 140°C Time [hr] Adhesion per unit area [ Mg/cm2 ] Attachment amount per unit area [mg/cm2 ] Attachment amount per unit area [mg/cm2 ] 24 0. 53 1. 11 1. 39 36 0. 73 2. 31 3. 08 48 1. 57 3. 92 5. 12 After the stripping solution is washed, 1. 12 1. 28 2. 81 After washing, 0. 42 0. 52 0. 82 实施 Example 2 and Comparative Example 2 The present inventors have found that the photoresist in the stripping liquid waste liquid supplied from the stripping liquid waste storage tank to the regenerating apparatus of Fig. 1 is mixed and exposed in a liquid crystal manufacturing process or the like. The photoresist and the photoresist that is not exposed, and this difference may affect the precipitation and adhesion of the photoresist. Then, the experimental apparatus is a re-disintegration apparatus which is connected to a peeling liquid waste storage tank (not shown) and which is made of stainless steel and is almost completely shielded from light (only a partial observation hole or the like can be exposed). In the above Comparative Example 1 and Example 1, since the beaker test was performed indoors, the peeling liquid was exposed. • In this test, both examples were performed by first concentrating the stripping liquid waste to a photoresist concentration of about 15% by mass using a rotary evaporator. Next, the obtained concentrated peeling liquid waste liquid was subjected to the following treatment. (1) Comparative Example 2: No exposure was carried out without adding sodium hydroxide. (2) Example 2-1: Conversion into a stripping liquid Waste liquid is added 0. 05% by mass of sodium hydroxide, but no exposure. Example 2-2: Conversion to a stripping liquid Waste liquid is added 0. 05% by mass of -23- 200927264 Sodium hydroxide, and exposed for ι min. Then, the test piece was placed in a container containing a concentrated stripping solution heated in an oil bath of 140 ° C for 48 hours. These tests were performed in a dark room. Table 4 shows the results of Comparative Example 1, Example 2-1, and Example 2-2. The adhesion amount of Comparative Example 1 was 8. 35 g/cm2, the attachment amount of Example 2-1 is 4. 46g/cm2, the adhesion amount of Example 2-2 was 4. 02g/cm2. From this result, it can be seen that the precipitation and adhesion of the photoresist can be reduced by performing exposure. Further, in the case of performing water washing and washing of the peeling liquid, it is easier to remove the deposit when sodium hydroxide is added than when sodium hydroxide is not added. Table 4 Adhesion test test conditions (temperature of concentrated stripping liquid waste 140 〇C) Comparative Example 1 Example 2-1 Example 2-2 Adhesion amount per unit area Adhesion amount per unit area Adhesion amount per unit area [hr ] [mg/cm2) [mg/cm2 ] [mg/cm2 ] 48 8. 35 4. 46 4. 02 After the stripping liquid waste is washed. 37 1. 88 1. 34 After washing with water 5. 30 0. 56 0. 03 Example 3 Fig. 6 shows an embodiment of a water-soluble inorganic basic compound adding device. The basic compound was uniformly mixed with a sodium hydroxide aqueous solution using a stirrer in an alkali adjusting tank. In the case of sodium hydroxide, the concentration adjustment is performed by using an alkali concentration detector to adjust the alkali concentration, and adjusting the amount of makeup water to adjust the concentration to a certain concentration. The amount of sodium hydroxide added is determined based on the adjusted concentration of sodium hydroxide -24-200927264 sodium and the concentration of photoresist in the waste liquid of the stripping solution. The supply of the alkaline compound in the stripping liquid waste liquid is supplied from a piping line in the [1] portion (the optimum portion from the supply line to the purified stripping line) shown in Fig. 1 using a metering pump. Behind the supply position, there is a mechanism for mixing a sodium hydroxide aqueous solution and a stripping liquid waste liquid, such as a static mixer. Fig. 6 shows an example in which an alkali adjusting tank can be omitted as long as a sodium hydroxide aqueous solution adjusted to a certain concentration can be supplied.实施 Embodiment 4 Figs. 7 and 8 show two embodiments of an exposure apparatus. Fig. 7 is a view showing an embodiment in which an exposure apparatus is inserted into a piping line, and piping which is changed to a light-transmissive pyrex (registered trademark) glass in the middle of the piping, and fluorescent lamps are used on both sides of the piping. A device having an ultraviolet (wavelength of 1 (T9m)-visible-infrared (wavelength l〇_4m) wavelength for exposure to cause an unreacted photoresist to react. The device of this example is used for fluorescence. The lamp is exposed for at least 5 minutes, and the length of the light-permeable portion of the pipe is set to be about 8 m in length according to the flow rate of the waste liquid. Fig. 8 is a film evaporator (FD-1) shown in Fig. 1. The apparatus for observing the window for ultraviolet exposure is provided in four places of the upper and lower observation windows. The falling film evaporation apparatus (FD-1) equipped with a mixer can be used to remove the liquid by a bumper attached to the mixer. The film thickness of about 1 mm is uniformly dispersed on the wall surface of the evaporator, and the exposure is not attenuated by the liquid depth, and uniform exposure can be performed even if the amount of light is small. -25 - 200927264 Example 5 Example 3 and Example 4 Alkaline compound The adding device and the exposing device are attached to the actual device shown in Fig. 1, and a comparison test is performed before the mounting. The alkaline compound adding device is inserted in the middle of the pipe shown in Fig. 1 (II). The exposure device is used by The φ 150 observation window of the falling film evaporator (FD-1) of the mixer is provided with mercury lamps at two upper and lower positions (four locations in total), and exposed at 1,000 lumens. Q The predetermined throughput of the stripping liquid regeneration device It is 540 kg/h, and its composition analysis is: 476 kg/h of the peeling liquid waste, high-boiling component such as photoresist, 1 kg/h, and low-boiling component of water such as 54 kg/h. 48% by mass of sodium hydroxide 5 40x0. 0 00 5 = 0. The amount of addition of 27 kg/h was quantitatively supplied. The amount of refined regeneration under each condition was compared. • The average recovery of the stripping solution was about 88% by mass, 41.9 kg/h, and the liquid storage part of the wall of 〇FD-1 and the lower part of FD-1. It is necessary to carry out regular (1 time / 3 days of automatic washing, 1 time / year of disassembly and washing) maintenance. (Improved effect of the addition of the basic compound of the present invention (no exposure) The average recovery of the purified stripper is about 90% by mass and 428 kg/h, and the stripping solution can be regenerated in a quantitative and stable state. The adhesion of the photoresist on the wall of the FD-1 and the deposition and adhesion of the photoresist in the liquid reservoir at the lower part of the FD-1 are almost invisible, but it must be cleaned periodically (one time/three days of automatic washing) -26-200927264. That is, by adding a basic compound, the solubility of the photoresist to the stripping solution can be increased, and the precipitation and adhesion of the photoresist can be reduced, so that the recovery rate of the stripper can be improved. The effect of improving the addition of the basic compound and the exposure of the present invention The average recovery of the purified stripper is about 95% by mass and 425 kg/h, and the stripping solution can be regenerated in a quantitative and stable state. The photoresist adhesion of Q on the wall of the FD-1 and the photoresist deposition and adhesion of the liquid reservoir in the lower part of the FD-1 are hardly visible, and it is avoided by performing periodic (one-time/three-day automatic washing) cleaning. Bad situation. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing an example of a flow of a specific peeling liquid regenerating apparatus of an embodiment of the present invention. Fig. 2 is a flow chart showing an example of a basic stripping liquid regenerating apparatus of the present invention. Fig. 3 is a view showing another example of the flow of the basic stripping liquid regenerating apparatus of the present invention. Fig. 4 is a view showing another example of the flow of the basic stripping liquid regenerating apparatus of the present invention. Fig. 5 is a view showing another example of the flow of the basic stripping liquid regenerating apparatus of the present invention. Figure 6 shows a base dosing device. Fig. 7 shows the piping line exposure device, (a) is a front view, and -27-200927264 (b) is a side view. Fig. 8 shows an exposure apparatus mounted on a film evaporator. Figure 9 shows the experimental apparatus for the adhesion test. Fig. 10 is a view showing the flow of a conventional stripping liquid regenerating apparatus. [Description of main component symbols] FD-1 : Thin film evaporator Q T-1 : Low boiler removal tower T-2 : Stripping liquid refining tower RB : Reboiler C : Condenser P : Pump (a ): Low connection Pipe (b) of the upper part of the boiling point removal tower and the first condenser: a piping (c) for connecting the bottom of the low-boiling substance removal tower and the second reboiler: a pipe for collecting the purified stripping liquid (d): Pipe at the bottom of the stripping refining tower and the upper part of the membrane evaporator (e): piping -28- connecting the upper part of the membrane evaporator and the middle section of the stripping refining tower