7719 A7 ___ B7 五、發明說明（i ) (請先閱讀背面之注意事項再填寫本頁) 本發明係關於一種製造纖維素模塑體的方法’特別是 平面與管狀薄層及纖維素平面與管狀薄層形式之薄膜，使 用將纖維素溶在水性三級氧化胺之溶液，以押出嘴將溶液 作押出，此案例中之溶液可包含添加劑如穩定及軟化劑、 細孔形成劑等，且將此押出模塑溶液通過一吹氣介質之間 隙而進入一沉澱槽且自沉澱槽中排除。 將纖維素溶在水性三級氧化胺中以製造纖維素模塑體 之方法係已知且敘述於例如U S — A 4，2 4 6 ，2 2 1及P C T — W〇 9 3 / 1 9 2 3 0。此已知方法於下 列敘述爲”氧化胺方法”。 就纖維素薄層而言此薄層之細孔結構代表一特殊性質 。其對薄層在各種用途之適合性具有決定性的影響，如作 爲包裝薄層或作爲薄膜。 經濟部智慧財產局員工消費合作社印製 尤其是具非對稱結構的平面及管狀薄層的纖維素，適 合於具透氣性質之包裝薄層，及作爲薄膜施壓分離方法如 超過濾、奈米過濾及逆滲透。其特色在它們係由多孔層與 薄的微孔相對緻密皮層所構成。當使用這些作爲薄膜多孔 層承擔支撐功能而實際分離效應係經由薄的微孔層執行。 此層較微小的厚度導致薄層的高滲透性，且同時有高強度 〇 依據已知方法（如黏度方法，扣歐撒（cuox am )方法 或更新近的氧化胺方法）製造的纖維素平面或管狀薄層， 通常不具有上述的非對稱結構。 如此U S - A 4，3 5 4，9 3 8敘述製造作爲透 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -4- 487719 A7 B7 五、發明說明（2 ) 析薄膜的管狀薄層之方法，其可依據黏度方法’其中將一 成形爲管筒形式之薄層’在乾燥之前在對角方向上延拉 4 0 %及1 2 0 % ’經由吹風方式促使薄膜在長軸與對角 方向上作相同之定向。當轉換乾燥薄膜爲於此描述之潮濕 狀態薄膜，將在長軸及對角方向上收縮〇 · 5 - 1 〇 %。 然而，在該文件中，全未提及薄層非對稱結構。 W〇 9 6 / 2 0 3 0 1敘述製造纖維素模塑體的方 法，其特色在將溶液（其中含有纖維素溶解於氧化胺）於 一模塑嘴作模塑，將此模塑溶液通過至少二種沉澱介質， 接著通過空氣間隙，一個接在一個之後，其關鍵點在於第 一沉澱介質至少比後者沉澱介質使纖維素凝結更慢。使用 作爲沉澱介質之溶劑無法相互混和且可由於密度之差異而 分層。 於此描述之模塑體（在其橫斷面），內部區域帶有高 的由一個以上分子所組成的規則，其形式爲精巧分散細孔 ，而包圍內部區域之外部區域具有低的一個以上分子所組 成的規則，而相較於內部區域且有較大的不均勻空穴。當 模塑體使用作爲薄膜，例如中空纖維或平面薄膜之形式， 外部粗糙地分散區域係作爲支撐層而精巧分散之內部區域 則執行實際分離。內部區域的相對低厚度造成模塑體之高 滲透性。 帶有精巧細孔核心及粗糙分散外部層之薄層僅勉強適 用於分離方法如超濾及逆滲透，因爲會非常快造成進料邊 細孔之阻塞。在這些方法中通常使用非對稱薄膜其中包含 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 裝.--------訂—#---- 經濟部智慧財產局員工消費合作社印製 - 5- 487719 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（3 ) 緻密皮層及大孔的主體以使緻密皮層總是面對進料邊。在 此種壓力驅動方法中，一對應的橫流（Cross-Flow )可降 低濃度極化之形成且因此在薄膜表面形成一層膠體，因而 使流經薄膜之液流可長時間保持高水準。當薄膜外層改爲 進料邊且具有比核心較粗的結構，橫流將無作用。待分離 之粒子無法自薄膜表面輸送且將堵塞細孔。 在氧化胺方法中已知須要在程序中保持沉ί殿槽中固定 之Ν Μ Μ 0含量，實務上之執行係固定性地供應對應量的 新鮮的沉澱劑與沖洗水。由於使用不同的沉澱介質且將其 重疊，這在上述方法中將顯得非常困難且非常複雜。 DE 44 21 482 C2敘述製造定向非對 稱纖維素薄片之方法，將非衍生纖維素（溶解於氧化胺） 經由一嘴而抽絲入一沉澱槽，以吹氣使薄層吹起。此非對 稱結構之達成係經由差異沉澱劑在押出管筒沉澱在其內部 及外邊。如此在內部與外部造成不同的凝結行爲而導致薄 層非對稱結構。 然而，使用不同的沉澱劑也是昂貴的，特別地當使用 其它沉澱劑如水或添加劑，加入沉澱劑中。 ΕΡ 〇 ° 4 2 517 Β1敘述再生纖維素透 析、?41膜Ζ仏：ia方法’其形式爲平面薄層、管狀薄層及中空 纖維，其爲下列之混合物：完全或部分地取代的纖維素、 二級氧化胺及司高達2 5重量百分比的非纖維素溶解稀釋 劑’及高達1 0重量百分比的一般添加劑，溶解於雙螺桿 押出機在溫度介於8 0與1 5 0 t：少於8 m 1 η，將[J：卜滚 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） (請先閱讀背面之注意事項再填寫本頁) 裝—— *-tr°J. -6- 7719 A7 B7 五、發明說明（4 ) (請先閱讀背面之注意事項再填寫本頁) 液押出於沉澱槽中，使用對應的成形介質，並在沖洗且以 甘油處理之後將凝固的模塑體乾燥，以避免收縮。此透析 薄膜具有高透析滲透性，在中分子範圍，其保持完好的， 即使由後續處理而使水的液壓的滲透性大幅下降。此後續 處理之執行係將薄膜在乾燥之前，在水性液體中暴露於高 溫某段時間。 然而，此產物未提及非對稱結構。 在E P 〇 8 0 7 4 6 0 A 1中敘述一製造纖 維素透析薄膜之方法，其形式爲平面、管狀或中空纖維薄 膜，將一纖維素溶液及/或改良的纖維素在水性三級氧化 胺中（及其它添加劑如穩定劑、細孔形成劑等）作抽絲， 使抽出速度至少等於3 〇m/m 1 η，且據此可製出高、 中及低通量面積之薄膜。薄膜細孔精細結構，主要由使用 經取代的纖維素達成，且分別地加入各種添加劑及後續處 理，且因此而成本較高。 然而，此方法未提及非對稱薄膜之製造。 經濟部智慧財產局員工消費合作社印製 本發明之目標在發展出薄層及薄膜細孔結構之製造方 法，其係依據氧化胺方法。在本發明中尤其是要發展出一 方法，其可得到具非對稱結構的薄層或薄膜。 本發明之目標係由如上敘述之方法達成，其特色在該 模塑溶液或沉丨殿的模塑體暴露於空氣間隙、在沉澱槽中或 在沉澱槽之後作超音波處理。 超音波處理可發生在空氣間隙中，例如經由超音波產 生器其溼潤以以水或直接在溶液進入沉澱槽之後，即當纖 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 7719 A7 _ B7 五、發明說明（5 ) (請先閱讀背面之注意事項再填寫本頁) 維素具有尙未或僅部分地自此模塑溶液中沉彳殿。然而，此 處理也可發生在沉澱槽中當模塑體沉澱實際完成，或當沉 澱的模塑體留在沉澱槽中，例如後續沖洗階段之—。 可看出經由對此模塑溶液與沉澱的模塑體作超音波處 理，可精細地控制此生成的薄層與薄膜之細孔結構。 特別地在本發明方法之較佳體系中，此模塑溶液與沉 澱的模塑體僅一邊暴露於超音波處理，可得到具非對稱細 孔結構之薄層。 在此”一邊”處理意指在此平面薄層案例中，只有此 模塑溶液與沉澱的模塑體的單面的表面暴露於超音波處理 。在管狀薄層案例中只有此模塑溶液與沉澱的模塑體內部 作處理，或只有此模塑溶液與沉澱的模塑體外部作處理。 經由此一邊超音波處理，模塑體細孔結構只有改變一 邊，導致上述非對稱細孔結構。在顯微鏡下，面對超音波 產生器之一面具有多孔結構，而遠離超音波之一邊具有緻 密結構其相同於押出薄層。此種模塑體很適於不同用途的 薄膜技術。 經濟部智慧財產局員工消費合作社印製 然而，模塑體兩面不同的細孔結構之達成，也可在兩 面作超音波處理而其執行係在各案例中採不同的能量及/ 或頻率及/或代以不同的纖維素沉澱速率。在此’自溶$ 中纖維素沉澱的程度係作爲，，沉澱速率”。自然地當此溶 液進入沉澱槽此沉澱速率將隨時間而增加。 對模塑體作兩邊式超音波處理，以相同頻率及相同能 量及給予相同沉澱速率，將造成對稱結構’且有較高的鬆 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -8- 487719 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（6 ) 度。 沖洗愈久則沉澱速率變化愈小。當沉澱的模塑體經過 數個淸洗槽，沉丨殿速率幾乎固定，例如在某種淸洗槽中。 當在此淸洗槽或後續淸洗槽中，沉澱的模塑體之兩面輪流 暴露於超音波處理短時間，之後仍可視爲”相同沉澱速率 μ 〇 已知對紡織品之超音波處理。例如其敘述於U S - A 4 ，3〇2 ，485或敘述於PCT— W〇 96/ 2 8 5 9 9之方法。此種超音波處理基本上用以增加紡織 品材料之處理效應如染色、漂白及最後修整等等 相反地，依據氧化胺方法處理纖維素薄層尤其是目前 技藝所不知。 用以處理此模塑溶液與沉澱的模塑體之超音波具有 1 8 k Η z到高達3 0 0 k Η z之頻率，理論上也可能用 較高的頻率。超音波之能量範圍可在1 0W至5 kW，且 較佳地在5 0 W至2 · 5 k W。 本發明方法一項較佳體系，其特色在將此模塑溶液與 沉澱的模塑體與超音波產生器接觸。如此，可以連續的方 法將此模塑溶液與沉澱的模塑體通過超音波產生器。從而 使此溶液與模塑體接觸超音波產生器。 將此（暴露於超音波處理的）模塑溶液與沉澱的模塑 體之表面接觸超音波產生器，較佳地越過全部的寬度與全 部的周邊。 在此可將超音波產生器安排於適當的位置’在空氣間 (請先閱讀背面之注意事項再填寫本頁) 裝 訂： #· 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -9- 487719 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（7 ) 隙中 '在沉澱槽中或在後處理線，於模塑體自沉澱槽浮現 之後。 若依據本發明用以製造纖維素管狀薄層及纖維素薄膜 之方法’其使用爲管狀薄層形式，則此溶液係經由一環狀 押1出間隙而押出。之後此模塑溶液與沉澱的管狀薄層可通 過圓筒狀超音波產生器且抽出。在此案例中係將此溶液之 外部與管狀薄層暴露於超音波處理。 一選擇方案，此模塑溶液與沉澱的管狀薄層可通過圓 筒狀超音波產生器上方且抽出。在此案例中係將此溶液內 部與管狀薄層暴露於超音波處理。此方法明確的體系，可 將超音波產生器安排在押出心軸之下以穩定此押出的管狀 薄層。從而押出管狀的纖維素溶液，並押出心軸且滑過安 排在其後之超音波產生器。 若依據本發明用以製造纖維素平面薄層及纖維素薄膜 之方法其使用爲平面薄層形式，則此溶液係經由一拉長的 押出間隙而押出。之後將此模塑溶液與沉澱的平面薄層接 觸超音波產生器且使其越過此溶液與薄層全部的寬度。在 此案例中超音波產生器較佳者係使用可經由邊緣發出超音 波，此邊緣長度至少等於此溶液與薄層之寬度。 押出溶液可在空氣間隙中延拉，使用已知方式，設定 此溶液抽出速度高於押出速度。也可能不延拉此押出溶液 或使抽出速度小於押出速度。 押出溶液與沉澱的模塑體也可就押出方向作對角延拉 。此對角延拉之執行可在空氣間隙中、於進入沉澱槽之後 (請先閱讀背面之注意事項再填寫本頁) 0 裝 訂-. 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -10- 487719 A7 B7 ----- 五、發明說明（8 ) 、在漂洗之間或甚至在乾燥乾燥與再溼潤之後。 (請先閱讀背面之注音？事項再填寫本頁) 本發明也關於一纖維素模塑體，特別是平面與管狀薄 層及纖維素平面與管狀薄層形式之薄膜，其係由本發明方 法而得到。 依據本發明模塑體一項較佳體系，其特色在有不同的 細孔結構存在於各薄層與薄膜之表面。如先前敘述，此非 對稱細孔結構可由對此溶液與沉澱的模塑體作一邊處理而 達成。在圖1 ，2及3中將詳細敘述本發明之較佳體系。 圖1爲一圖其係本發明方法製作纖維素平面薄層。圖 2及3係以圖形形式描述供選擇的體系，依本發明方法以 製作纖維素管狀薄層。 符號說明 1 ’ ，1 0 模塑溶液 1” ， 10 模塑體 2 沈澱槽 3 - 8 滾筒 經濟部智慧財產局員工消費合作社印製 9，1 1 超音波處理 圖1展示模塑溶液1 ’與沉澱的模塑體1 ”在沉澱槽 或漂洗槽2中之處理。此圖可用於第一沉澱槽2 ，於其中 此模塑溶液1 ’係由上方注入。然而，此方法也可在後續 漂洗槽2中以類似方式執行，於其中導入已沉澱的模塑體 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -11 - 487719 A7 B7 五、發明說明（9 ) (請先閱讀背面之注意事項再填寫本頁) 將沉澱與漂洗槽2中注入液體以促使纖維素沉澱。將 此模塑溶液1 ’與沉澱的模塑體1 ”經由數個滾軸3至8 導入沉澱槽，並加以沉澱且作沖洗。將超音波產生器9安 排在沉澱槽中。將此模塑溶液1 ’與沉澱的模塑體1 ”通過 此超音波產生器9使溶液1 ’與模塑體1 ”全部的寬度接 觸超音波產生器9。 在本發明此體系中，此模塑溶液1 ’與沉澱的模塑體 1 ”只有一表面作超音波處理。如此得到的薄層在兩面具 有不同的細孔結構。 圖2展示一本發明方法製作管狀薄層之體系。數字 1〇係指此模塑溶液，其爲管筒形狀與沉澱的管狀薄層。 將此溶液與管狀薄層通過圓筒狀超音波產生器1 1之上方 。從而將此溶液與薄層內部暴露於超音波處理。 圖3展示本發明方法製作管狀薄層供選擇的體系。在 此案例中將模塑溶液與沉澱的管狀薄層1 0導入並通過例 如管狀超音波產生器1 1。在此將此溶液與薄層之外部暴 露於超音波處理。 經濟部智慧財產局員工消費合作社印製 以上詳細敘述了本發明較佳體系之實施例。所使用之 纖維素溶液係依據敘述於E P - A —〇 3 5 6 4 1 9 之方法而製造。在所有實施例中，於纖維素沉澱之後將薄 層沖洗’且以甘油（在乾燥薄層中甘油含量約1 5 - 2 0 重量百分比）作處理，且最後張布架上乾燥，其中將薄層 扣緊在長軸及對角方向。 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 χ 297公釐） -12- 487719 Α7 Β7 經濟部智慧財產局員工消費合作社印製 五、發明說明（10 ) 實施例： 實施例1 使用平的噴嘴，將溫度1 0 0T：之纖維素溶液（其中 含有1 4重量百分比的纖維素、7 4 · 5重量百分比的 Ν Μ Μ〇及1 1 · 5重量百分比的水）作押出，該噴嘴的 押出間隙之長度爲4 0 c m且寬度爲5 0 0 // m，生產 爲3 7 · 8 k g / h，通過2 0 m m之空氣間隙而進入一 沉澱槽，其中包含8 0重量百分比的Ν Μ Μ〇及2 0重量 百分比的水。 纖維素溶液其形狀係以平面薄層自噴嘴出現，速度爲 2 · 5 m / m 1 η且兩倍於此之速度抽出。 將薄層沖洗，通過一槽其中有1 5 0 g / 1的用作爲 軟化劑之甘油，且最後作乾燥以防止收縮。 圖4係以使用光學顯微鏡（1 0 0 X倍）展示薄層表 面。 實施例2 採用如如在實施例1中相同方法，然而在薄層進入沉 澱槽之後，立即通過越過長方形超音波產生器之邊緣，使 此模塑溶液之單面將接觸寬度邊緣的全部。超音波產生器 之能量等於2 k W而頻率在2 0 0 k Η z。 圖5提供以此方法處理試樣之表面薄層外觀，使用光 學顯微鏡鏡（1 0 0 X倍率），相較於圖4可淸楚地看出 不同的細孔結構。 (請先閱讀背面之注意事項寫本頁) 裝 • ϋ ·ϋ n I H ϋ n #· 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐） -13- 487719 A7 _B7 五、發明說明（11 ) 實施例3 採用如在實施例1中相同方法，只有在進入沉澱槽之 後將此溶液直接通過超音波棒之頂端，故只有窄區域的薄 層接觸此頂端。 超音波產生器之能量爲1 5 0W且頻率爲5 0 kH z 〇 圖6展示一試樣之光學顯微鏡鏡（1 Ο Ο X倍率）照 片，該試樣係未經以超音波作全部寬度的處理。可淸楚地 看出已處理與未處理區域不同的結構。 (請先閱讀背面之注意事項寫本頁) I!裝 寫士 訂ί— % 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -14-7719 A7 ___ B7 V. Description of the invention (i) (Please read the notes on the back before filling out this page) The present invention relates to a method for manufacturing cellulose molded bodies', especially flat and tubular thin layers and cellulose flat and The thin film in the form of a tube is a solution in which cellulose is dissolved in an aqueous tertiary amine oxide, and the solution is extruded with a extrusion nozzle. The solution in this case may contain additives such as stabilizers and softeners, pore-forming agents, etc., and The extruded molding solution is passed through a gap of an air blowing medium into a precipitation tank and is eliminated from the precipitation tank. Methods for dissolving cellulose in aqueous tertiary amine oxides to produce cellulose molded bodies are known and described in, for example, US-A 4, 2 4 6, 2 2 1 and PCT-W0 9 3/1 9 2 3 0. This known method is described below as the "amine oxide method". As for the cellulose thin layer, the fine pore structure of this thin layer represents a special property. It has a decisive influence on the suitability of the thin layer for various applications, such as as a thin packaging layer or as a film. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, especially flat and tubular thin layers of cellulose with asymmetric structure, suitable for packaging thin layers with breathable properties, and used as a membrane pressure separation method such as ultrafiltration, nanofiltration And reverse osmosis. The special feature is that they are composed of a porous layer and a thin microporous relatively dense skin layer. When using these as thin-film porous layers to support functions, the actual separation effect is performed via a thin microporous layer. The small thickness of this layer results in a thin layer with high permeability and high strength at the same time. A cellulose plane made according to known methods (such as viscosity method, cuox am method or more recent amine oxide method) Or a thin tube, usually does not have the asymmetric structure described above. In this way, US-A 4, 3 5 4, 9 3 8 describes the manufacturing as the standard of the paper. The Chinese National Standard (CNS) A4 (210 X 297 mm) is applicable. -4- 487719 A7 B7 V. Description of the invention (2) The method of tubular thin layer of film, which can be based on the viscosity method 'wherein a thin layer formed into the form of a tube' is stretched diagonally 40% and 120% in a diagonal direction before drying. Make the same orientation in the long axis and diagonal direction. When the dry film is converted to a wet state film as described herein, it will shrink by 0.5-10% in the long axis and diagonal direction. However, in this document, no mention is made of thin-layer asymmetric structures. W〇 6 6/2 0 3 0 1 describes a method for manufacturing a cellulose molded body, which is characterized in that a solution (containing cellulose dissolved in amine oxide) is molded in a molding nozzle, and the molding solution is passed through The key point of at least two precipitation media, which then pass through the air gap, one after the other, is that the first precipitation medium causes the cellulose to coagulate more slowly than the latter precipitation medium. Solvents used as precipitation media cannot be mixed with each other and can be delaminated due to differences in density. The molded body described here (in its cross section) has an inner region with high rules consisting of more than one molecule in the form of delicately dispersed pores, while the outer region surrounding the inner region has more than one low The composition of the molecules is regular, and there are larger non-uniform cavities compared to the internal region. When the molded body is used in the form of a film, such as a hollow fiber or a flat film, the outer coarsely dispersed regions serve as a support layer and the finely dispersed inner regions perform actual separation. The relatively low thickness of the inner area results in a high permeability of the molded body. A thin layer with a fine pore core and a coarsely dispersed outer layer is only marginally suitable for separation methods such as ultrafiltration and reverse osmosis, as the pores on the feed side will be blocked very quickly. In these methods, asymmetric films are usually used, which contain the paper size applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) (please read the precautions on the back before filling this page). --- 定 — # ---- Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-5- 487719 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (3) The main body of the dense cortex and large holes So that the dense cortex always faces the feed edge. In this pressure-driven method, a corresponding cross-flow can reduce the formation of concentration polarization and thus form a layer of colloid on the film surface, so that the liquid flow through the film can maintain a high level for a long time. When the outer layer of the film is changed to the feed side and has a thicker structure than the core, cross flow will have no effect. The particles to be separated cannot be transported from the surface of the film and the pores will be blocked. In the amine oxide method, it is known that the fixed NM M 0 content in the sink tank must be maintained in the procedure. The practical implementation is to supply a fixed amount of fresh precipitant and rinse water. This will be very difficult and complicated in the above method due to the use of different precipitation media and their overlapping. DE 44 21 482 C2 describes a method for producing oriented asymmetric cellulose flakes. Non-derived cellulose (dissolved in amine oxide) is drawn through a mouth into a sedimentation tank, and the thin layer is blown by air. This asymmetric structure is achieved by depositing inside and outside the extruded tube via a differential precipitating agent. This causes different condensation behaviors inside and outside, resulting in a thin layer of asymmetric structure. However, the use of different precipitants is also expensive, especially when other precipitants such as water or additives are used and added to the precipitant. Ε ° 0 2 4 517 Β1 describes regenerated cellulose dialysis,? 41 membrane 仏: ia method 'in the form of a flat sheet, a tubular sheet, and a hollow fiber, which is a mixture of the following: completely or partially substituted cellulose 2, secondary amine oxide and non-cellulose soluble diluent up to 25 weight percent 'and general additives up to 10 weight percent, dissolved in a twin screw extruder at a temperature between 80 and 150 t: less than 8 m 1 η, [J: Bu Roll paper size applies Chinese National Standard (CNS) A4 specifications (210 X 297 public love) (please read the precautions on the back before filling this page)) Installation—— * -tr ° J. -6- 7719 A7 B7 V. Description of the invention (4) (Please read the precautions on the back before filling this page) The liquid is deposited in the precipitation tank, using the corresponding molding medium, and washed and treated with glycerin. The solidified molded body is dried to avoid shrinkage. This dialysis membrane has high dialysis permeability, and it remains intact in the middle molecular range, even if the hydraulic permeability of water is greatly reduced by subsequent processing. This subsequent treatment is performed by exposing the film to an aqueous liquid for a certain period of time before drying. However, this product does not mention asymmetric structures. A method for producing a cellulose dialysis membrane is described in EP 0 0 7 4 6 0 A 1 in the form of a flat, tubular or hollow fiber membrane, a cellulose solution and / or modified cellulose is oxidized in aqueous tertiary stage The amines (and other additives such as stabilizers, pore-forming agents, etc.) are used for drawing, so that the drawing speed is at least equal to 30 m / m 1 η, and according to this, films with high, medium, and low flux areas can be produced. The fine pores and fine structure of the film are mainly achieved by using substituted cellulose, and various additives and subsequent processing are added separately, and therefore the cost is higher. However, this method does not mention the manufacture of asymmetric thin films. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economics The objective of the present invention is to develop a thin layer and thin film pore structure manufacturing method based on the amine oxide method. In the present invention, in particular, a method is developed which can obtain a thin layer or film having an asymmetric structure. The object of the present invention is achieved by the method described above, which is characterized in that the molding solution or the molded body of the sink is exposed to an air gap, subjected to ultrasonic treatment in a precipitation tank, or after the precipitation tank. Ultrasonic treatment can occur in the air gap, for example, it is moistened by the ultrasonic generator to enter the precipitation tank with water or directly after the solution, that is, when the size of the fiber paper is applicable to the Chinese National Standard (CNS) A4 (210 X 297) 7719 A7 _ B7 V. Description of the invention (5) (Please read the precautions on the back before filling out this page.) Victoria has no or only part of it from this molding solution. However, this treatment can also take place in the precipitation tank when the precipitation of the molded body is actually completed, or when the precipitated molded body remains in the precipitation tank, for example in a subsequent washing stage. It can be seen that the pore structure of the resulting thin layer and thin film can be finely controlled by ultrasonic treatment of the molding solution and the precipitated molded body. Particularly in the preferred system of the method of the present invention, the molding solution and the precipitated molded body are exposed to ultrasonic treatment on only one side, and a thin layer having an asymmetric fine pore structure can be obtained. The "one side" treatment here means that in this case of the planar thin layer, only the one-sided surface of the molding solution and the precipitated molded body is exposed to the ultrasonic treatment. In the case of the tubular thin layer, only this molding solution is treated with the inside of the precipitated molded body, or only this molding solution is treated with the outside of the precipitated molded body. With this ultrasonic treatment on one side, only the pore structure of the molded body is changed, resulting in the asymmetric pore structure described above. Under a microscope, one side facing the ultrasonic generator has a porous structure, and one side away from the ultrasonic wave has a dense structure, which is the same as an extruded thin layer. This molded body is well suited for thin-film technology for different applications. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. However, the realization of different pore structures on both sides of the molded body can also be treated with ultrasound on both sides, and its implementation uses different energy and / or frequency and / Or substitute different cellulose precipitation rates. The degree of cellulose precipitation in this 'autolysis' is as, the precipitation rate. "Naturally, when this solution enters the precipitation tank, the precipitation rate will increase with time. The molded body is subjected to two-sided ultrasonic treatment to the same Frequency and the same energy and given the same precipitation rate will result in a symmetrical structure 'and a high Matsumoto paper size is applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) -8- 487719 A7 B7 Intellectual Property of the Ministry of Economic Affairs Printed by the Consumer Cooperative of the Bureau of the People's Republic of China. 5. Description of invention (6) degrees. The longer the flushing time, the smaller the sedimentation rate changes. When the precipitated molded body passes through several washing tanks, the sinking rate is almost fixed, for example, in some washing In this cleaning tank or subsequent cleaning tank, both sides of the precipitated molded body are alternately exposed to ultrasonic treatment for a short period of time, after which they can still be regarded as "same precipitation rate μ 〇 known ultrasonic treatment of textiles . For example, it is described in the method of U S-A 4, 30, 485 or PCT-WO 96/2 8 5 99. This kind of ultrasonic treatment is basically used to increase the processing effects of textile materials such as dyeing, bleaching, and final finishing. On the contrary, the treatment of thin cellulose layers according to the amine oxide method is not known in the current art. The ultrasonic waves used to process the molding solution and the precipitated molded body have a frequency of 18 k Η z up to 300 k Η z, and theoretically a higher frequency may be used. The ultrasonic energy range may be from 10 W to 5 kW, and preferably from 50 W to 2.5 kW. A preferred system of the method of the present invention is characterized in that the molding solution is contacted with the precipitated molding body and the ultrasonic generator. In this way, the molding solution and the precipitated molded body can be passed through an ultrasonic generator in a continuous method. This solution brought the solution into contact with the ultrasonic generator. This (exposed to the ultrasonic treatment) molding solution is brought into contact with the surface of the molded body of the ultrasonic generator, preferably across the entire width and the entire periphery. Here, the ultrasonic generator can be arranged in an appropriate position 'in the air room (please read the precautions on the back before filling this page) Binding: # · This paper size applies to China National Standard (CNS) A4 (210 X 297 -9- 487719 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (7) The gap is' in the sedimentation tank or in the post-treatment line after the molded body emerges from the sedimentation tank. If the method for producing a cellulose thin layer and a cellulose film according to the present invention is used in the form of a thin tube layer, the solution is extruded through a ring-shaped extruder. This molding solution and the deposited thin tube can then be passed through a cylindrical ultrasonic generator and extracted. In this case, the outer and tubular thin layers of this solution were exposed to ultrasonic treatment. Alternatively, the molding solution and the deposited thin tube layer can be passed through and extracted from a cylindrical ultrasonic generator. In this case, the solution and the thin tube were exposed to ultrasonic treatment. The clear system of this method can arrange the ultrasonic generator under the extruded mandrel to stabilize the extruded thin tube. Thereby, the tubular cellulose solution was extruded, and the mandrel was extruded and slid over the ultrasonic generator arranged behind it. If the method for producing a flat cellulose sheet and a cellulose film according to the present invention is used in the form of a flat sheet, the solution is extruded through an elongated extrusion gap. This molding solution is then brought into contact with the ultrasonic generator and the deposited flat sheet over the entire width of the solution and the sheet. In this case, the preferred ultrasonic generator uses ultrasonic waves that can be emitted through edges, the length of which is at least equal to the width of the solution and the thin layer. The extruded solution can be stretched in the air gap. Using a known method, set the extraction speed of the solution higher than the extruded speed. It is also possible not to pull the extruded solution or make the extraction speed less than the extrusion speed. The extruded solution and the precipitated molded body can also be drawn diagonally with respect to the extruded direction. This diagonal stretch can be performed in the air gap after entering the sedimentation tank (please read the precautions on the back before filling this page) 0 Binding-. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -10- 487719 A7 B7 ----- 5. Description of the invention (8), between rinsing or even after drying and re-wetting. (Please read the note on the back? Matters before filling out this page) The present invention also relates to a cellulose molded body, especially a film in the form of a flat and tubular sheet and a cellulose flat and tubular sheet, which are produced by the method of the present invention. get. A preferred system for a molded body according to the present invention is characterized in that different pore structures exist on the surfaces of the thin layers and films. As described earlier, the asymmetric fine pore structure can be achieved by treating the solution and the precipitated molded body on one side. The preferred system of the present invention will be described in detail in Figs. FIG. 1 is a diagram showing a method for preparing a thin flat cellulose layer by the method of the present invention. Figures 2 and 3 depict graphically alternative systems for making a thin cellulose tube according to the method of the present invention. DESCRIPTION OF SYMBOLS 1 ', 1 0 Molding solution 1 ", 10 Molding body 2 Precipitation tank 3-8 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 9, 1 1 Ultrasonic treatment Figure 1 shows the molding solution 1' and Treatment of the precipitated molded body 1 ″ in a sedimentation tank or a rinsing tank 2. This figure can be used for the first sedimentation tank 2 in which the molding solution 1 'is injected from above. However, this method can also be performed in a similar way in the subsequent rinse tank 2 in which the precipitated molded body is introduced. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -11-487719 A7 B7 V. Description of the invention (9) (Please read the precautions on the back before filling this page) Fill the precipitation and rinse tank 2 with liquid to promote cellulose precipitation. This molding solution 1 ′ and the precipitated molded body 1 ″ are introduced into the precipitation tank via a plurality of rollers 3 to 8 and are precipitated and rinsed. The ultrasonic generator 9 is arranged in the precipitation tank. This molding The solution 1 ′ and the precipitated molded body 1 ″ pass the ultrasonic generator 9 so that the solution 1 ′ and the entire width of the molded body 1 ″ contact the ultrasonic generator 9. In the system of the present invention, the molding solution 1 'With the precipitated molded body 1' only one surface is ultrasonically treated. The thin layer thus obtained has different pore structures in the two masks. Fig. 2 shows a system for making a thin tubular layer by the method of the present invention. The number 10 refers to this molding solution, which is a tube-shaped and precipitated thin tube. Pass this solution and the thin tube layer over the cylindrical ultrasonic generator 11. This solution and the interior of the thin layer are thus exposed to ultrasonic treatment. Figure 3 shows an alternative system for making a tubular thin layer by the method of the present invention. In this case, the molding solution and the deposited thin tube layer 10 are introduced and passed through, for example, a tubular ultrasonic generator 11. This solution and the outside of the thin layer were exposed to ultrasonic treatment. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The foregoing has described in detail an embodiment of the preferred system of the present invention. The cellulose solution used was produced according to the method described in EP-A-〇 3 5 6 4 1 9. In all examples, the thin layer was rinsed after cellulose precipitation and treated with glycerin (glycerol content of about 15-20 weight percent in the dried thin layer), and finally dried on a cloth rack, where the thin layer The layer is fastened on the long axis and diagonally. This paper size is in accordance with Chinese National Standard (CNS) A4 specification (21 × χ 297 mm) -12- 487719 Α7 Β7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (10) Example: Example 1 Use A flat nozzle, the cellulose solution at a temperature of 100 ° T (containing 14 weight percent of cellulose, 7 4 · 5 weight percent of NM MO and 1 1 · 5 weight percent of water) was extruded. The length of the extrusion gap of the nozzle is 40 cm and the width is 50 0 // m. The production is 37. 8 kg / h. It enters a sedimentation tank through an air gap of 20 mm, which contains 80 weight percent of NM Mo and 20 weight percent water. The shape of the cellulose solution emerged from the nozzle in a thin layer at a speed of 2.5 m / m 1 η and was withdrawn at twice the speed. Rinse the thin layer through a tank containing 150 g / 1 of glycerin as a softener, and finally dry to prevent shrinkage. Figure 4 shows a thin layer surface using an optical microscope (100 x magnification). Example 2 The same method as in Example 1 was used, but immediately after the thin layer entered the sedimentation tank, by passing over the edge of the rectangular ultrasonic generator, one side of this molding solution would contact the entire width edge. The energy of the ultrasonic generator is equal to 2 k W and the frequency is 2 0 0 k Η z. Figure 5 provides the appearance of the thin layer surface of the sample treated in this way. Using an optical microscope (100 × magnification), different pore structures can be clearly seen compared to Figure 4. (Please read the notes on the back first to write this page) Installation • ϋ · ϋ n IH ϋ n # · This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) -13- 487719 A7 _B7 V. Description of the invention (11) Example 3 The same method as in Example 1 is used, and only after entering the precipitation tank, the solution passes directly through the top of the ultrasonic rod, so only a thin layer in a narrow area contacts the top. The ultrasonic generator has an energy of 150 W and a frequency of 50 kHz. Figure 6 shows a photo of an optical microscope microscope (1 0 〇 X magnification) of a sample without the ultrasonic wave having the full width. deal with. It can be clearly seen that the treated and untreated areas have different structures. (Please read the notes on the back page first to write this page) I! Pre-ordered booklet%-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is printed in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) -14-