200303234 玫χ發明說明 (發明說麵麵:翻所屬之技麵域、先纖術、內容，訪式及圖式調翻) (一） 發所屬之技術領j；或 本發明乃有關複合膜，其包含具聚合物之陶瓷複合物及 選擇性之陶瓷分離層。 (二） 先前技術200303234 Description of the invention of the invention (Inventive aspects: technical field, fibrillation, content, interview and pattern adjustment) (1) the technical field j; or the present invention relates to a composite film, It comprises a ceramic composite with a polymer and a selective ceramic separation layer. (Ii) Prior technology
陶瓷薄膜問世已超過丨〇年，因其價昂故只用於要求須具 良好的溫度安定或良好的耐化學性的應用時。工業上此膜 是用於微濾（miCr〇filtrati〇n)及超濾（uitrafiitrati〇n)之應 用。此外，最近亦有報導係在，，全蒸發"（pervap〇rati〇n)及 ，，奈米過爐”（nan〇filtrati〇n)之各種應用（參閱κ _v卜—爪· 及S.P.Nunes，薄膜技術；2〇〇1年，vch書局）。 含陶瓷之複合材料已知有各種應用。Ceramic films have been around for more than 10 years, and because of their high cost, they are only used in applications that require good temperature stability or good chemical resistance. This membrane is used industrially for microfiltration (miCrOfiltration) and ultrafiltration (uitrafiitration) applications. In addition, there have been recent reports in various applications of pervaporation (pervap〇rati〇n) and nano-filament furnaces (nan〇filtrati〇n) (see κ_v 卜 — 爪 · and SPNunes , Thin Film Technology; 2001, VCH Book). Ceramic-containing composite materials are known for various applications.
陶瓷複合物之優點是對大多數的化學品（如有機物）而言 陶瓷塗層均爲惰性’而且對酸或鹼而頗安定。貞此理由， 金屬往往以陶瓷塗佈，以防止受到化學劑的侵蝕。此外， 陶瓷塗佈之複合層之多孔表面可供耐磨之保護層的塗佈而 提升耐磨耗性。陶瓷本身由於其多孔表面亦頗適做爲膜或 濾器。 陶瓷及陶瓷複合材料之缺點是陶瓷太脆1此陶瓷塗佈 之金屬怕碰撞’而陶瓷塗層只要受到機械應力，陶瓷表面 均會受損。即使此種陶瓷複合材料經過折_，陶瓷層均會 破損，所以此種陶瓷複合材料之應用領域目前仍受到局限。 儘管有這些缺點，陶瓷複a & ^ W 俊口材料亦往往用於過濾或隔膜 -6- 200303234 技術中。 歐洲專利0，3 5 8，3 3 8號記載之方法乃使表面（較佳爲平滑 之金屬表面）用陶瓷層保護着，亦即在該表面塗布含金屬氧 化物π溶膠’’（s ο 1)之水溶液，後並使該塗層固化。爲改善陶 瓷層和欲保護之表面的黏着力，可在水溶液中加入金屬氧 化物及/或黏着促進劑。此製程並未提到採用可滲透之支撐 材料層。 世界專利9 6 /0 0 1 9 8號教導在各種材料表面之陶瓷層製 法。此塗佈材料可用爲膜材。依此法，氧化鋁粉末分散於 二氧化鈦溶膠中，並用氫氯酸進行ί;膠溶f’（ p e p t i z i n g )。但 不可能將此法用在具有孔徑爲2微米至1 0 0奈米的多孔載 體上其塗孔徑小於5 0奈米之塗層，因爲顆粒及溶膠會充滿 著載體之孔洞而不是在多孔載體上形成塗層。 美國專利4，9 3 4，1 3 9號教示超濾及微濾用的陶瓷膜之製 法。此種陶瓷膜及使溶膠或顆粒懸浮液塗在多孔金屬載體 上，並燒結它。多孔載體可爲不銹鋼燒結之金屬，或不銹 鋼之織網（其網眼有金屬顆粒燒結於其上）。若沒有燒結之 金屬顆粒附於其上，則網眼大於1 〇 〇微米之金屬網無法加 工。此法防止懸浮液或溶膠滲入載體物質之網眼（間隙）。 爲使載體材料之間隙橋連，美國專利5，3 7 6，4 4 2號及 5,6 0 5，6 2 8號發表在塗佈溶液中加入有機黏合劑。在其後的 固化後，黏合劑必須去除，而在陶瓷導致不規則表面及/ 或結構。 200303234 同樣地’德國專利4，2 1 0，4 1 3號再提出利用聚合物樹脂 固定無機粉末。此樹脂亦須在固化後去除，而在陶瓷導致 不規則表面及/或結構。 世界專利9 9 / 1 5 2 6 2號記載基於多孔性載體材料而得可 撓性可滲透複合材料之製法。在此場合中，載體可爲各種 材料所構成，包含多孔性聚合物膜，聚合物之平織布，天 然纖維，玻璃’鋼或金屬不織布。塗佈可利用溶膠，後者 包含大量的水，或攪拌加入鋁、鈦、鐯或矽之氧化物顆粒 的強酸水溶液。此外，溶膠亦可含有有機矽化物，如甲基 —^乙興Ϊ夕丨兀。此寺η」丨參透複首材料尤其可用爲過滤膜。 目前所有的這些膜均缺乏可撓性。此外陶瓷塗層太脆， 且若陶瓷對載體之黏着不當，則容易和載體脫離。在此場 合下，陶瓷膜是不安定的。 (三）發明內容 因此，本發明之目的乃提供含陶瓷選擇性分離層之可撓 性膜，其比既有的膜更耐用，而且可低成本地製得。 如今我們很驚異地發現利用含聚合物纖維或天然纖維爲 基材（基材內或上有陶瓷成分）之複合物做爲活性分離層之 載體，則可製得具有孔徑在超濾（UF)或奈米過濾（NF)^ @ 的多孔性陶瓷分離層的可撓性膜。 爲製造具有基於聚合物纖維複合物之陶瓷分離層的超濾、 或奈米濾膜，必須採用完全嶄新的途徑，因爲傳統的超_ (UF)及奈米過濾（NF)製法不適用。已知之所有製程均須在 200303234 約4 5 0至1，2 〇 〇 C燒結，或用溶膠·凝膠塗佈，後者因有用 聚合物黏合劑，因此亦必須在相同的高溫煅燒以燒除黏合 ， 劑。但若採用本發明之複合膜則不必高溫，因高溫會無可 避免地導致聚合物纖維基材的完全崩解，使該膜減損其機 械強度。 方、疋本發明乃提供複合膜，較佳爲可撓性複合膜，其中 已a平坦、多孔、可撓性基材、其上或內或塗層，基材之 材料選自聚合物織布或不織布，而塗層乃多孔性陶瓷塗層| 本複合fe尙包含至少一種其他塗層做爲選擇性陶瓷分離 層。 本發明更提供具至少一選擇性分離層之複合膜的製法， 本複合膜含有平坦、多孔、可撓性基材、其內或上有塗層 基材之材料選自聚合物之織布及/或不織布，而塗層則爲 夕孔性陶瓷塗層，其乃將含無機成分之溶膠或懸浮液施塗 並固化而得。 本發明同樣地提供本發明複合膜之應用，包含用於壓力隹 &作之隔膜、氣體分離、全蒸發、蒸氣滲透、奈米過濾、 超濾或微濾，或膜反應器。 本發明複合膜之優點是其實質上比純有機聚合物膜，聚 口物Μ /聚合物載體，或聚合物膜/無機物複合物更爲耐溫 及尺寸更安定。本發明之複合膜更包含基於陶瓷塗佈之聚 口物纖維’其厚度薄且有高度之多撓性，故所得複合膜同 樣地極爲柔軟。和純聚合物膜比較起來，本複合膜在組件 -9- 200303234 及套罩方面實質上是沒限制的。於是本發明之複合膜有優 越的撓曲性，比基於純無機載體之奈米過濾及超濾用陶瓷 膜更耐機械負荷。 本發明複合膜之其他優點是極有利於生產，因爲聚合物 織布或不織布明顯優於金屬或玻璃的織布或不織布。此外 ，和玻璃纖維比較起來，聚合物纖維更不脆，於是原料之 操作簡單，故更爲有利。 (四）實施方式 茲以下列實施例在非限制本發明範圍下說明本發明之複 合膜。 本發明之可撓性複合膜包含平坦、多孔、柔軟基材，其 上或內有塗層，基材之材料選自聚合物纖維或天然纖維之 不織布，而塗層爲多孔性陶瓷塗層，其特徵係本複合膜尙 包含另一塗層做爲選擇性陶瓷分離層。該選擇性分離層可 決定本複合膜之應用。例如做爲奈米過濾或超濾膜。 本複合膜特殊之可撓性乃歸因於陶瓷塗佈之基材係聚合 物纖維及/或天然纖維。 陶瓷分離層較佳爲具有預定孔隙之多孔性分離層，其平 均孔徑爲小於5 0奈米。複合膜爲能用爲奈米過濾（N F )膜， 此陶瓷分離層較佳爲平均孔徑小於1 〇奈米，最佳爲〇 . 5至 5奈米。複合膜爲能用爲超濾（UF)膜，則陶瓷分離層之平 均孔徑小於5 0奈米，較佳爲5至2 5奈米。陶瓷分離層較 佳爲含鈦、矽、鍩、錫及/或鋁之氧化物，特佳爲含鈦、矽 -10- 200303234 、鉻及/或鋁之氧化物。做爲超濾（U F )膜時此等塗層用之較 佳顆粒尺寸小於2 5奈米’最佳爲小於1 5奈米；而做爲奈 米過濾（N F)膜時，較佳爲小於i 〇奈米，特佳爲小於5奈米。 較有利的是選擇性分離層之平均厚度小於1 〇微米，較佳 爲0.005至5微米，特佳爲0.005至3微米。由於厚度很 薄’有利於提供足夠高的透膜流動。 本發明複合膜較佳爲包含平坦、多孔、可撓性基材、其 上或內有無機成分，而基材原料選自聚合物纖維及/或天然 纖維之網織物、針織、氈或平織物，較佳爲聚合物纖維及/ 或天然纖維之網織物，而無機成分係多孔性陶瓷。由於利 用網織物，尤其是很薄且均勻的網織物，故可得均勻之透 膜流動。網織物之另一優點是孔隙率明顯地多於可對比之 平織物。 特佳的是所用的複合膜之基材厚度爲2〇〇微米以下。本 發明之複合膜特別有利的是其基材爲2 5至1 〇 〇微米，最好 是30至70微米。 A 口物纖維較佳爲選自聚丙稀腈、聚醯胺、聚醯亞胺、 聚丙烯酸酯、聚四氟乙烯、聚酯（如聚對酞酸乙撐酯）及/或 聚烯烴（如聚丙烯、聚乙烯），或此等聚合物之混合物。亦 可採用其他的已知聚合物纖維及許多種天然纖維，如亞麻纖 維、棉化或大麻纖維。本發明複合膜中之聚合物纖維的軟 化點大於1 0 0 C，熔點高於i丨〇 °c。若聚合物纖維軟化點或 熔點在溫度下限，則其應用領域受到局限。較佳之膜應用 200303234 溫度達1 5 0 °C ，較佳爲1 2 0 °C至1 5 0 °C ，特佳爲高至1 2 It： 。有利的是複合膜之基材纖維直徑爲1至2 5微米，較佳爲 2至1 5微米。若聚合物纖維比前述範圍粗，則基材之可撓 性，於是複合膜之可撓性會減損。 爲本發明之目的，聚合物纖維須先經化學或結構的部分 改質，例如用熱處理，使聚合物纖維部分炭化。 在基材上或內之陶瓷塗料包含至少一種金屬鋁、锆、矽 、錫、鈦及/或釔之氧化物，最佳爲鋁、鍩、鈦及/或矽之 氧化物做爲無機成分。 塗層較佳爲包至少一種無機成分，其顆粒尺寸有1至2 5 0 奈米的部分，或是其顆粒尺寸爲2 5 1至1 0,0 0 0奈米。較佳 爲本發明之複合膜的塗層包含至少兩種顆粒尺寸之分率的 至少一種無機成分。亦有利的是含至少兩顆粒尺寸分率的 至少兩種無機成分。此顆粒尺寸之比例爲1 : 1至1 : 1 〇，〇 〇 〇 ，較佳爲1 : 1至1 ; 1 〇 〇。在複合材料中之顆粒尺寸分率之比 例較佳爲0.0 1 : 1至1 : 0 . 〇 1。 有利的是複合材料中陶瓷塗層或無機成分是利用黏着促 進劑而和基材（尤指聚合物纖維）黏合。典型的黏着促進劑 爲有機官能之矽院，如Degussa公司之"Dynasilan”，然而 純的氧化物，如二氧化銷（Zr02)、二氧化鈦（Ti02)、二氧化 矽（si〇2)或三氧化二鋁（ai2o3)，對某些纖維材料而言，本 身就適做爲黏着促進劑。端賴於生產條件及所用之黏着促 進劑，黏着促進劑仍可發覺地存在於本發明之複合膜中。 -12- 200303234 有利的是先使網織物或平織物預塗以黏着促進劑。於是 複合膜中之網織物，較佳爲聚合物網織物的纖維，有用薄 層的黏着促進劑（如金屬氧化物或有機矽烷化物）做處理。 然後將多孔性陶瓷材料塗在預處理過之聚合物載體上或內。 本發明之複合膜的孔隙率爲1 〇 %至7 0 %，較佳爲2 0 %至 6 0 %，而特佳爲3 0 %至5 0 %。 本發明複合膜之特色是其抗張強度至少1牛頓/厘米，較 佳爲3牛頓/厘米，最佳爲大於6牛頓/厘米。本發明之複 合膜較佳爲具可撓性，以半徑而言，可彎至1 〇 〇米，較佳 爲彎至50毫米，特佳爲彎至2毫米，而不破裂。本發明複 合膜之優點是在用於過濾或氣體分離時容易抵抗突發的壓 力變動而不破損。此外，本複合膜可實質上形成符合應用 所需之形狀（捲繞模組、袋模組等）。 本發明複合膜較佳爲利用本發明製程由含選擇性陶瓷分 離層之複合膜製備之，其中包含平坦多孔柔軟之基材，基 材上或內有塗層，而基材之原料選自聚合物纖維及/或天然 纖維之織布或不織布，而塗層則爲多孔性陶瓷塗層，其包 含將溶膠或含有無機成分及溶膠之懸浮液塗佈而得之選擇 性分離層。 分離層較佳之製法乃將溶膠或含至少一種鋁、锆、矽、 錫、鈦及/或釔之金屬氧化物爲無機成分及溶膠之懸浮液於 複合膜上，然後至少加熱一次，使複合膜上之溶膠或懸浮 液固化。 -13- 200303234 有利的是使至少一種平均顆粒尺寸爲1至1 〇 〇奈米，較 佳爲2至4 0奈米，特佳爲2奈米至2 5奈米之無機成分懸 浮在至少一種溶膠中。 懸浮液或溶膠可利用印刷、壓榨、注射、輥滾、刮塗、 展塗、浸塗、噴灑或灌淋等方式塗在基材上。 懸浮液較佳爲將至少一種無機成分懸浮在至少一種溶膠 而得，故所得懸浮液包含至少一種前述無機成分及至少一 種溶膠，較佳爲至少一種金屬氧化物溶膠，至少一種半金 屬氧化物溶膠或至少一種混合金屬氧化物溶膠，或此種溶 膠之混合物。欲懸浮之無機成分特佳爲至少一種氧化物選 自銷、鋁、鈦及矽之氧·化物。被懸浮之成分係佔所用溶膠 重量的0.1至500倍。 溶膠乃由至少一種化合物，較佳爲至少一種金屬化合物 ，至少一種半金屬化合物或至少一種混合之金屬化合物經 水解而得。欲水解之化合物較佳爲至少一種金屬硝酸鹽、 金屬氯化物、金屬碳酸鹽、金屬烷氧化物，或至少一種半 金屬烷氧化物，其中特佳爲至少一種金屬烷氧化物。金屬 院氧化物或半金屬烷屬化物較佳爲元素锆、鋁、矽、鈦、 錫及釔之金屬烷氧化物，或其硝酸鹽、碳酸鹽、或鹵化物 做爲金屬化合物。水解較佳爲在水、水蒸氣、冰或酸，或 -其混合物之存在下進行。 依本發明之一種製法，微粒狀溶膠乃由欲水解之化合物 經水解而得。此等微粒溶膠之特色是水解而形成之溶膠的 -14- 200303234 顆粒尺寸小於15奈米，其特別適合做超濾膜。顆粒溶膠乃 如前述，或依世界專利9 9 / 1 5 2 6 2號所述方法製得。此等溶 膠通常具很高的水含量，較佳爲超過5 0重量％。有利的是 在水解前，將欲水解之化合物加入醇或酸或其混合液中。 水解之化合物可用至少一種有機或無機酸，較佳爲濃度1 〇 至6 0 %的有機或無機酸，特佳爲選自硫酸、氫氯酸、過氯 酸、磷酸及硝酸或其混合物的無機酸進行膠溶。 本發明之另一製法是聚合物溶膠乃由欲水解之化合物進 行水解而得。此等聚合物溶膠之特色是因水解在溶膠中所 形成的化合物是聚合物（亦即在較大的三度空間內交連成 鏈），且頗適合製造奈米過濾膜。聚合物溶膠通常含有水及 /或含量少於5 0重量％，最佳爲少於2 0重量％的含水酸。 爲得較佳的水及/或酸之比率，水解之條件較佳爲每莫耳的 可水解化合物之可水解基用0.5至1 0倍莫耳（最佳爲一半 的莫耳量）的水、水蒸氣或冰。若欲水解之化合物的水解速 率很慢（如四乙氧矽烷之場合），則可用高達1 〇倍量的水； 而水解速率很快的化合物（如四乙氧锆之場合），在此等條 件下很容易形成微粒溶膠，故用0 · 5倍量的水進行水解即 可。雖然用少於較佳量的水來做水解仍可得良好結果，但 落後於比起較佳量少5 〇 %以上的莫耳比，因爲低於此限度 時’水解不完全，由此種溶膠所得的塗層亦不太安定。 爲製備具所欲溶膠中低水含量及/或酸之聚合物溶膠，較 佳爲在實際之水解前，使欲水解之化合物先溶於有機溶劑， -15- 200303234 尤指乙醇、異丙醇、丁醇、戊醇、己烷、環己烷、醋酸乙 酯及/或其混合液。 懸浮液或溶膠之固化乃在5 0至3 5 0 °C，較佳爲5 0至2 2 0 °C ，特佳爲5 0至1 2 (TC加熱複合膜完成之；較佳爲在5 0至 1 〇 〇 °C加熱1 0分鐘至5小時，或在1 0 1至2 5 0 °C ，較佳爲 1 0 1至2 0 (TC ，特佳爲1 〇 5 t至1 5 0 t：加熱0 . 5至5分鐘。 固化溫度端賴於存在於複合膜中之聚合物纖維。大部分 的聚合物纖維（如聚丙烯）均可耐1 2 (TC之固化溫度，有些甚 至不耐到1 5 0 °C (如聚醯胺）。在較高的固化溫度下，較佳爲 在複合膜中採用會碳化而不會熔融之聚合物纖維。此種聚 合物例如是聚丙烯腈及芳族聚醯亞胺。 較佳爲在欲固化之懸浮液或溶膠中加入黏度調節劑，在 此場合下，黏度調節劑必須儘可能的具熱之不安定性。可 用的黏度調節劑例如羥乙基纖維素及聚乙二醇，其較佳爲 在觸媒存在下使用，該觸媒例如是硝酸或硫酸，其可催化 聚合物黏度調節劑之分解。此外，亦可採用聚丙烯酸或聚 丙烯醯胺做爲黏度調節劑。黏度調節劑可配合適當的觸媒 一起加入懸浮液或溶膠中。有利的是在懸浮液或溶膠中加 入0.0 1至1 0重量％，較佳爲0.0 5至1重量％，而特佳爲 少於1重量％的有機黏度調節劑。在加熱固化時，有機黏 度調節劑會分解而由塗層逸出，留下多孔性陶瓷層。 另一種可行的方法是採用無機系統而不用聚合物黏合劑 ，其後可殘留在材料中。無機系統之黏度調節劑例如常用 -16- 200303234 於塗料及食品工業之熱解矽石、二氧化鈦、氧化銷或氧化 鋁。在此場合下，此等材料之比表面積較佳爲明顯大於5 0 米2 /克。此等黏度調節劑由於有氫鍵故會實質上結團成較 大的結構。於是此等材料會提升黏度到像蕃茄醬。即使黏 度上升，亦能水液塗料進入吸收性多孔載體中。此外，此 等材料對於許多欲過濾的介質呈惰性，於是此等介質會殘 留在材料中。懸浮液中的無機黏度調節劑較佳爲佔懸浮液 中其他陶瓷成分之〇 . 1至5 0重量％，較佳爲0.2至3 0重量 %。 複合材料較佳爲複合膜，尤指微濾膜及超濾膜，其製法 例如如下：提供平坦、多孔、可撓性的基材，並於基材內 或上有塗層，基材原料選自聚合物纖維或天然纖維之網織 物，其孔隙率大於5 0 %，而塗層爲多孔性陶瓷塗層，其乃 將含至少一種鋁、锆、矽、鍚、鈦及/或釔之金屬氧化物的 懸浮液或溶膠塗在基材料，並至少加熱一次，而在基材上 固化得之。懸浮液中尙可含無機成分，尤指前述之無機成 分。 懸浮液塗在基材上的方法例如是印刷、壓榨、注射、輥 滾、刮塗、展塗、浸漬、噴灑或灌淋。 基材原料較佳爲選自厚度1 〇至2 0 0微米之聚合物纖維的 網織物。本發明之複合膜中之基材厚度爲3 0至1 0 0微米， 較佳爲2 5至5 0微米。 聚合物纖維較佳爲選自聚丙烯腈、聚醯胺、聚醯亞胺、 7 200303234 聚丙烯酸酯、聚四氟乙烯、聚酯，如聚對酞酸乙撐酯、及/ 或聚烯烴。然而亦可用所有已知的其他聚合物纖維及許多 種天然纖維。複合膜中之聚合物纖維的軟化點大於1 〇 〇 °c ，熔點大於1 1 〇 °c。若聚合物纖維之耐溫性差，則會限制 其應用之領域。此等複合膜之應用溫度可高達1 5 0 °c ，較 佳爲1 2 (TC至1 5 (TC，特佳爲達1 2 1 t。有利的是聚合物纖 維之直徑爲1至2 5微米，較佳爲2至1 5微米。若聚合物 纖維實質上比前述範圍粗，則基材（於是複合膜）之可撓性 會受損。 用於製備塗層之懸浮液含至少一種無機成分，較佳爲至 少一種鋁、鈦、矽及/或銷之無機氧化物，及至少一種溶膠 ，至少一種半金屬氧化物溶膠，至少一種混合金屬氧化物 溶膠，或此等溶膠之混合物，其乃使至少一種無機成分懸 浮於至少一種該溶膠而得。 溶膠乃由至少一種化合物，較佳爲至少一種金屬化合物 ，至少一種半金屬化合物或至少一種混合金屬化合物經水 解而得。欲水解之化合物較佳爲至少一種金屬硝酸鹽、金 屬氯化物、金屬碳酸鹽、金屬烷氧化物，或至少一種半金 屬烷氧化物，最佳爲至少一種金屬烷氧化物。金屬烷氧化 物較佳爲锆、鋁、矽、錫及釔之烷氧化物，而半金屬烷氧 化物較佳爲前述元素之金屬鹽，如硝酸鹽、碳酸鹽或鹵化 物，較佳爲在水、水蒸氣、冰或其混合物之存在下，進行 水解。 -18- 200303234 在本發明之一種製程中，微粒溶膠乃由欲水解之化合物 進行水解而得。此等微粒溶膠之特色乃水解後溶膠中之化 合物呈微粒狀。微粒溶膠可依前法或世界專利WO 9 9 / 1 5 2 62 號所述之方法製備之。此等溶膠通常含很高的水含量，較 佳爲大於5 0重量％的水。有利的是在水解之前加入欲水解 爲醇或酸或其混合液之化合物。水解之化合物的溶膠化乃 利用至少一種有機或無機酸，較佳爲濃度1 〇至6 0 %之有機 或無機酸，特佳爲選自硫酸、氫氯酸、過氯酸、磷酸及硝 酸或其混合物之無機酸處理之。 如此所得的微粒溶膠可用來製備懸浮液，該懸浮液可用 於塗佈天然纖維或聚合物纖維網織物，後者有用聚合物溶 膠預處理。 在另一本發明之製程中，聚合物溶膠乃由欲水解之化合 物進行水解而得。此等聚合物溶膠之特色是水解所得溶膠 中之化合物是聚合物（亦即在較大的三度空間交連成鏈）。 聚合物溶膠通常含少於5 0重量％，較佳爲遠低於2 0重量％ 的水及/或水性酸。爲得較佳的水及/或水性酸之比率，水 解之條件較佳爲每莫耳的可水解化合物之可水解基用〇 . 5 至1 〇倍莫耳（最佳爲半倍莫耳量）的水、水蒸氣或冰。若欲 水解之化合物的水解速率很慢（如四乙氧矽烷之場合），則 可用高達1 〇倍量的水。若化合物之水解速率很快（如四乙 氧锆），則在此等條件下很容易形成微粒溶膠，故用〇 . 5倍 量的水進行水解即可。雖然用少於較佳量的水來做水解仍 -19- 200303234 可得良好結果，但若比起較佳量少50%以上的莫耳比，則 . 不具意義，因爲低於此限度時，水解不完全，由此溶膠所. 得的塗層亦不很安定。 爲製備所欲的溶膠中有很低的水及/或酸之含量的聚合 物溶膠，有利的是使水解之化合物在實際水解前，先溶於有 機溶劑，尤ί曰乙醇、異丙醇、丁醇、戊醇、己烷、環己烷 、醋酸乙酯及/或其混合液。如此所得溶膠可用來製備本發 明之懸浮液’或在預處理步驟中做爲黏着促進劑。 微粒溶膠及聚合物溶膠均可在本發明製程中做爲溶膠以· 製備懸浮液。除前述所得的溶膠外，原則上尙可用市售之 溶膠，如硝酞錯彳谷膠或砂溶膠。由世界專利9 9 /丨5 2 6 2號可 知在載體上塗佈懸浮液並固化可得複合膜之製法’雖然並 非所有的參數及成分可直接用於本發明複合膜之製造，伸 可參考之。世界專利9 9/ 1 5 2 6 2號所述之操作未經修改是無 法用於聚口物網織物’因其中所述的頗爲水液狀之溶膠系 統往往無法潤溼正常的疏水聚合物網織物，即使深深浸入鲁 亦無法潤溼大部分的聚合物網織物。在網織物上即使有很 小塊的潤溼區，在製造複合膜時’亦會造成缺陷而不能用。 如今我們很驚異地發現本溶膠系統或懸浮液能充分擴散 到聚合物網織物’故可得無缺陷的塗層。亦即在本發明之 製程中’溶膠或懸浮液具可接受的潤溼行爲。聚合物溶膠 或聚合物溶膠之懸浮液的潤溼性是得自摻入一種或多種的 醇，如甲醇、乙醇或丙醇，或其混合液，亦可爲脂族烴。 -20- 200303234 然而，亦可在溶膠或懸浮液採用其他溶劑混合物，以便提 供其對於基材之潤溼性。 我們發現溶膠系統及所得懸浮液之基本改變可導致對聚 合物網織物上或內之陶瓷成分的黏着性的明顯改善。此種 良好的黏着強度往常是無法由微粒溶膠系統獲得。於是含 聚合物纖維之基材較佳乃利用基於聚合物溶膠之懸浮液塗 佈，或預先用黏着促進劑處理。 有利的是懸浮液是由做爲無機成分之元素釔、鍩、鋁、 矽、錫及鈦之氧化物懸浮於溶膠而得。較佳爲懸浮之無機 成分包含至少一種化合物選自氧化銘、二氧化欽、氧化鍩 及二氧化矽。懸浮成分是佔溶膠重量的0 . 1至5 0 0倍，最， 佳爲1至5 0倍，特佳爲5至2 5倍。 有利的是懸浮在至少一種溶膠之至少一種無機成分的平 均顆粒尺寸爲1至1 〇，〇 〇 〇奈米，較佳爲1至1 〇奈米，1 〇 至100奈米，100至1,0 0 0奈米或1，0 0 0至1 0,0 0 0奈米， 最佳爲250至1750奈米，而最好是300至1，250奈米。採 用平均顆粒大小爲2 5 0至1，2 5 0奈米之無機成分，可在複 合膜中提供高度合適的可撓性及孔隙率。 爲改善無機成分的聚合物纖維基材的黏着性，有利的是 在懸浮液中添加黏着促進劑，如有機官能的矽烷或純氧化 物，如二氧化锆，二氧化鈦、二氧化砂或三氧化二銘；而 該懸浮液較佳爲基於聚合物溶膠的。可用的黏着促進劑尤 指辛基矽烷、氟化辛基矽烷、乙燏矽烷、胺官能基化矽烷， -2 1- 200303234 及/或縮水甘油基化矽烷（如Degussa公司之Dynasilans®) 。聚四氟乙烯（PTFE)用之特佳黏着促進劑例如氟化辛基石夕 院；聚乙烯（PE)及聚丙烯（PP)用之黏着促進劑爲乙矯基、 甲基及辛基-矽烷，但單獨用甲基矽烷並不太適宜；用於聚 醯胺及聚胺者爲胺官能基化矽烷；用於聚丙靖酸醋及聚醋 者爲縮水甘油基化矽烷；而縮水甘油基化矽烷亦可用於聚 丙烯腈。亦可採用其他黏着促進劑，但必須配合各別的聚 合物。在世界專利WO 99/i 5 2 6 2號中，於塗佈聚合物載體 材料時’在溶膠中加入甲基三乙氧矽烷並無法解決陶瓷對 聚合物纖維之黏着性差之問題。此外，就抗水解之陶瓷材 料而言，所述之溶膠系統在6 0至1 〇 〇它乾燥3 〇至1 2 〇分 鐘的時間是不夠的。然而此等材料在水液介質中儲存太久 會溶解或受損。另方面，按世界專利W Ο 9 9 / 1 5 2 6 2號中所 述用局於3 5 0 °C之溫度處理會導致所用聚合物網織物燃燒 ’而破壞複合膜。因此，黏着促進劑之選擇須配合固化溫 度低於聚合物之熔點或軟化點及其分解溫度。本發明之懸 浮液較佳爲含明顯低於2 5重量％，較佳爲低於1 〇重量。/。的 做爲黏着促進劑之化合物。黏着促進劑之最適用量是使其 塗佈在纖維及/或顆粒之塗層厚度爲單分子層。符合此目的 之黏着促進劑的用量乃由氧化物及/或所用纖維量（克）乘 以材料之比表面積（米2 /克），並除以黏着促進劑之比容率 (米2/克’往往是300至400米2/克 下表綜合列出黏着促進劑之實例，其乃基於有機官能基 -22- 200303234 之矽化物，可用於典型的聚合物網織物。The advantages of ceramic composites are that ceramic coatings are inert to most chemicals (such as organics) and stable to acids or bases. For this reason, metals are often coated with ceramics to protect them from chemical attack. In addition, the porous surface of the ceramic-coated composite layer can be used to coat abrasion-resistant protective layers to improve wear resistance. The ceramic itself is also suitable as a membrane or filter due to its porous surface. The disadvantage of ceramics and ceramic composites is that ceramics are too brittle. This ceramic-coated metal is afraid of collisions, and as long as the ceramic coating is subjected to mechanical stress, the ceramic surface will be damaged. Even if this ceramic composite material is folded, the ceramic layer will be damaged, so the application field of this ceramic composite material is still limited. Despite these shortcomings, ceramic composite materials are often used in filtration or membrane technology. The method described in European Patent No. 3,58,3,38 is to protect the surface (preferably a smooth metal surface) with a ceramic layer, that is, to coat the surface with a metal oxide-containing π sol '' (s ο 1) aqueous solution, and then the coating is cured. To improve the adhesion of the ceramic layer and the surface to be protected, metal oxides and / or adhesion promoters can be added to the aqueous solution. This process does not mention the use of a permeable support material layer. World Patent No. 9 6/0 0 1 9 8 teaches the method of making ceramic layers on the surface of various materials. This coating material can be used as a film material. According to this method, alumina powder is dispersed in a titanium dioxide sol, and is peptized with hydrochloric acid f '(pe p t i z i n g). However, it is not possible to apply this method to a porous support having a pore size of 2 microns to 100 nanometers and a coating having a pore diameter of less than 50 nanometers, because particles and sols will fill the pores of the carrier instead of the porous carrier. A coating is formed on it. U.S. Patent No. 4,9 3 4, 1 39 teaches a method for manufacturing ceramic membranes for ultrafiltration and microfiltration. Such a ceramic film and a sol or particle suspension are coated on a porous metal support and sintered. The porous support may be a sintered metal of stainless steel, or a woven mesh of stainless steel with metal particles sintered on the mesh. Without sintered metal particles attached to it, metal meshes with a mesh size greater than 1000 microns cannot be processed. This method prevents the suspension or sol from penetrating into the meshes (gap) of the carrier material. In order to bridge the gap of the carrier material, U.S. Patent Nos. 5,3,7,6,4,4 and 5,60,5,28,8 have been added to the coating solution to add organic binders. After subsequent curing, the adhesive must be removed, resulting in irregular surfaces and / or structures on the ceramic. 200303234 Similarly, German Patent No. 4, 2 0, 4 1 3 proposes to fix the inorganic powder with a polymer resin. This resin must also be removed after curing, resulting in irregular surfaces and / or structures in the ceramic. World Patent No. 9 9/15 2 6 2 describes a method for producing a flexible permeable composite material based on a porous carrier material. In this case, the carrier may be composed of various materials, including a porous polymer film, a polymer plain cloth, natural fiber, glass' steel, or a metal non-woven cloth. Coating can be performed using a sol, which contains a large amount of water, or a strong acid aqueous solution in which oxide particles of aluminum, titanium, hafnium or silicon are added by stirring. In addition, the sol may also contain organic silicides, such as methyl ^ ethoxylate. This compound η ″ 丨 can be used as a filter membrane. All of these films currently lack flexibility. In addition, the ceramic coating is too brittle, and if the ceramic adheres to the carrier improperly, it is easy to detach from the carrier. In this case, the ceramic membrane is unstable. (3) Summary of the Invention Therefore, an object of the present invention is to provide a flexible membrane containing a ceramic selective separation layer, which is more durable than existing membranes and can be produced at low cost. Today, we are surprised to find that using a composite containing polymer fibers or natural fibers as a substrate (with ceramic components in or on the substrate) as the carrier of the active separation layer, UF Or nanofiltration (NF) ^ @ flexible membranes for porous ceramic separation layers. In order to manufacture ultrafiltration or nanofiltration membranes with ceramic separation layers based on polymer fiber composites, a completely new approach must be taken because the traditional ultrafiltration (UF) and nanofiltration (NF) manufacturing methods are not applicable. All known processes must be sintered at 20030234 to about 450 to 1,200 ° C, or coated with sol · gel. The latter is also required to be calcined at the same high temperature to burn off the bond because of the useful polymer binder. , Agent. However, if the composite film of the present invention is used, the high temperature is not necessary, because the high temperature will inevitably lead to the complete disintegration of the polymer fiber substrate, and the film will reduce its mechanical strength. The present invention provides a composite film, preferably a flexible composite film, in which a flat, porous, flexible substrate, on or inside or coated thereon, the material of the substrate is selected from polymer woven fabrics. Or non-woven, and the coating is a porous ceramic coating | This composite fe 尙 contains at least one other coating as a selective ceramic separation layer. The invention further provides a method for manufacturing a composite membrane with at least one selective separation layer. The composite membrane contains a flat, porous, flexible substrate, and the material in or on the substrate is selected from a woven fabric of a polymer and Non-woven fabric, and the coating is a porous ceramic coating, which is obtained by applying and curing a sol or suspension containing an inorganic component. The present invention likewise provides applications of the composite membrane of the present invention, including diaphragms for pressure 隹 & operation, gas separation, total evaporation, vapor permeation, nanofiltration, ultrafiltration or microfiltration, or membrane reactors. The advantages of the composite film of the present invention are that it is substantially more temperature-resistant and more stable in size than a pure organic polymer film, a polymer M / polymer carrier, or a polymer film / inorganic composite. The composite film of the present invention further comprises ceramic-coated polymer fibers', which is thin and highly flexible, so the obtained composite film is also extremely soft. Compared with pure polymer membranes, this composite membrane is essentially unlimited in terms of components and covers. Therefore, the composite membrane of the present invention has superior flexibility and is more resistant to mechanical load than ceramic membranes for nanofiltration and ultrafiltration based on pure inorganic carriers. Another advantage of the composite film of the present invention is that it is extremely advantageous for production because the polymer woven or non-woven fabric is significantly superior to the woven or non-woven fabric of metal or glass. In addition, compared with glass fiber, polymer fiber is less brittle, so the operation of the raw material is simple, so it is more advantageous. (IV) Embodiments The following examples illustrate the composite film of the present invention without limiting the scope of the present invention. The flexible composite film of the present invention comprises a flat, porous, and soft substrate with a coating on or in it. The material of the substrate is selected from polymer fiber or natural fiber nonwoven fabric, and the coating is a porous ceramic coating. It is characterized in that the composite membrane 尙 includes another coating layer as a selective ceramic separation layer. The selective separation layer can determine the application of the composite membrane. For example as a nanofiltration or ultrafiltration membrane. The special flexibility of this composite film is attributed to the ceramic-coated polymer fibers and / or natural fibers. The ceramic separation layer is preferably a porous separation layer having predetermined pores, and its average pore diameter is less than 50 nm. The composite membrane is a nanofiltration (N F) membrane. The ceramic separation layer preferably has an average pore diameter of less than 10 nm, and most preferably 0.5 to 5 nm. The composite membrane can be used as an ultrafiltration (UF) membrane, so the average pore diameter of the ceramic separation layer is less than 50 nm, preferably 5 to 25 nm. The ceramic separation layer is preferably an oxide containing titanium, silicon, hafnium, tin, and / or aluminum, and particularly preferably an oxide containing titanium, silicon -10- 200303234, chromium, and / or aluminum. When used as an ultrafiltration (UF) membrane, the preferred particle size for these coatings is less than 25 nanometers', preferably less than 15 nanometers; and as a nanofiltration (NF) membrane, it is preferably less than i 〇nm, particularly preferably less than 5nm. It is more advantageous that the average thickness of the selective separation layer is less than 10 microns, preferably 0.005 to 5 microns, and particularly preferably 0.005 to 3 microns. Since the thickness is very thin, 'it is advantageous to provide a sufficiently high transmembrane flow. The composite film of the present invention preferably comprises a flat, porous, flexible substrate with inorganic components on or in it, and the raw material of the substrate is selected from a mesh fabric, knitted, felt or plain fabric of polymer fibers and / or natural fibers. It is preferably a mesh fabric of polymer fibers and / or natural fibers, and the inorganic component is a porous ceramic. Due to the use of mesh fabrics, especially thin and uniform mesh fabrics, a uniform membrane flow is obtained. Another advantage of mesh fabrics is that they have significantly more porosity than comparable plain fabrics. It is particularly preferred that the substrate thickness of the composite film used is 200 μm or less. The composite film of the present invention is particularly advantageous in that the substrate thereof is 25 to 100 µm, preferably 30 to 70 µm. The fiber of mouthpiece is preferably selected from the group consisting of polyacrylonitrile, polyimide, polyimide, polyacrylate, polytetrafluoroethylene, polyester (such as polyethylene terephthalate), and / or polyolefin (such as Polypropylene, polyethylene), or a mixture of these polymers. Other known polymer fibers and many types of natural fibers such as flax, cotton or hemp fibers can also be used. The softening point of the polymer fibers in the composite film of the present invention is greater than 100 ° C, and the melting point is higher than 10 ° C. If the softening point or melting point of the polymer fiber is at the lower temperature limit, its application field is limited. The preferred film application is 200303234 with a temperature of 150 ° C, preferably 120 ° C to 150 ° C, and particularly preferably up to 12 It:. Advantageously, the substrate fiber diameter of the composite film is 1 to 25 microns, preferably 2 to 15 microns. If the polymer fiber is thicker than the aforementioned range, the flexibility of the base material is reduced, so that the flexibility of the composite film is impaired. For the purpose of the present invention, the polymer fibers must first be chemically or structurally modified, such as by heat treatment, to partially carbonize the polymer fibers. The ceramic coating on or in the substrate comprises at least one oxide of metal aluminum, zirconium, silicon, tin, titanium and / or yttrium, preferably an oxide of aluminum, hafnium, titanium and / or silicon as an inorganic component. The coating preferably includes at least one inorganic component having a particle size of 1 to 250 nanometers, or a particle size of 2 51 to 10.0 nanometers. The coating of the composite film of the present invention preferably contains at least one inorganic component in at least two particle size fractions. Also advantageous are at least two inorganic components containing at least two particle size fractions. The ratio of this particle size is from 1: 1 to 1: 1,000,000, preferably from 1: 1 to 1; 100%. The ratio of the particle size fraction in the composite material is preferably from 0.0 1: 1 to 1: 0.01. Advantageously, the ceramic coating or inorganic component of the composite is bonded to the substrate (especially polymer fibers) using an adhesion promoter. Typical adhesion promoters are organic-functional silicon institutes, such as "Dynasilan" from Degussa, but pure oxides, such as doped dioxide (Zr02), titanium dioxide (Ti02), silicon dioxide (SiO2), or trioxide. Aluminum oxide (ai2o3) is suitable as an adhesion promoter for certain fiber materials. Depending on the production conditions and the adhesion promoter used, the adhesion promoter can still be found in the composite film of the present invention. -12- 200303234 It is advantageous to pre-coat the mesh fabric or plain fabric with an adhesion promoter. Then the mesh fabric in the composite film, preferably the fiber of the polymer mesh fabric, has a thin layer of adhesion promoter (such as Metal oxide or organic silane)). Then the porous ceramic material is coated on or in the pretreated polymer carrier. The porosity of the composite film of the present invention is 10% to 70%, preferably 20% to 60%, and particularly preferably 30% to 50%. The composite film of the present invention is characterized by its tensile strength of at least 1 Newton / cm, preferably 3 Newton / cm, and most preferably greater than 6 Newton / cm. The composite film of the present invention is preferably Flexible, in terms of radius, it can be bent to 100 meters, preferably to 50 mm, particularly preferably to 2 mm without breaking. The advantage of the composite membrane of the present invention is that it is used for filtration or gas separation. It is easy to resist sudden pressure changes without breakage. In addition, the composite film can be substantially formed into a shape (winding module, bag module, etc.) that meets the application requirements. The composite film of the present invention preferably uses the process of the present invention. It is prepared from a composite membrane containing a selective ceramic separation layer, which comprises a flat, porous and soft substrate with a coating on or in the substrate, and the raw material of the substrate is selected from the woven fabric of polymer fibers and / or natural fibers or Non-woven fabric, and the coating is a porous ceramic coating, which includes a selective separation layer obtained by coating a sol or a suspension containing an inorganic component and a sol. The separation layer is preferably prepared by coating the sol or containing at least one kind of aluminum, Metal oxides of zirconium, silicon, tin, titanium, and / or yttrium are suspensions of inorganic components and sols on the composite film, and then heated at least once to cure the sols or suspensions on the composite film. -13- 200303234 Is making At least one inorganic component having an average particle size of 1 to 100 nm, preferably 2 to 40 nm, particularly preferably 2 to 25 nm, is suspended in at least one sol. The suspension or sol may be It is applied to the substrate by printing, pressing, injection, rolling, blade coating, spreading coating, dip coating, spraying or irrigation, etc. The suspension is preferably obtained by suspending at least one inorganic component in at least one sol, so The resulting suspension contains at least one of the foregoing inorganic components and at least one sol, preferably at least one metal oxide sol, at least one semi-metal oxide sol or at least one mixed metal oxide sol, or a mixture of such sols. The inorganic component is particularly preferably at least one oxide selected from the group consisting of pins, aluminum, titanium, and silicon oxides. The suspended components are 0.1 to 500 times the weight of the sol used. The sol is obtained by hydrolysis of at least one compound, preferably at least one metal compound, at least one semi-metal compound or at least one mixed metal compound. The compound to be hydrolyzed is preferably at least one metal nitrate, metal chloride, metal carbonate, metal alkoxide, or at least one semi-metal alkoxide, and particularly preferably at least one metal alkoxide. The metal oxide or semimetal alkane is preferably a metal alkoxide of the elements zirconium, aluminum, silicon, titanium, tin, and yttrium, or a nitrate, carbonate, or halide thereof as the metal compound. The hydrolysis is preferably performed in the presence of water, water vapor, ice or acid, or a mixture thereof. According to a method of the present invention, the particulate sol is obtained by hydrolyzing a compound to be hydrolyzed. The characteristic of these particulate sols is that the sol formed by hydrolysis has a particle size of less than 15 nm, which is particularly suitable for ultrafiltration membranes. The granular sol is prepared as described above, or according to the method described in World Patent No. 9 9/15 2 6 2. These sols usually have a high water content, preferably more than 50% by weight. It is advantageous to add the compound to be hydrolyzed to an alcohol or an acid or a mixture thereof before the hydrolysis. The hydrolyzed compound may be at least one organic or inorganic acid, preferably an organic or inorganic acid having a concentration of 10 to 60%, particularly preferably an inorganic material selected from the group consisting of sulfuric acid, hydrochloric acid, perchloric acid, phosphoric acid, and nitric acid or a mixture thereof. The acid is peptized. Another method of the present invention is to obtain a polymer sol by hydrolyzing a compound to be hydrolyzed. The characteristic of these polymer sols is that the compounds formed by hydrolysis in the sol are polymers (that is, cross-linked in a large third degree space) and are suitable for manufacturing nanofiltration membranes. Polymeric sols usually contain water and / or an aqueous acid in an amount of less than 50% by weight, preferably less than 20% by weight. In order to obtain a better ratio of water and / or acid, the conditions for the hydrolysis are preferably 0.5 to 10 times the molar amount of the hydrolyzable group of the hydrolyzable compound (preferably half the molar amount) of water. , Water vapor or ice. If the hydrolysis rate of the compound to be hydrolyzed is slow (such as in the case of tetraethoxysilane), up to 10 times the amount of water can be used; and the compound with a fast hydrolysis rate (such as in the case of tetraethoxyzirconium) Particulate sols are easily formed under the conditions, so hydrolysis with 0.5 to 5 times the amount of water is sufficient. Although good results can still be obtained by using less than a good amount of water for hydrolysis, it lags behind the Mohr ratio by more than 50%, because below this limit, the hydrolysis is incomplete. The coating obtained by the sol is also less stable. In order to prepare a polymer sol with a low water content and / or acid in the desired sol, it is preferred that the compound to be hydrolyzed is dissolved in an organic solvent before the actual hydrolysis, -15-200303234, especially ethanol, isopropanol , Butanol, pentanol, hexane, cyclohexane, ethyl acetate and / or a mixture thereof. Suspension or sol is cured at 50 to 350 ° C, preferably 50 to 220 ° C, particularly preferably 50 to 12 (Completed by TC heating composite film; preferably at 5 Heating from 0 to 100 ° C for 10 minutes to 5 hours, or at 1101 to 2500 ° C, preferably 10 1 to 2 0 (TC, particularly preferably 10 5 t to 15 0 t: Heating for 0.5 to 5 minutes. The curing temperature depends on the polymer fibers present in the composite film. Most of the polymer fibers (such as polypropylene) can withstand the curing temperature of 1 2 (TC, some are not even Resistance to 150 ° C (such as polyamide). At higher curing temperatures, it is preferable to use polymer fibers that will carbonize and not melt in composite films. Such polymers are, for example, polyacrylonitrile And aromatic polyimide. It is preferable to add a viscosity modifier to the suspension or sol to be cured. In this case, the viscosity modifier must be as thermally unstable as possible. Available viscosity modifiers such as hydroxyl Ethylcellulose and polyethylene glycol are preferably used in the presence of a catalyst, such as nitric acid or sulfuric acid, which can catalyze the decomposition of polymer viscosity modifiers. In addition, polyacrylic acid or polyacrylamide can also be used as a viscosity modifier. The viscosity modifier can be added to the suspension or sol with a suitable catalyst. It is advantageous to add 0.0 1 to 10 in the suspension or sol. % By weight, preferably from 0.05 to 1% by weight, and particularly preferably less than 1% by weight organic viscosity modifier. During heat curing, the organic viscosity modifier will decompose and escape from the coating, leaving porosity Ceramic layer. Another feasible method is to use an inorganic system instead of a polymer binder, which can then remain in the material. Viscosity modifiers for inorganic systems such as commonly used -16-200303234 pyrolytic silica for coatings and food industry, Titanium dioxide, oxidized pins or alumina. In this case, the specific surface area of these materials is preferably significantly greater than 50 m 2 / g. These viscosity modifiers will substantially agglomerate due to hydrogen bonding. Structure. So these materials will increase the viscosity to tomato sauce. Even if the viscosity rises, water-based coatings can enter the absorbent porous carrier. In addition, these materials are inert to many media to be filtered. These media will remain in the material. The inorganic viscosity modifier in the suspension preferably accounts for 0.1 to 50% by weight, more preferably 0.2 to 30% by weight, of other ceramic components in the suspension. Composite materials Composite membranes are preferred, especially microfiltration membranes and ultrafiltration membranes. The preparation method is as follows: provide a flat, porous, flexible substrate, and have a coating in or on the substrate. The substrate raw material is selected from polymerization Natural or natural fiber mesh fabrics with a porosity greater than 50%, and the coating is a porous ceramic coating that will contain at least one metal oxide of aluminum, zirconium, silicon, hafnium, titanium and / or yttrium The suspension or sol is coated on the base material and heated at least once while curing on the substrate. The rhenium in the suspension may contain inorganic components, especially the aforementioned inorganic components. The method of applying the suspension to the substrate is, for example, printing, pressing, injection, rolling, doctoring, spreading, dipping, spraying, or pouring. The base material is preferably a mesh fabric selected from polymer fibers having a thickness of 10 to 200 microns. The thickness of the substrate in the composite film of the present invention is 30 to 100 microns, and preferably 25 to 50 microns. The polymer fiber is preferably selected from the group consisting of polyacrylonitrile, polyamide, polyimide, 7 200303234 polyacrylate, polytetrafluoroethylene, polyester, such as polyethylene terephthalate, and / or polyolefin. However, all other known polymer fibers and many types of natural fibers can be used. The softening point of the polymer fibers in the composite film is greater than 1000 ° C, and the melting point is greater than 110 ° C. If the temperature resistance of polymer fibers is poor, it will limit the fields of application. The application temperature of these composite films can be as high as 150 ° C, preferably 1 2 (TC to 15 (TC, particularly preferably up to 1 2 1 t. Advantageously, the diameter of the polymer fiber is 1 to 2 5 Micron, preferably 2 to 15 micron. If the polymer fiber is substantially thicker than the aforementioned range, the flexibility of the substrate (thus the composite film) is impaired. The suspension used to prepare the coating contains at least one inorganic The components are preferably at least one inorganic oxide of aluminum, titanium, silicon and / or pins, and at least one sol, at least one semi-metal oxide sol, at least one mixed metal oxide sol, or a mixture of these sols, which It is obtained by suspending at least one inorganic component in at least one sol. The sol is obtained by hydrolysis of at least one compound, preferably at least one metal compound, at least one semi-metal compound or at least one mixed metal compound. Compounds to be hydrolyzed Preferably it is at least one metal nitrate, metal chloride, metal carbonate, metal alkoxide, or at least one semimetal alkoxide, and most preferably at least one metal alkoxide. Metal alkoxide The compounds are preferably alkoxides of zirconium, aluminum, silicon, tin, and yttrium, and the semimetal alkoxides are preferably metal salts of the foregoing elements, such as nitrates, carbonates, or halides, preferably in water, water Hydrolysis is performed in the presence of steam, ice, or a mixture thereof. -18- 200303234 In one process of the present invention, the particulate sol is obtained by hydrolysis of the compound to be hydrolyzed. The characteristics of these particulate sols are The compound is in the form of a particulate. A particulate sol can be prepared according to the previous method or the method described in World Patent No. WO 9 9/15 2 62. These sols usually contain a high water content, preferably greater than 50% by weight. Water. It is advantageous to add compounds that are to be hydrolyzed to alcohols or acids or mixtures thereof before hydrolysis. The solization of the hydrolyzed compounds utilizes at least one organic or inorganic acid, preferably an organic or organic compound having a concentration of 10 to 60%. Inorganic acids, particularly preferably treated with an inorganic acid selected from the group consisting of sulfuric acid, hydrochloric acid, perchloric acid, phosphoric acid, and nitric acid or mixtures thereof. The particulate sol thus obtained can be used to prepare suspensions, which can be used to coat natural materials. Dimensional or polymer fiber web fabric, which is pretreated with polymer sol. In another process of the present invention, polymer sol is obtained by hydrolyzing the compound to be hydrolyzed. The characteristic of these polymer sols is the hydrolyzed sol The compounds in it are polymers (ie cross-linked into chains in a large third degree space). Polymer sols usually contain less than 50% by weight, preferably much less than 20% by weight of water and / or aqueous acids. In order to obtain a better ratio of water and / or aqueous acid, the conditions of hydrolysis are preferably 0.5 to 10 times the mole of the hydrolyzable group per mole of the hydrolyzable compound (preferably half times the mole Amount of water, water vapor or ice. If the hydrolysis rate of the compound to be hydrolyzed is slow (such as in the case of tetraethoxysilane), up to 10 times the amount of water can be used. If the hydrolysis rate of the compound is fast (such as four Zirconium ethoxylate), it is easy to form a particulate sol under these conditions, so hydrolysis with 0.5 times the amount of water is sufficient. Although using less than a good amount of water for hydrolysis still yields -19-200303234, good results can be obtained, but if it is more than 50% less than the better amount, it is not meaningful, because below this limit, The hydrolysis is incomplete, and the coating obtained from this sol is not very stable. In order to prepare a polymer sol with a very low water and / or acid content in the desired sol, it is advantageous to make the hydrolyzed compound soluble in an organic solvent, especially ethanol, isopropanol, Butanol, pentanol, hexane, cyclohexane, ethyl acetate and / or a mixture thereof. The sol thus obtained can be used to prepare a suspension ' of the present invention or as an adhesion promoter in a pretreatment step. Both the particulate sol and the polymer sol can be used as a sol in the process of the present invention to prepare a suspension. In addition to the sols obtained previously, in principle, commercially available sols such as nitrophthalocyanine or sand sol can be used. According to World Patent No. 9 9 / 丨 5 2 6 2 it can be known that the method for preparing a composite film by coating a suspension on a carrier and curing it can be used. 'Although not all parameters and components can be directly used in the production of the composite film of the present invention, please refer to it for reference. Of it. The operation described in World Patent No. 9 9/1 5 2 6 2 cannot be used in poly mouth mesh fabrics without modification because the sol system described in it is often unable to wet normal hydrophobic polymers. Mesh fabric, even if deeply immersed in Lu, can not wet most polymer mesh fabrics. Even if there is a small piece of wet area on the mesh fabric, it will cause defects and cannot be used in the manufacture of the composite film. Now we are surprised to find that the present sol system or suspension can sufficiently diffuse into the polymer mesh 'so that a defect-free coating can be obtained. That is, the 'sol or suspension has acceptable wetting behavior in the process of the present invention. The wettability of the polymer sol or suspension of the polymer sol is obtained by incorporating one or more alcohols, such as methanol, ethanol or propanol, or a mixture thereof, and may also be an aliphatic hydrocarbon. -20- 200303234 However, other solvent mixtures can also be used in sols or suspensions to provide their wettability to the substrate. We have found that basic changes in the sol system and the resulting suspension can lead to a significant improvement in the adhesion to ceramic components on or in the polymer mesh. Such good adhesion strength is often not available from microsol systems. Therefore, the polymer fiber-containing substrate is preferably coated with a polymer sol-based suspension or treated with an adhesion promoter in advance. Advantageously, the suspension is obtained by suspending the oxides of the elements yttrium, osmium, aluminum, silicon, tin and titanium as sols in the sol. It is preferred that the suspended inorganic component comprises at least one compound selected from the group consisting of oxidized oxide, dioxin, hafnium oxide, and silicon dioxide. The suspended component is 0.1 to 500 times the weight of the sol, most preferably 1 to 50 times, and particularly preferably 5 to 25 times. Advantageously, the average particle size of the at least one inorganic component suspended in the at least one sol is from 1 to 100,000 nm, preferably from 1 to 100 nm, from 10 to 100 nm, from 100 to 1, 0 0 0 nm or 1, 0 0 to 1 0, 0 0 0 nm, preferably 250 to 1750 nm, and most preferably 300 to 1, 250 nm. The use of inorganic components with an average particle size of 250 to 1,250 nanometers provides a highly suitable flexibility and porosity in the composite film. To improve the adhesion of inorganic polymer fiber substrates, it is advantageous to add adhesion promoters, such as organic functional silanes or pure oxides, such as zirconium dioxide, titanium dioxide, sand dioxide or trioxide, to the suspension. The suspension is preferably based on a polymer sol. Useful adhesion promoters are in particular octylsilane, fluorinated octylsilane, acetosilane, amine-functionalized silane, -2 1-200303234 and / or glycidylated silane (such as Degussa's Dynasilans®). Special adhesion promoters for polytetrafluoroethylene (PTFE) such as fluorinated octyl sulphide; adhesion promoters for polyethylene (PE) and polypropylene (PP) are ethynyl, methyl and octyl-silane However, methylsilane alone is not suitable; those used for polyamines and polyamines are amine-functionalized silanes; those used for polyacrylic acid and polyacetate are glycidyl silanes; and glycidylated Silane can also be used for polyacrylonitrile. Other adhesion promoters can also be used, but they must be formulated with individual polymers. In World Patent No. WO 99 / i 5 2 62, when coating a polymer carrier material ', adding methyltriethoxysilane to the sol cannot solve the problem of poor adhesion of ceramics to polymer fibers. In addition, in the case of ceramic materials that are resistant to hydrolysis, the sol system is not sufficient to dry it for 30 to 120 minutes at 60 to 1000. However, these materials can dissolve or be damaged if they are stored for too long in aqueous media. On the other hand, treatment at a temperature of 350 ° C as described in World Patent No. W 99/15 2 62 will cause the polymer mesh used to burn and damage the composite membrane. Therefore, the choice of adhesion promoter must be matched with the curing temperature lower than the melting point or softening point of the polymer and its decomposition temperature. The suspension of the present invention preferably contains significantly less than 25% by weight, and more preferably less than 10% by weight. /. As a compound of adhesion promoter. The most suitable amount of adhesion promoter is that the thickness of the coating applied to the fibers and / or particles is a single molecular layer. The amount of adhesion promoter that meets this purpose is calculated by multiplying the amount of oxides and / or fibers (g) by the specific surface area of the material (m2 / g) and dividing by the specific volume of the adhesion promoter (m2 / g 'Often 300 to 400 m2 / g The table below lists examples of adhesion promoters based on silicides based on organic functional groups 22-200303234, which can be used in typical polymer mesh fabrics.
聚合物 有機官能基之類型 黏着促進劑 PAN 縮水甘油基（g 1 y C i d 1 y) GL YMO 甲基丙儲醯基（methacryloyl) MEMO PA 胺基（amino) AMEO,D AMO PET 甲基丙燒醯基（methacryloyl) MEMO 乙烯基（vinyl) VTM03VTE0?VTM0E0 PE，PP 胺基（amino) AMEO, AMMO 乙烯基（vinyl) VTMO, VTEO，Silfin 甲基丙稀醯基（methacryloyl) MEMO 註：AMEO:3 -胺丙基二乙氧5夕院 D Α Μ Ο ·· 2 -胺乙基-3 -胺丙基三甲氧矽烷 GL ΥΜΟ:3-縮水甘油氧三甲氧矽烷 ΜΕΜΟ:3 -甲基丙烯醯氧丙基三甲氧矽烷Type of polymer organic functional group Adhesion promoter PAN Glycidyl (g 1 y C id 1 y) GL YMO methylacryloyl MEMO PA amino AMEO, D AMO PET methyl propane (Methacryloyl) MEMO vinyl VTM03VTE0? VTM0E0 PE, PP amino AMEO, AMMO vinyl VTMO, VTEO, Silfin methylacryloyl MEMO Note: AMEO: 3-amine Propyl diethoxy 5 yawin D Α Μ Ο · 2 -aminoethyl-3 -aminopropyltrimethoxysilane GL ΜΜΟ: 3-glycidyloxytrimethoxysilane ΜΜΟ: 3 -methacryloxypropyl Trimethoxysilane
Silfin:乙烯矽烷+引發劑+觸媒 VTEO:乙烯三乙氧矽烷 VTMO:乙烯三甲氧矽烷 VTMOEO:乙烯三（2-甲氧乙氧）矽烷 將本發明之塗料施於基材，亦即使懸浮液在基材上及內 固化。依本發明在基材上及內之懸浮液係在5 0至3 5 0 °C加 熱。因爲採用聚合物基材，最高溫度取決於基材，必須配 合之。於是依本發明之具體製法，基材上及內的懸浮液係 在1 0 0至3 5 0 °c加熱固化；特佳爲在1 1 0 °c至2 8 0 °c加熱固 化。有利的是在1 0 0至3 5 0 °C加熱1秒至6 0分鐘。較佳爲 -23- 200303234 在1 1 0 °C至3 0 0 t：，特佳爲在1 1 〇 °C至2 8 0 °C ，加熱固化懸 浮液〇 . 5至1 0分鐘。 就某些聚合物而言，端賴於所選之溫度高低，膜之固化 所用溫度可能會改變化學結構，故其後之聚合物已和原先 或改質之狀態不一樣。例如聚醯亞胺可能部分碳化，或在 聚丙烯腈之場合會形成所謂的”階梯形聚合物"（ladder polymers)。此等效應總會改變載體的性質。端賴應用而定 ，此種改變亦可能是故意的，因爲利用此方式可提升對溶 劑、酸及鹼之抵抗性。利用溫度及時間可影響轉化度。 依本發明本組件之加熱可利周加熱之空氣、熱空氣、紅 外線輻射或其他習用加熱法。 在本發明製程之一實施例中，前述的黏着促進劑乃預先 施於基材，尤其是聚合物基材。爲此目的，其先溶於合適 的溶劑，如乙醇。此溶液亦可含有少量的水（較佳爲其莫耳 量爲欲水解基莫耳數的〇 . 5至1 0倍），及少量的酸，如氫 氯酸或硝酸，做爲S i - 0 R基之水解及縮合的觸媒。利用已 知的技術，如噴灑、印刷、壓榨、注射、輥滾、刮塗、展 塗、浸漬或灌淋，可將溶液塗在基材上，並在5 0至最高 3 5 (TC將黏着促進劑固定在基材上。按此實施例，先施用黏 着促進劑後，才施用懸浮液。 在另一本發明製程之實施例是在預處理步驟中施用聚合 物溶膠及黏着促進劑並固化之。仿懸浮液之方法，將聚合 物溶膠施用並固化。經施用此等聚合物溶膠，基材（特別是 -24- 200303234 聚合物網織物）以做爲黏着促進劑之鋁、鈦、鍩或矽的氧化 物處理，而使基材具親水性。然後如世界專利9 9/ 1 5 2 6 2號 中所述，使如此處理之基材再做多孔性的塗佈，顯示前面 之預處理可提供塗層對尤其是聚合物網織物有更好的黏着 性。 預處理用之典型聚合物溶膠例如是金屬氧化物（如乙氧 鈦或丙氧鍩）之2至1 0重量％濃度的醇溶液，其中尙可含 〇 . 5至1 0莫耳分率的水及少量的酸觸媒。將此種溶膠施用 於基材（較佳爲聚合物網織物）後，就在最高3 5 0 °C之溫度處 理。如此在基材纖維上形成金屬氧化物之不滲透膜，如此 使基材可被懸浮液容易地潤溼，或被基於市售硝酸锆或矽 溶膠之懸浮液容易潤溼。 因爲聚合物溶膠會形成不滲透膜而非微粒膜，而且因微 粒溶膠在微粒間之孔隙微結構中總是有較多量的水，所以. 欲乾燥聚合物溶膠比微粒溶膠更爲容易。此外，複合膜必 須在1 5 0 °C以上的溫度乾燥，才能使陶瓷材料對載體呈現 足夠的黏着強度。在至少2 0 (TC之溫度可能特別良好的黏 着強度，而在2 5 0 °C以上之溫度更佳。於是聚合物必須亦 具對應的溫度安定性，例如是聚對酞酸乙撐酯（PET)、聚丙 烯腈（PAN)、聚四氟乙烯（PTEF)、聚偏二氟乙烯（PVDF)或 聚醯胺。若載體不具適當的溫度安定性，則複合膜須在低 溫（1 0 0 °C以下）先做初步的乾燥（預固化）。在其後的升溫固 化時，陶瓷層就做爲載體之支架，故載體不再熔掉。此種 -25- 200303234 製法參數不僅可應用於當做黏着促進劑之聚合物溶膠的施 用及固化，亦可應用於基於聚合物溶膠之懸浮液的施用及 Λ 固化。 在實際施用懸浮液前，先施用黏着促進劑之此兩種模式 均可改善對基的黏着性，特別是水性微粒溶膠更是如此， 這就是何以如此預處理之基材可依本發明塗以市售之溶膠 (如硝酸銷溶膠或矽溶膠）。然而此施用黏着促進劑之步驟 表示本發明之複合膜製程必須多一中間處理步驟或預處理 | 步驟。此法可行，但比採用已加有黏着促進劑之市售溶膠 之方式更爲複雜；然而，即使採用基於市售溶膠之懸浮液 ，此法是可得較佳的結果。 本發明之製程可例如包含自料捲中拉出基材，依1米/ 小時至2米/秒，較佳爲0.5米/分鐘至20米/分鐘，較佳爲 1米/分鐘至5米/分鐘之速率通入至少一裝置，例如是塗輥.. . ... ，將懸浮液塗於基材上及內，並再通過至少另一裝置，例 如是電熱爐，使懸浮液在載體上及內進行加熱固化，最後 ¥ 在第二料輥捲取複合膜。如此可連續地製得本發明之複合 膜。預處理步驟亦可依前述參數連續進行。 合適的複合膜較佳爲具有1至1，〇 〇 〇奈米，較佳爲2至 500奈米，特佳爲3至100奈米之孔徑。本複合膜較佳爲 具撓曲性。具約略良好的抗張強度，較佳爲至少1牛頓/ 厘米，特佳爲至少3牛頓/厘米。最好是在機械加工方面（ 尤其是採用聚合物網織物時），本複合膜之抗張強度至少6 -26- 200303234 牛頓/厘米。 採用高抗張強度之複合材料，表示複合膜之抗張強度就 和複合材料一樣好。有利的是所用複合材料乃依本發明所 製之複合膜。特別有利的是所得之複合膜的孔徑小於1 5 奈米。在此場合下，有利的是先利用本發明之方法由微濾 膜製備平均孔徑小於2 5奈米之超濾膜，然後再由該超濾膜 製造平均孔徑小於1 5奈米之奈米膜。端賴所欲之複合膜的 平均孔徑及做爲原料之複合膜的孔徑，可依本發明方法做 多次的塗佈而完成之。 由於、孑L徑太大會造成吸進懸浮液太遠之分、別塗層，故所 用複合膜之孔徑亦有限制，而孔徑太小亦會對複合膜中流 動造成太大的阻力。此外，因爲在某些場合下孔徑太小亦 不好，因分離層之黏着力太低，而在應用時會剝離而造成 複合膜完全破壤。爲此理由，所用之複合膜的最小孔徑是，.. 3奈米，較佳爲12奈米，特佳爲25奈米。 依本發明複合膜之製程亦可包含自料捲拉出複合材料， 依1米/小時至2米/秒，較佳爲0.5米/分鐘至20米/分鐘 ，特佳爲0.5米/分鐘至5米/分鐘之速率通過至少一裝置， 其中可適合製造選擇性陶瓷分離層之懸浮液塗佈在複合材 料，並再通過至少一裝置可加熱複合材料而使懸浮液固化 ，最後在第二料輥捲取所得的複合膜。如此可連續地製造 複合膜。 本發明之複合膜可用於超濾及奈米過濾（NF)。本發明之 •27- 200303234 NF膜亦可如以往的技藝所知之方式用於氣體分離，全蒸發 及蒸氣滲透。 本發明複合膜之優點主要是在高壓高溫、或在溶劑、酸 及/或鹼中有較高的安定性。 茲以非限制本發明範圍的實施例說明本發明複合膜及其 製法。 實例1 a : S450PETMF膜之製法 首先在160克乙醇中加入15克5重量％濃度之鹽酸，10 克四乙氧矽烷，2.5克甲基三乙氧矽烷及7.5克戴那西蘭葛 來莫（Dy nasi lan GLYMO)(三縮水甘油氧三甲氧矽烷， Degussa公司）。先攪拌數小時，接著使各1 25克的氧鋁 (Martinswerke 公司之 Martoxid MZS-1 及 MZ-3)懸浮在此 溶膠中。利用磁力攪拌器攪拌此懸浮液又至少2 4小時，此 時攪拌槽必須加蓋以防溶劑散失。 利用連續的輥塗法，將此懸浮液塗佈在厚度約3 0微米， 基重約2 0克/米2之聚酯（P E T )網織物（帶速約8米/小時， 溫度2 0 (TC )。在此輥塗法中，塗輥移動的方向和網織物傳 動帶移動的方向相反。接著使網織物通過所述溫度之爐中 。在下列試驗中，採用相同的方法及裝置。如此得平均孔 徑爲4 5 0奈米之微濾膜。 實例1 b : S240PANMF臈之製法 首先在1 6 0克乙醇中加入1 5克5重量％濃度的鹽酸，1 0 克四乙氧矽烷，2.5克甲基三乙氧矽烷及7.5克戴那西蘭葛 -28- 200303234 來莫（Dynasilan GLYMO)。先攪拌此溶膠數小時使： 氧化鋁（A 1 C 〇 A C T 1 2 0 0 S G )懸浮在此溶膠中。利用® 拌器又攪拌至少2 4小時，此時攪拌槽必須加蓋以防 逸失。 利用連續輥塗法將前述懸浮液塗佈在厚度約1 0 0 基重22克/米2之聚丙烯腈（PAN)網織物（Freudenbe 之Viledon® 1 7 7 3 )，帶速約8米/小時，溫度2 5 0 °C 0 均孔徑爲2 4 0奈米之微濾膜。 實例 1 c : S100PETMF臆夕製法 首先在1 6 0克乙醇中加入1 5克5重量％濃度的鹽 克四乙氧矽烷，2.5克甲基三乙氧矽烷及7 . 5克戴那 來莫（Dynasilan GLYMO)。先攪拌此溶膠數小時’嚷、 浮2 8 0克氧化鋁（A 1 C 〇 A C T 3 0 0 0 )。利用磁力攪拌器 懸浮液至少2 4小時，此時，攪拌槽須加蓋以防溶劑 利用連續輥塗法將所得懸浮液塗佈在厚度約3 0携 重約20克/米2之PET網織物（帶速約8米/小時，溫度 。得平均孔徑1 〇 〇奈米之微濾膜。 實例 1 d : S100PANMF膣夕製法 首先在160克乙醇中加入15克5重量％濃度之_ 克四乙氧矽烷，2.5克甲基三乙氧矽烷及7.5克戴那 來莫（Dynasilan GLYMO)。先攪拌此溶膠數小時，赞、 3 0 〇克氧化鋁（A 1 C 〇 A C T 3 0 0 )懸浮於其中。利用磁力 攪拌懸浮液至少24小時，此時攪拌槽加蓋以防止溶劑 280克 玄力攪 止溶劑 微米， rg出品 得平 酸，1 0 西蘭葛 U菱懸 又攪拌 散失一。 S[米，基 2 00°C ) 酸，1 0 西蘭葛 U戔將 攪拌器 散失。 -29- 200303234 利用連續輥塗法將前述懸浮液塗佈在厚度約1 〇 〇微 基重22克/米2之PAN網織物（Freudenberg出品之Vil 1 7 7 3 )，帶速約8米/小時，溫度2 5 0 °C。得平均孔徑1 奈米之微濾膜。 實例2a : Z025PAN之製法 利用連續輥塗法將含有3.0%奈米粒氧化锆（〇41^^ 司之VP25)，1%氧化銷溶膠（MEL公司）及1.0%約諾西 300(Aerosil 300)(Degussa公司，做爲黏度調節劑）/脫 水之懸浮液塗佈在實例1 b所得之孔徑約2 4 0奈米之複 並固化之，帶速約8米/小時，溫度2 5 0 °C。 得平均孔徑2 5奈米之超濾膜，其具很好的黏着強度 即使在高鹼介層（pH>10)中亦很安定。 實例2b : T010PAN之製法 在14.21克四異丙氧化鈦（Fluk a )/27.1克異丙醇之混 中攪拌慢慢滴入1 80克脫離子水及0.69克6 5%濃度硝 混合物。使所形成的二氧化鈦偶而攪拌膠溶化歷經1 7 使如此所得溶膠進一步加工成塗佈懸浮液；亦即混合爸 體積％之二氧化鈦（乃前述之溶膠）及0.2體積％卡爾波 9 8 0 ( C a r b ο ρ ο 1 9 8 0 )而形成懸浮液；然後將此懸浮液塗-實例2a所得之複合膜（帶速約8米/小時，溫度2 5 0 °C ) 1 所得超濾膜之平均孔徑爲1 2奈米，其塗層具良好的 強度。 實例2c : T002PAN之製法 米， e d ο η 00 公 離子 合膜 ’且 合物，. 酸之 天。 r 0.3 普 佈在 〇 黏着 200303234 在1 · 8克水及3 3 0克異丙醇（A 1 d r i c h公司）混合物中慢慢 混入1 Ο . 5 1克二乙醇胺（F 1 ii k a )和1 1 . 4 1克原鈦酸四乙酯混 合物。攪拌所形成的聚合物溶膠1小時，然後塗在實例2b 所得之複合膜並固化之（帶速約0.5米/分鐘，溫度23 Ot )。 如此得奈米過濾膜，平均孔徑約1至2奈米。 實例2d : Z025PET之製法 將含有3 %奈米級氧化鍩（D e g u s s a公司之V P 2 5 )，1 %氧化 锆溶膠（Μ E L公司）及1 · 0 %約諾西3 0 0 ( A e r 〇 s i 1 3 0 0 ) (Degussa公司，做爲黏度調節劑）/脫離子水之懸浮液，依 連續輥塗法塗佈在實例lc所得孔徑約1GG奈米之複合膜 (帶速約8米/小時，溫度2 5 0 t：)。 所得超濾膜之平均孔徑2 5奈米，其活性分離層之黏着強 度很好。 實例2 e : Z 0 2 5 P A之製法Silfin: Ethylene Silane + Initiator + Catalyst Cured on and in the substrate. The suspension on and in the substrate according to the invention is heated at 50 to 350 ° C. Because polymer substrates are used, the maximum temperature depends on the substrate and must be matched. Therefore, according to the specific manufacturing method of the present invention, the suspension on and in the substrate is heat-cured at 100 to 350 ° C; particularly preferably, it is heat-cured at 110 to 280 ° C. It is advantageous to heat at 100 to 350 ° C for 1 second to 60 minutes. It is preferably -23- 200303234 at 110 ° C to 300 t: particularly preferably, the suspension is cured by heating at 110 ° C to 280 ° C for 0.5 to 10 minutes. For some polymers, depending on the selected temperature, the temperature at which the film is cured may change the chemical structure, so the subsequent polymer is not the same as the original or modified state. For example, polyimide may be partially carbonized, or in the case of polyacrylonitrile, so-called "ladder polymers" will be formed. These effects will always change the properties of the carrier. Depending on the application, this kind of The change may also be intentional, because using this method can improve the resistance to solvents, acids and alkalis. Using temperature and time can affect the degree of conversion. The heating of the component according to the invention can benefit the heated air, hot air, and infrared rays. Radiation or other conventional heating methods. In one embodiment of the process of the present invention, the aforementioned adhesion promoter is pre-applied to a substrate, especially a polymer substrate. For this purpose, it is first dissolved in a suitable solvent, such as ethanol This solution may also contain a small amount of water (preferably with a molar amount of 0.5 to 10 times the number of moles to be hydrolyzed), and a small amount of acid, such as hydrochloric acid or nitric acid, as S i -0 R-based hydrolysis and condensation catalysts. The solution can be applied to the substrate using known techniques, such as spraying, printing, pressing, injection, rolling, scraping, spreading, dipping or irrigation, And between 5 0 and up to 3 5 (TC will stick The adhesion promoter is fixed on the substrate. According to this embodiment, the suspension is applied after the adhesion promoter is first applied. In another embodiment of the process of the present invention, a polymer sol and an adhesion promoter are applied in a pretreatment step and Cured. The method of simulating a suspension is to apply and cure the polymer sol. After applying these polymer sols, the substrate (especially -24-200303234 polymer mesh) is used as an adhesion promoter for aluminum, titanium, The substrate is treated with rhenium or silicon oxide to make the substrate hydrophilic. Then, as described in World Patent No. 9 9/1 5 2 6 2, the substrate thus treated is then subjected to porous coating, showing the former Pretreatment can provide better adhesion of the coating to polymer meshes in particular. Typical polymer sols for pretreatment are, for example, 2 to 10% by weight of metal oxides (such as titanium ethoxylate or propoxyfluorene). Concentration of alcohol solution, which can contain 0.5 to 10 mole fraction of water and a small amount of acid catalyst. After applying this sol to a substrate (preferably polymer mesh fabric), the highest 3 5 0 ° C. So on the substrate fiber Forms an impermeable film of metal oxides, so that the substrate can be easily wetted by the suspension or can be easily wetted by suspensions based on commercially available zirconium nitrate or silica sol. Because polymer sols form an impermeable film instead of Particle film, and because the particle sol always has a large amount of water in the pore microstructure between the particles, it is easier to dry the polymer sol than the particle sol. In addition, the composite film must be above 150 ° C. Drying temperature can make the ceramic material exhibit sufficient adhesive strength to the carrier. At a temperature of at least 20 ° C, the adhesive strength may be particularly good, and a temperature above 250 ° C is better. Therefore, the polymer must also have a corresponding Temperature stability, such as polyethylene terephthalate (PET), polyacrylonitrile (PAN), polytetrafluoroethylene (PTEF), polyvinylidene fluoride (PVDF) or polyamide. If the carrier does not have proper temperature stability, the composite film must be dried (pre-cured) first at low temperature (below 100 ° C). In the subsequent temperature curing, the ceramic layer serves as a support for the carrier, so the carrier no longer melts away. Such -25-200303234 method parameters can be applied not only to the application and curing of polymer sols as adhesion promoters, but also to the application and curing of polymer sol-based suspensions. Before the actual application of the suspension, the two modes of application of the adhesion promoter can improve the adhesion to the substrate, especially the aqueous particulate sol. This is why the substrate thus pretreated can be coated according to the present invention. Commercially available sols (such as nitric acid sol or silica sol). However, this step of applying an adhesion promoter indicates that the composite film manufacturing process of the present invention must have an additional intermediate processing step or pretreatment step. This method is feasible, but more complicated than using a commercially available sol to which an adhesion promoter has been added; however, even if a suspension based on a commercially available sol is used, this method can achieve better results. The process of the present invention may include, for example, pulling out the substrate from the roll, in the range of 1 m / h to 2 m / s, preferably 0.5 m / min to 20 m / min, preferably 1 m / min to 5 m Rate per minute into at least one device, such as a coating roller..., To apply the suspension on and in the substrate, and then pass the at least one other device, such as an electric furnace, to the suspension in the carrier. The upper and inner parts are heated and cured. Finally, the composite film is taken up on the second roll. Thus, the composite film of the present invention can be continuously produced. The pretreatment step can also be performed continuously according to the aforementioned parameters. A suitable composite film preferably has a pore diameter of 1 to 1,000 nm, preferably 2 to 500 nm, and particularly preferably 3 to 100 nm. The composite film is preferably flexible. It has a slightly good tensile strength, preferably at least 1 Newton / cm, and particularly preferably at least 3 Newton / cm. In terms of mechanical processing (especially when using polymer mesh fabrics), the tensile strength of this composite film is at least 6 -26- 200303234 N / cm. The use of a high tensile strength composite material indicates that the tensile strength of the composite film is as good as that of the composite material. Advantageously, the composite material used is a composite film made according to the present invention. It is particularly advantageous that the pore size of the resulting composite film is less than 15 nm. In this case, it is advantageous to first use the method of the present invention to prepare an ultrafiltration membrane with an average pore diameter of less than 25 nanometers from a microfiltration membrane, and then manufacture a nanomembrane with an average pore diameter of less than 15 nanometers from the ultrafiltration membrane. . Depending on the average pore diameter of the desired composite film and the pore diameter of the composite film as a raw material, it can be completed by multiple coatings according to the method of the present invention. Because the diameter of 孑 L is too large, it will cause the suspension to be drawn too far apart and coating. Therefore, the pore size of the composite membrane used is also limited. If the pore size is too small, it will cause too much resistance to flow in the composite membrane. In addition, because the pore diameter is too small in some cases, it is not good, because the adhesive force of the separation layer is too low, and the composite film will be completely peeled when it is peeled during application. For this reason, the minimum pore size of the composite membrane used is .. 3 nanometers, preferably 12 nanometers, and particularly preferably 25 nanometers. The manufacturing process of the composite film according to the present invention may also include pulling out the composite material from the roll, according to 1 m / hour to 2 m / second, preferably 0.5 m / minute to 20 m / minute, particularly preferably 0.5 m / minute to A rate of 5 m / min passes through at least one device, wherein a suspension suitable for manufacturing a selective ceramic separation layer is coated on the composite material, and the composite material is heated by at least one device to solidify the suspension, and finally the second material The obtained composite film was rolled up. Thus, a composite film can be continuously produced. The composite membrane of the present invention can be used for ultrafiltration and nanofiltration (NF). The 27-200303234 NF membrane of the present invention can also be used for gas separation, total evaporation and vapor permeation in a manner known in the art. The advantages of the composite film of the present invention are mainly high stability at high pressure and temperature, or in solvents, acids and / or bases. The non-limiting examples of the scope of the present invention are used to illustrate the composite film of the present invention and a method for producing the same. Example 1a: S450PETMF film production method First, 160 grams of ethanol was added to 15 grams of 5% strength hydrochloric acid, 10 grams of tetraethoxysilane, 2.5 grams of methyl triethoxysilane and 7.5 grams of danasilan gramme ( Dy nasi lan GLYMO) (triglycidyl trimethoxysilane, Degussa). After stirring for several hours, 125 g each of aluminum oxide (Martoxid MZS-1 and MZ-3 by Martinswerke) was suspended in the sol. Use a magnetic stirrer to stir the suspension for at least 24 hours. At this time, the stirring tank must be covered to prevent solvent loss. Using continuous roll coating, this suspension was coated on a polyester (PET) mesh fabric with a thickness of about 30 microns and a basis weight of about 20 g / m2 (belt speed of about 8 m / h, temperature of 20 ( TC). In this roll coating method, the direction of movement of the coating roller is opposite to that of the transmission belt of the mesh fabric. Then the mesh fabric is passed through the furnace at the temperature described above. In the following tests, the same method and device were used. A microfiltration membrane with an average pore size of 450 nm. Example 1 b: S240PANMF 臈 Preparation Method First, 150 grams of 5% by weight hydrochloric acid, 10 grams of tetraethoxysilane, 2.5 grams are added to 160 grams of ethanol. Methyl triethoxysilane and 7.5 grams of Dynasilan GLYMO. First stir this sol for several hours to suspend: alumina (A 1 C ACT 1 2 0 0 SG) In the sol. Stir for at least another 24 hours with a ® blender. At this time, the stirring tank must be covered to prevent it from escaping. The continuous suspension coating method is used to coat the suspension at a thickness of about 100 basis weight 22 g / m2. Polyacrylonitrile (PAN) mesh fabric (Viledon® 1 7 7 3 by Freudenbe), belt speed of about 8 m / h, temperature 2 50 ° C 0 Microfiltration membrane with an average pore diameter of 2 to 40 nanometers. Example 1 c: S100PETMF method of preparation of glutamate. Firstly, 150 grams of 5% by weight salt, tetraethoxysilane, and 2.5 grams of methyl are added to 160 grams of ethanol. Triethoxysilane and 7.5 grams of Dynasilan GLYMO. Stir this sol for several hours first, float 280 grams of alumina (A 1 C ACT 3 3 0 0). Use a magnetic stirrer The suspension should be covered for at least 24 hours. At this time, the stirring tank must be covered to prevent the solvent. The resulting suspension is coated on a PET mesh fabric with a thickness of about 30 and a weight of about 20 g / m2 by a continuous roll coating method (belt speed about 8 m / h, temperature. A microfiltration membrane with an average pore size of 100 nm was obtained. Example 1 d: S100PANMF production method Firstly, 15 g of 5% by weight _ gram of tetraethoxysilane was added to 160 g of ethanol, 2.5 Grams of methyltriethoxysilane and 7.5 grams of Dynasilan GLYMO. Stir this sol for a few hours, and 3,000 grams of alumina (A 1 COACT 300) is suspended in it. Use magnetic force Stir the suspension for at least 24 hours. At this time, the stirring tank is covered to prevent the solvent from 280 grams. Ping acid, 10 Zelan Ge U Ling suspended and stirred to lose one. S [meter, base 200 ° C) acid, 10 Ze Lang Ge U to lose the agitator. -29- 200303234 using continuous roller coating method The aforementioned suspension was coated on a PAN mesh fabric (Vil 1 7 7 3 manufactured by Freudenberg) with a thickness of about 1,000 microbasis and a weight of 22 g / m 2 at a belt speed of about 8 m / h and a temperature of 250 ° C. A microfiltration membrane with an average pore size of 1 nm was obtained. Example 2a: The manufacturing method of Z025PAN uses a continuous roll coating method to contain 3.0% nano-sized zirconia (VP41 of Division 41), 1% oxide sol (MEL) and 1.0% Aerosil 300 (Degussa Company, as a viscosity modifier) / dehydrated suspension, coated and cured with a pore diameter of about 240 nm obtained in Example 1b, a belt speed of about 8 m / hour, and a temperature of 250 ° C. An ultrafiltration membrane with an average pore diameter of 25 nanometers was obtained, which has very good adhesive strength and is very stable even in a high alkali interlayer (pH > 10). Example 2b: Production method of T010PAN In a mixture of 14.21 g of titanium tetraisopropoxide (Fluk a) /27.1 g of isopropyl alcohol, 1 80 g of deionized water and 0.69 g of a 6 5% strength nitrate mixture were slowly dropped into the mixture. The titanium dioxide formed was occasionally stirred and peptized. After 17, the sol thus obtained was further processed into a coating suspension; that is, mixed with vol% titanium dioxide (the aforementioned sol) and 0.2 vol% Carbo 9 8 0 (C arb ο ρ ο 1 9 8 0) to form a suspension; then apply this suspension to the composite membrane obtained in Example 2a (belt speed about 8 m / h, temperature 2 50 ° C) 1 average pore diameter of the obtained ultrafiltration membrane It is 12 nanometers, and its coating has good strength. Example 2c: Production method of T002PAN rice, e d ο η 00 public ion composite film ′ and compound, acid day. r 0.3 pu at 200303234 in 1.8 g of water and 3 300 g of isopropanol (A 1 drich) was slowly mixed into 10 0.5 1 g of diethanolamine (F 1 ii ka) and 1 1 4 1 g of tetraethyl orthotitanate mixture. The formed polymer sol was stirred for 1 hour, and then coated on the composite film obtained in Example 2b and cured (belt speed about 0.5 m / min, temperature 23 Ot). In this way, a nanofiltration membrane was obtained with an average pore size of about 1 to 2 nanometers. Example 2d: The manufacturing method of Z025PET will contain 3% nano-grade hafnium oxide (VPeg 5 of Degusus), 1% zirconia sol (M EL), and 1.0% Jonoxi 3 0 0 (A er 〇si 1 3 0 0) (Degussa company, as viscosity modifier) / deionized water suspension, coated with a composite film with a pore diameter of about 1GG nanometer (belt speed of about 8 meters / hour) by continuous roll coating method in Example lc , Temperature 2 5 0 t :). The average pore diameter of the obtained ultrafiltration membrane was 25 nm, and the adhesion strength of the active separation layer was very good. Example 2 e: Z 0 2 5 P A
將含3 . 0 %奈米級氧化锆（D e g u s s a公司之V P 2 5 )，1 %氧化 鉻溶膠（Μ E L公司）及1 · 0 %約諾西3 0 0 ( A e r 〇 s i 1 3 0 0 ) (Degussa公司，做爲黏度調節劑）/脫離子水之懸浮液用連 續輥塗法塗佈在實例1 d所得孔徑約1 0 0奈米之複合膜並固 化之（帶速約8米/小時，溫度2 5 0 °C )。 所得超濾膜平均孔徑2 5奈米，其活性分離層具良好黏着 強度。 •3 1-It will contain 3.0% nano-grade zirconia (VPeg 5 of Degusus), 1% chrome oxide sol (MEL) and 1.0% Jonossi 3 0 0 (Aer 〇si 1 3 0 0 ) (Degussa company, as a viscosity modifier) / suspension of deionized water was applied to the composite film with a pore diameter of about 100 nanometers obtained in Example 1d by a continuous roll coating method and cured (belt speed of about 8 meters / Hours, temperature 2 50 ° C). The average pore diameter of the obtained ultrafiltration membrane was 25 nm, and the active separation layer had good adhesion strength. • 3 1-