201223615 六、發明說明： 【發明所屬之技術領域】 本發明係有關於液晶顯示器配向溶液之純化方法及裝 置，且特別是有關於高效率之配向溶液之純化方法及裝置。 【先前技術】 配向膜為控制液晶顯不裔顯不品質的關鍵材料。配向 膜通常設置於液晶顯示器上下電極基板的内側，呈現鋸齒 狀的溝槽，用以使液晶分子沿著溝槽整齊排列方向，用以 控制液晶在電場中的旋轉角度，方可使液晶分子有效做為 顯示器開關。配向膜一般是由雙胺及雙酐反應形成的聚亞 醢胺組成，一般先將含聚亞醯胺的配向溶液塗佈於玻璃基 板表面上，經過特定角度定向後，將聚亞醯胺表面分子以 光或熱聚合後可形成固定均一的方向排列，以形成控制液 晶旋轉角度的配向膜。 除聚亞醯胺或其前驅物外，配向溶液内通常還包含配 向溶劑及添加劑，添加劑的成分視需求而有所不同。然而， 當配向溶液久置或接觸至空氣時，水氣及空氣中的金屬離 子即有可能進入至配向溶液中，使得配向溶液中的水分及 總金屬離子含.量過高，導致所形成之配向膜膜厚不均、低 電壓保持率（voltage holding ratio，VHR )與高殘餘直流電 壓性（residual direct current，RDC)等缺點。如此，可能 會使所生產之液晶螢幕有殘像的問題發生。再者，在目前 的液晶面板廠中，在產線上使用後多餘的配向溶液，有7 0 %以上無法繼續使用，而僅能當作廢液丟棄。 .201223615 目前，已有數種方法來將這些久置或使用後但多餘的 液晶顯示器之配向溶液（此後通稱為配向廢液）純化，將 匕配向廢液回收純化再使用。例如，美國專利 M20,440揭示了 一種配向材料之回收方法’包含以乙醚將 聚亞醯胺或其前驅物固化、過濾以與有機溶液分離，隨後 再加入與未使用之配向溶液（以下皆以原液稱之）相同之 有機溶劑溶解，得到回收的配向材料。另一種方法，韓國 專利No. 66749亦揭示類似之方法，但所得到之有機濾液 則可蒸館再时使m方法雖可將配向材料之回收溶 液中的水分去除’然而，亦會將配向溶液十原本就含有的 添加劑給濾'掉，且亦可能使廢液巾的金屬料含量增加。 因此’就算將此㈣得到之紐重新應用於生產線上，呈 品質及特性仍與原液具有極大差異，使所形成之配向膜無 法達到原有品質。 因此，本專利所提出的是一種液晶顯示器之配向廢液 =、、、屯化方法與裝置，其能以高效率去除廢液中的水分及金 =子’除可得到極佳的純化效率外，也不會破壞配向溶 之中成分與添加劑’可用於各種配向溶液的純化與廢液的 純化再利用。 【發明内容】 ， 、 核明之實施例係提供—種配向溶液之純化方法，包 .&供-配向溶液或配向廢液，其中此配向溶液或 配向 共沸溶劑至此 少包含⑷聚亞醯胺或其前驅物、⑻配向溶劑 添加劑及（d)水及金屬離子至少其一；加入 201223615 配向廢液中’並以共沸（C〇_evap〇raU〇n)同時去除此配向 廢液中的水及此共沸溶劑；以及以一過濾材過濾此配向廢 液，得到一經純化之配向溶液，其中此過濾材包含一吸附 劑及一濾膜，且此吸附劑包含高純度以上之氧化鋁或矽酸 銘化合物化合物。 本發明之實施例亦提供一種配向溶液之純化裝置，包 含·一反應槽，用以容置一配向廢液；一水分去除系統， 包含：一溫度控制單元，用以控制此反應槽之溫度；及一 減壓單元，用以降低此反應槽之壓力及去除此配向廢液中 的水；以及一金屬離子去除系統，用以接收來自此水分去 除系統中的配向廢液，此金屬離子去除系統至少包含一吸 附劑及一濾膜，其中此濾膜位於此反應槽之底部，且此吸 附劑位於此濾膜之上。 為讓本發明之上述和其他目的、特徵、和優點能更明 顯易懂，下文特舉出較佳實施例，並配合所附圖式，作詳 細說明如下： 【實施方式】 本發明係提供一種液晶顯示器之配向溶液之純化方 法此方法包έ以共沸（co_evaporation)去除配向溶液中 的水，及以過遽材去除配向溶液中的金屬雜質。此純化方 法可在不破壞配向溶液原液之成分的條件下，有效去除配 向廢液中的水分和金屬離子。同時，配向溶液中的聚㈣ 胺或其前驅物、添加劑或其他成分將可依照其原比例保留 下來，經純化後的配向溶液所形成之配向膜成分與原本被 .201223615 純化的配向溶液相同，所形成之配向膜亦與原配向溶液所 形成之配向膜有相同的品質。此外，本發明亦提供一種液 晶顯示器之配向溶液之純化裝置，此裝置包含反應槽、水 分去除系統及金屬離子去除系統。在一實施例中，此純化 裝置可用以提供實施上述之液晶顯示器之配向溶液之純化 方法。 、 第1圖顯示本發明一實施例之配向溶液之純化方法之 流程圖。第2圖顯示本發明一實施例之液晶顯示器之配向 溶液之純化裝置。參見第丨圖，首先，步驟S10為提供配 向廢液。例如，如第2圖所示，可將配向廢液由進料口 2〇2 加入至配向溶液純化裝置2〇〇的反應槽2〇4中。在一實施 例中，配向廢液可至少包含(3)聚亞醯胺或其前驅物、（…配 向溶劑、（c)添加劑及（d)水及金屬離子至少其一，其中 聚亞醯胺或其前驅物、(b)配向溶劑、⑷添加劑為配向溶液 原液（未經使用）+所含之成分，而（d)水或金屬離子為配 向廢液中欲除去之雜質。在一實施例中，聚亞醯胺或其前 驅物可由雙酐及雙胺反應形成，其可視液晶種類（例如tn Uwisted nematic )型態或 VA ( vertical alignmem )型態） 形成聚亞醯胺或聚醯胺酸。配向溶劑可包含N_甲基咯烷酮 jNMP)、乙、二醇單丁基醚（BCS)、Y_丁内酿（二或 别述之組合。在一實施例中，添加劑可視需要包含任意種 類之添加成分。例如，需防止帶電時，添加劑可包含二止 帶電劑；需提升基板黏著性時，添加劑可包含㈣轉合劑 或鈦系耦合劑；及需提升塗佈性時，添加劑可包含界面活 201223615 溶，能在上述溫度及壓力下可達到㈣點而—併蒸發 貝施例中，；減堡單元2〇8更與冷凝單元训連接 接著，參見第1圖，進行步驟S12，其係為加入共沸溶 劑至配向廢液中，並使共沸溶劑與配向溶液中的水一起共 沸而去除。例如，如第2圖所示，共沸溶劑係由進料口 2〇2 導入至反應槽204中，與配向廢液均勻混合。配向溶液純 化裝置200中的水分去除系統2〇6具有減壓單元2〇8及加 熱單元212，減壓單元208及加熱單元2]2可各自控制反 應槽204中的壓力及溫度，以使反應槽2G4中的配向廢液 中202的水及共彿溶劑能一起達到共沸點蒸發。共沸溶劑 可包含甲醇、乙醇、丙醇、異丙醇、正丁醇、異戊醇、二 嗔院三四氫。夫喃、丙_、乙晴、甲基異頂或前述之組合。 在貝施例中’共沸溶劑之加入量為配向廢液之約5至％ wt% ’較佳為10至2〇 wt%。在本實施例中，共沸去除水 及共沸溶劑的步驟可在壓力小於30 Torr，且溫度介於約 2〇C至50°C之下，較佳在溫度介於約30°C至40〇C之下進 Ϊ避^溫度過高而使配向廢液中的其他成分變質。值 付注思的疋’由於配向廢液中之配向溶劑沸點均遠高於 ^因而_以與水或制溶卿成共_，而水與共彿201223615 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method and apparatus for purifying a liquid crystal display alignment solution, and more particularly to a method and apparatus for purifying a highly efficient alignment solution. [Prior Art] The alignment film is a key material for controlling the quality of liquid crystal display. The alignment film is usually disposed on the inner side of the upper and lower electrode substrates of the liquid crystal display, and presents a zigzag groove for aligning the liquid crystal molecules along the groove to control the rotation angle of the liquid crystal in the electric field, so that the liquid crystal molecules can be effectively used. As a display switch. The alignment film is generally composed of a polyamidamine formed by the reaction of a bisamine and a dianhydride. Generally, the polyamidamine-containing alignment solution is first coated on the surface of the glass substrate, and after being oriented at a specific angle, the polyimide surface is coated. The molecules are aligned in a uniform direction by light or thermal polymerization to form an alignment film that controls the rotation angle of the liquid crystal. In addition to polyamine or its precursors, the alignment solution usually contains an alignment solvent and an additive, and the components of the additive vary depending on the needs. However, when the alignment solution is left for a long time or is exposed to the air, the metal ions in the water vapor and the air may enter the alignment solution, so that the water in the alignment solution and the total metal ion content are too high, resulting in formation. The alignment film has the disadvantages of uneven thickness, low voltage holding ratio (VHR) and high residual direct current (RDC). As a result, there may be a problem that the produced liquid crystal screen has a residual image. Furthermore, in the current liquid crystal panel factory, more than 70% of the excess alignment solution after use on the production line cannot be used continuously, and can only be discarded as waste liquid. .201223615 At present, there are several methods for purifying these overdose or used liquid crystal display alignment solutions (hereinafter referred to as alignment waste liquids), and recycling and purifying the hydrazine to waste liquid. For example, U.S. Patent No. M20,440 discloses a method of recovering an alignment material comprising: solidifying polymethyleneamine or its precursor with diethyl ether, filtering to separate from the organic solution, and then adding and using an alignment solution (hereinafter all The same organic solvent is dissolved in the original solution to obtain a recovered alignment material. In another method, Korean Patent No. 66749 also discloses a similar method, but the obtained organic filtrate can be steamed and the m method can remove the moisture in the recovery solution of the alignment material. However, the alignment solution will also be used. Ten additives originally contained in the filter are filtered off, and the metal content of the waste liquid towel can also be increased. Therefore, even if this (4) is re-applied to the production line, the quality and characteristics are still very different from the original liquid, so that the formed alignment film cannot achieve the original quality. Therefore, the present patent proposes a method and a device for aligning waste liquids of liquid crystal displays, which can remove moisture and waste in the waste liquid with high efficiency, and can obtain excellent purification efficiency. It also does not destroy the components and additives in the alignment. It can be used for the purification of various alignment solutions and the purification and reuse of waste liquids. SUMMARY OF THE INVENTION The present invention provides a method for purifying a solution, a package. & an orient solution or an alignment waste liquid, wherein the alignment solution or the azeotrope solvent contains less (4) polyamidamine. Or a precursor thereof, (8) an alignment solvent additive, and (d) at least one of water and metal ions; added to the 201223615 alignment waste liquid and simultaneously removed the alignment waste liquid by azeotropy (C〇_evap〇raU〇n) Water and the azeotropic solvent; and filtering the alignment waste liquid with a filter material to obtain a purified alignment solution, wherein the filter material comprises an adsorbent and a filter membrane, and the adsorbent comprises alumina of high purity or higher Citrate compound compound. The embodiment of the present invention also provides a purification device for the alignment solution, comprising: a reaction tank for accommodating an alignment waste liquid; and a moisture removal system comprising: a temperature control unit for controlling the temperature of the reaction tank; And a decompression unit for reducing the pressure of the reaction tank and removing water in the alignment waste liquid; and a metal ion removal system for receiving the alignment waste liquid from the moisture removal system, the metal ion removal system At least one adsorbent and a filter are disposed, wherein the filter is located at the bottom of the reaction tank, and the adsorbent is located above the filter. The above and other objects, features and advantages of the present invention will become more <RTIgt; Method for Purifying the Alignment Solution of Liquid Crystal Display This method comprises removing the water in the alignment solution by co-evaporation and removing the metal impurities in the alignment solution by using the coffin. This purification method can effectively remove moisture and metal ions in the alignment waste liquid without destroying the components of the alignment solution stock solution. At the same time, the poly(tetra)amine or its precursor, additive or other component in the alignment solution can be retained according to its original ratio, and the alignment film formed by the purified alignment solution is the same as the alignment solution originally purified by 201223615. The alignment film formed also has the same quality as the alignment film formed by the original alignment solution. Further, the present invention provides a purification apparatus for an alignment solution of a liquid crystal display, which comprises a reaction tank, a water removal system, and a metal ion removal system. In one embodiment, the purification apparatus can be used to provide a purification method for performing the alignment solution of the liquid crystal display described above. Fig. 1 is a flow chart showing a method of purifying an alignment solution according to an embodiment of the present invention. Fig. 2 is a view showing a purification apparatus for an alignment solution of a liquid crystal display according to an embodiment of the present invention. Referring to the figure, first, step S10 is to provide an alignment waste liquid. For example, as shown in Fig. 2, the alignment waste liquid can be added from the feed port 2〇2 to the reaction tank 2〇4 of the alignment solution purification unit 2〇〇. In one embodiment, the alignment waste liquid may comprise at least (3) polymethyleneamine or a precursor thereof, (... an alignment solvent, (c) an additive, and (d) at least one of water and metal ions, wherein the polyamidamine Or a precursor thereof, (b) an alignment solvent, (4) an additive is a component of a solution solution (not used) +, and (d) water or a metal ion is an impurity to be removed in the alignment waste liquid. In an embodiment The polymethyleneamine or its precursor may be formed by the reaction of a dianhydride and a bisamine, which may form a polyamidamine or a polyaminic acid depending on the liquid crystal species (for example, tn Uwisted nematic type or VA (vertical alignmem) type). . The aligning solvent may comprise N_methylrrolidone jNMP), B, diol monobutyl ether (BCS), Y_ butyl internal (two or a combination of the other. In one embodiment, the additive may optionally contain any Adding ingredients of the kind. For example, when the charging is to be prevented, the additive may include a second charging agent; when the adhesion of the substrate is to be improved, the additive may include (4) a coupling agent or a titanium coupling agent; and when the coating property is to be improved, the additive may include The interface activity 201223615 dissolves, can reach (4) point under the above temperature and pressure - and evaporate the shell example, and the minus unit 2〇8 is further connected with the condensation unit. Next, referring to Fig. 1, step S12 is performed. The azeotropic solvent is added to the alignment waste liquid, and the azeotropic solvent is removed by azeotropy with the water in the alignment solution. For example, as shown in Fig. 2, the azeotropic solvent is introduced from the feed port 2〇2. The reaction waste liquid is uniformly mixed with the alignment waste liquid. The moisture removal system 2〇6 in the alignment solution purification device 200 has a decompression unit 2〇8 and a heating unit 212, and the decompression unit 208 and the heating unit 2]2 can each be Controlling the pressure in the reaction tank 204 and Degree, so that the water in the alignment waste liquid in the reaction tank 2G4 and the solvent can reach the boiling point together. The azeotropic solvent may include methanol, ethanol, propanol, isopropanol, n-butanol, isoamyl alcohol. , 嗔 嗔 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三Preferably, it is 10 to 2% by weight. In this embodiment, the step of azeotropically removing water and the azeotropic solvent may be at a pressure of less than 30 Torr and a temperature of from about 2 ° C to 50 ° C, preferably. When the temperature is between about 30 ° C and 40 ° C, the temperature is too high and the other components in the ration waste liquid are deteriorated. The value of the 疋 思 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于Higher than ^ thus _ to be with the water or the dissolution of the _, while the water and the Buddha
減塵單元208甲。在_ 灸者，此冷凝單元210可直接設置於 實施例中，冷凝單元之溫度在約-；^^ 201223615 以下。在經共沸去除水及共沸溶劑之步驟後，配向廢液中 的3水里係小於約0_5wt% (相較於配向廢液總重），較佳 小於約0.4wt%。 接著，繼續進行步驟S14,其係以過濾材去除配向廢液 中的金屬離子或其他雜質。例如，如第2圖所示，金屬離 子去除系統214接收已除水之配向廢液，並以過遽材去除 配向廢液中的金屬離子及其他雜質。過遽材可包含吸附劑 216及濾膜218。在一實施例中，吸附劑216可為純度達約 • 99%以上之氧化銘或石夕酸銘，且較佳為純度達以上 之氧化鋁或矽酸鋁。氧化鋁可包含p相及γ相之氧化鋁， 且較佳為γ相。在另一實施例中，吸附劑216可包含二氧 化矽、氧化鎂、二氧化鈦，且純度達99%以上較佳。在一 貫知例中，及附劑216為粒控約6 〇〜2 5 0 μιη之顆粒，以具 有較大的表面積且能均勻分散在配向廢液中，重量百分比 與配向廢液相比較約為i至2〇%。在約5%的添加吸附時， 對配向廢液中的金屬離子有較佳的單位吸附效率。遽膜21 $ 係設置於整個反應槽204之底部，用以過濾和阻擋所有懸 洋顆粒（例如吸附劑216)和其他固體雜質。濾膜可由複 數層具有不同材料及孔徑大小的濾膜組成。例如，濾膜218 可包含孔徑約0.1〜0.5 mm之不鏽鋼板218a及複數層微孔 濾膜218b。不鏽鋼板218a位於濾膜218的最上層，以阻 擋分散於配向廢液中的吸附劑216，且可防止不鏽鋼板 218a底下的微孔遽膜218b受減壓單元208在反應槽204 中所造成的壓力差而脫落。微孔濾膜218b可由聚乙烯、聚 201223615 四氣乙稀、聚偏氟乙稀或前述之組合組成，且其 徑' 自為約0.2〜〇·8 μιη、約〇】〜〇5叫或〇〇5〜 二以過/慮或吸附尺寸較小的吸附劑或其他固體雜質。 ^實施例中’經金屬離子去除系統純化後之配向廢液中 3之總共的金屬離子含量係小於約卜較佳小於約 300 pPb，更佳小於約7〇ppb。 接著，繼續進行步驟㈣，其係為收集經上述步驟純化 之配向廢液。例如，如筮？阁 _ 如第2圖所不，經純化之配向廢液係 j卸料口 220流至收集槽222中。在一實施财，經純 乂之配向廢液之含水量小於約〇趣％，金屬離子小於約 ppb’且如添加劑等成分皆依原比例保留。例如，經純 1 匕後之配向廢液中的添加劑與聚亞醒胺或其前驅物之比例 ”原配向洛液大體上相同。因此，經上述純化回收得到之 1 己向溶液係可重新應用於生產線上，且所形成之配向膜亦 此保持與原液所形成之配向膜具有相同的品質及特性。 上 、此外，在一實施例中，更可視需要進行步驟S18，1係 為加入配向溶劑至經純化的配向溶液中’以補償在水分去 除系統中可能損失的配向溶劑。—般僅需加人約i wt %的 配向溶劑（相較於配向溶液總重），即可將經純化的配向 溶液中之各成分的濃度調整至均與原液相等。再者，配向 廢液在經純化後之回收率可達90%以上，較佳達95%以 上述之純化方法係可在不破壞配向溶液原液之成分的 條件下’同時去除配向廢液中的水和金屬離子。相較於傳 201223615 統方法需經固化、分離、真空乾燥等複雜步驟，本發明之 方法不僅所需時間較短，且成本亦較低。此外，以本發明 方法或裝置純化之配向溶液中的聚亞醯胺或其前驅物、添 加劑或其他成分將可依照其原比例保留下來，經純化後的 配向溶液所形成之配向膜成分與原液相同。因此，因久置 或與接觸空氣之配向廢液，皆可可經由本發明所提供之配 向廢液之純化方法或裝置純化及回收，大幅減少液晶面板 中之配向膜之製造成本，且配向膜之品質與特性皆與原液 • 所形成之配向膜相同。 【實施例1】 提供一配向廢液（用於VA type液晶）至如第2圖所 示之純化裝置中，其中反應槽底部設有孔徑〇 5 mm之不鏽 鋼板及孔徑0.1〜〇#m之多層的聚敦乙烯濾膜。配向廢 液包含6 wt%之聚亞醯胺、93 Wt%之配向溶劑及！ _%之 _ 矽烷耦合劑，固含量6.8 wt%，黏度22.3、含水量3.9 wt %、金屬離子含量515 ppb。加入約20 wt%之異丙醇（相 對於液晶配廢液）至反應槽中。接著，加熱反應槽之溫度 至約36 C，並以真空冷凝裝置去除配向廢液中的異丙醇及 水:接著，添加5 wt·% (相對於配向廢液）之純度99 9% ，氧化鋁至反應槽中。最後，配向廢液流經不鏽鋼板及聚 貺乙烯濾膜，通過卸料口至收集槽中，得到經純化之配向 溶液’其分析結果列於表1。 201223615 【實施例2】 同實施例1之步驟，但配向廢液（用於TN type液晶） 包含6 wt%之聚醯胺酸、93 wt%之配向溶劑及1 wt%之 添加劑，固含量6.0 wt%，黏度20、含水量3.84 wt%、 金屬離子含量93.1 ppb。此外，異丙醇之加入量由20 wt %降至1 Owt%。得到之經純化之配向溶液之分析結果列於 表2。 【實施例3】 _ 同實施例1之步驟，所用配向廢液與實施例2相同， 但以10wt%之丙酮取代10 wt%之異丙醇，得到之經純化之 配向溶液之含水量為0.29 wt%。除水效率較異丙醇佳提升 約25%效率，且其他性質與異丙醇萃取後大體相同。 【比較例】 依照美國專利No. 6,420,440之配向材料之回收方法進 行純化。提供如實施例2之配向廢液，添加乙醚至配向廢 鲁 液中，析出聚亞醯胺固體。接著，過濾除去剩餘的有機溶 液，且將固體真空乾燥。最後，添加與原液相同之有機溶 劑溶解該固體，得到經純化之配向溶液。 . 表1顯示為未使用過之配向溶液（原液，用於VA type 液晶）、未純化之配向廢液、純化後之配向溶液（實施例 1 )及配向溶液之商品化規格的比較。表2顯示為未使用過 12 201223615 之配向溶液（原液，用於TN type液晶）、未純化之配向 廢液、純化後之配向溶液（實施例2)及配向溶液之商品 化規格的比較。由表1、2可看出，純化後之配向溶液之含 水量及金屬離子含量顯然遠較純化前之配向廢液低，且甚 至降低至與配向溶液之原液大體上相同。並且，純化後之 配向溶液之其他性質，例如固含量及黏度皆與配向溶液之 原液大體上相同，並符合商品化規格。 鲁 表1 : 原液 純化前 純化後 商品化規格 固含量（wt%) 6,5 6.8 6.6 6.3±0.3 黏度（Cps) 20.7 22.3 20.5 19±4 含水量（wt%) 0.62 3.9 0.7 <1 總金屬離子含量（ppb) 255 515 231 <500 表2 : 原液 純化前 純化後 商品化規格 固含量（wt%) 5.9 6.0 6.1 6.0±0.3 黏度（Cps) 22.9 20 22 25+5 含水量（wt%) 0.34 3.84 0.36 <0.40 總金屬離子含量（ppb) 49.9 93.1 53.0 <500 201223615 第3 3 4圖各自顯示實施例1及2之純化後之配向溶 液之傅立綠外線光譜（FT_IR)圖及其與原液之比較。在 第3及4圖中’可看到實施例]及2之純化後之配向溶液 的所有吸收峰的位置及強度皆與原液大致相同。此外，在 1728 cm #位置無吸收峰出現’顯示沒有產生環化的亞醯 胺。因此，可知道的是’純化後之配向溶液不會環化變質， 且高分子成分的比例大體上相同。 、第5及6圖各自顯示實施例1及2之純化後之配向溶 液之凝勝渗透層析㈤㈣腿⑽咖嶋吨吻啦） 圖及其與原液之比較。第7圖顯示比較例（美國專利胤 6,420,440 )之純化後之配向材料之凝膠渗透層析 permeation chromat〇graphy，Gpc)圖及其與原液之比較。 j第5及6圖中，純化後之配向溶液與原液之停留時間大 體上皆相同，顯示經純化後之配向溶液之高分子成分皆與 原液大體上相同。在第5圖中，可看到在停留時間為約^ =童和16分鐘的地方各自有波峰，其各自為聚亞酿胺和石夕 燒LHfl號，可看出經純化後之配向溶液中的石夕 合劑相較於原液仍依原比例存在。在第6圖中，更 聚醯胺酸（約5分鐘時出現）與矽烷耦合劑（約7 =)為兩個明顯分隔.的波峰，且聚酿胺酸與錢輕合劑 比例大體上與原液相同。相較之下，在第7圖中，經純化 後之配向溶液中所含的梦絲合劑（約】7分鐘時出現 量顯然大幅減少，大量的我轉合劑在分離固化的二 胺時即已被濾除’因而依照比較例之純化方法無法依原比 201223615 例保留配向溶液中的矽烷耦合劑。 此外，表3顯示實施例1及2之配向溶液之回收率。 結果顯示回收率皆可達90%以上，具有極高的效率。 表3 : 配向溶液取樣量（g) 實際純化量（g) 回收率（％ ) 實施例1 432 395 91.4% 實施例2 2105 2009 95.1 % 由上述實驗可知，依本發明實施例之純化方法或純化 裝置所純化之配向溶液確實具有原液相同的成分及性質， 且如水及金屬離子等雜質亦已被去除。因此，能夠重新應 用於產線上，大幅減低液晶面板之製造成本。 雖然本發明已以數個較佳實施例揭露如上，然其並非 用以限定本發明，任何所屬技術領域中具有通常知識者， φ 在不脫離本發明之精神和範圍内，當可作任意之更動與潤 飾，因此本發明之保護範圍當視後附之申請專利範圍所界 定者為準。 15 201223615 【圖式簡單說明】 第1圖顯示本發明一實施例之配向溶液之純化方法之 流程圖。 第2圖顯示本發明一實施例之配向溶液之純化裝置。 第3及4圖各自顯示實施例1及2之純化後之配向溶 液之傅立葉紅外線光譜（FT-IR)圖及其與原液之比較。 第5及6圖各自顯示實施例1及2之純化後之配向溶 液之凝膠滲透層析圖及其與原液之比較。 第7圖顯示比較例之純化後之配向材料之凝膠滲透層 春 析圖及其與原液之比較。 【主要元件符號說明】 200〜配向溶液之純化裝置； 202〜進料口； 204〜反應槽； 206〜水分去除系統； 208〜減壓單元； 210〜冷凝單元； 212〜加熱單元； 214〜金屬離子去除系統；216〜吸附劑； 鲁 218〜濾膜； 218a〜不鏽鋼板； 218b〜微孔濾膜； 220〜卸料口； 222〜收集槽。 16Dust removal unit 208A. In the moxibustion, the condensing unit 210 can be directly disposed in the embodiment, and the temperature of the condensing unit is about -; ^^ 201223615 or less. After the step of azeotropically removing water and azeotropic solvent, the amount of 3 water in the ration waste liquid is less than about 0-5 wt% (compared to the total weight of the alignment waste liquid), preferably less than about 0.4 wt%. Next, proceeding to step S14, the metal ions or other impurities in the alignment waste liquid are removed by the filter material. For example, as shown in Fig. 2, the metal ion removal system 214 receives the dewatered alignment waste liquid and removes metal ions and other impurities from the alignment waste liquid with the excess material. The over-coffin may comprise adsorbent 216 and filter 218. In one embodiment, the adsorbent 216 may be oxidized or lyophilized with a purity of greater than about 99%, and is preferably alumina or aluminum silicate having a purity of greater than the above. The alumina may comprise alumina of the p phase and the gamma phase, and is preferably a gamma phase. In another embodiment, the adsorbent 216 may comprise cerium oxide, magnesium oxide, titanium dioxide, and preferably has a purity of 99% or more. In a well-known example, the auxiliary agent 216 is a particle controlled particle size of about 6 〇~2 5 0 μιη, which has a large surface area and can be uniformly dispersed in the alignment waste liquid, and the weight percentage is compared with the alignment waste liquid. i to 2〇%. At about 5% of the addition of adsorption, there is a preferred unit adsorption efficiency for the metal ions in the alignment waste liquid. The ruthenium film 21$ is disposed at the bottom of the entire reaction tank 204 to filter and block all of the suspended particles (e.g., adsorbent 216) and other solid impurities. The membrane may consist of a plurality of membranes having different materials and pore sizes. For example, the filter membrane 218 may comprise a stainless steel plate 218a having a pore size of about 0.1 to 0.5 mm and a plurality of microporous membranes 218b. The stainless steel plate 218a is located at the uppermost layer of the filter membrane 218 to block the adsorbent 216 dispersed in the alignment waste liquid, and prevents the microporous membrane 218b under the stainless steel plate 218a from being caused by the decompression unit 208 in the reaction tank 204. The pressure is poor and falls off. The microporous membrane 218b may be composed of polyethylene, poly 201223615 tetraethylene, polyvinylidene fluoride or a combination thereof, and the diameter 'from about 0.2 to 〇8 μιη, about 〇 〇 〇 叫 5 〇 or 〇 〇5~2 to pass/consider or adsorb small size adsorbents or other solid impurities. In the embodiment, the total metal ion content in the alignment waste liquid purified by the metal ion removal system is preferably less than about 300 pPb, more preferably less than about 7 ppb. Next, proceeding to step (4), which is to collect the directional waste liquid purified by the above steps. For example, what? Cabinet _ As shown in Fig. 2, the purified dispensing waste system j discharge port 220 flows into the collecting tank 222. In one implementation, the water content of the pure waste liquid is less than about 5%, the metal ion is less than about ppb', and the components such as additives are retained in the original proportion. For example, the ratio of the additive in the ration waste liquid after pure hydrazine to the polyamidamine or its precursor is substantially the same as that of the original solution. Therefore, the solution obtained by the above purification can be re-applied. In the production line, the formed alignment film also maintains the same quality and characteristics as the alignment film formed by the stock solution. In addition, in an embodiment, step S18 may be further performed as needed, and 1 is to add an alignment solvent. To the purified alignment solution to compensate for the loss of the alignment solvent that may be lost in the moisture removal system. Generally, only about 1/4% of the alignment solvent (compared to the total weight of the alignment solution) is added, and the purified The concentration of each component in the alignment solution is adjusted to be equal to the original liquid phase, etc. Further, the recovery rate of the alignment waste liquid after purification is up to 90% or more, preferably 95%, and the above purification method can be used without destroying the alignment. Under the condition of the composition of the solution stock solution, 'water and metal ions in the aligning waste liquid are simultaneously removed. Compared with the complicated method such as curing, separation, vacuum drying, etc., the method of the present invention Not only is the time required to be shorter, but the cost is also lower. In addition, the polymethyleneamine or its precursor, additive or other component in the alignment solution purified by the method or apparatus of the present invention may be retained according to its original ratio. The alignment film component formed by the purified alignment solution is the same as the original solution. Therefore, the waste liquid can be purified and recovered by the purification method or device of the alignment waste liquid provided by the present invention due to the long-term or the contact with the air. The manufacturing cost of the alignment film in the liquid crystal panel is reduced, and the quality and characteristics of the alignment film are the same as those of the original liquid film. [Example 1] An alignment waste liquid (for VA type liquid crystal) is provided to the second In the purification device shown in the figure, the bottom of the reaction tank is provided with a stainless steel plate having a pore diameter of mm5 mm and a polydene ethylene membrane having a pore size of 0.1 to 〇#m. The alignment waste liquid contains 6 wt% of polyamidamine, 93 Wt% of the alignment solvent and! _%_ decane coupling agent, solid content 6.8 wt%, viscosity 22.3, water content 3.9 wt%, metal ion content 515 ppb. Add about 20 wt% of isopropanol (relative to liquid crystal The waste liquid is transferred to the reaction tank. Then, the temperature of the reaction tank is heated to about 36 C, and the isopropanol and water in the alignment waste liquid are removed by a vacuum condensing device: then, 5 wt.% is added (relative to the alignment waste liquid) The purity of 99 9%, alumina into the reaction tank. Finally, the distribution waste liquid flows through the stainless steel plate and the polystyrene filter, and passes through the discharge port to the collection tank to obtain the purified alignment solution. Table 1. 201223615 [Example 2] The same procedure as in Example 1, except that the alignment waste liquid (for TN type liquid crystal) contains 6 wt% of polylysine, 93 wt% of an alignment solvent, and 1 wt% of an additive. The solid content is 6.0 wt%, the viscosity is 20, the water content is 3.84 wt%, and the metal ion content is 93.1 ppb. Further, the amount of isopropanol added was reduced from 20 wt% to 1 wt%. The analysis results of the obtained purified alignment solution are shown in Table 2. [Example 3] _ Same as the procedure of Example 1, the use of the ration waste liquid was the same as in Example 2, except that 10 wt% of isopropyl alcohol was replaced by 10 wt% of acetone, and the purified aligning solution had a water content of 0.29. Wt%. The water removal efficiency is about 25% higher than that of isopropanol, and the other properties are substantially the same as after isopropanol extraction. [Comparative Example] Purification was carried out in accordance with the recovery method of the alignment material of U.S. Patent No. 6,420,440. An alignment waste liquid as in Example 2 was supplied, and diethyl ether was added to the alignment waste liquid to precipitate a polyamidamine solid. Next, the remaining organic solution was removed by filtration, and the solid was dried under vacuum. Finally, the same solid solvent as the stock solution was added to dissolve the solid to obtain a purified alignment solution. Table 1 shows a comparison of the commercial specifications of the unused alignment solution (stock solution for VA type liquid crystal), unpurified alignment waste liquid, purified alignment solution (Example 1), and alignment solution. Table 2 shows a comparison of the commercial specifications of the alignment solution (stock solution for TN type liquid crystal), the unpurified alignment waste liquid, the purified alignment solution (Example 2), and the alignment solution which have not been used 12 201223615. As can be seen from Tables 1 and 2, the water content and metal ion content of the purified alignment solution were significantly lower than those of the alignment waste liquid before purification, and even decreased to substantially the same as the original solution of the alignment solution. Further, other properties of the purified alignment solution, such as solid content and viscosity, are substantially the same as those of the alignment solution, and are in compliance with commercial specifications. Lu Table 1: Commercial product solid content (wt%) after purification of raw liquid, 6,5 6.8 6.6 6.3±0.3 Viscosity (Cps) 20.7 22.3 20.5 19±4 Water content (wt%) 0.62 3.9 0.7 <1 Total metal Ion content (ppb) 255 515 231 <500 Table 2: Commercial product purified by pre-purification. Solid content (wt%) 5.9 6.0 6.1 6.0±0.3 Viscosity (Cps) 22.9 20 22 25+5 Moisture (wt%) 0.34 3.84 0.36 <0.40 Total metal ion content (ppb) 49.9 93.1 53.0 <500 201223615 The third figure shows the Fourier green outer spectrum (FT_IR) pattern of the purified alignment solutions of Examples 1 and 2, respectively. Comparison with the stock solution. In the third and fourth graphs, it can be seen that the positions and the intensities of all the absorption peaks of the purified alignment solution of Examples 2 and 2 are substantially the same as those of the original solution. In addition, the absence of an absorption peak at the 1728 cm # position showed that no cyclized hydrazine was produced. Therefore, it is known that the 'aligned solution after purification does not cyclize and the proportion of the polymer component is substantially the same. Figures 5 and 6 each show the osmotic permeation chromatography of the purified alignment solutions of Examples 1 and 2 (5) (4) Legs (10) Curry and the comparison with the stock solution. Figure 7 shows the gel permeation chromatography of the purified alignment material of the comparative example (U.S. Patent No. 6,420,440) permeation chromatography, Gpc) and its comparison with the stock solution. In Figures 5 and 6, the residence time of the purified alignment solution and the stock solution are substantially the same, indicating that the polymer component of the purified alignment solution is substantially the same as the stock solution. In Fig. 5, it can be seen that there are peaks in the place where the residence time is about ^=child and 16 minutes, and each of them is a poly-branched amine and a sulphur LHfl number, which can be seen in the purified alignment solution. The Shixi mixture is still present in proportion to the original solution. In Figure 6, more lysine (appearing at about 5 minutes) and decane couplant (about 7 =) are two distinctly separated peaks, and the ratio of poly-aracine to Qian light mixture is substantially the same as the stock solution. the same. In contrast, in Figure 7, the amount of the Mengsi mixture contained in the purified alignment solution (about 7 minutes) is obviously greatly reduced, and a large amount of my conversion agent is already separated from the solidified diamine. It was filtered out. Therefore, the purification method according to the comparative example could not retain the decane coupling agent in the alignment solution according to the original ratio of 201223615. In addition, Table 3 shows the recovery rates of the alignment solutions of Examples 1 and 2. The results showed that the recovery rates were all up to More than 90%, with extremely high efficiency. Table 3: Alignment solution sampling amount (g) Actual purification amount (g) Recovery rate (%) Example 1 432 395 91.4% Example 2 2105 2009 95.1 % As can be seen from the above experiment, The alignment solution purified by the purification method or the purification device according to the embodiment of the present invention does have the same composition and properties as the original solution, and impurities such as water and metal ions have also been removed. Therefore, it can be newly applied to the production line, and the liquid crystal panel is greatly reduced. The present invention has been disclosed above in several preferred embodiments, but it is not intended to limit the invention, and any one of ordinary skill in the art, φ The scope of protection of the present invention is defined by the scope of the appended claims. 15 201223615 [Simple description of the drawings] Figure 1 A flow chart showing a method for purifying an alignment solution according to an embodiment of the present invention. Fig. 2 is a view showing a purification apparatus for an alignment solution according to an embodiment of the present invention. Figs. 3 and 4 each show a purified alignment solution of Examples 1 and 2. The Fourier transform infrared spectroscopy (FT-IR) pattern and its comparison with the stock solution. Figures 5 and 6 each show the gel permeation chromatogram of the purified alignment solution of Examples 1 and 2 and comparison with the stock solution. Figure 7 shows the chromatographic layer of the purified alignment material of the comparative example and its comparison with the stock solution. [Main component symbol description] 200~ alignment solution purification device; 202~feed port; 204~ reaction tank 206~ moisture removal system; 208~ decompression unit; 210~condensation unit; 212~ heating unit; 214~ metal ion removal system; 216~ adsorbent; Lu 218~ filter; 218a~ stainless steel ; 218b ~ microporous membrane; 220 ~ discharge port; 222 ~ collection tank. 16