TWI398291B - Method and device for recycling liquid crystal alignment solution - Google Patents
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
- B01D3/36—Azeotropic distillation
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
- Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Description
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。The invention relates to a method and a device for purifying a liquid crystal display alignment solution, and in particular to a method and a device for purifying a high efficiency alignment solution.
配向膜為控制液晶顯示器顯示品質的關鍵材料。配向膜通常設置於液晶顯示器上下電極基板的內側，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醯胺組成，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。The alignment film is a key material for controlling the display quality of the 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.
除聚亞醯胺或其前驅物外，配向溶液內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70%以上無法繼續使用，而僅能當作廢液丟棄。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 the formed alignment film. There are disadvantages such as uneven film 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.
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，將此配向廢液回收純化再使用。例如，美國專利No. 6,420,440揭示了一種配向材料之回收方法，包含以***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餾再回收使用。以上方法雖可將配向材料之回收溶液中的水分去除，然而，亦會將配向溶液中原本就含有的添加劑給濾掉，且亦可能使廢液中的金屬離子含量增加。因此，就算將此回收得到之溶液重新應用於生產線上，其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。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 recovering and separating the alignment waste liquid. For example, U.S. Patent No. 6,420,440 discloses a method of recovering an alignment material comprising curing a polymethyleneamine or a precursor thereof with diethyl ether, filtering to separate from an organic solution, and then adding an unused alignment solution (hereinafter all The same organic solvent is dissolved in the original solution to obtain a recovered alignment material. In another method, a similar method is disclosed in Korean Patent No. 66749, but the obtained organic filtrate can be distilled and reused. Although the above method can remove the moisture in the recovery solution of the alignment material, the additive originally contained in the alignment solution is also filtered off, and the metal ion content in the waste liquid can also be increased. Therefore, even if the recovered solution is reapplied to the production line, its quality and characteristics are still greatly different from the original liquid, so that the formed alignment film cannot reach the original quality.
因此，本專利所提出的是一種液晶顯示器之配向廢液之純化方法與裝置，其能以高效率去除廢液中的水分及金屬離子，除可得到極佳的純化效率外，也不會破壞配向溶液中成分與添加劑，可用於各種配向溶液的純化與廢液的純化再利用。Therefore, the present patent proposes a method and a device for purifying an alignment waste liquid of a liquid crystal display, which can remove water and metal ions in the waste liquid with high efficiency, and can not obtain excellent purification efficiency and will not be destroyed. The components and additives in the solution can be used for the purification of various alignment solutions and the purification and reuse of waste liquids.
本發明之實施例係提供一種配向溶液之純化方法，包括：提供一配向溶液或配向廢液，其中此配向溶液或配向廢液至少包含(a)聚亞醯胺或其前驅物、(b)配向溶劑、(c)添加劑及(d)水及金屬離子至少其一；加入一共沸溶劑至此配向廢液中，並以共沸(co-evaporation)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鋁化合物化合物。An embodiment of the present invention provides a method for purifying an alignment solution, comprising: providing an alignment solution or an alignment waste liquid, wherein the alignment solution or alignment waste liquid comprises at least (a) polymethyleneamine or a precursor thereof, (b) Aligning solvent, (c) additive and (d) at least one of water and metal ions; adding an azeotropic solvent to the alignment waste liquid, and simultaneously removing the water in the alignment waste liquid by co-evaporation and the total a boiling 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 a high purity or higher alumina or aluminum niobate compound Compound.
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。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.
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：The above and other objects, features and advantages of the present invention will become more <RTIgt;
本發明係提供一種液晶顯示器之配向溶液之純化方法，此方法包含以共沸(co-evaporation)去除配向溶液中的水，及以過濾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本被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。The present invention provides a method for purifying an alignment solution of a liquid crystal display, which comprises removing water in an alignment solution by co-evaporation, and removing metal impurities in the alignment solution by a filter material. The 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 polymethyleneamine 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 originally purified alignment solution. The alignment film formed also has the same quality as the alignment film formed by the original alignment solution. In addition, the present invention also provides a purification device for an alignment solution of a liquid crystal display, which comprises a reaction tank, a moisture 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.
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1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202加入至配向溶液純化裝置200的反應槽204中。在一實施例中，配向廢液可至少包含(a)聚亞醯胺或其前驅物、(b)配向溶劑、(c)添加劑及(d)水及金屬離子至少其一，其中(a)聚亞醯胺或其前驅物、(b)配向溶劑、(c)添加劑為配向溶液原液(未經使用)中所含之成分，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(twisted nematic)型態或VA(vertical alignment)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(NMP)、乙二醇單丁基醚(BCS)、γ-丁內酯(γ-BL)或前述之組合。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，添加劑可包含防止帶電劑；需提升基板黏著性時，添加劑可包含矽烷耦合劑或鈦系耦合劑；及需提升塗佈性時，添加劑可包含界面活性劑。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 Fig. 1, first, step S10 is to provide an alignment waste liquid. For example, as shown in FIG. 2, the alignment waste liquid may be fed from the feed port 202 to the reaction tank 204 of the alignment solution purification apparatus 200. In one embodiment, the alignment waste liquid may include at least one of (a) polymethyleneamine or a precursor thereof, (b) an alignment solvent, (c) an additive, and (d) water and a metal ion, wherein (a) Polyimide or a precursor thereof, (b) an alignment solvent, (c) an additive is a component contained in a solution solution solution (not used), and (d) water or a metal ion is an alignment waste liquid to be removed. Impurities. In one embodiment, the polymethyleneamine or its precursor may be formed by the reaction of a dianhydride and a bisamine, which may form a polyamidene depending on the liquid crystal species (eg, TN (twisted nematic) type or VA (vertical alignment) type). Or poly-proline. The alignment solvent may comprise N-methylrrolidone (NMP), ethylene glycol monobutyl ether (BCS), γ-butyrolactone (γ-BL) or a combination of the foregoing. In one embodiment, the additive may optionally comprise any of a variety of additional ingredients. For example, when it is desired to prevent charging, the additive may include an antistatic agent; when the substrate adhesion is required, the additive may include a decane coupling agent or a titanium coupling agent; and when the coating property is to be improved, the additive may include a surfactant.
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202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206具有減壓單元208及加熱單元212，減壓單元208及加熱單元212可各自控制反應槽204中的壓力及溫度，以使反應槽204中的配向廢液中202的水及共沸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、二噁烷、四氫呋喃、丙酮、乙晴、甲基異丁酮或前述之組合。在一實施例中，共沸溶劑之加入量為配向廢液之約5至50 wt%，較佳為10至20 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20℃至50℃之下，較佳在溫度介於約30℃至40℃之下進行，以避免溫度過高而使配向廢液中的其他成分變質。值得注意的是，由於配向廢液中之配向溶劑沸點均遠高於水，因而較難以與水或共沸溶劑形成共沸物，而水與共沸溶劑能在上述溫度及壓力下可達到共沸點而一併蒸發。在一實施例中，減壓單元208更與一冷凝單元210連接，以在提供反應槽減壓時，同時凝結共沸蒸發的水及共沸溶劑於此冷凝單元210中，以避免蒸發的水及共沸溶劑再度凝結回到配向廢液中。或者，此冷凝單元210可直接設置於減壓單元208中。在一實施例中，冷凝單元之溫度在約-10℃以下。在經共沸去除水及共沸溶劑之步驟後，配向廢液中的含水量係小於約0.5wt%(相較於配向廢液總重)，較佳小於約0.4wt%。Next, referring to Fig. 1, step S12 is carried out by adding an azeotropic solvent to the alignment waste liquid, and azeotropic solvent is removed by azeotropy together with water in the alignment solution. For example, as shown in Fig. 2, the azeotropic solvent is introduced into the reaction tank 204 from the feed port 202, and is uniformly mixed with the alignment waste liquid. The moisture removal system 206 in the alignment solution purification device 200 has a decompression unit 208 and a heating unit 212, and the decompression unit 208 and the heating unit 212 can each control the pressure and temperature in the reaction tank 204 to make the alignment waste in the reaction tank 204 The water in the liquid 202 and the azeotropic solvent can together reach the azeotropic evaporation. The azeotropic solvent may comprise methanol, ethanol, propanol, isopropanol, n-butanol, isoamyl alcohol, dioxane, tetrahydrofuran, acetone, acetonitrile, methyl isobutyl ketone or a combination of the foregoing. In one embodiment, the azeotropic solvent is added in an amount of from about 5 to 50% by weight, preferably from 10 to 20% by weight, based on the amount of the effluent. 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 between about 20 ° C and 50 ° C, preferably at a temperature of between about 30 ° C and 40 ° C. Perform to avoid excessive temperature and deteriorate other components in the alignment waste liquid. It is worth noting that since the boiling point of the alignment solvent in the alignment waste liquid is much higher than that of water, it is difficult to form an azeotrope with water or an azeotropic solvent, and the water and the azeotropic solvent can reach a total of the above temperature and pressure. The boiling point is evaporated together. In an embodiment, the decompression unit 208 is further connected to a condensing unit 210 to simultaneously condense azeotropically evaporated water and azeotropic solvent in the condensing unit 210 to provide evaporated water when the reaction vessel is decompressed. And the azeotropic solvent is again condensed back into the ration waste liquid. Alternatively, the condensing unit 210 may be disposed directly in the decompression unit 208. In one embodiment, the temperature of the condensing unit is below about -10 °C. After the step of azeotropically removing water and azeotropic solvent, the water content in the alignment waste liquid is less than about 0.5% by weight (compared to the total weight of the alignment waste liquid), preferably less than about 0.4% by weight.
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，並以過濾材去除配向廢液中的金屬離子及其他雜質。過濾材可包含吸附劑216及濾膜218。在一實施例中，吸附劑216可為純度達約99%以上之氧化鋁或矽酸鋁，且較佳為純度達99.5%以上之氧化鋁或矽酸鋁。氧化鋁可包含β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。在一實施例中，吸附劑216為粒徑約60～250 μm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1至20%。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。濾膜218係設置於整個反應槽204之底部，用以過濾和阻擋所有懸浮顆粒(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底下的微孔濾膜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、聚丙烯、聚四氟乙烯、聚偏氟乙烯或前述之組合組成，且其孔徑可各自為約0.2～0.8 μm、約0.1～0.5μm或0.05～0.3μm，以過濾或吸附尺寸較小的吸附劑或其他固體雜質。在本實施例中，經金屬離子去除系統純化後之配向廢液中所含之總共的金屬離子含量係小於約500 ppb，較佳小於約300 ppb，更佳小於約70 ppb。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 degreased waste liquid that has been dehydrated, and removes metal ions and other impurities in the alignment waste liquid with the filter material. The filter material can include an adsorbent 216 and a filter membrane 218. In one embodiment, the adsorbent 216 can be alumina or aluminum niobate having a purity of greater than about 99%, and preferably alumina or aluminum niobate having a purity of greater than 99.5%. The alumina may comprise alumina of the beta 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 one embodiment, the adsorbent 216 is a particle having a particle diameter of about 60 to 250 μm to have a large surface area and can be uniformly dispersed in the alignment waste liquid, and the weight percentage is about 1 to 20% compared with the aligned waste liquid phase. . At about 5% of the addition of adsorption, there is a preferred unit adsorption efficiency for the metal ions in the alignment waste liquid. A membrane 218 is disposed at the bottom of the entire reaction vessel 204 to filter and block all suspended particulates (e.g., adsorbent 216) and other solid impurities. The filter membrane can be composed of a plurality of membranes having different materials and pore sizes. For example, filter membrane 218 can comprise a stainless steel plate 218a having a pore size of about 0.1 to 0.5 mm and a plurality of microporous filter 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 filter membrane 218b under the stainless steel plate 218a from being affected 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, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride or a combination thereof, and may have a pore diameter of about 0.2 to 0.8 μm, about 0.1 to 0.5 μm or 0.05 to 0.3 μm, respectively. To filter or adsorb small size adsorbents or other solid impurities. In this embodiment, the total metal ion content contained in the alignment waste liquid purified by the metal ion removal system is less than about 500 ppb, preferably less than about 300 ppb, more preferably less than about 70 ppb.
接著，繼續進行步驟S16，其係為收集經上述步驟純化之配向廢液。例如，如第2圖所示，經純化之配向廢液係經由卸料口220流至收集槽222中。在一實施例中，經純化後之配向廢液之含水量小於約0.4wt%，金屬離子小於約500 ppb，且如添加劑等成分皆依原比例保留。例如，經純化後之配向廢液中的添加劑與聚亞醯胺或其前驅物之比例與原配向溶液大體上相同。因此，經上述純化回收得到之配向溶液係可重新應用於生產線上，且所形成之配向膜亦能保持與原液所形成之配向膜具有相同的品質及特性。Next, step S16 is continued to collect the alignment waste liquid purified by the above steps. For example, as shown in FIG. 2, the purified alignment waste liquid flows into the collection tank 222 through the discharge port 220. In one embodiment, the purified alignment waste liquid has a water content of less than about 0.4% by weight, a metal ion of less than about 500 ppb, and a component such as an additive remains in the original proportion. For example, the ratio of the additive in the purified alignment waste liquid to the polyamidamine or its precursor is substantially the same as the original alignment solution. Therefore, the alignment solution obtained by the above purification can be reused on the production line, and the formed alignment film can maintain the same quality and characteristics as the alignment film formed by the original solution.
此外，在一實施例中，更可視需要進行步驟S18，其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。一般僅需加入約1 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。Further, in an embodiment, step S18 may be performed as needed to add an alignment solvent to the purified alignment solution to compensate for the loss of alignment solvent that may be lost in the moisture removal system. Generally, it is only necessary to add about 1 wt% of the alignment solvent (compared to the total weight of the alignment solution), and the concentration of each component in the purified alignment solution can be adjusted to be equal to the original liquid phase and the like. Furthermore, the recovery rate of the alignment waste liquid after purification is more than 90%, preferably more than 95%.
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。The above purification method can simultaneously remove water and metal ions in the alignment waste liquid without destroying the components of the alignment solution stock solution. Compared with the conventional method, which requires complicated steps such as curing, separation, vacuum drying, etc., the method of the invention not only requires less time but also has lower cost. 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, and the alignment film component and stock solution formed by the purified alignment solution the same. Therefore, the separation liquid or the contact waste liquid can be purified and recovered by the purification method or device for providing the alignment waste liquid provided by the present invention, thereby greatly reducing the manufacturing cost of the alignment film in the liquid crystal panel, and the alignment film is The quality and characteristics are the same as those of the alignment film formed by the stock solution.
【實施例1】[Example 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0.5 mm之不鏽鋼板及孔徑0.1～0.8μm之多層的聚氟乙烯濾膜。配向廢液包含6 wt%之聚亞醯胺、93 wt%之配向溶劑及1 wt%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℃，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%之氧化鋁至反應槽中。最後，配向廢液流經不鏽鋼板及聚氟乙烯濾膜，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。Providing an alignment waste liquid (for VA type liquid crystal) to the purification device as shown in Fig. 2, wherein the bottom of the reaction tank is provided with a stainless steel plate having a pore diameter of 0.5 mm and a polyvinyl fluoride filter having a pore diameter of 0.1 to 0.8 μm. . The alignment waste liquid contains 6 wt% polyamidamine, 93 wt% of the alignment solvent and 1 wt% of decane coupling agent, the solid content is 6.8 wt%, the viscosity is 22.3, the water content is 3.9 wt%, and the metal ion content is 515 ppb. About 20% by weight of isopropanol (relative to the liquid crystal waste liquid) was added to the reaction tank. Next, the temperature of the reaction vessel was heated to about 36 ° C, and the isopropanol and water in the alignment waste liquid were removed by a vacuum condenser. Next, 5 wt% (relative to the alignment waste liquid) of 99.9% purity alumina was added to the reaction tank. Finally, the alignment waste liquid flows through the stainless steel plate and the polyvinyl fluoride filter, and passes through the discharge port to the collection tank to obtain a purified alignment solution. The analysis results are shown in Table 1.
【實施例2】[Example 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10wt%。得到之經純化之配向溶液之分析結果列於表2。The same as the procedure of Example 1, but the alignment waste liquid (for TN type liquid crystal) comprises 6 wt% of polyamic acid, 93 wt% of an alignment solvent and 1 wt% of an additive, a solid content of 6.0 wt%, a viscosity of 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 10 wt%. The analysis results of the obtained purified alignment solution are shown in Table 2.
【實施例3】[Example 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。In the same manner as in Example 1, the alignment waste liquid used was the same as in Example 2 except that 10 wt% of isopropanol was replaced with 10 wt% of acetone to obtain a water content of the purified alignment solution 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.
【比較例】[Comparative example]
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***至配向廢液中，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。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 solid is dissolved in the same organic solvent as the stock solution to obtain a purified alignment solution.
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。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 unused alignment solution (stock solution for TN type liquid crystal), unpurified alignment waste liquid, purified alignment solution (Example 2), and alignment solution. It can be seen from Tables 1 and 2 that the water content and metal ion content of the purified alignment solution are obviously lower than those of the alignment waste liquid before purification, and even reduced to substantially the same as the original solution of the alignment solution. Moreover, 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.
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。在第3及4圖中，可看到實施例1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-1 的位置無吸收峰出現，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。Figures 3 and 4 each show the Fourier infrared spectroscopy (FT-IR) pattern of the purified alignment solution of Examples 1 and 2 and comparison with the stock solution. In Figures 3 and 4, it can be seen that the positions and intensities of all the absorption peaks of the purified alignment solutions of Examples 1 and 2 are substantially the same as those of the original solution. In addition, no absorption peak appeared at the position of 1728 cm -1 , indicating that no cyclized sulfonamide was produced. Therefore, it is known that the purified alignment solution does not undergo cyclization deterioration, and the ratio of the polymer components is substantially the same.
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(gel permeation chromatography，GPC)圖及其與原液之比較。第7圖顯示比較例(美國專利No. 6,420,440)之純化後之配向材料之凝膠滲透層析(gel permeation chromatography，GPC)圖及其與原液之比較。在第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14分鐘和16分鐘的地方各自有波峰，其各自為聚亞醯胺和矽烷耦合劑的訊號，可看出經純化後之配向溶液中的矽烷耦合劑相較於原液仍依原比例存在。在第6圖中，更可看出聚醯胺酸(約5分鐘時出現)與矽烷耦合劑(約7分鐘時出現)為兩個明顯分隔的波峰，且聚醯胺酸與矽烷耦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矽烷耦合劑(約17分鐘時出現)含量顯然大幅減少，大量的矽烷耦合劑在分離固化的聚亞醯胺時即已被濾除，因而依照比較例之純化方法無法依原比例保留配向溶液中的矽烷耦合劑。Figures 5 and 6 each show a gel permeation chromatography (GPC) pattern of the purified alignment solutions of Examples 1 and 2 and comparison with the stock solution. Fig. 7 is a view showing a gel permeation chromatography (GPC) pattern of a purified alignment material of a comparative example (U.S. Patent No. 6,420,440) and comparison with a stock solution. In Figures 5 and 6, the retention 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 Figure 5, it can be seen that there are peaks in the residence time of about 14 minutes and 16 minutes, each of which is a signal of polyamine and decane coupling agent, which can be seen in the purified alignment solution. The decane coupling agent is still present in the original ratio compared to the original solution. In Figure 6, it can be seen that polylysine (appearing at about 5 minutes) and decane coupling agent (appearing at about 7 minutes) are two distinctly separated peaks, and the ratio of poly-proline to decane coupling agent It is basically the same as the stock solution. In contrast, in Figure 7, the content of the decane coupling agent (appearing at about 17 minutes) contained in the purified alignment solution is significantly reduced, and a large amount of decane coupling agent is used to separate the cured polyamine. That is, it has been filtered out, and thus the decane coupling agent in the alignment solution cannot be retained in the original ratio according to the purification method of the comparative example.
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。Further, Table 3 shows the recoveries of the alignment solutions of Examples 1 and 2. The results show that the recovery rate can reach more than 90%, which has extremely high efficiency.
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。It can be seen from the above experiments that the alignment solution purified by the purification method or the purification apparatus of 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 reapplied to the production line, and the manufacturing cost of the liquid crystal panel is drastically reduced.
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，在不脫離本發明之精神和範圍內，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。While the invention has been described above in terms of several preferred embodiments, it is not intended to limit the scope of the present invention, and any one of ordinary skill in the art can make any changes without departing from the spirit and scope of the invention. And the scope of the present invention is defined by the scope of the appended claims.
200．．．配向溶液之純化裝置200. . . Purification device for alignment solution
202．．．進料口202. . . Inlet
204．．．反應槽204. . . Reaction tank
206．．．水分去除系統206. . . Moisture removal system
208．．．減壓單元208. . . Decompression unit
210．．．冷凝單元210. . . Condensing unit
212．．．加熱單元212. . . Heating unit
214．．．金屬離子去除系統214. . . Metal ion removal system
216．．．吸附劑216. . . Adsorbent
218．．．濾膜218. . . Filter
218a．．．不鏽鋼板218a. . . Stainless steel plate
218b．．．微孔濾膜218b. . . Microporous membrane
220．．．卸料口220. . . Discharge port
222．．．收集槽222. . . Collection tank
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。Fig. 1 is a flow chart showing a method of purifying an alignment solution according to an embodiment of the present invention.
第2圖顯示本發明一實施例之配向溶液之純化裝置。Fig. 2 shows a purification apparatus for an alignment solution according to an embodiment of the present invention.
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。Figures 3 and 4 each show the Fourier infrared spectroscopy (FT-IR) pattern of the purified alignment solution of Examples 1 and 2 and comparison with the stock solution.
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。Figures 5 and 6 each show gel permeation chromatograms of the purified alignment solutions of Examples 1 and 2 and their comparison with the stock solution.
第7圖顯示比較例之純化後之配向材料之凝膠滲透層析圖及其與原液之比較。Figure 7 is a graph showing the gel permeation chromatogram of the purified alignment material of the comparative example and its comparison with the stock solution.
200．．．配向溶液之純化裝置200. . . Purification device for alignment solution
202．．．進料口202. . . Inlet
204．．．反應槽204. . . Reaction tank
206．．．水分去除系統206. . . Moisture removal system
208．．．減壓單元208. . . Decompression unit
210．．．冷凝單元210. . . Condensing unit
212．．．加熱單元212. . . Heating unit
214．．．金屬離子去除系統214. . . Metal ion removal system
216．．．吸附劑216. . . Adsorbent
218．．．濾膜218. . . Filter
218a．．．不鏽鋼板218a. . . Stainless steel plate
218b．．．微孔濾膜218b. . . Microporous membrane
220．．．卸料口220. . . Discharge port
222．．．收集槽222. . . Collection tank
Claims (16)
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| CN201010621762.5A CN102559204B (en) | 2010-12-13 | 2010-12-24 | Method and apparatus for purifying alignment solution |
| KR20110039899A KR101350360B1 (en) | 2010-12-13 | 2011-04-28 | Method and device for recycling liquid crystal alignment solution |
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