200904760 九、發明說明 【發明所屬之技術領域】 本發明係有關使來自製造偏光薄膜時產生廢液之原料 之碘與硼進行循環使用之偏光薄膜製造藥液之循環使用方 法及系統。 【先前技術】 用於液晶顯示器等之偏光薄膜例如一般吸附碘予以定 向之聚乙烯醇系薄膜（PVA薄膜）爲人所知。此偏光薄膜中 ，碘系偏光薄膜通常係將吸附碘予以定向之PVA薄膜於 含硼酸之水溶液中進行浸漬處理來製造。此製造步驟產生 含碘離子、硼酸、鉀離子及水溶性有機物等之廢液。這種 製造廢液通常係藉由凝聚法、吸附法、離子交換法及過濾 法等’含於其中所含之特定成份以廢水基準規定値以下後 ’以工業廢水排出，或藉由濃縮縮減容量後，以產業廢棄 物處理。 惟’近年來廢水基準更爲嚴格，凝聚法、吸附法、離 子交換法及過濾法等以往之處理方法中，不易使廢水中硼 濃度處理至基準値以下。又，產業廢棄物由處理成本及環 境問題等方面而言，被期待減少排出量。 另外，只要可由這些廢水有效回收硼及碘，作爲製造 偏光薄膜時之原料’循環再利用時，可減低產業廢棄物， 同時亦可試圖降低原料成本。 一般’由廢水回收碘及硼，循環再利用時，此等製造 -5- 200904760 廢液務必進行濃縮分離。 先行技術中所揭示之偏光板製造廢液之處理方法（如 :專利文獻1)係經由偏光板製造步驟所排出之廢液進行 電透析’分離成爲主要含有有機物成份之脫鹽液與主要含 有無機物成份之濃縮液。 但是不僅單純處理這種偏光板製造廢液，而且可以此 作爲原料循環使用時，可減少原料成本及廢液成本，同時 因產業廢棄物減少，可構築考量環境之製造系統。 惟’前述之先行技術’終究以廢液處理爲主，完全未 檢討分離回收後之碘及硼以高效率循環使用的技術及循環 使用時之詳細條件。 [專利文獻1]特開2001-314864號公報 【發明內容】 本發明鑑於上述問題而提案者，提供一種使來自製造 偏光薄膜時產生廢液之製造藥液，可以高效率進行循環使 用’偏光薄膜製造藥液之循環使用方法及系統爲其目的。 本發明所適用之偏光薄膜製造藥液之循環使用系統爲 解決上述課題’其特徵係具備爲使來自製造偏光薄膜用之 PV A(聚乙烯醇）薄膜浸漬於含有碘及碘化鉀之染色用溶液 染色浴中之廢液進行貯存之廢液貯存槽、與使該廢液貯存 槽所貯存之廢液pH調整爲未達7，之後藉由電滲析法將 該廢液中之碘成份進行分離’作成碘化鉀濃縮液之電滲析 裝置’與於來自該電滲析裝置之該碘化鉀濃縮液中，追加 -6- 200904760 新的碘成份藉由混合調整該染色溶液後’將此供應於該染 色浴中之再循環處理部份。 本發明係具有爲使來自製造偏光薄膜用之PV A(聚乙 烯醇）薄膜浸漬於含有碘及碘化鉀之染色用溶液染色浴中 之廢液調整成pH7以下之pH調整步驟，與經由電滲析法 使該廢液中之碘進行分離，作成碘化鉀濃縮液之分離步驟 ，與於該碘化鉀濃縮液中藉由追加新的碘混合後’調整該 染色用溶液，將此供應於該染色浴之再循環步驟，因此， 使碘化鉀濃縮液與碘混合後，作成染色用溶液調整後，再 次供應於染色浴等，可構築所謂再循環系統。爲此，除降 低產業廢棄物，同時亦可意圖降低原料成本。 【實施方式】 [發明實施之最佳形態] 以下，有關爲了實施本發明之最佳形態，參考添附圖 面後，進行詳細說明。 圖1係代表適用於本發明之偏光薄膜製造藥液之循環 使用系統1之構成。該偏光薄膜製造藥液之循環使用系統 1係針對爲使製造偏光薄膜2用之PVA(聚乙烯醇）薄膜2 進行浸漬之染色浴Π，與爲使浸漬於染色浴1 1後之PV A 薄膜2 a進行浸漬之交聯浴1 2，與爲洗淨浸漬於交聯浴1 2 之PV A 2b之洗淨浴1 3所成之製造線20進行配設。該循 環使用系統1係具備爲使來自染色浴1 1，交聯浴1 2，洗 淨浴之廢液暫時貯存之廢液貯存槽1 4，與來自此廢液貯 200904760 存槽1 4之廢液所供應之活性碳槽1 5，以及通過該活性碳 槽15之廢液所供應之電滲析裝置16，與來自該電緣析裝 置16之脫鹽液所供應之電滲析裝置17。 PVA薄膜2係使聚乙烯醇、乙烯-乙酸乙烯酯共聚物 皂化物，或含少量其他之共聚成份之此等樹脂經製膜所得 之薄膜。作爲其他之聚合物成份者，亦可適用如：不飽和 羧酸，烯烴，不飽和磺酸等。 PVA樹脂之聚合度通常爲1〇〇〇〜10000，較佳者爲 1 5 00〜5000 ° PVA樹脂之皂化度通常約爲85〜100莫耳％，較佳者 約爲9 8〜1 0 0莫耳％。 此PVA薄膜2任意PVA樹脂之製膜方法均可適用。 該偏光薄膜2之膜厚並未特別限定，一般如：約爲 3 0 μπι〜1 5 0 μπι 0 該PVA薄膜係於水中充分膨潤後，於染色浴1 1內進 行染色。 染色浴11係置入含有碘及碘化鉀之染色用溶液。染 色用溶液之組成如：其水：碘：碘化鉀之重量比爲10 0 : 0.01〜0.5 : 0.1~10。於該重量組成所成之染色用溶液中， 經由浸漬PV A薄膜2後’可作成使碘吸附於表面之PV A 薄膜2a。該染色浴11中之溫度通常爲20〜50 °C者宜。 交聯浴〗2係置入含有硼酸與碘化鉀之交聯用溶液。 交聯用溶液之組成係如：其水：硼酸：碘化鉀之重量比爲 1 0 0 : 1 . 0〜7.0 : 1.0〜8 . 〇。於該重量組成所成之交聯用溶液 -8- 200904760 中，經由浸漬PVA薄膜2後’於PVA薄膜2a之表面使 碘的聚合物被交聯後可作成穩定化的P V A薄膜2 b。亦即 ，該交聯浴1 2之溫度爲4 0 °C以上者宜，更佳者爲5 0 °C 〜8 5 °C。又，該交聯用溶液之PVA薄膜2之浸漬時間並未 特別限定，一般爲1〇〜1 200秒，較佳者爲30〜600秒。 洗淨浴1 3係以洗淨水塡滿之。使來自交聯浴12之 PVA薄膜2b浸漬於該洗淨浴13，可去除附著於其表面之 雜質等。之後經過乾燥步驟後，由P V A薄膜2製造偏光 薄膜。 浸漬於此等染色浴1 1〜洗淨浴13之過程中，該pV A 薄膜2被延伸。對於未延伸PVA薄膜2之初期長度之延 伸PVA薄膜2之最後長度之比率通常爲3倍〜7倍，較佳 者爲4~6倍。 又，爲了取得偏光薄膜之步驟可利用寬滾輥，導布器 等適當的裝置，往該延伸方向呈交叉之方向進行延伸處理 〇 又’由上述PVA薄膜2取得偏光薄膜爲止之製造步 驟並未受限於上述之形態，亦可適用任意之其他方法。 又，亦可將保護薄膜貼附於如上述取得之偏光薄膜之 單面或雙面。其中’保護薄膜係以提昇偏光薄膜之耐水性 '使用性等爲目的所附加者，其形成中可使用適當的透明 物質。特別是，透明性 '機械強度、熱穩定性、水份遮蔽 性等均良好之塑膠等爲理想使用者。亦即，作爲其一例者 如··聚酯系樹脂、乙酸酯系樹脂、聚醚颯系樹脂、聚碳酸 -9- 200904760 酯系樹脂、聚醯胺系樹脂、聚醯亞胺系樹脂、聚烯烴系樹 脂' 及丙烯系樹脂、等熱塑性樹脂、丙烯系、胺基甲酸乙 酯系丙烯胺基甲酸乙酯系、環氧系及聚矽氧系等之熱硬化 性樹脂或紫外線硬化性樹脂等例，較佳之保護薄膜如：乙 醯纖維素（TAC)等例，作爲聚烯烴系樹脂者如：非晶性聚 稀烴系樹脂中具有原菠烯、或多環狀原菠烯系單體類之環 狀聚烯烴之聚合單元之樹脂例。又，用於保護層之透明保 護薄膜在不損及本發明目的下，亦可以硬塗層處理，抗反 射處理’抗黏結、擴散至抗光等爲目的進行處理等。 偏光薄膜與保護薄膜之黏合處理更無特別限定，一般 如：藉由乙烯醇系聚合物所成之黏著劑、或硼酸、硼砂、 戊一醒、蜜g女、早酸等之乙嫌醇系聚合物之水溶性交聯劑 所成之黏合劑、透明性良好環氧系、聚醋系、乙酸乙烯酯 等之溶劑型黏著劑’或丙烯系聚合樹脂、胺基甲酸乙酯樹 脂等之聚合反應硬化後介由取得之黏合性樹脂等進行之。 亦即’來自此#各浴11〜13之廢液收集於分別之浴中 ’或於聚集之廢液貯存槽14中。亦可配設爲了濃縮取集 於此廢液貯存槽1 4之廢液的設備。 來自此廢液貯存槽1 4之廢水係於p Η調整步驟2 1中 ，調整爲pH未達7。更藉由通過活性碳槽15，去除水溶 性有機化合物（Τ Ο C)。之後’將此廢液導入電滲析裝置i 6 。亦即，省略該活性碳槽1 5之構成亦可。又，亦可使該 活性碳槽1 5設定於電滲析丨7之後段，取代設置於廢液貯 存槽〗4之後段，去除T〇c。 -10- 200904760 本發明所使用之該電滲析裝置1 6係於陽極與陰極間 交互配置陽離子交換膜與陰離子交換膜，藉由此等陽離子 交換膜與陰離子交換膜構成複數之吸收池。該電滲析裝置 於陽極與陰極間以外加直流電流之狀態，將廢液導入中央 之電解槽後，廢液中之碘離子（碘成份）及鉀離子分別移至 陽極側及陰極側，於中央電解槽雨側之吸收池中，生成碘 化鉀（KI)。而，由電滲析裝置16排出含有50~150g/l KI 之水溶液（ΚΙ濃縮液）與碘量降至1 _〇g/l以下之脫鹽液。 此時，若導入電滲析裝置16之廢液pH超出7時， 則共存之硼酸（Η3Β03)解離後，硼酸離子量變多，於電滲 析時，硼酸離子混入KI濃縮液。反之，廢液pH未達7 時，則大部份硼酸未解離呈分子存在之，因此，即使進行 電滲析，硼酸仍未移動，直接排出脫鹽液中。藉此，可有 效分離廢液中之硼與碘。 圖2係於橫軸取pH，縱軸取非解離硼酸（H3B〇3)之濃 度，代表溶液之pH與硼之存在形態之關係圖。於溶液pH 未達7時，大部份硼酸未解離呈硼酸分子存在。因此，投 入電滲析裝置16之廢液pH作成未達7。藉此，可抑制硼 酸之解離，即使進行電滲析仍未移動硼酸，直接排出，廢 液中之硼量未變化，可降低碘量。 另外，廢液爲酸性時，生成游離碘’離子交換膜劣化 後降低電滲析之效率，因此，廢液P Η爲3以上者宜。藉 此，碘離子之空氣氧化亦可抑制游離碘之生成。或’亦可 抑制藉由未生成碘之亞硫酸鉀等之還原劑後之氧化還原電 -11 - 200904760 位。此時，藉由使用可移動1價離子之陰離子交換膜之選 擇性膜後，可防止於KI濃縮液中混入硫酸離子。 如此取得之KI濃縮液係藉由追加新的碘混合後，調 整作成染色用溶液再度供應於染色浴1 1。又，此KI濃縮 液亦可追加新的硼酸混合後，作成交聯用溶液調整後，再 度作成對於交聯浴12之製造藥液再行利用。如此，由廢 液分離KI濃縮液，此再次作爲製造藥液使用，可構築所 謂的再循環系統。因此，可降低產業廢棄物，同時可意圖 降低原料成本。 另外，此KI濃縮液之再循環可以任意之染色用溶液 ，交聯用溶液做爲對象進行。 更，含有由電滲析裝置16所分離之硼酸（H3B〇3)及有 機物等之脫鹽液係添加NaOH、KOH等之氫氧化鉀、較佳 者爲KOH，於pH調整步驟23中，調整爲PH7以上，較 佳者爲9以上後，導入電滲析裝置17。該電滲析裝置17 中，使硼分離，可分離含有〗〇〇〜500g/l之NaB(OH)4， KB (OH)4之水溶液（硼酸濃縮液卜而，爲使硼酸濃縮液作 爲交聯用溶液進行循環再使用時，去除游離鹼，於pH調 整步驟23中作成pH4〜7狀態之硼酸者宜，該方法中，經 由酸中和，經由離子交換進行鹼的去除，調整碘交聯用溶 液，再次供應於交聯浴12亦可。亦即，該p Η調整步驟 23中，作爲pH調整用之酸爲碘化氫酸者宜。藉此，本發 明中，不僅KI濃縮液，硼酸濃縮液之再循環亦可實現。 即，使該硼酸濃縮液進行再循環時，與此混合之碘化鉀溶 -12 - 200904760 液亦可使用上述生成之ΚΙ濃縮液。 又，上述之實施形態中，至少針對使適用本發明之循 環使用系統1依染色浴1 1與交聯浴1 2及洗淨浴1 3之順 序，對於所配設之製造線20，進行設置時，作成說明， 而該構成並未受限。適用本發明之循環使用系統1亦對於 任意存在爲使PVA薄膜浸漬之浴之製造線均適用之。 爲浸漬此PVA薄膜之浴中，任意注入含有碘及碘化 鉀之溶液，含有硼酸及碘化鉀之溶液，含有碘化鉀之溶液 ，含有碘及碘化鉀與硼酸之溶液。 來自浴之廢液係貯存於廢液貯存槽1 4，與上述製程 相同，取得硼酸濃縮液及/或碘化鉀濃縮液。此硼酸濃縮 液及/或碘化鉀濃縮液依其情況相互混合之外，藉由分別 送往上述浴中後，使此進行循環使用。 以下，藉由實施例進行本發明更詳細說明，惟，本發 明並未受限於此。另外，實施例所示之透過率，偏光度之 評定係如下進行之。 以1片測定所得偏光薄膜時之透過率爲Ts，使2片 偏光薄膜呈相同於其吸收軸方向進行重疊時之透過率爲平 行位透過率Tp，使2片偏光薄膜其吸收軸呈交叉重疊時 之透過率爲交叉位置透過率Tc。 透過率T係於3 80〜780nm之波長領域下，求取所定 波長間隔d；L(此爲l〇nm)之分光透過率τλ ，藉由下式 (1)算出。式中’ ΡΑ代表標準光（C光源）之分光分佈，y又 代表2度視野等色關係。 -13- 200904760 ίηο ' ’ 式⑴ 尸八· y八· τ λ · d λ _ t8Q_____ 1 — ' [Ρλ · y λ · ά λ iso 分光透過率r λ係利用分光光度計[日立公司製“υ· 4 1 0 0 ” ]進行測定之。偏光度py係由平行位透光率τρ及 交叉位透過率Tc’經由下式（2)求取。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recycling method and system for producing a chemical solution for a polarizing film which circulates iodine and boron from a raw material for producing a waste liquid when a polarizing film is produced. [Prior Art] A polarizing film for a liquid crystal display or the like is known, for example, a polyvinyl alcohol-based film (PVA film) which is generally adsorbed with iodine. In the polarizing film, the iodine-based polarizing film is usually produced by immersing a PVA film in which iodine is adsorbed in an aqueous solution containing boric acid. This manufacturing step produces a waste liquid containing iodide ions, boric acid, potassium ions, and water-soluble organic substances. Such a waste liquid is usually discharged by industrial wastewater by a coagulation method, an adsorption method, an ion exchange method, a filtration method, or the like, and the specific components contained therein are classified as waste water, or reduced by concentration. After that, it is treated with industrial waste. However, in recent years, the wastewater standard has become stricter, and in the conventional treatment methods such as the coacervation method, the adsorption method, the ion exchange method, and the filtration method, it is difficult to treat the boron concentration in the wastewater to be below the standard enthalpy. In addition, industrial waste is expected to reduce emissions in terms of processing costs and environmental issues. Further, as long as boron and iodine can be efficiently recovered from these waste waters, the raw materials used in the production of the polarizing film can be recycled, and industrial waste can be reduced, and the raw material cost can be reduced. Generally, when iodine and boron are recovered from waste water, when they are recycled, they are manufactured. -5- 200904760 The waste liquid must be concentrated and separated. The method for treating a waste liquid for manufacturing a polarizing plate disclosed in the prior art (for example, Patent Document 1) is subjected to electrodialysis through a waste liquid discharged from a polarizing plate manufacturing step, and is separated into a desalting liquid mainly containing an organic component and mainly containing an inorganic component. Concentrate. However, it is possible to reduce the cost of raw materials and the cost of waste liquid by simply recycling the waste liquid for manufacturing such a polarizing plate, and to reduce the amount of industrial waste, and to construct a manufacturing system that considers the environment. However, the "precedented technology described above" was mainly treated with waste liquid, and the technology for recycling iodine and boron after separation and recovery and the detailed conditions for recycling were not examined at all. [Patent Document 1] JP-A-2001-314864 SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and proposes to manufacture a chemical liquid which generates a waste liquid from the production of a polarizing film, and can be recycled in a highly efficient manner. The recycling method and system for manufacturing the chemical liquid are for the purpose. In order to solve the above problems, a recycling system for producing a chemical solution for a polarizing film to which the present invention is applied is characterized in that a PV A (polyvinyl alcohol) film for producing a polarizing film is immersed in a dyeing solution containing iodine and potassium iodide. The waste liquid storage tank for storing the waste liquid in the bath and the pH of the waste liquid stored in the waste liquid storage tank are adjusted to less than 7, and then the iodine component in the waste liquid is separated by electrodialysis. An electrodialysis device for potassium iodide concentrate and a potassium iodate concentrate from the electrodialysis device, -6-200904760, a new iodine component is adjusted by mixing to adjust the dye solution, and then supplied to the dye bath. Loop processing part. The present invention has a pH adjustment step for adjusting a waste liquid from a PV A (polyvinyl alcohol) film for producing a polarizing film in a dyeing bath for dyeing solution containing iodine and potassium iodide to pH 7 or less, and electrodialysis The iodine in the waste liquid is separated to prepare a potassium iodide concentrate, and the mixture is added to the potassium iodide concentrate by adding new iodine, and the dye solution is adjusted to be recycled to the dye bath. In the step, the potassium iodide concentrate is mixed with iodine, adjusted for the dyeing solution, and then supplied to the dye bath or the like to construct a so-called recycling system. To this end, in addition to reducing industrial waste, it is also intended to reduce raw material costs. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the best mode for carrying out the invention will be described in detail with reference to the accompanying drawings. Fig. 1 is a view showing the constitution of a recycling system 1 for a polarizing film producing chemical solution to which the present invention is applied. The recycling system for producing a polarizing film is a dye bath for impregnating the PVA (polyvinyl alcohol) film 2 for producing the polarizing film 2, and a PV A film for immersing in the dye bath 1 1 . The cross-linking bath 1 2 which is immersed in 2 a is disposed in a manufacturing line 20 formed by washing the washing bath 1 3 of PV A 2b immersed in the crosslinking bath 1 2 . The recycling system 1 is provided with a waste liquid storage tank 14 for temporarily storing the waste liquid from the dyeing bath 1 1 and the washing bath, and the waste from the waste liquid storage 200904760 storage tank 14 The activated carbon tank 15 supplied from the liquid, and the electrodialysis unit 16 supplied through the waste liquid of the activated carbon tank 15 and the electrodialysis unit 17 supplied from the desalted liquid from the electric edge separating unit 16. The PVA film 2 is a film obtained by forming a polyvinyl alcohol, an ethylene-vinyl acetate copolymer saponified product, or a resin containing a small amount of other copolymerized components. As other polymer components, for example, unsaturated carboxylic acids, olefins, unsaturated sulfonic acids, and the like can be used. The degree of polymerization of the PVA resin is usually from 1 Torr to 10,000, preferably from 1 500 to 5,000 °. The saponification degree of the PVA resin is usually about 85 to 100 mol%, preferably about 9 8 to 1 0 0. Moer%. This PVA film 2 can be applied to any PVA resin film forming method. The film thickness of the polarizing film 2 is not particularly limited, and is generally about 30 μm to 1 50 μm. The PVA film is sufficiently swollen in water and then dyed in the dyeing bath 1 1 . In the dyeing bath 11, a dyeing solution containing iodine and potassium iodide was placed. The composition of the dyeing solution is as follows: water: iodine: potassium iodide weight ratio is 10 0: 0.01~0.5: 0.1~10. In the dyeing solution formed by the weight composition, the PV A film 2a which adsorbs iodine on the surface can be formed by immersing the PV A film 2. The temperature in the dyeing bath 11 is usually 20 to 50 ° C. Cross-linking bath 2 is a solution for crosslinking which contains boric acid and potassium iodide. The composition of the solution for cross-linking is as follows: water: boric acid: potassium iodide weight ratio is 100: 1. 0~7.0: 1.0~8. In the crosslinking solution -8-200904760 formed by the weight composition, the iodine polymer is crosslinked on the surface of the PVA film 2a by immersing the PVA film 2 to form a stabilized P V A film 2b. That is, the temperature of the crosslinking bath 1 2 is preferably 40 ° C or higher, and more preferably 50 ° C to 8 5 ° C. Further, the immersion time of the PVA film 2 of the crosslinking solution is not particularly limited, but is usually 1 to 1 200 seconds, preferably 30 to 600 seconds. The washing bath 1 3 is filled with washing water. The PVA film 2b from the crosslinking bath 12 is immersed in the cleaning bath 13, and impurities and the like adhering to the surface thereof can be removed. Thereafter, after the drying step, a polarizing film was produced from the P V A film 2. The pV A film 2 is stretched during the immersion in the dye bath 1 1 to the washing bath 13 . The ratio of the final length of the extended PVA film 2 to the initial length of the unstretched PVA film 2 is usually 3 to 7 times, preferably 4 to 6 times. Further, in order to obtain the polarizing film, a manufacturing process such as a wide roll or a guide can be used to extend the direction in which the extending direction is crossed, and the manufacturing process of obtaining the polarizing film from the PVA film 2 is not performed. Any form other than the above may be applied. Further, the protective film may be attached to one side or both sides of the polarizing film obtained as described above. Among them, the 'protective film is added for the purpose of improving the water resistance of the polarizing film', and a suitable transparent substance can be used for the formation. In particular, plastics with good transparency, such as mechanical strength, thermal stability, and moisture shielding properties, are ideal users. In other words, examples thereof include a polyester resin, an acetate resin, a polyether oxime resin, a polycarbonate-9-200904760 ester resin, a polyamide resin, and a polyimide resin. Thermosetting resin or ultraviolet curable resin such as polyolefin resin, propylene resin, or other thermoplastic resin, propylene or urethane acrylamide, epoxy or polyoxyn For example, a preferred protective film such as acetaminophen (TAC) or the like, and a polyolefin-based resin such as an amorphous poly-alkaline resin has a raw spintenene or a polycyclic raw spinel-based single. An example of a resin of a polymerization unit of a cyclic polyolefin of a body type. Further, the transparent protective film for the protective layer can be treated for the purpose of anti-reflection treatment, anti-blocking, diffusion to light resistance, etc. without impairing the object of the present invention. The adhesion treatment between the polarizing film and the protective film is not particularly limited, and is generally, for example, an adhesive made of a vinyl alcohol polymer, or a B-acid of boric acid, borax, pentyl, honey, and acid. A polymerization agent made of a water-soluble crosslinking agent of a polymer, a solvent-based adhesive which is excellent in transparency, such as an epoxy resin, a polyester or a vinyl acetate, or a polymerization reaction of a propylene-based polymer resin or a urethane resin. After hardening, it is carried out by the obtained adhesive resin or the like. That is, the waste liquid from the respective baths 11 to 13 is collected in a separate bath or in the collected waste liquid storage tank 14. It can also be equipped with a device for concentrating and collecting the waste liquid of the waste liquid storage tank 14. The wastewater from this waste storage tank 14 is in the p Η adjustment step 21 and adjusted to a pH of less than 7. Further, the water-soluble organic compound (Τ Ο C) is removed by passing through the activated carbon tank 15. Thereafter, the waste liquid is introduced into the electrodialysis unit i 6 . That is, the configuration of the activated carbon tank 15 may be omitted. Further, the activated carbon tank 15 may be set in the subsequent stage of the electrodialysis unit 7, and T 〇c may be removed instead of being disposed in the subsequent stage of the waste liquid storage tank. -10-200904760 The electrodialysis device 16 used in the present invention is a system in which a cation exchange membrane and an anion exchange membrane are alternately disposed between an anode and a cathode, whereby a cation exchange membrane and an anion exchange membrane constitute a plurality of absorption cells. The electrodialysis device applies a direct current between the anode and the cathode, and after introducing the waste liquid into the central electrolytic cell, the iodide ions (iodine component) and potassium ions in the waste liquid are respectively moved to the anode side and the cathode side, respectively. Potassium iodide (KI) is formed in the absorption tank on the rain side of the electrolytic cell. On the other hand, the electrodialysis unit 16 discharges an aqueous solution (ΚΙ concentrated solution) containing 50 to 150 g/l of KI and a desalting liquid having an iodine amount of less than 1 〇 g/l. At this time, when the pH of the waste liquid introduced into the electrodialysis unit 16 exceeds 7, the amount of boric acid ions increases after the coexisting boric acid (Η3Β03) dissociates, and the boric acid ions are mixed into the KI concentrate at the time of electrodialysis. On the other hand, when the pH of the waste liquid is less than 7, most of the boric acid does not dissociate in the presence of a molecule. Therefore, even if electrodialysis is carried out, the boric acid does not move and is directly discharged into the desalting liquid. Thereby, boron and iodine in the waste liquid can be effectively separated. Figure 2 shows the pH on the horizontal axis and the concentration of non-dissociated boric acid (H3B〇3) on the vertical axis, which represents the relationship between the pH of the solution and the form of boron. When the pH of the solution is less than 7, most boric acid is not dissociated and is present as a boric acid molecule. Therefore, the pH of the waste liquid charged into the electrodialysis unit 16 is less than 7. Thereby, the dissociation of boric acid can be suppressed, and even if boric acid is not moved by electrodialysis, the amount of boron in the waste liquid is not changed, and the amount of iodine can be reduced. Further, when the waste liquid is acidic, the free iodine ion exchange membrane is deteriorated to reduce the efficiency of electrodialysis, and therefore, the waste liquid P Η is preferably 3 or more. Therefore, air oxidation of iodide ions can also inhibit the formation of free iodine. Or, it is also possible to suppress redox power -11 - 200904760 by a reducing agent such as potassium sulfite which does not generate iodine. At this time, by using a selective membrane of an anion exchange membrane capable of moving monovalent ions, it is possible to prevent the penetration of sulfate ions into the KI concentrate. The KI concentrate thus obtained is mixed with a new iodine, and then adjusted to form a dye solution for re-supply to the dye bath 1 1 . Further, the KI concentrate may be mixed with a new boric acid and adjusted for the trade-off solution, and then reused as a production liquid for the crosslinking bath 12. In this way, the KI concentrate is separated from the waste liquid, and this is used again as a production chemical solution, so that a so-called recirculation system can be constructed. Therefore, industrial waste can be reduced while reducing the cost of raw materials. In addition, the recycling of the KI concentrate can be carried out by using any solution for dyeing and the solution for crosslinking. Further, a desalting liquid containing boric acid (H3B〇3) and an organic substance separated by the electrodialysis device 16 is added with potassium hydroxide such as NaOH or KOH, preferably KOH, and is adjusted to pH 7 in the pH adjustment step 23. The above is preferably 9 or more, and then introduced into the electrodialysis device 17. In the electrodialysis device 17, boron is separated, and an aqueous solution containing NaB(OH)4, KB(OH)4 containing 〇〇~500 g/l (boric acid concentrate) is used to make the boric acid concentrate as cross-linking. When the solution is recycled and reused, the free base is removed, and boric acid in a pH of 4 to 7 is preferably produced in the pH adjustment step 23. In this method, the alkali is removed by ion exchange through acid neutralization, and the iodine crosslinking is adjusted. The solution may be supplied to the crosslinking bath 12 again. That is, in the p Η adjusting step 23, the acid for pH adjustment is preferably hydrogen iodide. Thus, in the present invention, not only the KI concentrate but boric acid The recycling of the concentrated liquid can also be achieved. In other words, in the above embodiment, when the boric acid concentrate is recycled, the potassium iodide solution -12 - 200904760 mixed therewith can also be used. At least for the recycling system 1 to which the present invention is applied, in the order of the dye bath 1 1 and the crosslinking bath 1 2 and the washing bath 1 3, the manufacturing line 20 to be disposed is provided, and the composition is made. Not limited. Applicable to the recycling of the present invention The system 1 is also applicable to any manufacturing line in which a bath for impregnating a PVA film is applied. In the bath for impregnating the PVA film, a solution containing iodine and potassium iodide, a solution containing boric acid and potassium iodide, and a solution containing potassium iodide are optionally injected. a solution containing iodine and potassium iodide and boric acid. The waste liquid from the bath is stored in the waste liquid storage tank 14 and is obtained in the same manner as the above process to obtain a boric acid concentrate and/or a potassium iodide concentrate. The boric acid concentrate and/or potassium iodide concentrate In addition, the present invention is further disclosed in the following examples, and the present invention is not limited thereto. The transmittance and the degree of polarization measured in the examples were evaluated as follows. The transmittance of the polarizing film obtained in one piece was measured as Ts, and the transmittance of the two polarizing films when they were overlapped in the absorption axis direction. The parallel transmittance Tp is such that the transmittance of the two polarizing films when the absorption axes are overlapped is the intersection position transmittance Tc. The transmittance T is based on the wavelength of 380 to 780 nm. In the domain, the spectral transmittance τλ of the predetermined wavelength interval d; L (this is l〇nm) is calculated by the following formula (1). In the formula, ΡΑ represents the spectral distribution of the standard light (C light source), and y Represents a 2 degree field of view color relationship. -13- 200904760 ίηο ' ' (1) 尸八· y 八 · τ λ · d λ _ t8Q_____ 1 — ' [Ρλ · y λ · ά λ iso split light transmittance r λ system using splitting The photometer [manufactured by Hitachi, Ltd. "υ·4 1 0 0 ") was measured. The degree of polarization py was obtained from the parallel transmittance τρ and the crossover transmittance Tc' by the following formula (2).
Py={(Tp-Tc)/(Tp + Tc)},/2xl00 式（2) 色相係相 JIS Z 8 72 9爲基準，藉由國際照明委員會 (C 〇 m m i s s i ο η I n t e r n a t i ο n a 1 e d e 1 ’ E c 1 a i r a g e，略稱 CIE)之 a*，b *求取° [實施例Π 碘量爲1 6 g/1，硼量爲5·4 g/1 ’鉀量爲4.9 g/1，TOC 爲0.01 g/1，pH爲5.2之偏光薄膜製造廢液5.71藉由電滲 析裝置（股份公司Astom製’ Asilyza-S3型）作濃縮液使用 1 β的水，以1 0 V之定電壓進行3小時滲析。又，此電 滲析裝置之膜面積爲〇.〇55m2。陰離子交換膜中使用ACS-8T(股份公司 Astom製）。陽離子交換膜中使用K5〇l-SB( 股份公司A s t 〇 m製）。其結果’電渗析後之濃縮液之播:量 爲 87 g/Ι，硼量爲 1.0 g/1’ 鉀爲 26.7 g/1，TOC 爲 0 g/1’ 碘移動率爲9 4 %，硼移動率爲1 · 9 %。又，脫鹽液之碘量 -14 - 200904760 爲 1.0 g/l，硼量爲 5.3 g/l’ 鉀量爲 0.3 g/1，TOC 爲 0.01 g/1。 [實施例2] 於實施例1之移動碘後之1 β脫鹽液（碘量爲1.0 g/1 ，硼量爲 5.3 g/1、鉀量爲 0.3 g/1、TOC 爲 〇·〇1 g/1，pH 爲5.2之溶液）中’添力口 0.026 β之48〇/〇KOH水溶液，pH 作成1 1之溶液藉由電滲析裝置（股份公司 Astom製 Asilyza-S3型），作成濃縮液使用0_2 β之水，以10V之 定電壓進行3小時滲析。於陰離子交換膜中使用C MB (股 份公司Astom製），陽離子交換膜中使用AHA(股份公司 Astom製）。其結果，電滲析後之濃縮液其碘濃度爲4.75 g/Ι，硼濃度爲25 g/Ι。硼之移動率爲94%。又，脫鹽液之 碘量爲 0.05 g/Ι，硼濃度爲 0.3 g/1，TOC 爲 0.01 g/1。 將皂化度爲99%以上，平均聚合度爲2400之PV A(聚 乙烯醇）薄膜（Clare公司製，商品名：AF-PS)浸漬於30°C 溫水中2分鐘，進行膨潤處理。使膨潤處理之薄膜於碘（ 純正化學公司製）0.1 %與實施例1所回收之碘化鉀1.4 %之 濃縮液以水稀釋後調整爲1.0%之染色浴中，30°C下浸漬3 分鐘後，進行染色處理。 將染色取得之薄膜於實施例2所回收之硼酸14·3%濃 縮液中以57%碘化氫溶液將調整pH爲4~7之硼酸濃縮液 與來自實施例1之碘化鉀1 1.4 %之濃縮液進行混合以水稀 釋後’使硼酸濃度爲4%、碘化鉀濃度爲5 %所調製之交聯 -15- 200904760 浴中，5 (TC下浸漬3分鐘以5倍之倍率進行延伸處理。更 使交聯浴內所延伸處理之薄膜於置入3 0 °C洗淨水之洗淨 浴中進行3 0秒洗淨，洗淨處理後，於7 0 °C下乾燥2分鐘 後取得偏光薄膜。 將乾燥取得之偏光薄膜與鹼處理之三乙醯纖維素薄膜 (富士照相薄膜公司製商品名：TD-80U)利用聚乙烯系黏合 劑，層合後取得偏光板。 [實施例4] 以下，將皂化度爲99%以上，平均聚合度爲240 0之 PVA(聚乙烯醇）薄膜（ClareCI公司製，商品名：VF-PS)浸 漬於3 CTC溫水中2分鐘，膨潤處理作爲比較例1。將膨潤 處理之薄膜調整爲碘（純正化學公司製）〇」％，與碘化鉀（ 純正化學公司製）1.〇%之染色浴中，30 °c下浸漬3分鐘， 進行染色處理。將染色取得之薄膜於硼酸（Societa Chemica Larderello s.p.a公司製）4%與缺化鉀（純正化學公 司製）5 %所調製之5 0 °C交聯浴中，以5倍之倍率進行3分 鐘延伸處理。 將交聯浴內所延伸處理之薄膜於置入3 0 °C洗淨水之 洗淨浴中洗淨3 0秒，洗淨處理後，於7 0 °C下乾燥2分鐘 後，取得偏光薄膜。 所使用之碘、碘化鉀、硼酸均爲工業用試藥，加工條 件係與實施例1相同條件作成偏光薄膜。 將乾燥取得之偏光薄膜與鹼處理之三乙醯纖維素薄膜 -16- 200904760 (富士照相薄膜公司製，商品名：TD-8 0U)利用聚乙烯醇系 黏合劑’層合後取得偏光板。 將實施例3及比較例1取得之偏光藉由分光光度計測 定光學特性之結果，如表1所示。 [表1]Py={(Tp-Tc)/(Tp + Tc)},/2xl00 Equation (2) The hue system phase JIS Z 8 72 9 is the reference, by the International Commission on Illumination (C 〇mmissi ο η I nternati ο na 1 ede 1 ' E c 1 airage, abbreviated CIE) a*, b * ° ° [Example Π Iodine amount is 16 g / 1, boron amount is 5.4 g / 1 'potassium amount is 4.9 g / 1 A liquid crystal for the production of a polarizing film having a TOC of 0.01 g/1 and a pH of 5.2 was prepared by using an electrodialysis apparatus (Asilyza-S3 type manufactured by Astom Corporation) as a concentrate using 1β of water at a constant voltage of 10 V. Dialysis was carried out for 3 hours. Further, the membrane area of this electrodialysis unit was 〇.〇55 m2. ACS-8T (manufactured by Astom Corporation) was used for the anion exchange membrane. K5〇l-SB (manufactured by the company A s t 〇 m) was used for the cation exchange membrane. As a result, the concentration of the concentrated solution after electrodialysis was 87 g/Ι, the amount of boron was 1.0 g/1', the potassium was 26.7 g/1, the TOC was 0 g/1', the iodine mobility was 94%, and boron. The movement rate is 1 · 9 %. Further, the iodine content of the desalting solution was 1.0 g/l of -14 - 200904760, the amount of boron was 5.3 g/l', the amount of potassium was 0.3 g/1, and the TOC was 0.01 g/1. [Example 2] The 1 ? desalting solution after moving iodine in Example 1 (Iodine amount was 1.0 g / 1, boron amount was 5.3 g / 1, potassium amount was 0.3 g / 1, TOC was 〇 · 〇 1 g /1, pH 5.2 solution) Adding a force of 0.026 β of 48 〇 / 〇 KOH aqueous solution, pH of the solution of 1 1 by electrodialysis unit (Asilyza-S3 type manufactured by the company Astom), used as a concentrate 0_2 β water, dialysis was carried out for 3 hours at a constant voltage of 10V. CBA (manufactured by Astom Co., Ltd.) was used for the anion exchange membrane, and AHA (manufactured by Astom Co., Ltd.) was used for the cation exchange membrane. As a result, the concentrated solution after electrodialysis had an iodine concentration of 4.75 g/Ι and a boron concentration of 25 g/Ι. The mobility of boron was 94%. Further, the desalting liquid had an iodine content of 0.05 g/Ι, a boron concentration of 0.3 g/1, and a TOC of 0.01 g/1. A PV A (polyvinyl alcohol) film (trade name: AF-PS, manufactured by Clare Co., Ltd.) having a degree of saponification of 99% or more and an average degree of polymerization of 2400 was immersed in warm water of 30 ° C for 2 minutes to carry out swelling treatment. The swelled film was immersed in an iodine (manufactured by Pure Chemical Co., Ltd.) 0.1% and the potassium iodide 1.4% concentrated solution recovered in Example 1 in a dye bath diluted with water and adjusted to 1.0%, and immersed at 30 ° C for 3 minutes. Dyeing treatment. The film obtained by dyeing was concentrated in a 14.3% concentrated boric acid recovered in Example 2, and a concentrated boric acid solution having a pH of 4 to 7 and a concentration of 1.4% of potassium iodide from Example 1 in a 57% hydrogen iodide solution. After the liquid was mixed and diluted with water, the cross-link -15-200904760 prepared in a bath having a boric acid concentration of 4% and a potassium iodide concentration of 5% was subjected to a stretching treatment at 5 times under immersion for 3 minutes at TC. The film stretched in the crosslinking bath was washed in a washing bath in which 30 ° C of washing water was placed for 30 seconds, and after washing, it was dried at 70 ° C for 2 minutes to obtain a polarizing film. The polarizing film obtained by drying and the alkali-treated triacetone cellulose film (trade name: TD-80U, manufactured by Fuji Photo Film Co., Ltd.) were laminated with a polyethylene-based adhesive to obtain a polarizing plate. [Example 4] A PVA (polyvinyl alcohol) film (manufactured by ClareCI Co., Ltd., trade name: VF-PS) having a degree of saponification of 99% or more and an average degree of polymerization of 240% was immersed in 3 CTC of warm water for 2 minutes, and the swelling treatment was carried out as Comparative Example 1. The swelled film was adjusted to iodine (manufactured by Junsei Chemical Co., Ltd.) 〇%%, and iodinated (manufactured by Pure Chemical Co., Ltd.) 1. In a dyeing bath of 〇%, immersed at 30 °C for 3 minutes to carry out dyeing treatment. The film obtained by dyeing was made up of boric acid (Societa Chemica Larderello spa) 4% and potassium deficiency (pure The chemical company made) 5 % of the 50 ° C cross-linking bath was stretched at a magnification of 5 times for 3 minutes. The film stretched in the cross-linking bath was placed in a washing water at 30 ° C. After washing in a washing bath for 30 seconds, after washing, it was dried at 70 ° C for 2 minutes to obtain a polarizing film. The iodine, potassium iodide and boric acid used were industrial reagents, and the processing conditions were carried out. A polarizing film was prepared under the same conditions as in Example 1. The polarizing film obtained by drying and the alkali-treated triacetone cellulose film-16-200904760 (manufactured by Fuji Photo Film Co., Ltd., trade name: TD-8 0U) were made of a polyvinyl alcohol-based adhesive. 'A polarizing plate was obtained after lamination. The results of measuring the optical characteristics of the polarized light obtained in Example 3 and Comparative Example 1 by a spectrophotometer are shown in Table 1. [Table 1]
Ts A*s b*s Tp a*p b*p Tc a*c b*c Py 實施例3 43.09 -1.47 3.33 37.24 -2.59 6.03 0.009 0.08 -0.47 99.98 比較例1 42.80 -1.55 3.07 37.05 -2.66 5.65 0.009 0.15 -0.61 99.98 表中之S · ρ · C .分別代表偏光板之單體、平行位、交叉 位。 將實施例3及比較例1取得之偏光板切成40x40mm 之尺寸，進行耐久試驗。 耐久試驗係將偏光板置入乾熱雰圍95 °C及濕熱雰圍 6 5 °C ’相對濕度9 5 %之試驗器中，進行比較試驗前與投入 506小時後之單體透過率（Ts)與偏光膜（Py)之變化量。 試驗結果示於表2及表3。 [表2] (試驗條1 牛：95°C -dry) 試驗前Ts 試驗前Py 506h Ts 506h Py Ts變化量 Py變化量 實施例3 42.98 99.97 43.46 99.87 +0.48 •0.10 比較例1 42.78 99.98 43.16 99.92 +0.38 -0.06 -17 - 200904760 [表3] (試驗條件：65°C x95%RH) 試驗前Ts 試驗前Py 506h Ts 506h Py Ts變化量 Py變化量 實施例3 42^.97 99.96 44.90 98.28 +1.93 -1.68 比較例1 42.77 99.97 44.94 98.27 +2.17 -1.70 由以上實施例，比較例及表1、表2顯示使用來自製 造偏光薄膜之含碘及碘化鉀及硼之廢液的偏光薄膜製造藥 液之循環使用系統使用，回收之碘化鉀水溶液及硼酸濃縮 水溶液後，確定可製造出光學特性及耐久性均良好之偏光 薄膜。 【圖式簡單說明】 [圖1]代表適用本發明之偏光薄膜製造藥液之循環使 用系統的構成圖。 [圖2 ]代表橫軸取p Η，縱軸取非解離硼酸（Η3 B 0 3)之 濃度之溶液ρ Η與硼存在形態之關係圖。 【主要元件符號說明】 1 :原料再循環系統 2 :偏光薄膜 11 :染色浴 12:交聯浴 1 3 :洗淨浴 1 4 :廢液貯存槽 -18- 200904760 1 5 :活性碳槽 1 6、1 7 :電滲析裝置 2 〇 :製造線Ts A*sb*s Tp a*pb*p Tc a*cb*c Py Example 3 43.09 -1.47 3.33 37.24 -2.59 6.03 0.009 0.08 -0.47 99.98 Comparative Example 1 42.80 -1.55 3.07 37.05 -2.66 5.65 0.009 0.15 -0.61 99.98 S · ρ · C in the table represents the monomer, parallel, and cross positions of the polarizing plate, respectively. The polarizing plates obtained in Example 3 and Comparative Example 1 were cut into a size of 40 x 40 mm to carry out an endurance test. In the endurance test, the polarizing plate was placed in a tester with a dry heat atmosphere of 95 ° C and a moist heat atmosphere of 65 ° C 'relative humidity of 95 %, and the monomer transmittance (Ts) before and after the comparison test was performed for 506 hours. The amount of change in the polarizing film (Py). The test results are shown in Tables 2 and 3. [Table 2] (Test strip 1 cattle: 95 ° C -dry) Before the test Ts before the test Py 506h Ts 506h Py Ts change amount Py change amount Example 3 42.98 99.97 43.46 99.87 +0.48 •0.10 Comparative example 1 42.78 99.98 43.16 99.92 +0.38 -0.06 -17 - 200904760 [Table 3] (Test conditions: 65 °C x95% RH) Ps 506h before test Ts 506h Py Ts change amount Py change amount Example 3 42^.97 99.96 44.90 98.28 + 1.93 -1.68 Comparative Example 1 42.77 99.97 44.94 98.27 +2.17 -1.70 From the above examples, comparative examples and Tables 1 and 2 show the use of a polarizing film from a waste liquid containing iodine and potassium iodide and boron for producing a polarizing film. After the recycling system is used, the recovered potassium iodide aqueous solution and the boric acid concentrated aqueous solution are determined to produce a polarizing film having excellent optical characteristics and durability. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] Fig. 1 is a configuration diagram showing a system for recycling a polarizing film producing chemical solution to which the present invention is applied. [Fig. 2] A graph showing the relationship between the solution ρ Η of the concentration of the non-dissociated boric acid (Η3 B 0 3) and the form of boron, which represents p Η on the horizontal axis. [Explanation of main component symbols] 1 : Raw material recycling system 2 : Polarizing film 11 : Dyeing bath 12 : Cross-linking bath 1 3 : Washing bath 1 4 : Waste liquid storage tank -18 - 200904760 1 5 : Activated carbon tank 1 6 , 1 7 : Electrodialysis unit 2 〇: Manufacturing line