1276667 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明Ο ) 發明範圍 本發明係關於利用水溶液中以電化學方式產生之還原 或氧化劑的作用改變已染色之紡織物料的顏色之方法。 漂白在製造紡織品時具有其根本之重要性，漂白最初 的功能係於染色作業前，破壞該纖維性材料之原本的著色 成分。各種漂白方法皆可使用。直到最近才廣泛使用之漂 白方法使用經氧化之氯化合物（次氯酸鹽、二氧化氯），由於 ΑΟΧ造成廢水處理的沉重負擔，已經從紡織產業廣泛的消 失。如今，習慣上使用無機或有機過氧化物（過氧化氫、過 酸類）。染紡淸洗業中，高硼酸化合物及過碳酸鹽係廣泛使 用之漂白藥劑。此等方法都很普遍，上述之物料係依預定 用量以固態或液態化學藥品的方式直接添加至該漂白浴， 等該作業結束之後，與該處理浴一起導入廢水。程序控制 項目限於適當處理情況之界定及維持，特別是該化學藥品 之添加速率、pH、溫度、處理時間及液比。如今使用氯化 合物，特別是次氯酸鹽之漂白作業僅用於特別用途。特別 重要的用途係漂白整件都染成靛藍色的衣服。例如，丁尼 布衣服係於大型滾筒淸洗機中漂白，在40°C及10 : 1之液 比時，以10毫升/升次氯酸鈉溶液及1.0克/升碳酸鈉處理 • 20分鐘。因爲該經控制之染料破壞能發揮廣大的效用，所 以此生產技術係用於各種處理方法。本質上並非要使染料 完全漂白，而是部分破環各物件上之染料。（EP 0 002423 A1) 對偶氮染料之還原性漂白方法係用於各處理階段。例 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） " I—Γ---：--1衣-------1T------ (請先閲讀背面之注意事項再填寫本頁) 1276667 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明P ) 如，在紡織印刷中，通常係以偶氮染料之還原性破壞爲主 ，局部施用還原劑（甲酸硫氧酸鹽）而達到染料脫色。同樣地 ，再藉由適當的還原劑（二亞硫磺酸鈉）洗去亮白（off-shade) 染料，亦即，脫色，使該紡織物料可再染料。此等方法係 關於該染料之完全破壞，因此選擇該施用條件以產生實質 上的漂白。 文獻中已經說明產生還原劑及氧化劑之各種電化學方 法，但此等方法大部分係用以製造整批的化學藥品，非現 場製造。然而，咸知使用電化學方法在現場產生還原劑或 氧化劑可得到各種優點。例如，根據WO90/1 5 1 82，鐵-三乙 醇胺錯合物可用作染色的變當染料（vat dye)、含硫染料及靛 藍之可再生還原劑，亦可用以使偶氮染料脫色。同樣地， 根據Bechtold等人（化學協會法拉第會刊1 993年，第89卷 14冊，245 1至2456頁；應用電化學期刊，2001年，第31 卷第363至3 68頁），其它如古洛糖酸、羥乙二胺三醋酸等 之錯合劑亦係適合的。DE 1 95 1 3 839 A1揭示變當染料之電 化學還原方法，該方法在具備大陰極表面積（石墨製氈型電 極）之電化學裝置中使用鹼性鐵-三乙醇胺錯合物。此等方法 皆將電化學還原當作染色處理之一部分，亦即在各例子中 該染料悉皆完全還原。此等方法亦於WO90/1 5 1 82之實施例 3中用於該偶氮染料之還原性破壞。在該專利中由陰極產生 之鐵（II)-三乙醇胺錯合物係用於製備隨後再染色用之非完美 染色訪織物料。 在現場產生次氯酸鹽的電化學已經硏究已久，在此方 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） -6 - I~一---τ--衣----Ί.--II-----— (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 1276667 A7 _ B7 五、發明説明（？) 面的刊物皆關注於隨後用於漂白作業之含次氯酸鹽溶液的 產生（Rengaranjan等人，印度電化學期刊，1 993年，第9卷 11至12冊，第642至643頁，及唐發表的CN88101765)。 同樣地，該陽極產生次氯酸鹽已經見於紡織物料淸洗及漂 白（見 EP 0 002423 A1)。 儘管此等方法係特地硏究用於紙漿漂白（Varennes S.等 人，Can· Appita J·，1994 年，第 47 卷 1 冊，第 45 至 49 頁 ，Fadali 0·，埃及電化學期刊，1993年，第9卷1冊，第 21至24頁及纖維化學技術，1991年，第25卷3至4冊， 第181至187頁，Schwab G.，美國專利案第4,617,099號， Nassar M.M.等人，應用電化學期刊，1983年，第13卷5冊 ，第663至667頁），但是Nishibe K.(電氣化學及工業物理 化學，1980年，第48卷4冊，第267至270頁）及 Vijayarghavan Κ.等人（色彩技術，2001年，第117卷，第49 至53頁）舉例說明在紡織物料上及廢水中的反應性染料以電 化學的方式產生次氯酸鹽脫色。 DE 198 43 571 A1及DE 197 23 889 A1中揭示以電化學 產生漂白靛藍牛仔褲材料用之氧化有機化合物。第一份參 考資料說明關於工作電極（陽極）之恆電位（potentiostatic)或 恆電流（gaWanostatic)操作，然而第二份僅指出使用電壓。 〇loman(Can. Tappi. J·，1 993 年，第 76 卷 10 冊，第 139 至 147頁，Tappi，1994年，第77卷7冊，第115至126頁）深 入地硏究紙漿漂白時使用錳的金屬錯合物及鐵的金屬錯合 物以維持該電化學氧漂白。文獻（Copper J.F.，美國專利案 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐) I - ^ ^IT. (請先閲讀背面之注意事項再填寫本頁) 1276667 A7 B7 五、發明説明（4 ) 第5，456,809)中同樣地說明以氣體消耗電極在陰極產生過氧 化氫。 (請先閱讀背面之注意事項再填寫本頁) 因此可由先前技藝得知可以電化學方式轉成「活性」 形態之廣大範圍氧化還原系統，該活性形態可係還原態或 氧化態。但此等系統當中至今無一仍用於業界，這全都是 因爲不當的技術性能及不良的本益比。先前技藝致力於使 用電化學技術代替習知化學技術。因此，此等電化學操作 係以工作電極之恆電流或恆電壓方式進行。該恆電壓模式 中，工作電極（陰極或陽極）之電位係相對於置於溶液中之參 考電極界定，然而該恆電流模式中，係將電流導入經界定 之電解電池配置中。此等技術係公認有用於製備化學製品 ，但完全不適用於再生預定顏色變化並且必須花數天才能 製成各款式，特別是時尙流行的，衣服之類型（可參考例如 用於製造習知款式之「石洗（stone-wash)」法，該方法係製 造牛仔褲時最重要的）。此等特別應用DE 197 23 889 A1及 DE 198 43 57 A1所教示的。 經濟部智慧財產局員工消費合作社印製 本發明之目的在提供將已染色或著色之紡織物料變成 預定並且可再生之顏色的方法。經發現以該電化學步驟施 於欲處理之紡織物料時將可達到此等目的。換句話說，適 當氧化還原電位之設定極其重要。 本發明提供利用電化學方式產生還原劑或氧化劑之水 溶液處理已染色之紡織物料以改變已染色紡織物料之顏色 ’該方法包括該溶液與已染色之紡織物料接觸時，使該溶 液具有適當的氧化還原電位以改變顏色的方式控制電池電 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） _ 8 - 1276667 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明f ) 流。 爲達本發明之目的，顏色變化特別指的是變淡、色調 偏移及故意造成的不均勻性（微觀或巨觀）。 爲獲得該所欲之顏色變化所需之還原劑或氧化劑係根 據本發明之方法以電化學方式產生，習慣上用可執行電解 電池之功能的電解電池或裝置。換句話說，將適當的氧化 還原系統或氧化還原電極置於該電池中，以電化學方式產 生還原劑或氧化劑。各種適當的電解電池皆係熟於此藝之 士所習知。大體而言該等電池係由工作電池、相反電極及 電源線及電源供應器組成。該電池較佳包含區隔該陽極及 陰極空間的薄膜；但是，端視所使用之氧化還原系統而定 ，也有可能使用較簡易並且較便宜未做區隔的電池。特別 適當的電解電池具有大活性電極面積，因此較佳不僅平面 電極，例如板形，也可能係三維形式的電極（孔質薄片、線 織布、網、毛氈、流動電極、震動電極、多孔性燒結板）， 特佳係多重陰極系統。使用大電極面積時，可將所需之活 性氧化還原系統濃度維持於低濃度下，對於根據本發明之 方法而言在經濟可行性的方面特別重要。適當的電極材料 爲熟於此藝之士所熟知並且能根據所需加以選擇，特佳係 貴重金屬、不銹鋼、石墨及碳以及鈦薄片被覆貴重金屬氧 化物。 該電解電池較佳係製成流通式電池（flowthrough cell)， 該電池與處理裝配直接連通，注入含還原劑或氧化劑之水 溶液（處理液），使該紡織物料產生顏色改變。隨後該溶液可 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐] - rLL---r--裝-----——訂-------- (請先閲讀背面之注意事項再填寫本頁) 1276667 A7 ___ B7_ 五、發明説明（6 ) (請先閲讀背面之注意事項再填寫本頁) 返回該電解電池再生。機械不需持續裝載及卸載，所以不 用事先沖洗或電化學處理步驟之後的淸洗。對於欲使用之 電解電池較佳於電化學處理步驟期間依序連結用於複數個 處理裝配，等該處理結束之後切斷該循環。有用的處理裝 配包含習知用於溼式處理或淸洗紡織物料之裝置。具體而 言，適當的裝配係紡織機械，例如染紗機、捲染機、噴染 機或連續型機械。管式紡織物料之處理係於溢流機械或噴 染機械中進行，片狀物料之處理以束染機進行，整件染色 之衣服的處理以全成形的機械或變染機進行。 經濟部智慧財產局員工消費合作社印製 根據本發明方法之特定具體實施例中，該電解電池直 接就構成處理裝配，或以該處理裝配之零件用作電極，如 此得以免除電解電池及處理裝配之間的電解液循環。該等 電極可以此方式直接設置於該紡織物料旁邊，以達到局部 指定染料之改變。該電極之幾何形狀視所欲之結果而定。 如果產生該還原劑或氧化劑之電極係以例如壓花的形式壓 著於含電解液之紡織物料上，或對處理浴通過電流之後， 可獲得依照圖案形狀的顏色改變。根據本發明之另一變數 中，整件染色的部分，例如褲子，係拖過適當形狀之導電 支架，該支架係用作電極，施以如本發明之處理。 根據本發明方法之較佳具體實施例中，已染色之紡織 物料在施以還原劑或氧化劑之作用時，係同時施以機械及/ 或水處理。此等可於處理裝置中攪拌或再循環而達成。如 果使用滾筒淸洗機，該機械處理係藉由例如在旋轉滾筒中 攪動該紡織物料，而已染色之繩狀或自由寬度之紡織物料 本紙張尺度it财酬家縣（CNS ) A4規格（210X 297公釐)^ΊΌ - 一 1276667 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（7 ) 的處理例中可使用例如壓漿系統、捲取或滾筒，例如浸沒 式壓漿系統等。然而，任何所需之機械處理皆可將硏磨材 料加至處理液而產生作用。有用的硏磨材料包含例如浮石 、適當的塑料或金屬。以微細方式機械處理可添加適當的 硏磨粉末，例如硏磨劑或金屬粉末。機械處理在噴染機械 或溢流機械處理期間，亦可結合，例如壓漿系統、滾筒淸 洗機之水處理。密集液流（噴管、吸槍、篩鼓淸洗機）或例如 震動或超音波亦會造成特定的水應力。 爲達到顏色變化再現，重要的是該溶液就在已染色紡 織物料旁之氧化還原電位之適當調整。該氧化還原電位不 需保持於固定値，各電位之後可能接著預定之不同氧化還 原電位。對於含同一內容物之系統而言，熟於此藝之士將 可以簡單的試驗輕易決定所欲顏色改變所需之氧化還原電 位。爲達此等目的，該處理液之氧化還原電位可利用氧化 還原電極，例如Pt組合電極與Ag/AgCl之3M KC1參考電 極結合而測量。 上述例子中，該電解電池及處理裝置形成單一單元， 該處理液中之氧化還原電位較佳可藉由殘餘電位之測量而 測量並控制，其中該工作電極亦用作測量電極，電位測量 時阻斷該電解電池。因爲僅於該工作電極無電時進行電位 測量，因此所需之參考電極可與該工作電極並排設立。因 爲，一旦該電池關閉，必須耗費一短時間將該工作電極接 至該溶液電位，所以測量電位所需之時間必須預先試驗決 定。 笨紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -11 _ M ^IT (請先閲讀背面之注意事項再填寫本頁) 1276667 A7 _____ B7 五、發明説明（8 ) (請先閲讀背面之注意事項再填寫本頁) 爲獲得可再生的結果，該氧化還原電位以該處理裝置 測量’更佳就在已染色紡織物料旁測量。大體而言，該氧 化還原電位必需隨著染料及一般條件而變，但在氧化情況 下較佳介於+ 100至+2000 mV，更佳介於+400至+1 600 mV， 在還原情況下較佳介於-300至- 1 800 mV，更佳介於-400至-1 200 mv。所需之電位藉由控制電池電流而調整，電流密度 通常介於0.1 mA/cm2至1 A/cm2，較佳介於1 mA/cm2至0.1 A/cm2 〇 本發明之方法可利用還原或氧化劑進行。可逆的氧化 還原電位系統中還原劑係在陰極產生，氧化劑係以陽極產 生。例如，鹵化物，如氯化鈉或溴化鈉，可進行陽極氧化 以形成氧化劑次鹵酸。一般而言，任何無機或有機氧化還 原系統皆可使用’藉以獲得所需之電位。因此熟於此藝之 士得輕發現適當的氧化還原系統。本發明之方法較佳以無 機類還原劑或氧化劑進行。 舉例來說，有用的還原劑包含： 經濟部智慧財產局員工消費合作社印製 -在陰極產生具有無機或有機配位基之金屬錯合物， 其中該金屬係以低價狀態，亦即還原狀態出現，較佳具有 無機或有機配位基之鐵（Π)或錫（II)錯合物，更佳配位基含 2-羥乙基或聚羥基羧酸之鐡（II)錯合物， -經取代的。實施例係三乙醇胺及聚羥基羧酸，例如 1,2-二羧基蒽醒或蒽醌磺酸之鐵（II)錯合物， -錫（II)化合物，例如溶於鹼溶液之六羥基亞錫酸鹽， -在陰極還原產生之連二亞硫酸鹽，可用於中性及弱 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -12 - 1276667 五、發明説明（9 酸性溶液中。 舉例來說，有用的氧化劑包含： (請先閱讀背面之注意事項再填寫本頁) - _素-氧化合物，較佳次氯酸鹽及次溴酸鹽。特佳係 由NaCl (〇·01莫耳/升至5莫耳/升）及NaBr (〇〇1莫耳/升至 1旲耳/升）之混合物組成之次溴酸鹽及次氯酸鹽混合物的電 化學產物’導致不欲之漂白效應增強。該氯化物：溴化物 莫耳比較佳介於5及1〇〇之間， 一含無機或有機配位基之金屬錯合物，其中該金屬係 以高價狀態’亦即氧化狀態出現，較佳爲含無機或有機配 位基之鐵（III)的金屬錯合物及錳（ΙΠ)的金屬錯合物，更佳爲 2,2、二吡啶基鐵（111)、六氰基高鐵酸鐵（ΠΙ)及反式環己烷_ 1，2-二胺-Ν,Ν，Ν，，Ν、四醋酸錳（III))， 一含NO、ΝΟΗ或HNR-OH基之脂環族、雜環或芳香族 化合物，更佳爲2,2,6,6-四甲基哌啶-1-基氧基（TEMPO)及紫 尿酸或 -藉由氧還原或其它可電化學再生之無機或有機過氧 化物在陰極產生過氧化氫。 經濟部智慧財產局員工消費合作社印製 上述之還原劑及氧化劑亦可分別與其它還原劑及氧化 劑混合使用，其中各混合物之混合比並不重要。該還原劑 及氧化劑較佳使用介於0.1毫莫耳/升至5毫莫耳/升之間的 濃度，更佳介於1毫莫耳/升及0.1莫耳/升之間。 根據本發明之方法通常在適合該染料、適合氧化還原 系統以及特別是適合所欲獲得之顏色改變之溫度下進行。 根據本發明之方法較佳在15°C至150°C之間進行，更佳介 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1276667 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（i〇 ) 於20°C至95°C之間，最佳介於40°C至60°C之間。 至於欲處理之已染色紡織物料，因爲根據本發明之方 法適用於該材料，所以並沒有技術上的限制。該等材料可 出現之形式爲纖維、紗線、織布、編織物料或已完全完成 或部分完成之產品。已染色之紡織物料較佳係由纖維素纖 維、合成纖維或其摻混物組成之纖維材料構成。 特佳係由纖維素纖維及該纖維素纖維與已製成纖維， 例如聚酯或聚醯胺纖維之摻混物組成的已染色紡織物料。 但由聚酯或聚醯胺組成之紡織物料亦可使用。 對於欲改變之染料並無任何限制。例如，反應型染料 、變當染料、含硫染料、直接染料、萘酚染料、分散型染 料、酸性染料、陽離子型染料或金屬化染料皆可按照本發 明的方式改變顏色。纖維素纖維可用此等物料習慣使用之 任何等級的染料染色，較佳爲反應型染料、變當染料、含 硫染料或直接染料。由聚酯纖維組成之物料可用例如分散 型染料染色。根據本發明之方法特別適於處理已染成靛藍 色的棉質物料。由此可見染料及氧化還原系統必須相互適 應，亦即該還原劑或氧化劑必須能夠與能改變染色之染料 反應。例如，可還原性地割裂含偶氮基之染料或可對靛藍 染料施以可逆的還原。 處理液較佳循環於處理裝配與電解電池之間，以電化 學產生活性化學物質亦可運送至該處理裝配中，所以預定 濃度之反應用化學物質不會限制該電解電池之電流密度。 此等調整可以所使用之電解電流及氧化還原系統爲主的習 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） _ 14 - ^ 裝 „ 訂 , (請先閱讀背面之注意事項再填寫本頁) 1276667 經濟部智慧財產局員工消費合作社印製 Α7 …、 Β7 五、發明説明& ) 知計算進行。舉例來說，如果該電池電流係20安培並且該 氧化還原系統之濃度係0·05莫耳/升並且使起始化學物質之 濃度不低於0·04莫耳/升，則該處理裝配及該電流之間需要 1.24升/分鐘之計算速率。 根據本發明之方法其它必須列入考慮的參數係液比、 pH以及輔助試劑，例如分散劑、清潔劑、潤滑劑或酵素。 因爲該氧化還原電位會產生特定濃度之活性化學物質及該 化學物質的量會隨著液比而變，所以該液比必須列入考慮 。因爲許多氧化還原化學物質具有強的pH依數性，該pH 不但會影響測得之氧化還原電位，也會影響該化學物質之 化學活性。添加分散劑及/或溼潤劑至該處理液可改質該處 理液之滲入欲處理之已染色紡織物料，也可改質該染色顏 料自該紡織物料之分離及分散。潤滑劑可用以降低任何經 引起之剪切效應。如纖維素酶之酵素可分離已染色之纖維 斷片及欲處理之已染色紡織物料，如此可增強任何硏磨處 理。如之氧化還原活性酵素可於適當條件下增強染料破壞 ，因而增強或改質所欲之顏色變化。前述所有輔助試劑皆 係便宜的。如果使用的話，在本發明之方法中何種類型必 須用何種用量皆可由熟於此藝之士確認。 【圖式簡單說明】 第1圖係適於進行本發明方法之配置的槪略圖式。由 工作電極b、薄膜d、相反電極e、電源線c及於該電解液k 中產生還原劑或氧化劑（所欲使用之氧化還原組合）用之電源 供應器a組成之電解電池，該電解液k經由循環系統g抽 取至該處理裝配m中。該處理裝配包含欲處理之已染色之 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 29*7公釐） (請先閲讀背面之注意事項再填寫本頁)1276667 Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives A7 B7 V. INSTRUCTIONS STATEMENT OF THE INVENTION The present invention relates to a method for changing the color of a dyed textile material by the action of an electrochemically produced reduction or oxidizing agent in an aqueous solution. Bleaching is of fundamental importance in the manufacture of textiles. The initial function of bleaching is to destroy the original coloring components of the fibrous material prior to the dyeing operation. Various bleaching methods can be used. The bleaching method, which has only recently been widely used, uses oxidized chlorine compounds (hypochlorite, chlorine dioxide), which has been extensively lost from the textile industry due to the heavy burden of wastewater treatment due to hydrazine. Today, it is customary to use inorganic or organic peroxides (hydrogen peroxide, peracids). In the dyeing and spinning industry, high-boric acid compounds and percarbonate are widely used as bleaching agents. These methods are common, and the above materials are directly added to the bleaching bath in the form of solid or liquid chemicals at a predetermined amount, and after the end of the operation, the wastewater is introduced together with the treatment bath. Program Control Items are limited to the definition and maintenance of appropriate treatment conditions, particularly the chemical addition rate, pH, temperature, treatment time, and liquid ratio. The use of chlorides, especially hypochlorite bleaching operations, is now only used for special purposes. A particularly important use is for bleaching the entire piece to be dyed in indigo. For example, Tenneb clothing is bleached in a large drum dryer, treated with 10 ml/liter sodium hypochlorite solution and 1.0 g/l sodium carbonate at 40 ° C and a liquid ratio of 10:1 for 20 minutes. Since the controlled dye destruction can exert a wide range of effects, the production technique is applied to various treatment methods. Essentially, it is not necessary to completely bleach the dye, but to partially break the dye on each object. (EP 0 002 423 A1) A reductive bleaching process for azo dyes is used in each treatment stage. For example, the paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) " I—Γ---:--1 clothing -------1T------ (please read the back first) Note: Please fill in this page again) 1276667 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A7 B7 V. Invention description P) For example, in textile printing, it is usually based on the reduction of azo dyes, local application reduction The dye (formate oxysulfate) is used to achieve dye decolorization. Similarly, the off-shade dye is washed away by a suitable reducing agent (sodium disulfite), i.e., decolored to render the textile material re-dyeable. These methods relate to complete destruction of the dye, and thus the application conditions are selected to produce substantial bleaching. Various electrochemical methods for producing reducing agents and oxidizing agents have been described in the literature, but most of these methods are used to make a batch of chemicals, not on-site. However, it is known that the use of an electrochemical method to produce a reducing agent or an oxidizing agent in the field provides various advantages. For example, according to WO 90/1 5 1 82, an iron-triethanolamine complex can be used as a dyed vat dye, a sulfur-containing dye and a reversible reducing agent of indigo, which can also be used to decolorize an azo dye. Similarly, according to Bechtold et al. (Chemical Association Faraday Journal, 193, Vol. 89, No. 14, pp. 245 1 to 2456; Applied Electrochemistry Journal, 2001, Vol. 31, pp. 363 to 3 68), others such as A complexing agent such as gulonic acid, hydroxyethylenediamine triacetic acid or the like is also suitable. DE 1 95 1 3 839 A1 discloses an electrochemical reduction method for dyes which uses an alkaline iron-triethanolamine complex in an electrochemical device having a large cathode surface area (graphar felt-type electrode). These methods all take electrochemical reduction as part of the dyeing process, i.e., in each case the dye is completely reduced. These methods are also used in Example 3 of WO 90/1 5 1 82 for the reductive destruction of the azo dye. The iron (II)-triethanolamine complex produced by the cathode in this patent is used to prepare imperfect dyed fabrics for subsequent dyeing. The electrochemistry of producing hypochlorite in the field has been studied for a long time. In this paper, the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -6 - I~1---τ--衣----Ί.--II------ (Please read the notes on the back and fill out this page) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1276667 A7 _ B7 V. Invention Description (?) The publications are focused on the subsequent production of hypochlorite-containing solutions for bleaching operations (Rengaranjan et al., Indian Electrochemical Journal, 193, vol. 9, pp. 11-12, pp. 642-643, and Don Published by CN88101765). Similarly, the hypoxic acid produced by the anode has been found in textile materials for washing and bleaching (see EP 0 002 423 A1). Although these methods are particularly useful for pulp bleaching (Varennes S. et al., Can. Appita J., 1994, Vol. 47, Vol. 45, p. 45-49, Fadali 0., Egyptian Electrochemical Journal, 1993 Year, Volume 9, Volume 1, pages 21 to 24 and Fiber Chemistry Technology, 1991, Volume 25, Volumes 3 to 4, pages 181 to 187, Schwab G., US Patent No. 4,617,099, Nassar MM et al. , Applied Electrochemistry Journal, 1983, Vol. 13, Volume 5, pp. 663-667), but Nishibe K. (Electrical Chemistry and Industrial Physical Chemistry, 1980, Vol. 48, No. 4, pp. 267-270) Vijay arghavan et al. (Color Technology, 2001, Vol. 117, pp. 49-53) illustrate the electrochemical degradation of hypochlorite by reactive dyes on textile materials and in wastewater. Oxidative organic compounds for the electrochemical production of bleached indigo jeans materials are disclosed in DE 198 43 571 A1 and DE 197 23 889 A1. The first reference note describes the potentiostatic or gaWanostatic operation of the working electrode (anode), whereas the second part only indicates the voltage used. 〇loman (Can. Tappi. J., 193, vol. 76, vol. 10, pp. 139-147, Tappi, 1994, vol. 77, vol. 7, pp. 115-126). In-depth study of pulp bleaching A metal complex of manganese and a metal complex of iron are used to maintain the electrochemical oxygen bleaching. Literature (Copper JF, US Patent Paper Standard for Chinese National Standard (CNS) A4 Specification (210X297 mm) I - ^ ^IT. (Please read the note on the back and fill out this page) 1276667 A7 B7 V. Invention Description (4) In Chapter 5, 456, 809), hydrogen peroxide is generated at the cathode by a gas-consuming electrode. (Please read the precautions on the back and then fill out this page.) It is therefore possible to know from a prior art a broad range of redox systems that can be electrochemically converted to an "active" form, which can be either reduced or oxidized. However, none of these systems are still used in the industry, all due to improper technical performance and poor P/E ratio. Previous techniques have focused on the use of electrochemical techniques in place of conventional chemical techniques. Therefore, these electrochemical operations are carried out in the form of a constant current or a constant voltage of the working electrode. In this constant voltage mode, the potential of the working electrode (cathode or anode) is defined relative to the reference electrode placed in solution, whereas in this constant current mode, current is directed into the defined electrolytic cell configuration. These techniques are recognized for the preparation of chemicals, but are completely unsuitable for regenerating predetermined color changes and must take several days to make each style, especially when it is popular, the type of clothing (for example, for manufacturing purposes) The "stone-wash" method of the style, which is the most important when making jeans. These are taught in particular by DE 197 23 889 A1 and DE 198 43 57 A1. Printed by the Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative The purpose of the present invention is to provide a method of converting a dyed or colored textile material into a predetermined and reproducible color. It has been found that this objective can be achieved when the electrochemical step is applied to the textile material to be treated. In other words, the setting of the appropriate oxidation-reduction potential is extremely important. The present invention provides for the treatment of dyed textile materials by electrochemically producing an aqueous solution of a reducing agent or an oxidizing agent to modify the color of the dyed textile material. The method comprises contacting the dyed textile material with an appropriate oxidation of the solution. The reduction potential is controlled by changing the color. The battery paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) _ 8 - 1276667 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing A7 B7 V. Invention description f ) Flow . For the purposes of the present invention, color change specifically refers to lightening, hue shift, and intentional inhomogeneity (micro or macroscopic). The reducing agent or oxidizing agent required to obtain the desired color change is electrochemically produced according to the method of the present invention, and an electrolytic cell or device which can function as an electrolytic cell is conventionally used. In other words, a suitable redox system or redox electrode is placed in the cell to electrochemically produce a reducing agent or oxidizing agent. A variety of suitable electrolytic cells are known to those skilled in the art. Generally, the batteries are composed of a working battery, an opposite electrode, and a power cord and a power supply. The battery preferably comprises a film that separates the anode and cathode spaces; however, depending on the redox system used, it is also possible to use a battery that is relatively simple and relatively inexpensive and not separated. Particularly suitable electrolytic cells have a large active electrode area, and therefore it is preferred to have not only planar electrodes, such as plate shapes, but also three-dimensional electrodes (porous sheets, wire woven fabrics, nets, felts, flow electrodes, vibrating electrodes, and porosity). Sintered plate), especially for multiple cathode systems. Maintaining the desired concentration of the active redox system at a low concentration when using a large electrode area is particularly important in terms of economic viability for the method according to the present invention. Suitable electrode materials are well known to those skilled in the art and can be selected as desired, particularly precious metals, stainless steel, graphite and carbon, and titanium flakes coated with precious metal oxides. The electrolytic cell is preferably formed as a flowthrough cell which is in direct communication with the process assembly and injects a water solution (treatment liquid) containing a reducing agent or an oxidizing agent to cause a color change in the textile material. The solution can then be applied to the Chinese National Standard (CNS) A4 specification (210X297 mm) on this paper scale. - rLL---r--装---------------- (Read first Precautions on the back page Fill in this page) 1276667 A7 ___ B7_ V. Invention description (6) (Please read the note on the back and fill out this page) Return to the regeneration of the electrolytic cell. The machine does not need to be continuously loaded and unloaded, so there is no need to Washing after rinsing or electrochemical treatment steps. It is preferred for the electrolytic cell to be used to be sequentially connected for a plurality of processing assemblies during the electrochemical processing step, and the cycle is cut off after the end of the treatment. Useful processing assembly includes A device for wet processing or washing textile materials. Specifically, a suitable assembly is a textile machine, such as a yarn dyeing machine, a jigger, a dyeing machine or a continuous machine. In the overflow machine or the dyeing machine, the processing of the sheet material is carried out by a beam dyeing machine, and the processing of the whole dyed clothes is carried out by a fully formed machine or dyeing machine. Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative root According to a particular embodiment of the method of the invention, the electrolysis cell directly constitutes a process assembly, or the part assembled by the process is used as an electrode, thereby eliminating electrolyte circulation between the electrolysis cell and the process assembly. This method is placed directly next to the textile material to achieve a localized change in dye. The geometry of the electrode depends on the desired result. If the reducing agent or oxidant is produced, the electrode is pressed, for example, in the form of embossing. In the textile material containing the electrolyte, or after passing the current through the processing bath, a color change according to the shape of the pattern can be obtained. According to another variation of the invention, the entire dyed portion, such as pants, is dragged through a suitable shape. a stent for use as an electrode for the treatment of the present invention. In a preferred embodiment of the method of the invention, the dyed textile material is simultaneously applied by a reducing agent or an oxidizing agent. And / or water treatment. These can be achieved by stirring or recycling in the treatment unit. If a drum washing machine is used, the machine The processing is carried out by, for example, agitating the textile material in a rotating drum, and the dyed rope-like or free-width textile material is on the paper scale. It is a county (CNS) A4 specification (210X 297 mm) ^ ΊΌ - 1276667 economy Ministry of Intellectual Property Office Staff Consumer Cooperatives Print A7 B7 5. In the treatment examples of the invention (7), for example, a grouting system, a coiling or drum, such as an immersion type grouting system, etc. can be used. However, any required mechanical treatment The honing material can be added to the treatment liquid to produce a function. Useful honing materials include, for example, pumice, a suitable plastic or metal. Mechanical treatment in a fine manner can add a suitable honing powder, such as a honing agent or a metal powder. The mechanical treatment may also be combined with water treatment of a grouting system or a drum washing machine during the processing of the spray machine or the overflow machine. Dense liquid flows (nozzles, sniffer guns, screen blowers) or vibrations or ultrasonic waves, for example, can also cause specific water stresses. In order to achieve color change reproduction, it is important that the solution be properly adjusted for the redox potential beside the dyed textile material. The redox potential need not be maintained at a fixed enthalpy, and subsequent potentials may be followed by a predetermined different oxidative reduction potential. For systems containing the same content, those skilled in the art will be able to easily determine the redox potential required for the desired color change. For this purpose, the redox potential of the treatment liquid can be measured by a combination of a redox electrode such as a Pt combination electrode and a 3M KC1 reference electrode of Ag/AgCl. In the above example, the electrolytic cell and the processing device form a single unit, and the oxidation-reduction potential in the treatment liquid is preferably measured and controlled by measurement of a residual potential, wherein the working electrode is also used as a measuring electrode, and the potential measuring time resistance is Break the electrolytic cell. Since the potential measurement is performed only when the working electrode is de-energized, the required reference electrode can be set side by side with the working electrode. Since, once the battery is turned off, it takes a short time to connect the working electrode to the solution potential, so the time required to measure the potential must be determined in advance. Stupid paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) -11 _ M ^IT (Please read the note on the back and fill out this page) 1276667 A7 _____ B7 V. Invention description (8 ) (Please first Read the notes on the back and fill out this page.) To obtain reproducible results, the redox potential is measured by the processing unit 'better than next to the dyed textile material. In general, the redox potential must vary with the dye and general conditions, but in the case of oxidation, it is preferably between +100 and +2000 mV, more preferably between +400 and +1 600 mV, preferably in the case of reduction. From -300 to - 1 800 mV, more preferably between -400 and -1 200 mv. The desired potential is adjusted by controlling the battery current, typically between 0.1 mA/cm2 and 1 A/cm2, preferably between 1 mA/cm2 and 0.1 A/cm2. The method of the invention can be carried out using a reducing or oxidizing agent. . The reductant in the reversible oxidation reduction potential system is produced at the cathode, and the oxidant is produced at the anode. For example, a halide such as sodium chloride or sodium bromide can be anodized to form an oxidant hypohalous acid. In general, any inorganic or organic oxidation reduction system can be used to obtain the desired potential. Therefore, people who are familiar with this art have to find a suitable redox system. The process of the present invention is preferably carried out with an inorganic reducing agent or oxidizing agent. For example, useful reducing agents include: Printed by the Ministry of Economic Affairs, the Intellectual Property Office, the Consumer Cooperative, which produces a metal complex with an inorganic or organic ligand at the cathode, wherein the metal is in a low-cost state, that is, in a reduced state. Appearing, preferably an iron (ruthenium) or tin (II) complex having an inorganic or organic ligand, more preferably a ligand containing a 2-hydroxyethyl or polyhydroxycarboxylic acid ruthenium (II) complex, - replaced. Examples are triethanolamine and polyhydroxycarboxylic acids, such as 1,2-dicarboxy oxime or iron (II) complex of sulfonic acid, -tin (II) compounds, such as hexahydroxy hydride dissolved in an alkaline solution. Stannate, - the dithionite produced by cathodic reduction, can be used for neutral and weak paper scales. Applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) -12 - 1276667 V. Description of invention (9 Acidic In solution, for example, useful oxidants include: (Please read the notes on the back and fill out this page) - _--oxygen compounds, preferably hypochlorite and hypobromite. Electrochemical product of a mixture of hypobromite and hypochlorite composed of a mixture of 〇·01 mol/liter to 5 mol/L) and NaBr (〇〇1 mol/liter to 1 旲/L) Resulting in an undesired bleaching effect. The chloride: bromide molar is preferably between 5 and 1 ,, a metal complex containing an inorganic or organic ligand, wherein the metal is in a high price state That is, an oxidized state occurs, preferably a metal complex of iron (III) containing an inorganic or organic ligand and (ΙΠ) a metal complex, more preferably 2, 2, dipyridyl iron (111), hexacyanoferrate ferric (ruthenium) and trans cyclohexane _ 1,2-diamine-ruthenium, ruthenium , hydrazine, hydrazine, manganese (III) acetate, an alicyclic, heterocyclic or aromatic compound containing a NO, hydrazine or HNR-OH group, more preferably 2,2,6,6-tetramethyl Piperidin-1-yloxy (TEMPO) and uric acid or - Hydrogen peroxide is produced at the cathode by oxygen reduction or other electrochemically regenerable inorganic or organic peroxide. Printed by the Intellectual Property Office of the Ministry of Economic Affairs and the Consumer Cooperatives. The above reducing agents and oxidizing agents can also be mixed with other reducing agents and oxidizing agents, respectively. The mixing ratio of each mixture is not important. Preferably, the reducing agent and oxidizing agent are used at a concentration of between 0.1 millimole/liter and 5 millimoles per liter, more preferably between 1 millimol/liter and 0.1 mole/liter. The process according to the invention is generally carried out at temperatures suitable for the dye, suitable for the redox system and especially for the color change desired. The method according to the present invention is preferably carried out between 15 ° C and 150 ° C, and the paper size is better applicable to the Chinese National Standard (CNS) A4 specification (210×297 mm). 1276667 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed A7 B7 V. Description of the invention (i〇) Between 20 ° C and 95 ° C, preferably between 40 ° C and 60 ° C. As for the dyed textile material to be treated, since the method according to the present invention is applicable to the material, there is no technical limitation. Such materials may be in the form of fibers, yarns, woven fabrics, woven materials or products that have been fully or partially completed. The dyed textile material is preferably composed of a fibrous material composed of cellulose fibers, synthetic fibers or blends thereof. Particularly preferred are cellulosic fibers and dyed textile materials comprising the blend of the cellulosic fibers and fibers which have been formed into fibers, such as polyester or polyamide fibers. However, textile materials composed of polyester or polyamide may also be used. There are no restrictions on the dye to be changed. For example, reactive dyes, variable dyes, sulfur-containing dyes, direct dyes, naphthol dyes, disperse dyes, acid dyes, cationic dyes or metallized dyes can all be colored in the manner of the present invention. Cellulose fibers can be dyed with any grade of dye customarily used in such materials, preferably reactive dyes, variable dyes, sulfur-containing dyes or direct dyes. The material composed of the polyester fiber can be dyed with, for example, a dispersion type dye. The method according to the invention is particularly suitable for treating cotton materials which have been dyed in indigo. It can be seen that the dye and the redox system must be compatible with each other, that is, the reducing agent or oxidizing agent must be capable of reacting with the dye which can change the dyeing. For example, the azo-containing dye can be reductively cleaved or the indigo dye can be reversibly reduced. The treatment liquid is preferably recycled between the treatment assembly and the electrolysis cell, and the electrochemically generated active chemical substance can also be transported to the treatment assembly, so that the predetermined concentration of the reaction chemical does not limit the current density of the electrolysis cell. These adjustments can be based on the electrolytic current and redox system used. The standard paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) _ 14 - ^ 装 订, (Please read the back note first) Fill in this page again. 1276667 Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, Printed Α7 ..., Β7 5, Invention Description &) Knowledge calculation. For example, if the battery current is 20 amps and the concentration of the redox system is 0.05 mol/liter and the concentration of the starting chemical is not less than 0. 04 mol/l, then a calculation rate of 1.24 L/min is required between the process assembly and the current. Other methods according to the invention The parameter ratio, pH, and auxiliary reagents, such as dispersants, detergents, lubricants, or enzymes, must be included. Because the redox potential produces a specific concentration of active chemical and the amount of the chemical will follow the liquid. The ratio is changed, so the ratio of the liquid must be taken into consideration. Because many redox chemistries have strong pH dependence, this pH will not only affect the measured redox potential, The chemical activity of the chemical substance may also be affected. The dispersing agent and/or the wetting agent may be added until the treatment liquid can be modified to infiltrate the dyed textile material to be treated, and the dyeing pigment may be modified from the textile material. Separation and dispersion. Lubricants can be used to reduce any resulting shearing effects. For example, cellulase enzymes can separate dyed fiber fragments and dyed textile materials to be treated, thus enhancing any honing treatment. Reducing active enzymes can enhance dye damage under appropriate conditions, thereby enhancing or modifying the desired color change. All of the aforementioned auxiliary agents are inexpensive. If used, what type of dosage must be used in the method of the present invention It can be confirmed by those skilled in the art. [Simplified description of the drawings] Fig. 1 is a schematic diagram suitable for the arrangement of the method of the present invention. The working electrode b, the film d, the opposite electrode e, the power supply line c and An electrolytic cell composed of a power supply a for generating a reducing agent or an oxidizing agent (the redox combination to be used) in the electrolyte k, the electrolyte k passing through The system g is extracted into the process assembly m. The process assembly contains the dyed paper size to be processed according to the Chinese National Standard (CNS) A4 specification (210X 29*7 mm) (please read the notes on the back and fill in the form) This page)
-15· 1276667 經濟部智慧財產局員工消費合作社印製 Α7 Β7 五、發明説明（12 ) 紡織物料，該已染色之紡織物料係於處理裝配中施以額外 的機械及/或水應力。藉由該氧化還原裝置i測量該處理裝 配中之電解液h的氧化還原電位。經測得之數値將成爲經 由該控制迴圏之電源供應器a供應電流強度之調整基準。 此等將可供以控制該氧化還原電位並因而控制所欲於已染 色之紡織物料上達到之處理效果。使用之後，該處理液經 由該處理裝配之出口 j落下，該紡織物料接著進行沖洗處理 。落下之處理液可送至再生段。 第2圖顯示該電解電池及該處理裝配構成之單元並且 該二電極就置於欲處理之已染色紡織物料旁邊，以及該二 工作相之配置圖式。電解期間，該電源供應器a經由電源 線c供應電力至該工作電極b及相反電極e。欲處理之已染 色之紡織物料f包含電解所需之電解質用量，因而該電池 內容物h與該處理液k係相同的。因爲電位測量由於幾何 形狀故較昂貴並且較不方便，所以在中斷電源供應之後進 行測量，藉由該線路i，將該線路i接至該工作電極b，及 該參考電極η之輔助，測量殘餘電位。因此間歇性地測量 電位並控制電流以調整所欲之氧化還原電位。 實施例1 :於pH爲10.0至10.2時利用次氯酸鹽淡化靛藍色 電解電池之構成： 陽極：含鉑混合氧化物塗層之膨脹的鈦金屬，二電極 ，各活性長度爲10公分並且寬度3.0至3·1公分。 橫隔膜：那費（Nafion)陽離子交換膜 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐) Γ16 _ ILI--Ί--裝-----Γ---訂-------- (請先閱讀背面之注意事項再填寫本頁) 1276667 A7 B7 五、發明説明（13 ) 陰極··約100平方公分之不銹鋼 (請先閲讀背面之注意事項再填寫本頁) 藉由近靜態泵以150毫升/分之速率產生該處理裝置/電 解電池循環。在該處理裝置中，該電解液係以磁攪拌子（500 轉/分）攪動並加熱。該容器包含鉑電極及參考電極，以及溫 度測量及pH測量系統。電解期間依計量添加鹼性物至該陽 極電解液以保持固定的pH。 陽極電解液：體積850毫升，1克/升之碳酸鈉p.A及 10克/升之氯化鈉p. A。 陰極電解液體積：350毫升。陰極電解液組成與陽極電 解液同。 織物重量：11.18克之染成靛藍色的棉織布（丁尼布）。 起始溫度：23.5°C，處理溫度50°C。 將電池電流控制在1〇〇毫安培至5〇0毫安培（電池電壓 .2.40至5.10伏特）之間’俾於PH爲1〇.〇至10.2時將氧化還 原電位調整爲+440至+470毫伏特持續35分鐘。 樣品1係於此等條件下處理丨5分鐘，樣品2係處理3 5 分鐘。 經濟部智慧財產局員工消費合作社印製 移出之樣品以冷水沖洗，離心脫水並於1丨〇°C下乾燥。 持續淡化可由L値（CIELab系統）識別。 以Lab座標代表如下： L a b 原始樣品 24.30 + 1.02 -13.10 已處理樣品1 26.00 + 0.94 -13.98 已處理樣品2 27.13 + 0.83 -13.66 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐] 1276667 A7 B7 五、發明説明（14 ) 實施例2 :於pH爲7.8至8·6時利用次氯酸鹽淡化靛藍色 建構該電解電池並且以實施例1之方法進行。 (請先閱讀背面之注意事項再填寫本頁) 陽極電解液：體積850毫升，0.5克/升之碳酸鈉p.a、 〇·5克/升二碳酸鈉及1〇克/升之氯化鈉ρ·Α，陰極電解液組 成與陽極電解液相同。 織物重量：10.86克之染成靛藍色的棉織布（丁尼布）。 起始溫度：24.8°C，處理溫度50°C。 將電池電流控制在200毫安培至500毫安培（電池電壓 3.10至4· 80伏特）之間，俾於pH爲8.1時將氧化還原電位 調整爲+700至+720毫伏特持續32分鐘。 樣品1係於此等條件下處理12分鐘，樣品2係處理32 分鐘。 移出之樣品以冷水沖洗，離心脫水並於11 〇°C下乾燥。 持續淡化可由L値（CIELab系統）識別。 以Lab座標代表如下： L a b 原始樣品 24.30 + 1.02 -13.10 已處理樣品1 26.44 + 1.02 -13.89 已處理樣品2 27.48 + 0.99 -14.33 經濟部智慧財產局員工消費合作杜印製 實施例3 :於pH爲10.2至10.6時利用次氯酸鹽淡化靛 藍色 -18- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1276667 A7 B7 五、發明説明（15 ) 建構該電解電池並且以實施例1之方法進行。 陽極電解液：體積800毫升，1.0克/升之碳酸鈉p.A、 0.1克/升二碳酸鈉及10克/升之氯化鈉P.A，陰極電解液組 成與陽極電解液相同。 織物重量：10.93克之染成靛藍色的棉織布（丁尼布）。 起始溫度：21.1°C，處理溫度50°C。 將電池電流控制在0毫安培至500毫安培（電池電壓 5.15伏特）之間，俾於ρ Η爲10.5時將氧化還原電位調整爲 + 455至+555毫伏特持續45分鐘。 樣品1係於此等條件下處理25分鐘，樣品2係處理45 分鐘。 移出之樣品以冷水沖洗，離心脫水並於110°c下乾燥。 持續淡化可由L値（CIELab系統）識別。 以Lab座標代表如下： (請先閲讀背面之注意事項再填寫本頁) -裝. 、11 經濟部智慧財產局員工消費合作社印製 L a b 原始樣品 1 24.30 + 1.02 -13.10 已處理樣品1 26.75 + 0.72 -14.31 已處理樣品2 26.14 + 0.71 -14.39 ►線 實施例4 :於pH爲8.1至8.6時利用次氯酸鹽/溴化鉀淡化 靛藍色 建構該電解電池並且以實施例1之方法進行。 陽極電解液：體積800毫升，0.5克/升之碳酸鈉P. A、 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） -19 - 1276667 A7 ______ B7_ 五、發明説明（16 ) 0.5克/升二碳酸鈉、1〇克/升之氯化鈉ρ· A及0· 1克/升之溴 化鉀，陰極電解液組成與陽極電解液相同。 織物重量：10.90克之染成靛藍色的棉織布（丁尼布）。 起始溫度：22.9°C，處理溫度50°C。 將電池電流控制在50毫安培至500毫安培（電池電壓 2·4至5.0伏特）之間，俾於pH爲8.1至8.6時將氧化還原電 位調整爲+720至+750毫伏特持續40分鐘。 樣品1係於此等條件下處理20分鐘，樣品2係處理40 分鐘。 移出之樣品以冷水沖洗，離心脫水並於110°C下乾燥。 持續淡化可由L値（CIELab系統）識別。 以Lab座標代表如下： L a b 原始樣品 24.30 + 1.02 -13.10 已處理樣品1 48.89 -5.78 -2.56 已處理樣品2 54.27 -65.0 -0.89 實施例5 : pH爲8.9至9.5時利用次氯酸鹽/溴化鉀淡化靛 藍色 建構該電解電池並且以實施例1之方法進行。 陽極電解液：體積800毫升，0.5克/升之碳酸鈉ρ.A、 0.5克/升二碳酸鈉、10克/升之氯化鈉p.A及0.1克/升之溴 *化鉀，陰極電解液組成與陽極電解液相同。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） - (請先閲讀背面之注意事項再填寫本頁) 裝·-15· 1276667 Printing by the Intellectual Property Office of the Ministry of Economic Affairs, Employees' Consumption Cooperatives Α7 Β7 V. INSTRUCTIONS (12) Textile materials, which are subjected to additional mechanical and/or water stresses in the processing assembly. The redox potential of the electrolytic solution h in the treatment assembly was measured by the redox device i. The measured number will be the adjustment reference for the current intensity supplied by the power supply a returned by the control. These will be available to control the redox potential and thereby control the treatment effect desired on the dyed textile material. After use, the treatment liquid is dropped through the outlet j assembled by the treatment, and the textile material is then subjected to a rinsing treatment. The falling treatment liquid can be sent to the regeneration section. Figure 2 shows the electrolysis cell and the unit of the process assembly and the two electrodes are placed next to the dyed textile material to be treated, and the configuration of the two working phases. During electrolysis, the power supply a supplies power to the working electrode b and the opposite electrode e via the power supply line c. The dyed textile material f to be treated contains the amount of electrolyte required for electrolysis, and thus the battery contents h are the same as the treatment liquid k. Since the potential measurement is expensive and inconvenient due to the geometry, the measurement is performed after the power supply is interrupted, by which the line i is connected to the working electrode b, and the reference electrode η is assisted, and the residual is measured. Potential. Therefore, the potential is measured intermittently and the current is controlled to adjust the desired redox potential. Example 1: Composition of a hypochlorite evaporating indigo blue electrolytic cell at a pH of 10.0 to 10.2: Anode: expanded titanium metal with platinum mixed oxide coating, two electrodes, each having an active length of 10 cm and a width 3.0 to 3.1 cm. Diaphragm: Nafion cation exchange membrane This paper scale applies to China National Standard (CNS) A4 specification (210X 297 mm) Γ16 _ ILI--Ί--装-----Γ---订-- ------ (Please read the note on the back and fill out this page) 1276667 A7 B7 V. Description of invention (13) Cathode · About 100 square centimeters of stainless steel (please read the notes on the back and fill out this page) The treatment unit/electrolytic cell cycle was generated by a near static pump at a rate of 150 ml/min. In the treatment apparatus, the electrolytic solution was agitated and heated with a magnetic stirrer (500 rpm). The container contains a platinum electrode and a reference electrode, as well as a temperature measurement and pH measurement system. Alkaline is added to the anode electrolyte during electrolysis to maintain a fixed pH during electrolysis. Anolyte: volume 850 ml, 1 g/l sodium carbonate p.A and 10 g/l sodium chloride p. A. Catholyte volume: 350 ml. The catholyte composition is the same as the anode electrolyte. Fabric weight: 11.18 grams of cotton woven fabric (denib) dyed in indigo. Starting temperature: 23.5 ° C, processing temperature 50 ° C. Control the battery current between 1 〇〇 mA to 5 〇 0 mA (battery voltage 2.40 to 5.10 volts). Adjust the oxidation-reduction potential to +440 to +470 when the pH is 1 〇.〇 to 10.2. The millivolts last for 35 minutes. Sample 1 was treated for 5 minutes under these conditions, and sample 2 was treated for 3 5 minutes. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumer Cooperatives. The removed samples were rinsed with cold water, centrifuged and dried at 1 °C. Continuous fade can be identified by L値 (CIELab system). The Lab coordinates are represented as follows: L ab Original sample 24.30 + 1.02 -13.10 Processed sample 1 26.00 + 0.94 -13.98 Processed sample 2 27.13 + 0.83 -13.66 This paper size applies to Chinese National Standard (CNS) A4 size (210X297 mm) 1276667 A7 B7 V. INSTRUCTION DESCRIPTION (14) Example 2: The electrolytic cell was constructed by using hypochlorite to dilute indigo at a pH of 7.8 to 8. 6 and was carried out in the same manner as in Example 1. (Read the back side first) Precautions and fill in this page) Anode electrolyte: volume 850 ml, 0.5 g / l sodium carbonate pa, 〇 · 5 g / l sodium dicarbonate and 1 g / l sodium chloride ρ · Α, catholyte The composition is the same as the anolyte. Fabric weight: 10.86 g of cotton woven fabric (denib) dyed in indigo. Starting temperature: 24.8 ° C, processing temperature 50 ° C. Control battery current from 200 mA to 500 Between milliamperes (battery voltage 3.10 to 4.80 volts), the oxidation-reduction potential was adjusted to +700 to +720 millivolts for 32 minutes at pH 8.1. Sample 1 was treated under these conditions for 12 minutes. Sample 2 was treated for 32 minutes. Rinse with cold water, centrifuge and dehydrate and dry at 11 ° C. Continuous desalination can be identified by L値 (CIELab system). The Lab coordinates are as follows: L ab Original sample 24.30 + 1.02 -13.10 Processed sample 1 26.44 + 1.02 -13.89 Processed Sample 2 27.48 + 0.99 -14.33 Ministry of Economic Affairs Intellectual Property Office Staff Consumption Cooperation Du Printing Example 3: Use hypochlorite to dilute indigo -18 at pH 10.2 to 10.6 - This paper scale applies to Chinese national standards ( CNS ) A4 size (210X297 mm) 1276667 A7 B7 V. Description of the invention (15) The electrolytic cell was constructed and carried out as in Example 1. Anolyte: volume 800 ml, 1.0 g/l sodium carbonate pA, 0.1克 / liter of sodium dicarbonate and 10 g / liter of sodium chloride PA, the composition of the catholyte is the same as that of the anolyte. Fabric weight: 10.93 g of cotton woven fabric (denib) dyed in indigo. Starting temperature: 21.1 ° C, processing temperature 50 ° C. The battery current is controlled between 0 mA to 500 mA (battery voltage 5.15 volts), and the oxidation-reduction potential is adjusted to + 455 to +555 mA when ρ Η is 10.5. volt Continued for 45 min. For 25 minutes at a sample-based conditions thereto, based sample 2 for 45 minutes. The sample was removed to cold water, centrifugally extracted and dried at 110 ° c. Continuous fade can be identified by L値 (CIELab system). The Lab coordinates are represented as follows: (Please read the notes on the back and fill out this page) - Installation. 11 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed L ab Original Sample 1 24.30 + 1.02 -13.10 Processed Sample 1 26.75 + 0.72 - 14.31 Processed Sample 2 26.14 + 0.71 - 14.39 ► Line Example 4: The electrolysis cell was constructed using hypochlorite/potassium bromide to dilute indigo at pH 8.1 to 8.6 and was carried out as in Example 1. Anode electrolyte: volume 800 ml, 0.5 g / l sodium carbonate P. A, this paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -19 - 1276667 A7 ______ B7_ V. Invention description ( 16) 0.5 g / liter of sodium dicarbonate, 1 gram / liter of sodium chloride ρ · A and 0 · 1 g / liter of potassium bromide, the composition of the catholyte is the same as the anolyte. Fabric weight: 10.90 grams of cotton woven fabric (denib) dyed in indigo. Starting temperature: 22.9 ° C, processing temperature 50 ° C. The battery current was controlled between 50 mA and 500 mA (battery voltage 2.4 to 5.0 volts), and the redox potential was adjusted to +720 to +750 millivolts for 40 minutes at pH 8.1 to 8.6. Sample 1 was treated under these conditions for 20 minutes and sample 2 was treated for 40 minutes. The removed sample was rinsed with cold water, centrifuged and dried at 110 °C. Continuous fade can be identified by L値 (CIELab system). The Lab coordinates are represented as follows: L ab Original sample 24.30 + 1.02 -13.10 Processed sample 1 48.89 -5.78 -2.56 Processed sample 2 54.27 -65.0 -0.89 Example 5: Use hypochlorite / bromine at pH 8.9 to 9.5 The electrolytic cell was constructed by dephosphorizing indigo blue and was carried out in the same manner as in Example 1. Anode electrolyte: volume 800 ml, 0.5 g/l sodium carbonate ρ.A, 0.5 g/l sodium dicarbonate, 10 g/l sodium chloride pA and 0.1 g/l bromine potassium, catholyte The composition is the same as the anolyte. This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) - (Please read the note on the back and fill in this page)
、1T 經濟部智慧財產局員工消費合作社印製 1276667 A7 B7 五、發明説明（17 ) 織物重量：10.78克之染成靛藍色的棉織布（丁尼布）。 起始溫度：21.3°C，處理溫度21.3至22.2°C。 將電池電流控制在50毫安培至500毫安培（電池電壓 2.2至5.1伏特）之間，俾於pH爲8.9至9.5時將氧化還原電 位調整爲+710至+745毫伏特持續30分鐘。 樣品1係於此等條件下處理10分鐘，樣品2係處理30 分鐘。 移出之樣品以冷水沖洗，離心脫水並於110°c下乾燥。 持續淡化可由L値（CIELab系統）識別。 以Lab座標代表如下： (請先閱讀背面之注意事項再填寫本頁) -裝· L a b 原始樣品 24.30 + 1.02 -13.10 已處理樣品1 27.33 + 0.49 -14.95 已處理樣品2 30.53 -0.92 -15.481T Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 1276667 A7 B7 V. Invention description (17) Fabric weight: 10.78 grams of cotton woven fabric (Dinnibu) dyed in indigo. Starting temperature: 21.3 ° C, treatment temperature 21.3 to 22.2 ° C. The battery current was controlled between 50 mA and 500 mA (battery voltage 2.2 to 5.1 volts), and the redox potential was adjusted to +710 to +745 millivolts for 30 minutes at pH 8.9 to 9.5. Sample 1 was treated under these conditions for 10 minutes and sample 2 was treated for 30 minutes. The removed sample was rinsed with cold water, centrifuged and dried at 110 °C. Continuous fade can be identified by L値 (CIELab system). The Lab coordinates are represented as follows: (Please read the notes on the back and fill out this page) - Loading · L a b Original sample 24.30 + 1.02 -13.10 Processed sample 1 27.33 + 0.49 -14.95 Processed sample 2 30.53 -0.92 -15.48
、1T ▼線 經濟部智慧財產局員工消費合作杜印製 實施例6 :於pH爲7.5至7.7時利用次氯酸鹽/溴化鉀淡化 靛藍色 建構該電解電池並且以實施例1之方法進行。 陽極電解液··體積800毫升，1.0克/升二碳酸鈉、10 克/升之氯化鈉p. A及0.1克/升之溴化鉀，陰極電解液組成 與陽極電解液相同。 織物重量·· 10.78克之染成靛藍色的棉織布（丁尼布）。 起始溫度·· 21.9°C，處理溫度21.9至22.9°C。 本紙張尺度適用中國國家標準（CNS )八4規格< 21〇χ297公釐） -21 - 1276667 A7 B7 五、發明説明（18 ) (請先閱讀背面之注意事項再填寫本頁) 將電池電流控制在2 0毫安培至5 0 0毫安培（電池電壓 1· 65至5·1伏特）之間，俾於PH爲7.5至7.7時將氧化還原 電位調整爲+710至+815毫伏特持續30分鐘。 樣品1係於此等條件下處理33分鐘，樣品2係處理63 分鐘。 移出之樣品以冷水沖洗，離心脫水並於110°c下乾燥。 持續淡化可由L値（CIELab系統）識別。 以Lab座標代表如下： L a b 原始樣品 24.30 + 1.02 -13.10 已處理樣品1 38.32 + 0.27 -15.18 已處理樣品2 28.41 + 0.11 -15.31 實施例7 : pH爲7.1至7.7時利用次氯酸鹽/溴化鉀淡化靛 藍色 建構該電解電池並且以實施例1之方法進行。 經濟部智慧財產局員工消費合作社印製 陽極電解液：體積800毫升，1.0克/升二碳酸鈉、10 克/升之氯化鈉A及0.1克/升之溴化鉀，陰極電解液組成 與陽極電解液相问。 織物重量：10.34克之染成靛藍色的棉織布（丁尼布）。 起始溫度：21.1°C，處理溫度21.1至22.0°C。 將電池電流控制在500毫安培（電池電壓4·8至5.05伏 特）之間，俾於pH爲7.7至8.3時將氧化還原電位調整爲 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1276667 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明〇9 ) + 759至+825毫伏特持續30分鐘。 樣品1係於此等條件下處理i 〇分鐘，樣品2係處理30 分鐘。 移出之樣品以冷水沖洗，離心脫水並於110°C下乾燥。 持續淡化可由L値（CIELab系統）識別。 以Lab座標代表如下： L a b 原始樣品 24.30 + 1.02 -13.10 已處理樣品1 35.17 -3.05 -11.55 已處理樣品2 45.05 -5.70 -4.88 實施例8 :於pH爲4.6時利用紫尿酸淡化反應性染色織布 建構該電解電池並且以實施例1之方法進行。 陽極電解液：體積770毫升，1.0克/升之紫尿酸、12 克/升之醋酸及4克/升之氫氧化鈉， 陰極電解液：300毫升40克/升之氫氧化鈉水溶液。 織物重量：4.1克之反應性染色棉布（紅）。 起始溫度：26.7t：，處理溫度37.1至53IC。 將電池電流控制在0毫安培至500毫安培（電池電壓5·3 伏特）之間，俾於pH爲4.6時將氧化還原電位調整爲+640.7 至+ 6 3 3毫伏特持續3 6分鐘。 ’樣品1係於此等條件下處理16分鐘，樣品2係處理36 分鐘。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -23 - I—.---1------Ί--IT---- (請先閱讀背面之注意事項再填寫本頁) 1276667 A7 B7 五、發明説明p0 ) 移出之樣品以冷水沖洗，離心脫水並於1 lcrc下乾燥。 持續淡化可由L値（CIELab系統）識別。 以Lab座標代表如下： L a b 原始樣品 43.66 +64.15 + 6.26 已處理樣品1 43.57 +58.80 + 3.11 已處理樣品2 44.54 +57.51 + 2*91 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 實施例9 : pH爲4.6時利用紫尿酸淡化反應性染色織布 建構該電解電池並且以實施例1之方法進行。 陽極電解液：體積800毫升，1.0克/升之紫尿酸、12 克/升之醋酸及4克/升之氫氧化鈉， 陰極電解液：300毫升40克/升之氫氧化鈉水溶液。 織物重量：4·55克之反應性染色棉布（紅）。 起始溫度：35.5°C，處理溫度35.5至55.8°C。 將電池電流控制在200毫安培至500毫安培（電池電壓 3.2至4· 55伏特）之間，俾於PH爲4.6時將氧化還原電位調 整爲+608.7至+661毫伏特持續55分鐘。 樣品1係於此等條件下處理31分鐘，樣品2係處理55 分鐘。 移出之樣品以冷水沖洗，離心脫水並於110°C下乾燥。 持續淡化可由L値（CIELab系統）識別。 以Lab座標代表如下： 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） _ 24 - 1276667 A7 B7 五、發明説明p1 ) L a b 原始樣品 43.66 + 64.1 5 + 6.26 已處理樣品1 44.86 + 56.39 + 2.39 已處理樣品2 47.68 +53.40 + 1.67 實施例10 : pH爲4.6時利用紫尿酸淡化硫黑1染色之 織布 建構該電解電池並且以實施例1之方法進行。 陽極電解液：體積800毫升，1.0克/升之紫尿酸、12 克/升之醋酸及4克/升之氫氧化鈉， 陰極電解液：300毫升40克/升之氫氧化鈉水溶液。 織物重量：4.62克之以浸流法（pad-steam process)用180 克/升之硫黑1染色之棉布。 起始溫度：24°C，處理溫度24至53°C。 將電池電流控制在200毫安培至500毫安培（電池電壓 3 · 2 5至5.2伏特）之間，俾於p Η爲4.6時將氧化還原電位調 整爲+ 5 64至+ 615毫伏特持續31分鐘。 樣品1係於此等條件下處理31分鐘，樣品2係處理55 分鐘。 移出之樣品以冷水沖洗，離心脫水並於11 〇 °C下乾燥。 持續淡化可由L値（CIELab系統）識別。 以Lab座標代表如下： 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 「25- (請先閱讀背面之注意事項再填寫本頁) 裝- 、11 經濟部智慧財產局員工消費合作社印製 1276667 A7 B7 五、發明説明P2 ) L a b 原始樣品 20.00 + 0.34 -0.80 已處理樣品1 19.72 + 0.10 -0.41 已處理樣品2 20.67 + 0.30 + 0.35 經濟部智慧財產局員工消費合作社印製 實施例11 : pH爲4.6時利用紫尿酸淡化硫黑1染色之 織布 建構該電解電池並且以實施例1之方法進行。 陽極電解液：體積800毫升，1.0克/升之紫尿酸、12 克/升之醋酸及4克/升之氫氧化鈉， 陰極電解液：300毫升40克/升之氫氧化鈉水溶液。 織物重量：4.62克之以浸流法用180克/升之硫黑1染 色之棉布。 起始溫度：21.6°C，處理溫度21.6至52.6°C。 將電池電流控制在0毫安培至500毫安培（電池電壓5.2 伏特）之間，俾於pH爲4.6時將氧化還原電位調整爲+477 至+582毫伏特持續31分鐘。 樣品1係於此等條件下處理20分鐘，樣品2係處理40 分鐘。 移出之樣品以冷水沖洗，離心脫水並於11(TC下乾燥。 持續淡化可由L値（CIELab系統）識別。 以Lab座標代表如下： (請先閱讀背面之注意事項再填寫本頁) 裝· 灯 ▼線· 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） _ 26 - 1276667 Α7 Β7 五、發明説明) L a b 原始樣品 20.00 + 0.34 -0.80 已處理樣品1 18.61 -0.10 -0.59 已處理樣品2 18.94 -0.13 -0.22 實施例1 2 :用次氯酸鹽/溴化鉀局部破壞染料 已經用靛藍及紅色反應性染料染色並具有12.4克之織 布係以例如四倍量（約50毫升）之1·0克/升之二碳酸鈉、10 克/升之氯化鈉Ρ.Α.及0.1克/升之溴化鉀溶液溼潤。以表面 積爲2.25平方公分之鉑電極當作工作電極並以不銹鋼電極 當作相反電極。於電流中斷之後及電位調整經2分鐘延遲 時間之後測量該工作電極對銀/氯化銀之3Μ氯化鉀之電位 。以所達到之氧化還原電位爲函數而獲得之顏色變化（於電 流中斷2分鐘之後測量）係記載於表1中。原始的靛藍色樣 品見於實施例1，原始的反應性染色樣品見於實施例8。 IL.-------裝----Ί.--訂-----·線 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 -27^ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1276667 A7 _____ B7 五、發明説明（24 ) 表1 染料 電位 時間 電流 電壓 L a b (2分鐘） (毫安培） (秒） 慮安培） (伏特） 靛藍 +800 15 50 4.1 30.71 -0.36 -14.54 靛藍 +1070 30 50 4.0 34.15 -1.25 -13.68 靛藍 +1130 60 50 4.1 41.39 -3.25 -11.78 靛藍 +1230 180 50 4.1 54.44 -6.45 -2.80 紅 +1110 15 50 4.1 61.34 +27.33 +10.10 紅 +1040 30 50 4.1 58.59 +31.57 +9.09 紅 +1130 60 50 4.1 62.28 +26.07 +10.93 紅 +1100 180 50 4.1 67.99 +20.99 +15.67 裝-- (請先閱讀背面之注意事項再填寫本頁) ......^ ·1T ▼ Line Ministry of Economic Affairs Intellectual Property Bureau Staff Consumption Cooperation Du printing Example 6: The electrolysis cell was constructed by using hypochlorite/potassium bromide to dilute indigo at pH 7.5 to 7.7 and was carried out in the same manner as in Example 1. . Anode electrolyte · · volume 800 ml, 1.0 g / l sodium dicarbonate, 10 g / l sodium chloride p. A and 0.1 g / l potassium bromide, the composition of the catholyte is the same as the anolyte. Fabric weight · 10.78 grams of cotton woven fabric (Dinni cloth) dyed in indigo. Starting temperature · 21.9 ° C, processing temperature 21.9 to 22.9 ° C. This paper scale applies to the Chinese National Standard (CNS) VIII 4 specifications < 21〇χ297 mm) -21 - 1276667 A7 B7 V. Invention Description (18) (Please read the back note first and then fill out this page) Control between 20 mA to 500 mA (battery voltage 1 · 65 to 5.1 volts), adjust the redox potential to +710 to +815 millivolts at pH 7.5 to 7.7 for 30 minute. Sample 1 was treated for 33 minutes under these conditions and sample 2 was treated for 63 minutes. The removed sample was rinsed with cold water, centrifuged and dried at 110 °C. Continuous fade can be identified by L値 (CIELab system). The Lab coordinates are represented as follows: L ab Original sample 24.30 + 1.02 -13.10 Processed sample 1 38.32 + 0.27 -15.18 Processed sample 2 28.41 + 0.11 -15.31 Example 7: Use of hypochlorite/bromine at pH 7.1 to 7.7 The electrolytic cell was constructed by dephosphorizing indigo blue and was carried out in the same manner as in Example 1. Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed anolyte: volume 800 ml, 1.0 g / l sodium dicarbonate, 10 g / l sodium chloride A and 0.1 g / l potassium bromide, catholyte composition and The anolyte is asked. Fabric weight: 10.34 grams of cotton woven fabric (denib) dyed in indigo. Starting temperature: 21.1 ° C, treatment temperature 21.1 to 22.0 ° C. The battery current is controlled between 500 mAh (battery voltage 4·8 to 5.05 volts), and the oxidation-reduction potential is adjusted to the paper scale at the pH of 7.7 to 8.3. The Chinese National Standard (CNS) A4 specification (210X297) PCT) 1276667 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed A7 B7 V. Invention Description 〇 9 ) + 759 to +825 millivolts lasts 30 minutes. Sample 1 was treated for i 〇 minutes under these conditions, and sample 2 was treated for 30 minutes. The removed sample was rinsed with cold water, centrifuged and dried at 110 °C. Continuous fade can be identified by L値 (CIELab system). The Lab coordinates are represented as follows: L ab Original sample 24.30 + 1.02 -13.10 Processed sample 1 35.17 -3.05 -11.55 Processed sample 2 45.05 -5.70 -4.88 Example 8: Use of purple uric acid desalination reactive dyeing at pH 4.6 The electrolytic cell was constructed and carried out in the same manner as in Example 1. Anode electrolyte: volume 770 ml, 1.0 g/l of hyaluronic acid, 12 g/l acetic acid and 4 g/l sodium hydroxide, catholyte: 300 ml 40 g/l sodium hydroxide aqueous solution. Fabric weight: 4.1 grams of reactive dyed cotton (red). Starting temperature: 26.7 t:, processing temperature 37.1 to 53 IC. The battery current was controlled between 0 mA to 500 mA (battery voltage 5.3 volts), and the oxidation-reduction potential was adjusted to +640.7 to +63 3 mV for 3 6 minutes at pH 4.6. Sample 1 was treated under these conditions for 16 minutes and sample 2 was treated for 36 minutes. This paper scale applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -23 - I-.---1------Ί--IT---- (Please read the notes on the back first) Fill in this page) 1276667 A7 B7 V. INSTRUCTIONS p0) The removed sample is rinsed with cold water, centrifuged and dried under 1 lcrc. Continuous fade can be identified by L値 (CIELab system). The Lab coordinates are represented as follows: L ab Original sample 43.66 +64.15 + 6.26 Processed sample 1 43.57 +58.80 + 3.11 Processed sample 2 44.54 +57.51 + 2*91 (Please read the note on the back and fill out this page) Intellectual Property Office Staff Consumer Cooperative Print Example 9: The electrolytic cell was constructed using a purple uric acid desalination reactive dyeing woven fabric at a pH of 4.6 and was carried out in the same manner as in Example 1. Anolyte: volume: 800 ml, 1.0 g/l of uric acid, 12 g/l of acetic acid and 4 g/l of sodium hydroxide, catholyte: 300 ml of 40 g/l sodium hydroxide solution. Fabric weight: 4.55 grams of reactive dyed cotton (red). Starting temperature: 35.5 ° C, processing temperature 35.5 to 55.8 ° C. The battery current was controlled between 200 mA and 500 mA (battery voltage 3.2 to 4.5 volts), and the oxidation-reduction potential was adjusted to +608.7 to +661 millivolts for 55 minutes at a pH of 4.6. Sample 1 was treated for 31 minutes under these conditions, and sample 2 was treated for 55 minutes. The removed sample was rinsed with cold water, centrifuged and dried at 110 °C. Continuous fade can be identified by L値 (CIELab system). The Lab coordinates are represented as follows: This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) _ 24 - 1276667 A7 B7 V. Invention description p1 ) L ab Original sample 43.66 + 64.1 5 + 6.26 Processed sample 1 44.86 + 56.39 + 2.39 Treated Sample 2 47.68 +53.40 + 1.67 Example 10: The electrolytic cell was constructed using a purple uric acid desalinated sulfur black 1 dyed fabric at pH 4.6 and was carried out as in Example 1. Anolyte: volume: 800 ml, 1.0 g/l of uric acid, 12 g/l of acetic acid and 4 g/l of sodium hydroxide, catholyte: 300 ml of 40 g/l sodium hydroxide solution. Fabric weight: 4.62 grams of cotton cloth dyed with 180 grams per liter of sulfur black 1 in a pad-steam process. Starting temperature: 24 ° C, processing temperature 24 to 53 ° C. The battery current is controlled between 200 mA to 500 mA (battery voltage 3 · 25 to 5.2 volts), and the oxidation-reduction potential is adjusted to + 5 64 to + 615 mV for 31 minutes when p Η is 4.6. . Sample 1 was treated for 31 minutes under these conditions, and sample 2 was treated for 55 minutes. The removed sample was rinsed with cold water, centrifuged and dried at 11 °C. Continuous fade can be identified by L値 (CIELab system). The Lab coordinates are as follows: The paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) "25- (Please read the back note first and then fill out this page) Installation - , 11 Ministry of Economic Affairs Intellectual Property Bureau staff consumption Cooperative printing 1276667 A7 B7 V. Invention description P2 ) L ab Original sample 20.00 + 0.34 -0.80 Processed sample 1 19.72 + 0.10 -0.41 Processed sample 2 20.67 + 0.30 + 0.35 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing implementation Example 11: The electrolytic cell was constructed using a woven fabric of purple uric acid desalinated sulfur black 1 at a pH of 4.6 and was carried out as in Example 1. Anolyte: volume 800 ml, 1.0 g/l of hyaluronic acid, 12 g/ Acetic acid and 4 g/L sodium hydroxide, catholyte: 300 ml 40 g/l sodium hydroxide solution. Fabric weight: 4.62 g cotton cloth dyed with 180 g/l of sulfur black 1 by immersion method Starting temperature: 21.6 ° C, processing temperature 21.6 to 52.6 ° C. The battery current is controlled between 0 mA to 500 mA (battery voltage 5.2 volts), and the oxidation-reduction potential is adjusted to 4.6 at pH 4.6 + 477 to +582 millivolts for 31 minutes. Sample 1 was treated under these conditions for 20 minutes and sample 2 was treated for 40 minutes. The removed sample was rinsed with cold water, centrifuged and dried at 11 (TC).値 (CIELab system) identification. The Lab coordinates are as follows: (Please read the notes on the back and fill out this page) Installation · Lights ▼ Line · This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) _ 26 - 1276667 Α7 Β7 V. Inventive Note) L ab Original sample 20.00 + 0.34 -0.80 Processed sample 1 18.61 -0.10 -0.59 Processed sample 2 18.94 -0.13 -0.22 Example 1 2: Use hypochlorite / bromination The potassium partial destruction dye has been dyed with indigo and red reactive dyes and has a 12.4 g woven fabric such as four times the amount (about 50 ml) of 1.0 g/L sodium dicarbonate, 10 g/L sodium chloride. Ρ.Α. and 0.1 g/L of potassium bromide solution wet. A platinum electrode with a surface area of 2.25 cm ^ 2 was used as the working electrode and a stainless steel electrode was used as the opposite electrode. After the current interruption and the potential adjustment was delayed for 2 minutes. After measurement The potential of the working electrode against silver/silver chloride 3 Μ potassium chloride. The color change obtained as a function of the achieved redox potential (measured after 2 minutes of current interruption) is described in Table 1. Original indigo The color sample is shown in Example 1, and the original reactive dye sample is found in Example 8. IL.-------Install----Ί.--Book------Line (please read the notes on the back and fill in this page) Printed by the Ministry of Economic Affairs Intellectual Property Office Staff Cooperatives - 27^ This paper scale applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 1276667 A7 _____ B7 V. Invention description (24) Table 1 Dye potential time current voltage L ab (2 minutes) (milliamps) (seconds)安安培) (Volt) Indigo +800 15 50 4.1 30.71 -0.36 -14.54 Indigo +1070 30 50 4.0 34.15 -1.25 -13.68 Indigo +1130 60 50 4.1 41.39 -3.25 -11.78 Indigo +1230 180 50 4.1 54.44 -6.45 -2.80 Red+1110 15 50 4.1 61.34 +27.33 +10.10 Red+1040 30 50 4.1 58.59 +31.57 +9.09 Red+1130 60 50 4.1 62.28 +26.07 +10.93 Red+1100 180 50 4.1 67.99 +20.99 +15.67 Pack -- (Please Read the notes on the back and fill out this page) ......^
、1T 實施例13:用鐵（II/III)錯合物局部破壞染料 ▼線 經濟部智慧財產局員工消費合作社印製 已經用靛藍及紅色反應性染料染色並具有12.4克之織 布係以例如四倍量（約50毫升）之0.024莫耳/升之鐵（Π)錯合 物溶液（三乙醇胺及聚羥基羧酸當作配位基）溼潤。以表面積 爲2.25平方公分之鉑電極當作工作電極並以不銹鋼電極當 作相反電極。於電流中斷之後及電位調整經2分鐘延遲時 間之後測量該工作電極對銀/氯化銀之3M氯化鉀之電位。 以所達到之氧化還原電位爲函數而獲得之顏色變化（於電流 中斷2分鐘之後測量）係記載於表2中。原始的靛藍色樣品 見於實施例1，原始的反應性染色樣品見於實施例8。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -28 - 1276667 A7 B7 五、發明説明P5 ) 表2 染料 電位(2分鐘） 時間 電流 電壓 L a b (毫安培） (秒） (毫安培） (伏特） 靛藍 -950 30 15 2.0 40.79 -2.04 -11.98 靛藍 -938 60 15 2.0 39.99 -116 -13.96 靛藍 -945 180 15 2.2 38.38 -2.44 -11.73 紅 -825 30 15 1.9 46.91 +57.25 +2.01 紅 -916 60 15 L9 50.20 +53.11 +0.17 紅 -824 180 15 2.0 52.69 +48.00 -0.09 (請先閱讀背面之注意事項再填寫本頁) -裝· 經濟部智慧財產局員工消費合作社印製 元件對照表 a:電源供應器 b: 工作電極 c:電源線 d:薄膜 e:相反電極 f:已染色之紡織物料 g:循環系統 h:電解液 i:氧化還原測量裝置 j:出口 k:電解液 1:控制迴圈 m:處理裝配 訂 _線 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）1T Example 13: Partial destruction of dyes with iron (II/III) complexes ▼ Line Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives have printed woven fabrics with indigo and red reactive dyes and have a 12.4 g woven fabric such as four A double amount (about 50 ml) of a 0.024 mol/liter iron (Π) complex solution (triethanolamine and polyhydroxycarboxylic acid as a ligand) is wetted. A platinum electrode having a surface area of 2.25 square centimeters was used as the working electrode and a stainless steel electrode was used as the opposite electrode. The potential of the working electrode against silver/silver chloride 3M potassium chloride was measured after the current interruption and after the potential adjustment was delayed for 2 minutes. The color change obtained as a function of the achieved oxidation-reduction potential (measured after 2 minutes of current interruption) is shown in Table 2. The original indigo sample is found in Example 1, and the original reactive dye sample is found in Example 8. This paper scale applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -28 - 1276667 A7 B7 V. Inventive Note P5) Table 2 Dye potential (2 minutes) Time current voltage L ab (milliamps) (seconds) mAh) (Volt) Indigo-950 30 15 2.0 40.79 -2.04 -11.98 Indigo-938 60 15 2.0 39.99 -116 -13.96 Indigo-945 180 15 2.2 38.38 -2.44 -11.73 Red-825 30 15 1.9 46.91 +57.25 +2.01 Red-916 60 15 L9 50.20 +53.11 +0.17 Red-824 180 15 2.0 52.69 +48.00 -0.09 (Please read the note on the back and fill out this page) -Installation · Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed component comparison Table a: Power supply b: Working electrode c: Power supply line d: Film e: Reverse electrode f: Dyed textile material g: Circulation system h: Electrolyte i: Redox measuring device j: Exit k: Electrolyte 1 : Control loop m: Process assembly order _ line paper size applicable to China National Standard (CNS) A4 specification (210X297 mm)