0301325 A7 B7 五、發明説明（1 ) 發明領域 (請先閱讀背面之注意事項再填寫本頁) 本發明係有關一種用纖維素在三級胺氧化物水溶液中 的溶液製成的纖維素模製體，特別是纖維和含有彼等纖維 的裝配體，之處理方法，於該方法中係將該模製體與紡織 助劑接觸以賦與該模製體改良的性質。 爲本發明目的，”模製體”一詞也特別包括海綿。 作爲黏液法（viscose process)的替代者，最近數年內 已述及許多種方法，其中係將沒有形成衍生物的纖維素溶 解在有機溶劑，有機溶劑/無機鹽組合，或食鹽水溶液之內， 。用此等溶液製成的纖維素纖維稱爲”溶劑紡絲纖維”且 爲 BISF A ( The International Bu reau for the Standardisation of man made Fibres)接受爲 Lyocell 之通稱。有關 Lyocell ，BISFA係定義爲經由從有機溶劑以紡絲程序所得之纖維 素纖維。"有機溶劑〃一詞，BISFA理解爲有機化學品和水 的混合物，"溶劑紡絲"意指沒有衍化的溶解和紡絲。 經濟部智慧財產局員工消費合作社印製 不過，到目前爲止，只有單一種溶劑紡絲纖維素纖維 製造方法達到工業規模的實現。於此方法中，係使用三級 胺氧化物，特別者N-甲基嗎啉氧化物（NMMO)作爲溶 劑。此種方法載於例如US-A 4,246,221中且製得具有突出 的高韌度，高溫模數和高互扣強度（loop strength )。 W0 99/1 9 5 5 5述及一種溶劑紡絲纖維的處理方法，其 中係將該纖維分別與2,4-二氯-6-羥基-1，3,5-三畊或與其鹽 接觸。如此製成的纖維突顯出對原纖化作用（fibrillation) 的抗性。 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -5- 01325 A7 _____ B7_ 五、發明説明（2 ) 從US 5,728,823得知環糊精衍生物，與其他一起者， 2-氯-4-羥基-1，3,5-三啡基-環糊精的鈉鹽。US 5,72 8,823更 述及黏合環糊精衍生物的膜，膜材，紡織品或皮革。用環 糊精衍生物處理過的紡織品適合用於，例如，討厭的氣味 之吸收。 WO 01M 8025述及利用交聯劑以共價鍵結合到一多醣 的環糊精。 頃發現用纖維素在三級胺氧化物水溶液中的溶液製成 之纖維素質模製體可以使用包括環糊精及/或環糊精衍生物 的紡織助劑予以處理，由是造出具有改良的性質之產品。 較佳者，該模製體爲處理絕不乾狀態的纖維。該纖維 可在連續操作製造工廠的後處理階段中之絕不乾狀態下進 行處理。 已知者，環糊精可包括可於隨後，例如一段長時間之 後釋出之藥劑。於本發明方法中，可以在連續製造程序的 過程中，使用此等藥劑同時地及/或隨後地分別給入用環糊 精或環糊精衍生物處理過的纖維。 用紡織助劑進行的處理較佳者係在鹼性環境中實施。 此外也爲較佳者，該紡織助劑另外加添地包括交聯劑 。特別較佳者分別使用2,4-二氯-6-羥基三畊或其鹽 作爲交聯劑。 於根據US 5,72 8,823的技藝中，必須先大力製成環糊 精衍生物，如2-氯-I羥基-I，3,5-三畊基-環糊精的鈉鹽以隨 後將該衍生物施加到要處理的材料之上。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 裝· 、-口 經濟部智慧財產咼S(工消費合作社印製 -6 - 200301325 A7 經濟部智慧財產局工消費合作社印製 五、發明説明（3 ) 頃發現可以將環糊精和交聯劑，特別是2,4-二氯-6-羥 基-1，3,5-三啡添加劑要處理的纖維而不必事先製備該兩種 物質的化合物，由是達到良好的結果。 於本發明方法另一具體實例中，該紡織助劑包括個別 的2-氯-4-羥基-1，3,5-三畊基-環糊精（MCT-CD)或其鹽。 本發明也有關可根據本發明方法得到的溶劑紡絲，纖 維素質纖維，以及含有彼等纖維的纖維組裝物。 實施例1 : 對根據WO 93/ 1 923 〇中所述方法製成的且具有1.3 dtex 纖度的溶劑紡絲纖維依下述在其永不乾燥狀態下進行處理： 於1 : 1 〇的液體比之下，將該等纖維用含有2 0克/升 2,4-二氯-6-羥基-l53,5-三畊，16克/升NaOH和100克/升環 糊精（CAVAMAX W7，製造商 Messrs，Wacker-Chemie) ，的溶液在室溫下浸漬5分鐘。其後，利用擠乾器擠乾該 纖維到100%-1 10%之濕含量且用飽和蒸汽（100% )在100 °C下熱處理5分鐘，再洗脫及乾燥。 於如此製成的纖維中之活性環糊精含量係利用酚酞溶 液的脫色現象經由光度分析法評估且測得爲2.3 3重量％。 纖維的原纖化作用程度係經由個別纖維的抗濕磨鈾性 (wet abrasion resistance)(根據 WO 99/1 95 55 的檢驗方 法）予以測定。根據此檢驗方法，根據本發明處理過的樣 品會轉變成展現出2 1 〇轉之値。與此相比者，未處理的纖 維展現出只有40-6〇轉的濕磨蝕値。 (請先閲讀背面之注意事項再填寫本頁) 裝· 訂 -4ta ^—1 ·· · 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 200301325 A7 B7 五、發明説明（4 ) 實施例2 : 採用實施例1中的相同程序，處理溶液含有2 0克/升 的2,4-二氯-6-羥基-1，3,5-三哄的鈉鹽，16克/升的NaOH， 3〇克/升鈉鹼（soda)與50克/升的環糊精（CAVAMAX W7 ，製造商 Messrs, Wacker-Chemie)。 如此所得纖維中的活性環糊精含量達1.6 5重量％，其 濕磨蝕値爲4 7 0轉。 實施例3: 採用實施例1的相同程序，處理溶液含有3 0克/升鈉 驗和100克/升2 -氯-4-經基-1，3,5 -三D井基-環糊精（]^匸1'-CD; CAVASOL W7 MCT，製造商 Messrs，Wacker-Chemie )° 如此所得纖維中的活性MCT-CD含量爲1.89重量％。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慈財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐）0301325 A7 B7 V. Description of the invention (1) Field of the invention (please read the notes on the back before filling this page) The present invention relates to a cellulose molding made from a solution of cellulose in a tertiary amine oxide aqueous solution. A method for treating a body, particularly a fiber and an assembly containing them, in which the molded body is contacted with a textile auxiliary to impart improved properties to the molded body. For the purposes of the present invention, the term "molded body" also specifically includes sponges. As a substitute for the viscose process, many methods have been described in recent years, in which cellulose without forming derivatives is dissolved in an organic solvent, an organic solvent / inorganic salt combination, or a common salt solution, . Cellulose fibers made from these solutions are called "solvent-spun fibers" and are commonly referred to as Lyocell by BISF A (The International Bu reau for the Standardisation of man made Fibres). With regard to Lyocell, BISFA is defined as cellulose fibers obtained by spinning processes from organic solvents. The term " organic solvent " is understood by BISFA as a mixture of organic chemicals and water, " solvent spinning " means dissolution and spinning without derivatization. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs However, so far, only a single solvent-spun cellulose fiber manufacturing method has reached industrial scale. In this method, a tertiary amine oxide, specifically N-methylmorpholine oxide (NMMO) is used as a solvent. This method is described in, for example, US-A 4,246,221 and is produced with outstanding high toughness, high temperature modulus, and high loop strength. WO 99/1 9 5 5 5 describes a method for treating a solvent-spun fiber, wherein the fiber is respectively contacted with 2,4-dichloro-6-hydroxy-1,3,5-three ploughs or its salt. The fibers so produced highlight resistance to fibrillation. This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) -5- 01325 A7 _____ B7_ V. Description of the invention (2) The cyclodextrin derivative is known from US 5,728,823, together with others, 2 -Chloro-4-hydroxy-1,3,5-triphynyl-cyclodextrin sodium salt. US 5,72 8,823 further describes membranes, membranes, textiles or leathers to which cyclodextrin derivatives are bonded. Textiles treated with cyclodextrin derivatives are suitable, for example, for the absorption of offensive odors. WO 01M 8025 describes cyclodextrins that use a cross-linking agent to covalently bond to a polysaccharide. It was found that a cellulosic molded body made from a solution of cellulose in a tertiary amine oxide aqueous solution can be treated with a textile auxiliary agent including cyclodextrin and / or a cyclodextrin derivative, thereby creating an Products of the nature. Preferably, the molded body is treated with fibers in a never-dry state. The fiber can be processed in a non-drying state during the post-processing stage of a continuously operating manufacturing plant. As is known, cyclodextrins can include agents that can be released later, for example, over a long period of time. In the method of the present invention, the fibers treated with a cyclodextrin or a cyclodextrin derivative can be simultaneously and / or subsequently separately used during the continuous manufacturing process using these agents. The treatment with a textile auxiliary is preferably performed in an alkaline environment. It is also preferable that the textile auxiliary additionally includes a cross-linking agent. It is particularly preferable to use 2,4-dichloro-6-hydroxytrigenate or a salt thereof as a crosslinking agent, respectively. In the technique according to US 5,72 8,823, cyclodextrin derivatives such as 2-chloro-Ihydroxy-I, 3,5-trigenyl-cyclodextrin sodium salt must be vigorously prepared before Derivatives are applied to the material to be processed. This paper size applies to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling out this page). ···-口 Intellectual Property of the Ministry of Economic Affairs 咼 S (Printed by Industry and Consumer Cooperatives-6- 200301325 A7 Printed by the Industrial and Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (3) It was found that cyclodextrin and cross-linking agents can be used, especially 2,4-dichloro-6-hydroxy-1,3,5- The fiber to be treated by the trimorph additive does not need to prepare the two substances in advance, thereby achieving good results. In another specific embodiment of the method of the present invention, the textile auxiliary includes individual 2-chloro-4-hydroxy- 1,3,5-Tricotyl-cyclodextrin (MCT-CD) or a salt thereof. The present invention also relates to solvent spinning, cellulosic fibers, and fiber assemblies containing the fibers, which can be obtained according to the method of the present invention. Example 1: Solvent-spun fibers made according to the method described in WO 93/1 923 〇 and having a titer of 1.3 dtex are treated in their never-dried state as follows: liquid at 1: 1 In contrast, these fibers are used with a content of 20 g / L of 2,4-dichloro-6-hydroxyl-l. 53,5-Sangen, a solution of 16 g / L NaOH and 100 g / L of cyclodextrin (CAVAMAX W7, manufacturer Messrs, Wacker-Chemie) was immersed at room temperature for 5 minutes. After that, the squeeze dryer The fiber was squeezed out to a moisture content of 100% to 10% and heat-treated with saturated steam (100%) at 100 ° C for 5 minutes, and then eluted and dried. The active cyclodextrin content in the fiber thus prepared The decolorization phenomenon using a phenolphthalein solution was evaluated photometrically and was measured to be 2.33% by weight. The degree of fibrillation of the fibers is determined by the wet abrasion resistance of individual fibers (according to WO 99/1 95 55 test method). According to this test method, the sample treated according to the present invention will be transformed to exhibit a range of 2 1 0 revolutions. In comparison, the untreated fiber exhibits only 40 to 60 revolutions. (Please read the precautions on the reverse side before filling out this page) Binding · Staple -4ta ^ —1 ·· · This paper size applies to China National Standard (CNS) A4 (210X297 mm) 200301325 A7 B7 5 Description of the Invention (4) Example 2: The same as in Example 1 is used The treatment solution contains 20 g / L of 2,4-dichloro-6-hydroxy-1,3,5-trisodium salt, 16 g / L of NaOH, 30 g / L of sodium base (soda ) With 50 g / L of cyclodextrin (CAVAMAX W7, manufacturer Messrs, Wacker-Chemie). The content of the active cyclodextrin in the fiber thus obtained reached 1.65% by weight, and its wet abrasion 値 was 470 revolutions. Example 3: Using the same procedure as in Example 1, the treatment solution contained 30 g / L of sodium chloride and 100 g / L of 2-chloro-4-meryl-1,3,5-tri-D-well-based-cyclodextrin (] ^ 匸 1'-CD; CAVASOL W7 MCT, manufacturer Messrs, Wacker-Chemie) The active MCT-CD content in the fiber thus obtained was 1.89% by weight. (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Office of the Ministry of Economic Affairs This paper applies the Chinese National Standard (CNS) A4 specification (210X 297 mm)