1273148 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（1 ) 發明領域 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 BISFA ( The International Bureau 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。 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-N-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（l〇〇P 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-1，3,5·三哄或與其鹽 接觸。如此製成的纖維突顯出對原纖化作用（fibrillation) 的抗性。 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -5- 1273148 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-l，3,5-三畊基-環糊精的鈉鹽。US 5,728,823更 (請先閱讀背面之注意事項再填寫本頁) @及黏合環糊精衍生物的膜，膜材，紡織品或皮革。用環 _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 01/48025述及利用父聯劑以共價鍵結合到一*多醜 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。 經濟部智慧財產局員工消費合作社印製 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-1，3,5-三畊或其鹽 作爲交聯劑。 於根據US 5,728,823的技藝中，必須先大力製成環糊 精衍生物，如2-氯-4-羥基-1，3,5-三畊基-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（210X 297公釐） "~" -6- 1273148 Α7 Β7 五、發明説明（3 ) (請先閲讀背面之注意事項再填寫本頁) 頃發現可以將環糊精和交聯劑，特別是2，4 -二氯-6 ·經 基—1，3，5 -二哄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-l，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W0 93/1923〇中所述方法製成的且具有U 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1:10的液體比之下，將該等纖維用含有20克/升 2,4-二氯-6-羥基·l，3,5-三畊，16克/升NaOH和10Ό克/升環 糊精（CAVAMAX W7，製造商 Messrs，Wackei-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1 00%-1 10%之濕含量且用飽和蒸汽（100% )在1〇0 °C下熱處理5分鐘，再洗脫及乾燥。 經濟部智慧財產局員工消費合作社印製 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 5 5 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 0轉之値。與此相比者，未處理的纖 維展現出只有40-60轉的濕磨鈾値。 ϋ張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） '~~' -7- 1273148 A7 ___ Β7 一 五、發明説明（4 ) 實施例2 : (請先閱讀背面之注意事項再填寫本頁) 手未用貫S也例1中的相同程序，處理溶液含有2 0克/升 的2,4-一氯-6-經基-1，3,5-三哄的鈉鹽，16克/升的Na〇H， 30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1.65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 鹼和1〇〇克/升2-氯-4-羥基-l，3,5-三畊基-環糊精（1^(：1'-CD; CAVASOL W7 MCT，製造商 Messrs，Wacker-Chemie )0 如此所得纖維中的活性MCT-CD含量爲1 ·89重量％。 經濟部智慧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 ) Α4規格（210Χ297公楚） -8-1273148 A7 B7 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperatives Printing V. INSTRUCTIONS (1) Field of the Invention The present invention relates to a cellulose molded body made of a solution of cellulose in a tertiary amine oxide aqueous solution, in particular It is a method of treating fibers and assemblies comprising the fibers, in which the molded body is contacted with a textile aid to impart improved properties to the molded body. For the purposes of the present invention, the term "molded body" also includes, in particular, sponges. As an alternative to the viscose process, a number of methods have been described in recent years in which no cellulose is formed. Dissolved in an organic solvent, an organic solvent/inorganic salt combination, or an aqueous salt solution, cellulose fibers made from such solutions are called solvent-spun fibers, and are BISFA (The International Bureau for the Standardisation of man made Fibres) Accept as a general term for Lyocell. Regarding Lyocell,: BISFA is defined as a cellulose fiber obtained by a spinning process from an organic solvent. The term "organic solvent", BISFA is understood to mean a mixture of organic chemicals and water, and "solvent spinning" means dissolution and spinning without derivatization. However, to date, only a single solvent-spun cellulosic fiber manufacturing process has achieved industrial scale. In this method, a tertiary amine oxide, particularly N-methylmorpholine-N-oxide (NMMO), is used as a solvent. Such a method is described, for example, in US-A 4,246,221 and has a high toughness, high temperature modulus and high 互P strength. W0 99/1 9 5 5 5 describes a method of treating a solvent-spun fiber in which the fiber is contacted with 2,4-dichloro-6-hydroxy-1,3,5·triazine or a salt thereof, respectively. The fiber protrusion thus produced exhibits resistance to fibrillation. (Please read the notes on the back and fill out this page.) This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -5- 1273148 A7 B7 V. Description of invention (2) Known from US 5,728,823 A refined derivative, together with others, a sodium salt of 2-chloro-4-hydroxy-l,3,5-tri-n-n-cyclodextrin. US 5,728,823 (please read the note on the back and fill out this page) @ and film, film, textile or leather with a cyclodextrin derivative. Textiles treated with a ring-form derivative are suitable for use, for example, in the absorption of unpleasant odors. WO 01/48025 describes the use of a parent-linking agent to covalently bond to a ugly cyclodextrin. It has been found that a cellulosic molded body made of a solution of cellulose in a tertiary amine oxide aqueous solution can be treated with a textile auxiliary comprising a cyclodextrin and/or a cyclodextrin derivative, which is improved. The nature of the product. Preferably, the molded body is a fiber which is in a state of being in a dry state. The fibers can be processed in a dry state in the post-processing stage of a continuous operation manufacturing plant. It is known that cyclodextrin can include an agent that can be released afterwards, for example, over a long period of time. In the process of the present invention, the fibers treated with the cyclodextrin or the cyclodextrin derivative can be simultaneously and/or subsequently administered separately during the continuous manufacturing process. Printed by the Intellectual Property Office of the Ministry of Economic Affairs and the Consumer Cooperatives. The treatment with textile auxiliaries is preferably carried out in an alkaline environment. Further preferably, the textile auxiliary additionally comprises a crosslinking agent. It is particularly preferred to use 2,4-dichloro-6-hydroxy-1,3,5-trin or a salt thereof as a crosslinking agent, respectively. In the art according to US Pat. No. 5,728,823, it is necessary to vigorously prepare a cyclodextrin derivative such as a sodium salt of 2-chloro-4-hydroxy-1,3,5-tri-pungry-cyclodextrin to subsequently derivatize the derivative. Applied to the material to be treated. This paper scale applies to China National Standard (CNS) A4 specification (210X 297 mm) "~" -6- 1273148 Α7 Β7 V. Invention description (3) (Please read the note on the back and fill in this page) It has been found that the cyclodextrin and the cross-linking agent, in particular the 2,4-dichloro-6-transyl-1,3,5-diindole additive, can be processed without the need to prepare the compound of the two substances in advance. Is to achieve good results. In another embodiment of the method of the present invention, the textile auxiliary comprises individual 2-chloro-4-hydroxy-l,3,5-tri-n-cyclodextrin (MCT-CD) or a salt thereof. The invention also relates to solvent spinning, fiber quality fibers, and fiber assemblies comprising the fibers obtainable by the process of the invention. Example 1: Solvent-spun fibers made according to the method described in WO 93/1923(R) and having U dtex denier are treated as follows in their never-dried state: at a liquid ratio of 1:10 , the fibers are used to contain 20 g / liter of 2,4-dichloro-6-hydroxyl,3,5-three tillage, 16 g / l NaOH and 10 g / l cyclodextrin (CAVAMAX W7, manufacturer The solution of Messrs, Wackei-Chemie) was immersed for 5 minutes at room temperature. Thereafter, the fiber was extruded by a squeezer to a moisture content of 100% to 10% and heat-treated with saturated steam (100%) at 1 °C for 5 minutes, followed by elution and drying. The active cyclodextrin content printed in the fiber thus produced by the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs was evaluated by photometric analysis using a decolorization phenomenon of the phenolphthalein solution and was found to be 2.33% by weight. The degree of fibrillation of the fibers is determined by the wet abrasion resistance of individual fibers (test method according to WO 99/1 95 5 5). According to this test method, the sample treated according to the present invention is converted to exhibit a enthalpy of 210 rpm. In contrast, untreated fibers exhibited only 40-60 rpm wet-milled uranium. The metric scale applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm) '~~' -7- 1273148 A7 ___ Β7 1-5, invention description (4) Example 2: (Please read the precautions on the back) Fill in this page) The hand does not use the same procedure as in Example 1, the treatment solution contains 20 g / liter of sodium salt of 2,4-chloro-6-carbyl-1,3,5-triazine, 16 g/l Na〇H, 30 g/l sodium soda (soda) and 50 g/l cyclodextrin (CAVAMAX W7, manufacturer Messrs, Wacker-Chemie). The active cyclodextrin content in the fiber thus obtained was 1.65% by weight, and the wet abrasion enthalpy was 470 rpm. Example 3: Using the same procedure as in Example 1, the treatment solution contained 30 g/L of sodium base and 1 g/L of 2-chloro-4-hydroxy-l,3,5-tri-cultivation-cyclodextrin (1^(:1'-CD; CAVASOL W7 MCT, manufacturer Messrs, Wacker-Chemie) 0 The active MCT-CD content of the fiber thus obtained was 1.89% by weight. Printed by the Intellectual Property Office of the Ministry of Economic Affairs This paper scale applies to China National Standard (CNS) Α4 specifications (210Χ297 public Chu) -8-