鯉濟部中央標準局貝工消費合作社印製 五、發明説明（ί ) 本發明係有關一種製造溶劑拉紡（LYOCELL)纖維的 方法，該方法的步驟是將該纖維處於未經乾燥的狀態時， 與一鹼性金羼氫氧化物的一水性溶液進行接觸。 溶劑拉纺（LYOCELL)纖維早為人知，這類纖維的製 造方法在（比方說）美國專利US- 4 ,4 1 6,698中有所描述， 該專利的内容經以參考方式納入本文中。纖維素溶解到一 含有一叔胺N-氧化物（其亦可簡稱作胺氧化物），舉個例 來說，N-甲基氣氮雜環己烷N-氣化物（NMMO)溶劑中。該 溶劑通常另含有一部份的纖維素使用的非溶劑，比方説， 水。這樣生成的溶液經過擠壓通過一合適的模板生産出纖 維，該纖維經過凝結，在水中洗滌以除去溶劑，並經過乾 燥。這個擠壓和凝結的步驟被稱作”溶劑拉紡”，而藉由 這樣的方法所生産的纖維素纖維則被稱作”溶劑拉紡”的 纖維素纖維，或稱作溶劑拉紡（LYOCELL)纖維/大家都 知道，纖維素纖維可藉箸將一纖維素衍生物的溶液擠壓進 入到一凝結和再生的浴池中。像這樣的工法的一値例子是 粘液工法，在該工法中，該纖維素衍生物為纖維素黃原酸 物。溶劑伸拉比起用以製造長型的纖維素構件的其他方法 (比方說，粘膠液工法）來說，有許多優點（比方說，對 環境造成污染的排放物較少）。 我們知道，溶劑拉紡（LYOCELL) 纖維容易毛纖化。 毛纖化是一種現象，其主要發生在當溶劑拉紡（LYOCELL) 纖維在溼式的加工期間，受到機械力時，而其結果造成微 細的縱向的毛纖從該纖維飛出。毛餓化通常被認為在紡繼 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨OX297公釐）一仏〆 (請先閎讀背面之注意事項再填寫本頁) -策·Printed by Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Common Carriage. 5. Description of the invention (ί) The present invention relates to a method for manufacturing a solvent drawn (LYOCELL) fiber. And contacting with an aqueous solution of an alkaline gold rhenium hydroxide. LYOCELL fibers have been known for a long time. The manufacturing method of such fibers is described in, for example, U.S. Patent No. 4,4,1,698, the contents of which are incorporated herein by reference. Cellulose is dissolved in a solvent containing a tertiary amine N-oxide (which may also be simply referred to as an amine oxide), for example, N-methyl azacyclohexane N-gas (NMMO) solvent. The solvent usually contains another part of the non-solvent used in cellulose, for example, water. The solution thus produced is extruded through a suitable template to produce fibers. The fibers are coagulated, washed in water to remove the solvent, and dried. This extrusion and coagulation step is called "solvent drawing", and the cellulose fibers produced by this method are called "solvent drawing" cellulose fibers, or solvent drawing (LYOCELL) ) Fibers / Everyone knows that cellulose fibers can be used to squeeze a solution of a cellulose derivative into a coagulating and regenerating bath. An example of such a method is the viscous method, in which the cellulose derivative is cellulose xanthate. Solvent stretching has many advantages over other methods used to make long cellulosic components (for example, viscose fluid engineering) (for example, it has fewer emissions that pollute the environment). We know that LYOCELL fibers are prone to fibrillation. Wool fibrillation is a phenomenon that occurs mainly when a solvent-drawn (LYOCELL) fiber is subjected to mechanical force during wet processing, and as a result, fine longitudinal hair fibers fly out of the fiber. Mao Henghua is generally considered to be in accordance with the Chinese National Standard (CNS) A4 specification (2 丨 OX297 mm) in the paper size (please read the precautions on the back before filling this page)-policy ·
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經濟部中央標準局負工消費合作社印製 A7 B7 •— _________ ……----------.-—— _______ ____________ 五、發明説明（上） 品的最終用途來説，是不怡人的，而業界也努力試圖藉著 化學的後處理作業，來降低或消除毛纖化的傾向（如美國 專利US-A-5,310,424中所描述者），或藉由選擇適合的伸 拉參數，來降低或消除毛缕化的傾向（舉傾例說，如金球 專利WO-A-95/02082中所描述者）。 一項於1996年12月17日提出的、尚未公告的專利申請 851 15655敘述了一種用以製造一種擠壓成型的溶劑拉紡 (LYOCELL)産品（比方説，溶劑拉紡（LYOCELL) 纖維） 的工法，該步驟包括將一鹼性金屬氫氣化物的水性溶液（ 其含有重量比0 . 2 05K到3.85%的氫氣化物離子）施佈到經過 重行結構的但未經過乾燥的溶劑拉紡（LYOCELL)構件。 也可以使用一含有重量比0.5%到9X的氫氣化鈉的水性溶液 。該鹸性金羼氫氣化物水性溶液可方便地經從一循環的浴 池施佈到該纖維，該經過重行結構的産品在該浴池中停留 的時間可方便地在20秒到90秒之間。這樣的工法據說可以 讓製造出來的溶劑拉紡（LYOCELL)産品具有更好的著染 性、更高的白色度、降低的泛黃性及/或更高的吸收性。 我們知道，纖維素在水性氫氣化鈉溶液中，當氳氣化 鈉的濃度在重量比大約10%時，會顯現出最大泡脹性。另 外，我們也知道，纖維素在水性的氫氣化鈉溶液中的泡脹 程度通常會隨箸溫度的降低而增加。本方法的發明人發現 ,使用含有重量比5 %到15%的氫氧化納的水性溶液處理 未經乾燥的溶劑拉纺（LYOCELL)娥維時，除非待別注意 ，否則會損壞纖維，尤其是在較低的溫度時《這樣的損傷 可能表現在本身的拉張強度的減損、光澤豔度的減損、由 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X W7公釐）〆 (請先閲讀背面之注意事項再填寫本頁)Printed by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives A7 B7 • — _________ …… ----------.-—— _______ ____________ 5. Description of the Invention (Top) For the final use of the product, it is not Pleasant, and the industry is also trying to reduce or eliminate the tendency of fibrillation through chemical post-processing operations (as described in US-A-5,310,424), or by selecting appropriate stretching parameters To reduce or eliminate the tendency to become pilled (for example, as described in the Golden Ball patent WO-A-95 / 02082). An unpublished patent application 851 15655 filed on December 17, 1996 describes a method for manufacturing an extruded LYOCELL product (for example, LYOCELL fiber) The method includes applying an aqueous solution of an alkaline metal hydride (containing hydrogen ions in a weight ratio of 0.205K to 3.85% by weight) to a lyocated solvent-spun fabric that has not undergone drying. member. It is also possible to use an aqueous solution containing sodium hydride in a weight ratio of 0.5% to 9X. The alkaline gold hydroxide hydrous solution can be conveniently applied to the fiber from a circulating bath, and the restructured product can conveniently stay in the bath for between 20 seconds and 90 seconds. Such a method is said to allow the manufactured LYOCELL products to have better dyeing properties, higher whiteness, reduced yellowing, and / or higher absorption. We know that cellulose in aqueous sodium hydride solution exhibits maximum swellability when the concentration of tritium gaseous sodium is about 10% by weight. In addition, we also know that the degree of swelling of cellulose in aqueous sodium hydride solutions usually increases with decreasing temperature. The inventors of this method have found that when treating an un-dried solvent-drawn LYOCELL with an aqueous solution containing 5% to 15% by weight of sodium hydroxide, unless otherwise noted, the fibers will be damaged, especially At lower temperatures, "Such damage may be reflected in the reduction of its tensile strength, the loss of gloss, and the Chinese national standard (CNS) A4 specification (210 X W7 mm) applies to this paper size." (Please first (Read the notes on the back and fill out this page)
經濟部中央標準局貝工消費合#'社印裝 五、發明説明（> ) 於 毛 纖的 溶 解 或 由 於 毛 纖 的離散而造成 重量的 減損，或對 繼 維 造成 其 他 的 破 壞 0 這 造 成在前述 的英國 專利申請案 中 所 敘逑 的 X 法 難 以 控 制 〇 而 本發明卽 在尋求 克服困難之 道 0 根據 本 發 明 的 方 法 9 溶 劑拉紡（LY0CELL) 纖維藉由 一 種 方法 來 製 造 該 方 法 包 括 這樣的步驟：將纖維在未經 乾 燥 的狀 態 與 一 鹼 性 金 羼 氫 氣化物的 水性溶 液接觭，該 水 性 溶液 另 外 含有 1公克/公 升到50公克 /公升 (最好是5公 克 /公升到20公克/公 升 ) 的 一 鹺性金屬 矽酸鹽 (當作無水 的 矽 酸鈉 鹽 Na Si 〇5 計 算 ) 0 根據 本 發 明 提 供 了 一 種 製 造溶劑拉纺（LYOCELL)纖 维 的 方法 9 該 方法 包 括 依 下 述 順序的步 驟： ( 1) 將 纖 維 素 在 一 有 機 溶 劑 中的溶液 擠壓通 過一模.板， 藉 以 生 産 出 一 長 形 物 ( 2) 將 該 長 形 物 通 經 過 至 少 一個盛水 的浴池 ，以便將該 .有 機溶劑 白 該 長 形 物 中 除去，藉 以生産 出一重行結 構 的 纖 維 素 的 構 件 ( 3) 將 一 m 性 金 靥 氫 氣 化 物 的水性溶 液施佈 到該重行結 構 的 纖 維 素 的 構 件 9 ( 4) 將 該 重 行 結 構 的 纖 維 素 的構件洗 滌，以 便將鹼性金 屬 ter 氮 氣 化 物 白 其 上 除 去 ;以及 ( 5) 將 該 重 行 結 構 的纖 維 素 的構.件乾 燥，藉 以生成 溶 劑 拉 紡 ( LY0CELL) 纖維； 該方法 的特 徽 為 9 該 性 金屬氫氧 化物的 水性溶液另 外 含 有一 鹼 性 金 屬 矽 化 物 9 其 濃度在每 公升1到50公克， 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）一么一The Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumption Co., Ltd. Printing 5. Description of the invention () Dissolution of wool fibers or loss of weight due to dispersion of wool fibers, or other damage to Jiwei The X method described in the aforementioned British patent application is difficult to control, and the present invention seeks to overcome the difficulties. 0 The method according to the present invention. 9 Solvent drawn (LYOCELL) fibers are manufactured by a method. The method includes This step is to connect the fiber in an undried state with an aqueous solution of an alkaline gold hydrazone, which further contains 1 g / L to 50 g / L (preferably 5 G / L to 20) Gram / liter) of a monobasic metal silicate (calculated as anhydrous sodium silicate Na Si 〇5) 0 According to the present invention, a method for manufacturing a solvent drawn (LYOCELL) fiber is provided. 9 The method includes The following sequence of steps: (1) Put cellulose in The solution in the organic solvent is squeezed through a die plate to produce an elongated object (2) The elongated object is passed through at least one bath containing water to remove the organic solvent from the elongated object To produce a cellulose structure with a heavy structure (3) An aqueous solution of m-type gold hydrazone is applied to the cellulose structure with a heavy structure 9 (4) cellulose structure with a heavy structure Washing to remove the alkaline metal ter nitrogen compound; and (5) drying the restructured cellulose structure to form a solvent drawn (LYOCELL) fiber; the special feature of this method is 9 Aqueous solution of alkaline metal hydroxide also contains an alkali metal silicide 9 at a concentration of 1 to 50 grams per liter. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm).
經濟部中央標準局貝工消費合作社印製 五、發明説明（牛） 最好是每公升5到20公克（當作無水的矽酸鈉鹽NaiSiih 計算）。該纖維在步驟（5)中首次經過乾燥，因此，該重 行結構的纖維素的構件可另外稱作”未經乾燥”的纖維。 本發明的方法可適用到以連缠的單纖長絲、纖維束或 短纖為形式的溶劑拉紡（LY0CELL)纖維《該溶劑拉紡（ LY0CELL)纖維的纖維細度可在0.5到10分特之間。當本發 明的方法以連績的單纖長絲或纖維束形式施作到溶劑拉纺 (LY0CELL)纖維時，該纖維最好是能在本發明的特徽所 在的步驟裡，維持在鬆弛的狀態。 該鹼性金屬氫氧化物最好是氫氣化鈉，但是，其他化 合物，像是氫化鉀也可以使用。該鹼性金屬氫氧化物的水 性溶液可含有重量比5%到15!K(最好是重量比83；到13%)的 氫氧化鈉。 在該鹼性金屬矽化物裡的鹸性金屬最好是鈉。市面上 所販售的"水玻璃〃的材料，正是適合用來製備本發明中 的水性.溶液的矽酸鈉材料。 該鹾性金靥氫氧化物的水性溶液的溫度最好在〇eC到 60°C之間，更好是在15°C到30°C之間。 該驗性金屬氫氧化物的水性溶液可藉著任何傳統的方 式施佈到該纖維，舉個例來說，使用一循環的浴池、燈心 棉滾筒或噴佈方式。在使用一循環的浴池時，該纖維在該 浴池中的停留時間可方便地在5秒到1 2 0秒之間β 在經鹼性處理步驟之後，鹼性金屬氫氣化合物從該纖 維洗去。在本發明的一實施例中，該纗維以熱水洗滌，最 好繼之以稀釋的水性酸液進行酸洗，以使得該纖維酸鹼值 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐）一?一 (請先閲讀背面之注意事項再填寫本頁) •'樂· 11Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs. 5. Description of invention (cow) It is best to be 5 to 20 grams per liter (calculated as anhydrous sodium silicate NaSiih). The fiber is dried for the first time in step (5). Therefore, the restructured cellulose component may be otherwise referred to as "non-dried" fiber. The method of the present invention can be applied to LYOCELL fibers in the form of entangled single fiber filaments, fiber bundles or staple fibers. The LYOCELL fibers can have a fiber fineness of 0.5 to 10 dtex. between. When the method of the present invention is applied to LYOCELL fibers in the form of continuous single-filament filaments or fiber bundles, the fibers are preferably maintained in a relaxed state during the step where the special emblem of the present invention is located . The alkaline metal hydroxide is preferably sodium hydride, but other compounds such as potassium hydride may be used. The aqueous solution of the alkaline metal hydroxide may contain sodium hydroxide in an amount of 5% to 15! K (preferably 83: 13% by weight) by weight. The alkali metal in the basic metal silicide is preferably sodium. The commercially available " water glass tincture " material is exactly the sodium silicate material suitable for preparing the aqueous solution in the present invention. The temperature of the aqueous solution of the alkaline gold hydroxide is preferably between 0eC and 60 ° C, more preferably between 15 ° C and 30 ° C. The aqueous solution of the qualitative metal hydroxide can be applied to the fiber by any conventional means, for example, using a circulating bath, a core cotton drum, or a spray method. When using a circulating bath, the residence time of the fiber in the bath can conveniently be between 5 seconds and 120 seconds. After the alkaline treatment step, the alkaline metal hydrogen compound is washed away from the fiber. In an embodiment of the present invention, the hydrazone is washed with hot water, preferably followed by pickling with a dilute aqueous acid solution, so that the fiber pH value of this paper is applicable to the Chinese National Standard (CNS) A4 specification. (210X297mm) One? One (Please read the notes on the back before filling out this page) • '乐 · 11
aassii A7 B7 一、發明説明（犮） 低於7。在本發明的另一實施例中，該餓維以一水性酸溶 液洗滌。該酸液可為一礦物酸，像是鹽酸或硫酸，在該水 性的酸溶液中，該礦物酸的湊度在體積比的0.U到20X之 間，最好是體積比的15：到153；之間，或者，它可以是一有 機酸，像是醋酸，在該水性的酸溶液中，該有機酸的濃度 在體積比的25%到75%之間，最好是體積比的403：到60%之間 。該酸洗液可以藉著任何方便的方法施佈到該纖維，舉個 例說，使用一循環的浴池，或燈心棉滾筒，或噴佈方式》 當使用一水性酸液時，該纖維在這樣的一偁循環的浴池中 停留的時間，可方便地在5秒到120秒之間。 本發明的方法的好處是，它可以在傳統的裝備上進行 〇 毛纖化經誘發，並使用測試方法1以評估毛纖化的程 度。 測試方法1 大約0.05克的乾燥纖維經切割成10毫米的短段，放入 到一實驗室攪拌器《加入400毫升的清水、混合物，攪拌 30秒〜3分鐘。所需要實際的攪拌時間視所使用的攪拌葉 而定，且攪拌時間傜經選擇以使得標準的市售LY0CELL纖 維（天絲（Tenc.el),英國葛林斯比市（Grimsby),柯 德勞斯纖維控股公司的註册商標）的樣本毛纖化指數為 6 · 5 〜8.0 〇 收集經過攪拌的繼雒，並將一些繼維放到一顯撤鏡的aassii A7 B7 I. Description of the invention (犮) Less than 7. In another embodiment of the invention, the starvation is washed with an aqueous acid solution. The acid solution may be a mineral acid, such as hydrochloric acid or sulfuric acid. In the aqueous acid solution, the degree of the mineral acid is between 0. U and 20X in volume ratio, and preferably 15: to 15 in volume ratio. 153; or, it may be an organic acid, such as acetic acid, in the aqueous acid solution, the concentration of the organic acid is between 25% and 75% by volume, preferably 403 by volume. : Between 60%. The pickling solution can be applied to the fiber by any convenient method. For example, using a circulating bath, or a wick cotton drum, or spraying method. When using an aqueous acid solution, the fiber is in this way. The time spent in the bath of a round of circulation can conveniently be between 5 seconds and 120 seconds. The advantage of the method of the present invention is that it can be performed on conventional equipment. Hair fibrosis is induced, and Test Method 1 is used to assess the degree of hair fibrosis. Test method 1 Approximately 0.05 g of dried fiber is cut into short segments of 10 mm, and placed in a laboratory stirrer "Add 400 ml of water and mixture, and stir for 30 seconds to 3 minutes. The actual stirring time required depends on the stirring blades used, and the stirring time is selected so that the standard commercially available LYOCELL fiber (Tencel.el, Grimsby, UK, Cod Registered trademark of Rolls Fiber Holding Co., Ltd.) The sample's wool fibrillation index is 6.5 to 8.0. Collect the stirred relays and put some relays into a
i尺度適用中國國家標準（CNS ) A4規格（210X297公釐）_ & Xi scale applies Chinese National Standard (CNS) A4 specification (210X297 mm) _ & X
五、發明説明（b) 接物片上。.另外一些纖維則放到一第二接物片上。這些纖 維在一標準的經過刻度的照片進行比對。每一Μ接物Η上 取下三組的五個讀數，並平均以取得毛纖化指數（F.I.)。 ”零” F.I.對應〃零〃毛缫化。 茲以下述實施例對本發明作一說明，在該實施例中， 除非另有說明，否則所有份量及比例均為重量比。 實施例1 纖維素（1530在NMMO (75¾)與水（10¾)的溶液經 過摘壓通過一吐絲頭，進入一水性的凝結浴池中，以生 成1.7分特的單纖長絲。在以水洗滌除去NMM0之後，該等 單縷長絲在鬆弛的狀態在2 5°C的溫度下，以一水性溶液處 理30秒（該水性溶液含有重量/體積百分比為11%的氫氣 化鈉，以及不同數量的矽酸鈉），在鬆弛的狀態，以從體 積/體積百分比15%的水性硫酸溶液洗滌30秒，然後清洗 並經過乾燥。本項實驗的其他細節與結果如表1中所示： (請先閎讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印裝 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1 一 m A7 B7 五 、發明説明（9 表 矽酸鈉 纖維細度 顳度 延展 毛纖化指數 克/升（g/1) 分特（dtex) cN/tex % F. I. 末經處理的 比對樣本 1.84 37.3 15.2 6.2 0 1.87 29.1 13.7 2.1 10 1 .79 3 5.2 15.7 2.3 20 1.73 39.4 15.8 2.6 30 1.75 38.0 16.2 3 . 1 50 1.80 38.3 15.2 3.7 (請先閎讀背面之注意事項再填寫本頁) ，11* 經濟部中央標準局貞工消費合作社印製 實驗用的溶液係使用標稱含有24 4克/升的矽酸金羼鈉 鹽的"水玻璃"製備的。 經依照本發明的方法所處理的纖維展現了良好的拉張 待性和低的毛纖化傾向，以及良好的豔度，在受到鹼性處 理時，亦不會造成損傷。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）一V. Description of the invention (b) On the receiving piece. Other fibers are placed on a second adapter. These fibers are compared in a standard scaled photo. Five readings from three groups were taken on each spore and averaged to obtain a fibrillation index (F.I.). "Zero" F.I. corresponds to "zero" and "hairless". The following examples are used to illustrate the present invention. In this example, unless otherwise stated, all parts and ratios are weight ratios. Example 1 A solution of cellulose (1530 in NMMO (75¾) and water (10¾) was passed through a spinning head through a spinneret and entered into an aqueous coagulation bath to generate a 1.7 dtex monofilament filament. Washed with water After removing NMM0, the monofilament filaments were treated in a relaxed state at a temperature of 25 ° C for 30 seconds with an aqueous solution (the aqueous solution contains 11% sodium hydride in a weight / volume percentage, and different amounts Sodium silicate), in a relaxed state, was washed from a 15% volume / volume aqueous sulfuric acid solution for 30 seconds, then washed and dried. Other details and results of this experiment are shown in Table 1: (Please Read the notes on the back before filling this page) The printed paper size of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs applies to the Chinese National Standard (CNS) A4 (210X297 mm) 1 m A7 B7 V. Description of the invention (9 Table sodium silicate fiber fineness temporal extension hair fibrillation index g / l (g / 1) decitex (dtex) cN / tex% FI untreated comparison sample 1.84 37.3 15.2 6.2 0 1.87 29.1 13.7 2.1 10 1 .79 3 5.2 15.7 2.3 20 1 .73 39.4 15.8 2.6 30 1.75 38.0 16.2 3. 1 50 1.80 38.3 15.2 3.7 (Please read the notes on the back before filling out this page), 11 * Solutions for printing experiments printed by Zhengong Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs Prepared using " water glass " nominally containing 24 g / liter of sodium phosphonium sodium silicate. The fibers treated by the method according to the invention exhibit good stretchability and low hairiness Tendency, as well as good brightness, will not cause damage when subjected to alkaline treatment. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm)