406150 B7 經濟部中央搮準局貞工消费合作社印裝 五、發明说明（1 ) 發明領域 本發明係提供一種具有較低之粘度及低溫流動性之纖維 素溶液。 發明背景 在傳統製造再生纖維素纖維之方法中，大都使用酸、驗 化合物及含重金屬之化合物，並釋放出有毒氣體之溶劑，如 嫘縈法(Rayon)及銅氨法等。此類系統之溶劑處理繁雜，不 易回收再使用，對環境造成極大之衝擊與高度污染。為克服 此缺點，已有採用溶劑直纺法(Organic Solvent-Spun Cellulose Fibers)，將纖維素溶解於氧化胺水合物中以調製成高粘度纖 維素溶液，並由此溶液製造出織維或薄膜等成品的方法，如 美國專利第4,246,221號所示。其中從再生浴回收溶劑再以循 環使用，回收率可達98.5%以上。 在溶劑直紡製程中，纖維素溶液之粘度極高，約為一般 乾噴濕紡(Dry-jet Wet Spinning)所用之高分予溶液粘度之5〜 12倍之多。即使在80〜ll(TC高溫下，其溶液流動性亦低， 變形困難，降低紡絲時之可拉伸性能。採用較低粘度之紡絲 溶液，不僅易於變形流動，提高成形之穩定性，同時可使紡 絲時之拉伸倍率增大，有效得到優越之產品性能如拉張強 度、伸度等。 於美國專利第4，144,080號，第4，145,532號，第4，142,913 號，第4，196,282號，第4,211，574號及第4,246,221號中，於纖 維素木漿與氧化胺水合物中加入甲醇、正丙醇、丁醇等酵類 或甲苯、二甲苯、DMF、DMAC、NMP、DMS〇、hmpa或 一 3 — 本紙張尺度逋用中困國家樑準（CNS > A4规格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁)406150 B7 Printed by Zhengong Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs 5. Description of the invention (1) Field of the invention The present invention is to provide a cellulose solution with lower viscosity and low temperature fluidity. BACKGROUND OF THE INVENTION In traditional methods for producing regenerated cellulose fibers, most of them use acids, test compounds, and compounds containing heavy metals, and release solvents that are toxic, such as the Rayon method and the copper ammonia method. The solvent treatment of such systems is complicated, and it is not easy to recycle and reuse, which causes great impact on the environment and high pollution. In order to overcome this shortcoming, the solvent direct spinning method (Organic Solvent-Spun Cellulose Fibers) has been used to dissolve cellulose in amine oxide hydrate to prepare a high-viscosity cellulose solution, and use this solution to produce woven fabrics or films. The method of waiting for the finished product is shown in US Patent No. 4,246,221. Among them, the solvent is recovered from the regeneration bath and reused in a cycle, and the recovery rate can reach more than 98.5%. In the solvent direct spinning process, the viscosity of the cellulose solution is extremely high, which is about 5 to 12 times the viscosity of the solution used in ordinary dry-jet wet spinning (Dry-jet Wet Spinning). Even at a high temperature of 80 ~ 11 ° C, the solution has low fluidity and is difficult to deform, reducing the stretchability during spinning. The spinning solution with a lower viscosity is not only easy to deform and flow, but also improves the stability of forming. At the same time, it can increase the draw ratio during spinning and effectively obtain superior product properties such as tensile strength and elongation. In US Patent No. 4,144,080, No. 4,145,532, No. 4,142,913, No. In 4,196,282, 4,211,574 and 4,246,221, cellulose, wood pulp and amine oxide hydrate are added with methanol, n-propanol, butanol and other enzymes, or toluene, xylene, DMF, DMAC, NMP , DMS〇, hmpa, or 1-3 — This paper is scaled to the national standard of the poor countries (CNS > A4 size (210X297 mm) (Please read the precautions on the back before filling out this page)
T 裝· 1r 406150 A6 補无 經濟部中央樣準扃8工消費合作社印製 五、發明説明Γ ) •tm(Sulfolane)等有機系共溶劑，添加量達25wt%。此氧化胺 水合物和共溶劑之混合液有助於纖維木漿之均一吸收，促進 濕透直到膨潤(swells)。但此膨潤液易於粘結(aggl〇mera的， 同時亦造成貯存與輸送之困難。 鑑於上述習知技術之問題，本發明提供一種新溶劑組 成，在1Q〜75°C之溫度下可製得均質化且貯存穩定，易於輸 送生產纖維素纖維之泥漿物：在75〜13(TC之溫度下可製得 成形品用之纖維素紡絲溶液。發明概述 本發明之目的係提供一種纖維素泥漿物，包括5〜25wt% (a)纖維素木漿，以及95〜75wt%之（b)氧化胺水合物和⑹共 溶劑；此纖維素泥漿物係在10〜75°C之溫度下製備。 本發明之另一目的係提供一種纖維素溶液，包括5〜 25wt%⑻纖維素木漿，以及95〜75wt%4i(b)氧化胺水合物和 (c)共溶劑：此纖維素溶液係在75〜130°C之溫度下製備。圈式之簡單説明 為説明本發明之特徵，將參照所附之圖式，其中： 圖1(a)及1(b)分別表示本發明之溶劑组成物與先前技術之混合 液表現。 圖2⑻及2(b)各為本發明之溶劑组成物所製得之均質泥聚與先 前技術之比較。 圖3説明本發明所添加共溶劑之重量百分率與織維素溶液粘 度間之關係。 —4 一 （88.08.30修正頁） {請先閲讀背面之注意事項再填寫本頁) tan 家標準（CNS> 甲 4 规格（210 X 297 公*〉 406150 A6 B6 修正 補无4郃 經濟部t央樣旱局S工消费合作社印製 五、發明説明（） 由這些圖式，説明本發明可達成下述目的·· ⑴將N·氧^水合物與共溶親合成清澈溶液如圖l(b)與 圖1(a)先前技術之混合液比較，説明本發明無分層，沈澱 物產生，呈清澈化。 (2) 與纖維素木漿混合，易製得均質絲聚化泥漿物，無膨潤 枯結之現象如圖2(b)與先前技術2⑻之比較。 (3) 高纖維素木漿含量及具低溫流動性。 (4) 有效降低溶液粘度。 本發明之上述目的係藉由纖維素，氧化胺水合物與不能 溶解纖維素之共溶劑所組成之均一混合溶液所達成。 發明之詳知説明 氧化胺水合物係一種低污染，可回收及直紡纖維素纖維 之有機系溶劑，但其價格過於昂贵，因此製程要求高度監 控。本發明藉由在纖維素及氧化胺水合物中，添加一種共溶 劑，所製成之组成物除易於獲致織維素泥漿化產物外，更提 供一種可降低氧化胺水合物用量並具有較低之溶液粘度和增 加室溫流動之特性之織維素溶液。 本發明之纖維素泥漿物包括5〜25w^/〇⑻聚合度(@)為 200〜1500，較佳為200〜1000之纖維素木漿，以及95〜 75wt%之(b)氧化胺水合物與⑻共溶劑所構成之均一混合液， 以(a)，(b)及⑹總量lOOwt%計；其中⑻氧化胺水合物與⑻共溶 劑之混合重量比為95 : 5〜50 ·· 50。本文所稱均一混合液係 指共溶劑與氧化胺水合物具有相溶性並形成清徹均一溶液 者0 —5 — (88.08.30修正頁） {請先閱讀背面之注意事項再塡寫衣頁) -丨裝1 訂. 邊用中國國家標準（CNS>甲4规格（210 X 297 «釐） 406150T pack · 1r 406150 A6 supplemented by the central sample of the Ministry of Economic Affairs and printed by the 8th Industrial Cooperative Cooperative V. Description of the invention Γ) • tm (Sulfolane) and other organic co-solvents, with an added amount of 25wt%. This mixed solution of amine oxide hydrate and co-solvent helps uniform absorption of fiber wood pulp, and promotes wet penetration until swelling. However, this swelling liquid is easy to bind (agglomera), and it also causes difficulties in storage and transportation. In view of the problems of the conventional technology described above, the present invention provides a new solvent composition that can be prepared at a temperature of 1Q ~ 75 ° C. Homogeneous and stable storage, easy to transport cellulose fiber slurry: cellulose spinning solution for shaped products can be prepared at 75 ~ 13 ° C. Summary of the invention The object of the present invention is to provide a cellulose slurry Material, including 5 to 25 wt% (a) cellulose wood pulp, and 95 to 75 wt% (b) amine oxide hydrate and rhenium co-solvent; the cellulose slurry is prepared at a temperature of 10 to 75 ° C. Another object of the present invention is to provide a cellulose solution comprising 5 to 25 wt% of cellulose wood pulp, and 95 to 75 wt% of 4i (b) amine oxide hydrate and (c) co-solvent: the cellulose solution is Prepared at a temperature of 75 to 130 ° C. A brief description of the ring method To illustrate the features of the present invention, reference will be made to the accompanying drawings, where: Figures 1 (a) and 1 (b) represent the solvent composition of the present invention, respectively Performance of the mixed liquid with the prior art. Figures 2 (a) and 2 (b) are each the solvent of the present invention. Comparison of the homogeneous mud aggregate produced by the product with the prior art. Figure 3 illustrates the relationship between the weight percentage of the co-solvent added to the present invention and the viscosity of the oryzanol solution. —4 One (88.08.30 correction page) {please first Read the notes on the back and fill in this page again.) Tan Standard (CNS > A4 Specification (210 X 297 public *> 406150 A6 B6) Explanation () From these diagrams, it is shown that the present invention can achieve the following objectives: ⑴N · oxy ^ hydrate and co-solvent affinity clear solution as shown in Figure 1 (b) and Figure 1 (a) of the prior art mixed solution The comparison shows that the present invention has no delamination, and the precipitate is generated, and it is clear. (2) Mixing with cellulose wood pulp, it is easy to produce homogeneous silk polymerized mud, and the phenomenon of no swelling and swelling is shown in Figure 2 (b) and Comparison of the prior art 2⑻. (3) High cellulose wood pulp content and low temperature fluidity. (4) Effectively reduce the viscosity of the solution. The above object of the present invention is to use cellulose, amine oxide hydrate and insoluble cellulose. A homogeneous mixed solution composed of a co-solvent is achieved. The detailed description shows that amine oxide hydrate is a low-pollution, organic solvent that can be recycled and spun cellulose fibers, but its price is too expensive, so the process requires high monitoring. The present invention is used in cellulose and amine oxide hydrate. In addition, a co-solvent is added, and the composition is made in addition to easily obtaining the weaving vitamin sludge product, and it also provides a weaving fabric that can reduce the amount of amine oxide hydrate and has a lower solution viscosity and increased room temperature flow characteristics. The cellulose slurry of the present invention includes a cellulose wood pulp having a polymerization degree (@) of 5 to 25 w ^ / 〇⑻ of 200 to 1500, preferably 200 to 1,000, and (b) oxidation of 95 to 75 wt%. A homogeneous mixed solution composed of amine hydrate and rhenium co-solvent, based on (a), (b) and 100% by weight of total rhenium; wherein the mixing weight ratio of rhenium amine oxide hydrate and rhenium co-solvent is 95: 5 ~ 50 ·· 50. The "homogeneous mixed solution" in this article refers to the co-solvent and amine oxide hydrate that are compatible and form a clear and homogeneous solution. 0 —5 — (88.08.30 correction page) {Please read the precautions on the back before writing the clothing page)-丨 1 order. Side use Chinese national standard (CNS > A4 size (210 X 297 «cent) 406150
4 五、發明説明（） 在本發明中，混合溶劑組成中之氧化胺水合物，其水含 量控制在1〜20wt%，較佳為5〜15wt%，適用之氧化胺化合 物包括N-甲基嗎绋啉-N-氧化物、N-甲基六氫吡啶-N-氧化 物、N-甲基吡啶酮氧化物、N-甲基四氫吡咯-N-氧化物或 N-甲基氮雜環己淀-N-氧化物之類等。較佳之氧化胺化合物為 N-甲基嗎》弗淋-N-氧化物或N-甲基四氫吹洛-N-氧化物。 本發明中所使用之共溶劑可為雜環酮類或醇胺類。適用 的雜環酮類，包括N-乙基-2-吡咯烷酮，N-丁基-2--吡咯烷 酮，1,3-二甲基-2-丁撐脲，二甲基次丙尿素，二甲基次乙尿 素，N-乙烯-2-吡咯烷酮，1-(2-羧乙基)-2-吡咯烷酮，N-(3-幾 丙基)-2-吡咯烷酮或2-吡咯烷酮等，其中以二甲基次丙尿素、 2-吡咯烷酮及1-(2-羥乙基)-2-吡咯烷酮為佳〇 適用的酵胺類，包括2-甘醇胺，2-胺基-1-丙醇、乙醇 胺、異丙醇胺、2-胺基-1·丁酵，或3-胺基-1-丙醇等，其中較 佳為異丙醇胺及乙酵胺。 本發明中所用織維素木漿(pulp)之織維素含量至少 90wt%以上為佳。用來作為後道加工之纖維素木漿材料的形 狀可為片狀(sheet)、粒狀(grain)或粉末狀(powder)。與混合 溶劑摻合後在短時間内即可形成一種均質穩定之纖維素泥漿 物。纖維素木漿含量為5〜25wt%。製備泥漿之溫度為10〜 75°C。此均質穩定之泥漿物可直接迅速溶解而無粘結現象， 有效抑制纖維素及氧化胺化合物因溶解時間過長所導致之衰 解和氧化作用。製備纖維素溶液之溫度為75〜13(TC之範圍 内。當提高溶解溫度相對地增加系統之溶解速率，而且溶解 時間之長短直接影響成絲(as-spun fibers)後道水洗道數、纖維 性能及溶劑回收處理等性能。本發明在溶解與溶液輸送時間 均可控制在2分鐘内完成。顯著提高並穩定紡絲溶液之品質 及連續化生產效率。 -6 - (88.08.30修正頁） 請先閲讀背面之注意事項再堉寫本頁) i裝- 訂· -線 本紙张尺度適爾t國國家櫺準（CNS>甲4规格（210 X 297 Κ釐〉 406150 B6 五、發明説明（） 共溶劑之添加，不僅降低纖維素溶液之粘度(如圖3所 不）’亦提高低溫下溶液之流動性。經由本發明之溶劑組成所 製取之纖維素纺絲溶液可藉乾喷濕式wet)或濕纺法 (wet)，經齒輪計量幫浦(gear metejjjjg pyjjjp)定量輸送至纺口且 擠出進入凝固浴予以固化成絲或通過狹缝凝固呈薄膜狀產 品。 實施例 從以下之實施例中之試驗結果，更具體證明本發明之特 點。 實施例-1 將8wt%之含有5wt%水的纖維素木漿(其聚合度為860， 織維素含量為92.4%)和甲基嗎绋啉-N-氧化物水合物(其 水含量為10wt%)與表1所示之一系列共溶劑混合入挽拌容器 中，在250rpm挽拌速率，探討泥漿製備溫度，泥漿化程度、 溶解後之纖維素聚合度變化及其溶液流動性，其結果如下表 1所示。 ---------JJ. 1 一--.------^------裝 J-------訂 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準房R工消費合作社印$ 一 7 — (88.08.3瞭正頁) 本紙張尺度適用中國國家橒準（CNS)甲4规格（210 X 297 ϋ > 五、發明説明（） 6 406^50 表1 共溶劑 含量， wt% 製備泥 漿物 溫度，。C 泥漿態 溶解溫度 CC) 溶解後聚 合度(d) DP 溶液流 動性(在 30〇C 下） 2-»* 洛 烷酮 10 70 非均一 100 685 否 20 65 均一 105 770 可 30(a) 65 均一 110 748 可 40(b) 65 均一 110 815 可 二曱基次 丙尿素 10 60 非均一 95 710 否 20 50 非均一 105 650 否 30 60 均一 110 755 可 40(b) 55 均一 110 730 可 乙醉胺 10 70 非均一 95 740 否 20 60 均一 100 725 否 30 50 均一 110 680 可 40(b) 45 均一 110 685 可 50 50 均一 115 718 可 NMMO 水合物 • 在 85eC 僅膨潤， 粘結 100 630 80eC 下， 即逐漸 固化 a. ΝΜΜ0·Η20中水含量為 13.5wt%。 b. ΝΜΜ0·Η20 中水含量為5.7wt°/〇〇 c. 溶解時間為30分鐘。 d. OT之測定係以0.5gpulp溶於Cuen於25X下測得[»7】，再 代入下式[?/] =9.82Χ1〇-3 5P·9。 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局S工消費合作社印製 —8 —（88.08.30#正頁) 本紙張尺度逋用t a躅家標準（CNS) f 4规格（210 X 297 K釐） 、五 400150 A7 B7 實施例-2 依照實施例-1之泥漿物（製備溫度65。〇及溶液製備條 件，篩選3種不同聚合度之木漿，其特性如下： 纖維素木漿一A〇-纖維素：92.4%，玩二860) 棉木乘一Β(α-纖維素：91.8% » DP =600) 纖維素木聚一C(a-纖維素：95.7%，5?二300) 各以不同濃度(木漿切割成3cm X 3cm大小)與N-甲基嗎佛啦-N-氧化物水合物(其水含量為l〇wt%)中，添加入30wt%之2-吡咯 烷酮，所得之結果如表2。 ——Ί-----41- (請先閲讀背面之注意事項再填寫本頁) 經濟部中央梯準局貝工消费合作社印装 表2 木漿 木漿濃度，wt% 泥漿態 溶液流動性， 30〇C 下 A 6 均一 可 8 均一 可 10 均一 尚可> B 6 均一 可 10 均一 可 15 均一 可 C 8 均一 可 13 均一 可 20 均一 可 約20分鐘後，逐漸凝膠固化。 τ訂 本紙择又度逍用中國國家樣率（CNS ) Α4规格（21〇χ297公釐）4. V. Description of the invention () In the present invention, the water content of the amine oxide hydrate in the mixed solvent composition is controlled to 1 to 20% by weight, preferably 5 to 15% by weight. Suitable amine oxide compounds include N-methyl Morpholine-N-oxide, N-methylhexahydropyridine-N-oxide, N-methylpyridone oxide, N-methyltetrahydropyrrole-N-oxide or N-methylazepine Cyclohexane-N-oxide and the like. The preferred amine oxide compound is N-methyl? Fron-N-oxide or N-methyltetrahydro-N-oxide. The co-solvent used in the present invention may be a heterocyclic ketone or an alcohol amine. Applicable heterocyclic ketones, including N-ethyl-2-pyrrolidone, N-butyl-2--pyrrolidone, 1,3-dimethyl-2-butaneurea, dimethylhyperourea, dimethyl Diethylurea, N-vinyl-2-pyrrolidone, 1- (2-carboxyethyl) -2-pyrrolidone, N- (3-chipropyl) -2-pyrrolidone or 2-pyrrolidone, etc. Glypromine, 2-pyrrolidone and 1- (2-hydroxyethyl) -2-pyrrolidone are preferred. Suitable fermenting amines include 2-glycolamine, 2-amino-1-propanol, ethanolamine, Isopropanolamine, 2-amino-1 · butyrate, or 3-amino-1-propanol, etc., among these, isopropanolamine and ethionylamine are preferred. It is preferred that the weaving vitamin content of the pulp used in the present invention is at least 90% by weight or more. The shape of the cellulose wood pulp material used for subsequent processing may be sheet, grain, or powder. After blending with mixed solvents, a homogeneous and stable cellulose slurry can be formed in a short time. The content of cellulose wood pulp is 5-25% by weight. The temperature of preparing mud is 10 ~ 75 ° C. This homogeneous and stable slurry can be directly and quickly dissolved without sticking, which effectively inhibits the degradation and oxidation of cellulose and amine oxide compounds caused by too long dissolution time. The temperature for preparing cellulose solution is in the range of 75 ~ 13 ° C. When the dissolution temperature is increased, the dissolution rate of the system is relatively increased, and the length of the dissolution time directly affects the number of washed channels and fibers after as-spun fibers. Performance and performance of solvent recovery and treatment. The present invention can be completed within 2 minutes by controlling the dissolution and solution delivery time. It significantly improves and stabilizes the quality of the spinning solution and continuous production efficiency. -6-(88.08.30 revised page) Please read the precautions on the back before writing this page) i Binding-Binding ·-Thread Paper Size Applicable National Standards (CNS > A4 Specification (210 X 297 Κ 厘> 406150 B6) V. Description of the Invention ( The addition of co-solvent not only reduces the viscosity of the cellulose solution (as shown in Figure 3), but also improves the fluidity of the solution at low temperature. The cellulose spinning solution prepared by the solvent composition of the present invention can be wet-dried by spraying. Wet or wet spinning method, which is quantitatively conveyed to the spinning orifice through a gear metering pump (gear metejjjjg pyjjjp) and extruded into a coagulation bath to be solidified into silk or solidified into a film through a slit. Examples are as follows Of The test results in the examples more specifically prove the characteristics of the present invention. Example-1 8% by weight of cellulose wood pulp containing 5% by weight of water (the degree of polymerization is 860, and the oryzanol content is 92.4%) and methyl Morpholine-N-oxide hydrate (whose water content is 10% by weight) is mixed with a series of co-solvents as shown in Table 1 into a mixing container, and the mixing speed at 250 rpm is used to discuss the slurry preparation temperature, the degree of slurry formation, Changes in the degree of polymerization of cellulose after dissolution and the fluidity of its solution, the results are shown in Table 1. --------- JJ. 1 一 --.------ ^ ----- -Install J ------- Order (please read the precautions on the back before filling this page) Printed by the Central Standard Room of the Ministry of Economy, R Industrial Consumer Cooperative, $ 1 7 — (88.08.3 on the front page) This paper size applies China National Standard (CNS) A4 specification (210 X 297 ϋ > V. Description of the invention) 6 406 ^ 50 Table 1 Co-solvent content, wt% Preparation mud temperature, .C Mud state dissolution temperature CC) Degree of polymerization (d) Flowability of DP solution (at 30 ° C) 2-»* Lolone 10 70 Heterogeneous 100 685 No 20 65 Uniform 105 770 Can 30 (a) 65 Uniform 110 748 Can 40 (b) 65One 110 815 Dioxin 10 60 Heterogeneous 95 710 No 20 50 Heterogeneous 105 650 No 30 60 Heterogeneous 110 755 He 40 (b) 55 Heterogeneous 110 730 Hexamine 10 70 Heterogeneous 95 740 No 20 60 Uniform 100 725 No 30 50 Uniform 110 680 May 40 (b) 45 Uniform 110 685 May 50 50 Uniform 115 718 May NMMO hydrates • Swell only at 85eC, adhere to 100 630 80eC, that is, gradually a. NMMM0 · Μ20 The water content was 13.5 wt%. b. The water content in NMM0 · Η20 is 5.7wt ° / 〇〇 c. The dissolution time is 30 minutes. d. The measurement of OT is measured by dissolving 0.5g pulp in Cuen at 25X and measuring [»7], and substituting it into the following formula [? /] = 9.82 × 10-3 5P · 9. (Please read the precautions on the back before filling in this page) Printed by S Industry Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs—8— (88.08.30 # Front page) This paper uses the standard of ta 躅 standard (CNS) f 4 (210 X 297 K centi), five 400 150 A7 B7 Example-2 According to the slurry of Example-1 (preparation temperature 65.0 and solution preparation conditions), three types of wood pulp with different degrees of polymerization were screened, and its characteristics are as follows: Fiber Pure wood pulp-Ao-cellulose: 92.4%, play two 860) Cotton-wood multiply by one B (α-cellulose: 91.8% »DP = 600) Cellulose-wood C-a (a-cellulose: 95.7%, 5 ~ 2300) each with different concentrations (wood pulp cut into 3cm X 3cm size) and N-methylmorpho-N-oxide hydrate (whose water content is 10wt%), added 30wt% The results of 2-pyrrolidone are shown in Table 2. ——Ί ----- 41- (Please read the notes on the back before filling in this page) Printed by the Central Laboratories of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives, Table 2 Wood pulp and wood pulp concentration, wt% Mud solution flowability At 30 ° C, A 6 can be uniform, 8 can be uniform, 10 can be uniform, > B 6 is uniform, 10 is uniform, 15 is uniform, C 8 is uniform, 13 is uniform, and 20 is uniform. After about 20 minutes, the gel is gradually solidified. τ-order This paper has been chosen again and again using the Chinese National Sample Rate (CNS) Α4 specification (21 × 297 mm)