1224111 Α7 Β7 經濟部智慧財產局員工消費合作社印制衣 五、發明說明（1 ) 本發明係有關針 定之溶解性與高度之 者。 先行技術中羥丙 葡萄糖單位（C 6 Η I 非離子性聚合物，各 者。 羥丙基纖維素之 大。做爲取代基之顯 取代莫耳數（M S ) 取代度高之羥丙 爲溶於冷水，不溶於 取代度低者則不溶於 氫氧化鈉等之鹼水溶 由此等性質之低 散劑，結合劑使用之 做爲低取代度羥 38858號公報， 公開葡萄糖單位之羥 1 . 0之製造方法者 於鹼水溶液中，惟， 低。又，此等依鹼水 差異，因此，溶液之 在° 對鹼水溶液顯示於廣泛圍溫度下具安 溶液透明性之低取代度羥丙基纖維素 基纖維素係使3個纖維素結構單位之 〇〇5)之氫氧基具有羥丙基、醚化之 種有用之特性被利用於廣泛用途領域 特性依 示方法 所代表 基纖維 熱水者 水、有 液中具 取代度 ，做爲 丙基纖 特公昭 丙基平 。惟， 多半含 溶液之 安定性 其羥丙基取 者以葡萄糖 之方法最爲 素平均取代 可溶於酒精 機溶媒類， 有溶解性質 羥丙基纖維 鹼溶液之增 代量之不同差異極 單位之取代基平均 廣泛使用者。 莫耳數爲2〜3者 等有機溶媒類者。 與水接觸則膨脹， 者。 素做爲醫藥品之崩 粘劑使用者。 維素者於特公昭4 8 — 5 7-53 均取代基莫 藉由此等方 未溶解份因 溶解性依溫 上有限制其 1 0 0號公報等被 耳數爲0 . 0 5〜 法所製造者雖可溶 此溶液之透明性極 度不同而產生極大 使用條件之問題存 請 先 閱 讀 背 面 之 注 意 事 項 頁 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -4 - 1224111 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（2 ) 針對低取代度羥丙基纖維素之鹼水溶液之溶解性受經 丙基取代度影響極大。爲顯現良好溶解性之低取代度羥丙 基纖維素，其羥丙基之取代量管理，亦即，其結構單位之 葡萄糖單位之控丙基平均取代莫耳數與不同羥丙基取代莫 耳數之取代物之比率極爲重要。 如此控制羥丙基之取代量後，可提供一種具良好之溶 液透明性，具廣泛溫度下安定溶液狀態之低取代度羥丙基 纖維素之出現被熱切期待，惟，至今仍末實現。 本發明者爲解決上述問題，進行精度硏討後結果發現 ，葡萄糖單位（C6H1Q〇5)之羥丙基平均取代莫耳數爲 0 · 1〜0 . 4之低取代度羥丙基纖維素中，以2莫耳以 上之羥丙基被取代之葡萄糖單位數爲總葡萄糖單位數之5 %以下者，且，針對1 〇重量％氫氧化鈉水溶液於2重量 %濃度之溶液中其1 〇°C〜5 0°C之透光度爲9 0%以上 者爲其特徵之低取代度羥丙基纖維素溶於鹼溶液後呈現高 度透明性’且，廣範圍溫度下呈安定之溶液狀態者，進而 完成本發明。 〔發明之實施形態〕 以下針對本發明進行更詳細說明。 本發明之低取代度羥丙基纖維素其葡萄糖單位之羥丙 基平均取代莫耳數爲〇·1〜〇·4者。當其平均取代莫 耳數小於〇 · 1時，則溶於鹼溶液時藉由未溶解物其溶液 呈不透明者，反之，超出〇 · 4時，則溶液呈白濁化均爲 (請先閱讀背面之注意事項再 —裝.丨· 本頁： . --線· 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐) '5 - 經濟部智慧財產局員工消費合作社印製 A7 __B7___五、發明說明（3 .) 不滲明之溶液者。 又，本發明之低取代度羥丙基纖維素其羥丙基取代莫 耳數2以上之取代體（葡萄糖單位）之數爲總葡萄糖單位 數之5 %以下者宜。當羥丙基取代莫耳數2以上之取代體 比率大於5 %時，呈與上述相同溶液呈現白濁後爲不透明 溶液者。此係針對鹼溶液之溶解性低之無取代體以及羥丙 基取代莫耳數2以上之取代體比率增加後，而造成溶液透 明性消失者。 本發明低取代度羥丙基纖維素之製造係於第1階段中 使纖維素氫氧化鹼與之反應後產生鹼纖維素者。 做爲調製鹼纖維素之方法者係將原料紙漿浸漬於氫氧 化鹼水溶液後，壓榨之後，去除剩餘之氫氧化鹼水溶液， 適於做爲所期待之鹼纖維之組成之方法者。 做爲原料所使用之纖維素中，可以木材紙漿、棉短絨 纖維紙漿爲例，薄片狀、粉碎後之粉狀物等各種形狀均可 使用無任何限制。 又’做爲氫氧化鹼水溶液者可如用：氫氧化鈉、氫氧 化鉀、氫氧化鋰等水溶液者，惟，又以氫氧化鈉爲較佳者 〇 氫氧化鹼水溶液之濃度爲2 0〜4 5重量％，特別以 3 ◦〜4 0重量％之濃度者宜。當氫氧化鹼水溶液之濃度 小於2 0重量％時，則纖維素之膨脹不足未被活化，接下 去之醚化反應無法順利進行之。反2，大於4 5重量％時 ，所調製之鹼纖維素之組成呈不均勻狀，針對鹼溶液其溶 (請先閱讀背面之注意事項再本頁) -裝 士 . 線- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ^6- 1224111 A7 B7 經濟部智慧財彦局員工消費合作社印製 五、發明說明（4 ) 溶解性依溫度而異，溶液物性之溫度變化極大。 做爲鹼纖維素之調製方法者其他如··將紙漿於有機溶 齊fJ等之分散媒中與氫氧化鹼水溶液混合之方法，直接將氫 氧化鹼水溶液噴於紙漿之方法者等，惟，比起浸漬於氫氧 化鹼水溶液後取得之鹼纖維素其組成較爲不均，無法適於 做爲目的之鹼溶液溶解性良好之低取代度羥丙基纖維素之 製造。 鹼纖維素中之氫氧化鹼對於環氧丙烷之反應做爲重要 之觸.媒同時亦具有提高纖維素反應性之活化角色者。另外 ，鹼纖維素中之水份與環氧丙烷反應後不希望產生由生成 物非去除不可之不純物。 因此，藉由鹼纖維素與環氧丙烷反應後，爲使低取代 度羥丙基纖維素有效製造，於調製鹼纖維素時，務必控制 鹼纖維素中之氫氧化鹼量與水份量。 本發明低取代度羥丙基纖維素之製造中鹼纖維素中之 氫氧化鹼量與水份量針對纖維素之重量比其氫氧化鹼量爲 〇· 1〜1 · 0者，特別以0 · 2〜0 · 8者佳，水份量 爲〇.1〜2 . 0者，特別以0 · 3〜1 · 0者佳。 針對纖維素之重量比其氫氧化鹼量及水份量若小於上 述範圍時，則反應無法有效進行，反之，大於上述範圍時 ，則環氧丙烷與水反應後將增加不被期待之不純物之產生 ，無法取得所定量之羥丙基取代度，爲去除副產物之不純 物務必耗費極大力氣’均造成控制所期待之經丙基取代量 之困難度。 (請先閱讀背面之注意事項再 -裝Ί I ^^本頁) 訂· .線. 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公t ) 1224111 經濟部智慧財產局員工消費合作社印制农 A7 B7_五、發明說明（5 ) 因此，做爲本發明低取代度羥丙基纖維素製造中第1 階段之調製鹼纖維素之方法者以將原料紙漿浸漬於氫氧化 鹼水溶液後，去除壓榨後剩餘之氫氧化鹼水溶液，做成所 期後之鹼纖維組成之方法爲適當者。 本發明低取代度羥丙基纖維素之製造中之第2階段係 使鹼纖維素與環氧丙烷充份混合後進行反應之，反應溫度 爲3 0〜8 0 °C，特別以4 0〜7 0 °C者佳，針對纖維素 之莫耳比更加入0·15〜2·0之環氧丙烷後進行反應 0 . 當反應溫度小於3 0 °C時，反應進行極爲緩慢花費極 長時間極不實用，反之，大於8 0 °C時，則增加羥丙基纖 維素中之羥丙基取代莫耳數2以上之多取代體之生成比率 ’或藉由環氧丙烷與水反應後，增加不純物之生成量，極 不理想。 當環氧丙烷之添加量超出範圍量時，則無法取得所定 量之羥丙基取代度者。 做爲添加環氧丙烷之方法者，可使用一次將所定量之 環氧丙烷全量添加之方法，或，分數次連續添加等任一方 法均可實施。又，本反應以與環氧丙烷相互之反應性小之 有機溶媒做爲分散媒體之使用後進行者亦可。 本發明之反應生成物含有氫氧化鹼、環氧丙烷與水反 應後產生之不純物，惟，可藉由公知方法簡易精製後，取 得不含不純物之高純度之目的之低取代度羥丙基纖維素者 (請先閱讀背面之注意事項再 --- 本頁) 訂· i線- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公f ) - 8 - 1224111 經濟部智慧財產局員工消費合作社印制π A7 B7___五、發明說明（6 ) 本發明所取得之低取代度羥丙基纖維素之取代體組成 可藉由既知之方法，例如：Carbhydro.，Res·Vol· 1 70，ρ·207 ( 1 987)所載之方法等求取之。 取代物組成之測定方法之示例如，鹼存在下與碘代甲 烷等之甲基化劑反應後，使游離氫氧基經甲基化之低取代 度羥丙基纖維藉由三氟醋酸等酸分解後，還原之後做爲山 梨糖醇衍生物。使用無水醋酸等之後，乙醯化者若供與氣 體層析法則羥丙基之取代數及取代位置相異者被分離後， 可求取分別比率。 .本發明取得之低取代度羥丙基纖維素之透明性可藉由 透光度判定之。透光度係指使用光電比色計測定之精製水 之光透光率爲1 0 0時之同一條件下之低取代羥丙基纖維 素溶液之透光率者謂之。其測定方法具體而言載於實施例 者- 以下，更藉由實施例與比較例針對本發明進行詳細說 明，惟，本發明並非僅限於此實施例中。 (實施例1 ) (1 )低取代度羥丙基纖維素之製造 將1 0 0重量份之薄片狀紙漿浸漬於4 0重量％氫氧 化鈉水溶液後使氫氧化鈉水溶液吸收於紙漿後，以3 k g / c m 2加壓壓榨後去除剩餘之氫氧化鈉水溶液後，針 對纖維素之重量比調整氫氧化鹼量爲〇 · 5 5，水份量爲 〇· 9 0者。將所調製之鹼纖維細分之後，置入具有內部 氏張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐) -9 - 贿 (請先閱讀背面之注意事項再本'!) 瞻 女 · -線· 經濟部智慧財產局員工消費合作社印製 1224111 A7 B7____ 五、發明說明（7 ) 攪拌器之加壓反應器，反應器內充份取代氮之後，置入 2 4重量份之環氧丙烷（針對纖維素之莫耳比〇 . 6 7 ) ’ 5 0 °C下進行反應3小時。 反應物以醋酸將殘餘之氫氧化鈉進行中和處理後，以 5 0〜6 0 °C之溫水進行洗淨，於8 0 °C下進行送風乾燥 後取得無色固體之1 0 8重量份之低取代度羥丙基纖維素 。藉由Ze1Sel法所求取之羥丙基之平均取代莫耳數爲 〇· 2 6者。 (2 )取代物組成 > ‘ 將3重量份之（1 )所取得之低取代度羥丙基纖維素 溶解於2 5 0重量份之二甲亞碾中。於此溶液中加入3 0 重量份之粉狀氫氧化鈉後，攪拌同時加入1 〇 〇重量份确 甲烷後，於6 0 °C下進行反應4小時。將反應物注入 1 0 0 0 0重量份之熱水下析出甲基化羥丙基纖維素。回 收析出物後，7 0 t下進行乾燥6小時。於5重量份之甲 基化羥丙基纖維素中加入3 0 0重量份之2m ο 1 %三氟 醋酸水溶液後’於1 2 0 °C下進行處理3小時後，以碳酸 鋇調整P Η爲7。此再加入1 · 5重量份之氫化硼鈉後， 室溫下攪拌1小時後，1 〇 〇 °C下使蒸發乾固之，於殘餘 之內容物中加入1 〇 〇重量份之醋酸時，2 0 0重量份之 吡啶’於1 2 0 °C下進行處理3小時。冷卻後，將加入5 〇0重量份之水者以5 0重量份之四氯化碳進行2次萃取 。蒸發四氯化碳之殘留供與G C分析。由G C分析上之頂 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱)ΠΤΡ (請先閱讀背面之注意事項再本頁) · --線- 1224111 A7 _ B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（8 ) 點面積求取羥丙基取代莫耳數爲2以上之多取代物之合計 比率及無取代物之組成比率後結果如表1所示。 (3 )溶液物性及固體物性 將取得之低取代度羥丙基纖維素於1 〇重量％氫氧化 鈉水溶液中使呈低取代度羥丙基纖維素之濃度爲2重量％ 者後進行溶解。將溶解溫度變更爲1 〇 °c、3 0 °C . 50 °C後所調製之溶液以B型粘度計測定粘度後，利用光電比 色計（5 E型）針對空白試驗（水）之可視光線透光率進 行測定。以上測定結果如表1所示。本品之鹼溶液顯示於 廣範圍溫度下具高度透明性者。 (實施例2 ) 將1 0 0重量份之粉狀紙漿浸漬於4 5重量％氫氧化 鈉水溶液後，加壓壓榨後針對纖維素調製重量比爲氫氧化 鹼量0 · 46、水份量0 · 64之鹼纖維素。加入32重 量份之環氧丙烷（針對纖維素之莫耳比0 · 8 9 )後於7 5〜8 0 °C下進行反應2小時之外，與實施例1之（1 ) 同法進行製造後，取得1 1 2重量份之低取代度羥丙基纖 維素。羥丙基之平均取代莫耳數爲〇 · 39。 與實施例1同法求取此取代物組成及溶液物性之結果 如表1所示。本品之鹼溶液顯示於廣範_溫度下具高度透 明性。 (請先閱讀背面之注意事項再本頁) -裝 . •線· 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公f ) -11- 1224111 A7 經濟部智慧財產局員工消費合作社印製 B7______五、發明說明（9 .) (實施例3 ) 將1.0 0重量份之薄片狀紙漿浸漬於2 5重量％氫氧 化鈉水溶液後，加壓壓榨後，針對纖維素調製重量比爲氫 氧化鹼量0 · 20，水份量0 · 67之鹼纖維素。加入 8 · 7重量份之環氧丙烷（針纖維素莫耳比〇 · 2 4 )後 於3 5〜4 0 t下進行反應4小時之外，與實施例1之（ 1 )同法進行製造後，取得低取代度羥丙基纖維素爲1〇 3重量份。羥丙基之平均取代莫耳數爲〇.11者。 與實施例1相同方法求取此取代物組成及溶液物性後 ’結果如表1所示。本品鹼溶液顯示廣範圍溫度下具高度 透明性。 (比較例1 ) 環氧丙烷之置入量爲4 5重量份（針對纖維素莫耳比 1 · 2 6 )除外，與實施例1 ( 1 )同法進行製造後，取 得1 5重量份之低取代度羥丙基纖維素。羥丙基之平均取 代莫耳數爲0 · 4 5者。 與實施例1同法求取此取代物組成及溶液物性後，結 果，如表1所示。本品鹼溶液呈白濁、透明性極低者。 (比較例2 ) 除反應溫度爲8 5〜1 0 〇 下進行；1 · 5小時操作 之外’與實施例1之（1 )同法製造後，取得1 〇 6重量 份之低取代度經丙基纖維素。經丙基之平均取代莫耳數爲 (請先閱讀背面之注意事項再 -- 本頁) . -線- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公f ) T2 1224111 A7 ^------- 五、發明說明（10 ) 〇 · 2 4 者。 與實施例1同法求取此取代組成及溶液物性後，結果 如表1所示。本品鹼溶液爲白濁、透明性極低者。 (比較例3 ) 將1 0 0重量份之薄片狀紙漿浸漬於8重量％濃度之 氫氧化_水溶液中，針對纖維素調製成重量比爲氫氧化鹼 量0 · 〇 8、水份量1 · 〇之鹼纖維素之外，與實施例2 同法.進行製造後’取得1 〇 1重量份之低取代度羥丙基纖 維素。羥丙基之平均取代莫耳數爲〇 · 〇 6者。 與實施例1同法求取此者之取代物組成及溶液物性後 ，結果如表1所示。本品對於氫氧化鈉水溶液幾乎無法溶 解。 (請先閱讀背面之注意事項再本頁) 線1224111 Α7 Β7 Printed clothing by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (1) The present invention is related to the solubility and height of the needle. In the prior art, hydroxypropyl glucose units (C 6 Η I non-ionic polymers, each of which is large. It is a hydroxypropyl cellulose as a substituent. Substitute the mol number (MS) as a substituent to dissolve the hydroxypropanol with a high degree of substitution.) In cold water, those which are insoluble in low degree of substitution are insoluble in alkalis such as sodium hydroxide. Soluble low-dispersing agents of this nature are used. The binding agent is used as a low degree of substitution for hydroxylation. The manufacturing method is in the alkaline aqueous solution, but it is low. Moreover, the difference depends on the alkaline water. Therefore, the solution has a low degree of substitution to the alkaline aqueous solution at a wide range of temperature. Base cellulose is a kind of hydroxypropyl group, which has the useful properties of hydroxyl group of 3 cellulose structural units (0055). It is used in a wide range of applications. 2. There is a degree of substitution in the liquid, which is used as propylcellulose. However, the stability of most of the solutions containing hydroxypropyl is the most effective method to replace the soluble soluble organic solvents with glucose. The difference in the generation amount of the hydroxypropylcellulose solution is different. Substituents are widely used on average. Organic solvents such as those with a Mohr number of 2 to 3. Swells when in contact with water. It is used as a disintegrating adhesive for pharmaceuticals. The vitamine Yu Yugongzhao 4 8 — 5 7-53 are all substituted groups, so the undissolved part of these parties due to solubility depends on temperature, its number of ears such as 100 Bulletin is 0. 5 ~ law Although the manufacturer is soluble in this solution, the transparency is extremely different, and the problem of great use conditions exists. Please read the precautions on the back page. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -4 -1224111 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (2) The solubility of the alkaline aqueous solution of hydroxypropyl cellulose with a low degree of substitution is greatly affected by the degree of substitution with propyl groups. In order to show good solubility of hydroxypropyl cellulose with a low degree of substitution, the amount of hydroxypropyl substitution is managed, that is, the average number of propyl-substituted mols of the glucose unit of its structural unit and the hydroxypropyl-substituted mol The ratio of number substitutions is extremely important. After controlling the substitution amount of hydroxypropyl group in this way, it can provide a low degree of substitution of hydroxypropyl cellulose with good solution transparency and stable solution state at a wide range of temperatures, but it is eagerly anticipated, but it has not been achieved so far. In order to solve the above problems, the present inventors have conducted precision investigations and found that the average substitution molar number of hydroxypropyl groups of glucose units (C6H1Q〇5) is 0.1 to 0.4 in low-substituted hydroxypropyl cellulose. The number of glucose units substituted with hydroxypropyl groups of 2 moles or more is 5% or less of the total glucose units, and it is 10% for a 10% by weight sodium hydroxide aqueous solution in a 2% by weight solution. C ~ 50 0 ° C has a light transmittance of more than 90%. It is characterized by a low degree of substitution. Hydroxypropyl cellulose exhibits high transparency after dissolving in an alkaline solution. And, it has a stable solution state at a wide range of temperatures. To complete the present invention. [Embodiments of the Invention] The present invention will be described in more detail below. The low degree of substitution of hydroxypropyl cellulose according to the present invention is one in which the molar number of hydroxypropyl groups substituted in the glucose unit is 0.1 to 0.4. When its average substituted mole number is less than 0.1, the solution is opaque when it is dissolved in an alkali solution. On the other hand, when it exceeds 0.4, the solution is turbid. (Please read the back first Note for re-installation. 丨 · This page: .--- The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) '5-Printed by A7, Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs __B7___ V. Description of the invention (3.) Impervious solution. In addition, the low degree of substitution of hydroxypropyl cellulose of the present invention has a number of hydroxypropyl substituted Mohrs of 2 or more (glucose units) as the total The glucose unit number is less than 5%. When the ratio of the hydroxypropyl substituted Mohr number 2 or more is greater than 5%, the same solution as above is opaque after being cloudy. This is for the solubility of alkaline solutions. When the ratio of the low unsubstituted body and the substituted body with a hydroxypropyl substituted Mohr number of 2 or more is increased, the transparency of the solution disappears. The production of the low-substituted hydroxypropyl cellulose of the present invention is performed in the first stage by making fibers After reacting with alkali hydroxide Alkaline cellulose. As a method for preparing alkali cellulose, the raw pulp is immersed in an alkali hydroxide aqueous solution, and after pressing, the remaining alkali hydroxide aqueous solution is removed, which is suitable as the composition of the desired alkali fiber. Among the celluloses used as raw materials, wood pulp and cotton fluff fiber pulp can be taken as an example, and various shapes such as flakes and pulverized powders can be used without any restrictions. Also as hydroxide Alkali aqueous solution can be used: sodium hydroxide, potassium hydroxide, lithium hydroxide and other aqueous solutions, but sodium hydroxide is preferred. The concentration of the alkali hydroxide aqueous solution is 20 to 45% by weight, especially It is preferably a concentration of 3 to 40% by weight. When the concentration of the alkali hydroxide aqueous solution is less than 20% by weight, the swelling of the cellulose is not activated, and the subsequent etherification reaction cannot proceed smoothly. Converse 2 When it is greater than 45% by weight, the composition of the prepared alkali cellulose is uneven, and it is aimed at the dissolution of the alkali solution (please read the precautions on the back, and then this page). Standard (CNS) A4 (210 X 297 mm) ^ 6- 1224111 A7 B7 Printed by the Consumers ’Cooperative of the Wisconsin Bureau of the Ministry of Economic Affairs 5. Description of the invention (4) The solubility varies with temperature, and the temperature of the physical properties of the solution varies greatly. As a method for preparing alkali cellulose, other methods include mixing pulp with an aqueous alkali hydroxide solution in an organic solvent such as fJ, and spraying an alkali hydroxide aqueous solution directly onto the pulp. Compared with alkaline cellulose obtained by immersion in an aqueous solution of alkali hydroxide, its composition is more uneven and cannot be used for the purpose of producing a low-substitution hydroxypropyl cellulose with good solubility in the alkaline solution. The alkali hydroxide is an important catalyst for the reaction of propylene oxide. At the same time, the catalyst also has an activating role to improve the reactivity of cellulose. In addition, after the water in the alkali cellulose reacts with propylene oxide, it is not desirable to produce impurities that cannot be removed by the product. Therefore, after the reaction of alkali cellulose with propylene oxide, in order to effectively produce low-substituted hydroxypropyl cellulose, it is necessary to control the amount of alkali hydroxide and water in the alkali cellulose when preparing the alkali cellulose. In the production of the low-substitution hydroxypropyl cellulose of the present invention, the alkali hydroxide amount and water content in the alkali cellulose relative to the weight ratio of the cellulose and the alkali hydroxide amount are 0.1 · 1 · 0, especially 0 · 1. 2 ~ 0 · 8 is preferable, and water content is 0.1 ~ 2.0, especially 0.3 · 1 ~ 0. If the weight ratio of cellulose is less than the above range of alkali hydroxide and water content, the reaction cannot proceed effectively. Conversely, if it is greater than the above range, the reaction of propylene oxide with water will increase the generation of undesired impurities. It is impossible to obtain the quantitative degree of substitution of hydroxypropyl groups, and it is necessary to expend great effort in order to remove impurities of by-products, all of which cause difficulties in controlling the expected amount of substitution by propyl groups. (Please read the precautions on the back before you re-install I ^^ this page) Ordering ·. Thread. This paper size is applicable to China National Standard (CNS) A4 (210 X 297 g t) 1224111 Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Cooperative printed agricultural A7 B7_V. Description of the invention (5) Therefore, as the method for preparing alkali cellulose in the first stage of the production of the low substitution degree hydroxypropyl cellulose of the present invention, the raw material pulp is dipped in alkali hydroxide After the aqueous solution, the alkali hydroxide aqueous solution remaining after the pressing is removed, and the method for making the desired alkali fiber composition is appropriate. The second stage in the production of the low-substitution hydroxypropyl cellulose of the present invention is that the alkali cellulose and propylene oxide are fully mixed and then reacted, and the reaction temperature is 30 to 80 ° C, especially 40 to It is better to be at 70 ° C, and the molar ratio of cellulose to 0.15 to 2 · 0 of propylene oxide is added to the reaction. When the reaction temperature is less than 30 ° C, the reaction proceeds very slowly and takes a long time. It is extremely impractical. On the contrary, when it is higher than 80 ° C, the generation ratio of hydroxypropyl-substituted polymorphs with a number of 2 or more in hydroxypropyl cellulose is increased, or after the reaction of propylene oxide with water, Increasing the amount of impurities produced is highly undesirable. When the added amount of propylene oxide exceeds the range, it is impossible to obtain a predetermined amount of hydroxypropyl substitution. As a method for adding propylene oxide, either a method of adding the quantized amount of propylene oxide in a single amount, or a method of continuously adding a portion of a number of times may be used. The reaction may be carried out after the use of an organic solvent having low reactivity with propylene oxide as a dispersion medium. The reaction product of the present invention contains impurities that are generated after the reaction of alkali hydroxide, propylene oxide and water, but can be easily purified by a known method to obtain low-purity hydroxypropyl fibers with high purity without impurities. Prime (please read the precautions on the back page before --- this page) Order · i-line-This paper size applies to China National Standard (CNS) A4 (210 X 297 male f)-8-1224111 Intellectual Property Bureau, Ministry of Economic Affairs Printed by the employee consumer cooperative π A7 B7___ V. Description of the invention (6) The composition of the low-substitution degree hydroxypropyl cellulose obtained by the present invention can be obtained by known methods, such as Carbhydro., Res · Vol · 1 70, ρ · 207 (1 987) and other methods. An example of a method for measuring the composition of a substitute is, for example, after reacting with a methylating agent such as methyl iodide in the presence of a base, and methylating a free hydroxyl group with a low degree of substitution, hydroxypropyl fibers are subjected to an acid such as trifluoroacetic acid. After decomposition, it is used as a sorbitol derivative after reduction. After using anhydrous acetic acid, etc., if the acetylated person is separated from those with different numbers of hydroxypropyl substitutions and substitution positions by gas chromatography, the respective ratios can be obtained. The transparency of the low-substituted hydroxypropyl cellulose obtained by the present invention can be judged by the light transmittance. The light transmittance refers to the light transmittance of the low-substituted hydroxypropyl cellulose solution under the same conditions when the light transmittance of the purified water measured with a photoelectric colorimeter is 100. The measurement method is specifically described in the examples below, and the present invention will be described in more detail through examples and comparative examples. However, the present invention is not limited to this example. (Example 1) (1) Production of hydroxypropyl cellulose with low substitution degree After immersing 100 parts by weight of flaky pulp in a 40 wt% sodium hydroxide aqueous solution, the sodium hydroxide aqueous solution was absorbed into the pulp, and then After removing the remaining sodium hydroxide aqueous solution after pressing at 3 kg / cm2, the alkali hydroxide amount was adjusted to 0.55 and the water content was 0.90 for the weight ratio of cellulose. After subdividing the prepared alkali fiber, it is placed into an internal scale with applicable Chinese National Standard (CNS) A4 specifications (210 X 297 mm) -9-Bribe (please read the precautions on the back before copying this!) Female · -line · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1224111 A7 B7____ V. Description of the invention (7) The pressure reactor of the stirrer, after the reactor fully replaces nitrogen, it is placed in a ring of 2 4 parts by weight Oxypropane (Molar ratio 0.67 against cellulose) was reacted at 50 ° C for 3 hours. The reactant was neutralized with acetic acid to remove residual sodium hydroxide, and then washed with warm water at 50 to 60 ° C, and then dried at 80 ° C by air drying to obtain 108 parts by weight of a colorless solid. Low degree of substitution with hydroxypropyl cellulose. The average substitutional mole number of hydroxypropyl group obtained by the Ze1Sel method is 0.26. (2) Composition of Substitute > ‘3 parts by weight of the low degree of substitution of hydroxypropyl cellulose obtained in (1) is dissolved in 250 parts by weight of dimethylformaldehyde. After 30 parts by weight of powdery sodium hydroxide was added to the solution, 1,000 parts by weight of methane was added while stirring, and then the reaction was performed at 60 ° C for 4 hours. The reactant was poured into 100 parts by weight of hot water to precipitate methylated hydroxypropyl cellulose. After the precipitate was recovered, it was dried at 70 t for 6 hours. To 5 parts by weight of methylated hydroxypropylcellulose was added 300 parts by weight of 2m ο 1% trifluoroacetic acid aqueous solution. 'After processing at 120 ° C for 3 hours, adjust P with barium carbonate P Is 7. After adding 1.5 parts by weight of sodium borohydride and stirring at room temperature for 1 hour, it was evaporated to dryness at 1000 ° C. When 100 parts by weight of acetic acid was added to the remaining content, 2000 parts by weight of pyridine 'were treated at 120 ° C for 3 hours. After cooling, the person who added 5000 parts by weight of water was extracted twice with 50 parts by weight of carbon tetrachloride. The residue of evaporated carbon tetrachloride was analyzed by GC. The top of the paper analyzed by GC is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 public love) ΠTP (Please read the precautions on the back before this page) · --line-1224111 A7 _ B7 Ministry of Economic Affairs Wisdom Printed by the Employees' Cooperative of the Property Bureau. V. Description of the invention (8) The area ratio of the hydroxypropyl-substituted mol number of 2 or more and the total ratio of non-substitutes is shown in Table 1. (3) Solution physical properties and solid physical properties The obtained low-substitution degree hydroxypropyl cellulose was dissolved in a 10% by weight sodium hydroxide aqueous solution so that the concentration of the low-substitution degree hydroxypropyl cellulose was 2% by weight. Change the dissolution temperature to 10 ° C, 30 ° C. After the solution prepared at 50 ° C, use a B-type viscometer to measure the viscosity, and then use a photoelectric colorimeter (5 E type) to check the blank test (water). The light transmittance was measured. The above measurement results are shown in Table 1. Alkali solutions of this product are highly transparent at a wide range of temperatures. (Example 2) After 100 parts by weight of powdery pulp was immersed in a 45% by weight aqueous sodium hydroxide solution, the weight ratio of cellulose to the cellulose after pressing and pressing was adjusted to an alkali hydroxide amount of 0.46 and an amount of water of 0. 64 of alkali cellulose. After adding 32 parts by weight of propylene oxide (molar ratio of cellulose to 0.89), the reaction was carried out at 7 5 to 80 ° C for 2 hours, and the same method as in Example 1 (1) was used for production. Thereafter, 1 1 2 parts by weight of a low-substitution degree hydroxypropyl cellulose was obtained. The average substituted mole number of hydroxypropyl group was 0.39. Table 1 shows the results of obtaining the composition of this substitute and the physical properties of the solution in the same manner as in Example 1. The alkali solution of this product is highly transparent at a wide range of temperatures. (Please read the precautions on the back first, then this page) -Packing. • Thread · This paper size applies to China National Standard (CNS) A4 (210 X 297 male f) -11- 1224111 A7 Employee Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs Printing B7______ 5. Description of the invention (9.) (Example 3) After dipping 1.00 parts by weight of flake pulp in a 25% by weight aqueous sodium hydroxide solution, after pressing, the weight ratio of cellulose was adjusted to Alkali cellulose with alkali hydroxide content of 0 · 20 and water content of 0 · 67. After adding 8.7 parts by weight of propylene oxide (needle cellulose molar ratio 0.24), the reaction was carried out at 35 to 40 t for 4 hours, and was produced in the same manner as in Example 1 (1). Thereafter, a low degree of substitution with hydroxypropyl cellulose was obtained in an amount of 103 parts by weight. The average number of substituted mols of hydroxypropyl group is 0.11. Table 1 shows the results of obtaining the composition of the substitute and the physical properties of the solution in the same manner as in Example 1. This product alkali solution shows high transparency at a wide range of temperatures. (Comparative Example 1) Except that the amount of propylene oxide was 4 5 parts by weight (for cellulose mole ratio 1 · 2 6), it was produced in the same manner as in Example 1 (1), and 15 parts by weight were obtained. Low degree of substitution with hydroxypropyl cellulose. The average number of hydroxypropyl groups is 0.45. The composition of this substitute and the physical properties of the solution were determined in the same manner as in Example 1. The results are shown in Table 1. The alkali solution of this product is cloudy and extremely low in transparency. (Comparative Example 2) Except that the reaction temperature was 85 to 100 ° C; except for 1.5 hours of operation, after the same method as in Example 1 (1), a low degree of substitution of 1.06 parts by weight was obtained. Propyl cellulose. The average number of moles substituted by propyl groups is (please read the precautions on the back first-this page). -Line-This paper size is applicable to China National Standard (CNS) A4 (210 X 297 male f) T2 1224111 A7 ^ ------- V. Description of the invention (10) 〇 · 2 4 The substitution composition and the physical properties of the solution were determined in the same manner as in Example 1. The results are shown in Table 1. The alkali solution of this product is cloudy and extremely low in transparency. (Comparative Example 3) 100 parts by weight of flaky pulp was immersed in an 8% strength by weight aqueous hydroxide solution, and the weight ratio of cellulose to alkali hydroxide was 0 · 〇8, and water content was 1 ·. Except for the alkali cellulose, the same method as in Example 2 was performed. After the production, 101 parts by weight of hydroxypropyl cellulose with a low degree of substitution was obtained. Those with an average substitutional molar number of hydroxypropyl groups of 0.06. Table 1 shows the results of the substitution composition and the solution physical properties of this compound in the same manner as in Example 1. This product is almost insoluble in aqueous sodium hydroxide solution. (Please read the notes on the back before this page)
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)A4規格（210 X 297公f ) 1224111 A7 B7 明說· 明【發 (11 (Γ HCUIU) 3。0 5Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 male f) 1224111 A7 B7 Instructions · Ming [fa (11 (Γ HCUIU) 3.0 5.0
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