1359892 (1) 九、發明說明 【發明所屬之技術領域】 本發明係有關纖維的改質方法及·改質纖維。 【先前技術】 向來爲防止纖維的起毛，提高拉伸強度及耐摩耗性、 賦予抗電性或吸水性，創出纖維的手感的目的，提案於纖 φ維附著纖維黏液後，凝固、再生之後，經水洗、乾燥將纖 維的表面以再生纖維被覆之擬麻加工的方法。 但是，由纖維黏液之再生纖維被覆之纖維改質方法， 由於含有將纖維素以毒性強的二硫化碳變換製作之纖維素 黃酸酯溶於荷性鈉水溶液之溶液，即將纖維黏液附著於纖 維後’將纖維素凝固、再生之步驟，於纖維素黃酸酯的製 造步驟及凝固、再生步驟之從事製造者須承受曝露於二硫 化碳的問題。又，該纖維改質方法，由於被覆之再生纖維 ®素本身的吸水性不充分，殘留抗電性、吸水性、防縮性等 的改質效果不佳的問題。 爲解決如此由被覆纖維黏液的再生纖維素之纖維改質 方法的目的，提案將纖維素該物於荷性鈉水溶液經溶解後 附著於纖維後，凝固、再生以再生纖維素被覆纖維的表面 之方法（參閱專利文獻1:日本特開昭61-252369號公報 )° 但是，該方法，必要使用於低溫將纖維素溶解於荷性 鈉水溶液外，原料本身之纖維素亦以木漿加酸水解，於球 -5- (2) 1359892 磨機粉碎或由纖維黏液等所製造之再生纖維素等’減少結 晶構造提高溶解性之纖維素爲必要之限制。 〔專利文獻1〕日本特開昭6 1 -252369號公報 【發明內容】 〔發明所欲解決之課題〕 本發明有鑑於上述事實，提供無二硫化碳爲基本的毒 #性問題，且製造步驟簡單，可改善對耐鹼性低的纖維之改 質，防止起毛，拉伸強度、耐摩耗性、抗電性、吸水性優 之纖維的改質方法。 〔課題解決手段〕 本發明者提案（參閱日本特開2004-2 1 8 1 02號公報） 將纖維以低取代度之纖維素醚以荷性鈉等的鹼溶解之纖維 附著，有關其耐洗濯性經深入硏究改良的結果，發現於烷 #基及/或羥烷基莫耳取代度爲0.05 ~ 1.3的低取代度纖維素 醚水溶液添加交聯劑及/或水系樹脂乳膠，將該溶液附著 於纖維後，將附著之溶液以酸中和凝固經熱處理，或將低 取代度纖維素醚水溶液添加交聯劑及/或水系樹脂乳膠， 將該溶液附著於纖維後，將附著之溶液經熱處理後接著以 酸中和凝固，提高耐洗濯性，無二硫化碳的問題，發現可 防止起毛、提高拉伸強度、耐摩耗性、抗電性、吸水性優 之纖維改質加工，完成本發明。 因此，本發明爲提供以下纖維的改質方法及改質纖維 -6- (3) (3)1359892 申請項1 : 於烷基及/或羥烷基之莫耳取代度爲0.05〜1.3之低取 代度纖維素醚經溶解後之鹼性水溶液中添加交聯劑及/或 水系樹脂乳膠，將該溶液附著於纖維後，將附著溶液以酸 中和凝固，接著加熱處理的改質方法。 申請項2 : 於烷基及/或羥烷基之莫耳取代度爲0.05〜1.3之低取 代度纖維素醚經溶解後之鹼性水溶液中添加交聯劑及/或 水系樹脂乳膠，將該溶液附著於纖維後，加以熱處理，接 著以酸中和的纖維的改質方法。 申請項3 : 交聯劑爲異氰酸酯系交聯劑之第1或2項之纖維改質 方法。 申請項4 : 水系樹脂乳膠爲水系胺基甲酸酯乳膠或反應性有機聚 矽氧烷的0/W型乳膠之第1或2項之纖維改質方法。 申請項5 : 低取代度纖維素醚爲莫耳取代度〇.1〜0.7的低取代度 羥基丙基纖維素之如第1〜4項中任一項之纖維改質方法。 申請項6 : 鹼性水溶液爲荷性鈉水溶液之如第1 ~5項中任—項之 纖維改質方法，其中鹼性水溶液爲荷性鈉水溶液。 申請項7 : (4) 1359892 一種改質纖維，其特徵爲被覆烷基及/或羥烷基之莫 耳取代度爲〇·〇5〜1.3之低取代度纖維素醚與交聯劑及/或 水系樹脂乳膠所成。 〔發明之效果〕 依本發明由於不使用二硫化碳等有毒之溶劑可將纖維 改質，安全性高製造步驟不煩雜，可得到防止起毛、提高 #拉伸強度、耐摩耗性、抗電性、吸水性優的改質纖維。又 ’依本發明所得的改質纖維持有提高通氣性、清爽感、結 實撓性觸感。 〔用以實施發明之最佳型態〕 本發明所使用的纖維無特別的限制，具體的可例示如 聚乙烯纖維，聚丙烯纖維、聚酯纖維、尼龍纖維、丙烯酸 纖維、維尼龍纖維 '人造絲纖維、聚乙烯纖維、聚偏氯乙 •烯纖維的合成纖維，或綿、纖維素、麻等的天然纖維、羊 毛、絲、羊毛絨等的動物纖維。依本發明亦可適合使用於 對耐鹼性差的羊毛、絲、羊毛絨等的動物性纖維。此處纖 維係含紗狀的纖維之編織布、或紗狀纖維的不織布。 於本發明之低取代度纖維素醚爲構成纖維之葡糖環的 羥基之氫以烷基或羥烷基取代之纖維素醚中，莫耳代度爲 0.05〜1.3，理想爲0.1〜0.7者，不溶於水，可溶於鹼性水 溶液者即可。上述莫耳取代度低於0.05時不易溶於鹼性 水溶液，超過1.3時水的溶解性提高，對鹼性水溶液的溶 -8 - (5) 1359892 解性變差。 如此之低取代度纖維素醚，可列舉如低取代度甲基纖 維素 '低取代度乙基纖維素等的低取代度烷基纖維素，低 $代度經乙基纖維素、低取代度羥丙基纖維素等的羥烷基 纖維素’低取代度羥丙甲基纖維素、低取代度羥乙基甲基 纖維素'低取代度羥乙基乙基纖維素等的羥烷基烷基纖維 素等’特別以低取代度羥丙基纖維素爲理想。 ©本發明的纖維改質，由以下2種方法進行，第1方法 爲於上述低取代度纖維素醚溶解的鹼性水溶液添加交聯劑 及/或水系樹脂乳膠，將該溶液塗佈或浸漬附著於纖維後 ’依必要使用離心脫水機、軋液機、括刀塗敷機等將多餘 的附著液去除後，將附著液以酸中和凝固，依必要經水洗 、乾燥後，加處理的方法。 第2方法爲於上述低取代度纖維素醚溶解的鹼性水溶 液添加交聯劑及/或水系樹脂乳膠，將該溶液塗佈或浸漬 β附著於纖維後》依必要使用離心脫水機、軋液機、括刀塗 敷機等將多餘的附著液去除後，經加熱處理，接著將殘留 驗以酸中和凝固後，乾燥的方法。任一方法之交聯反應及 #系樹脂乳膠的硬化皮膜化均於加熱步驟進行，交聯反應 及水系樹脂乳膠的硬化皮膜化均爲提高低取代度纖維素醚 的附著量，其結果將耐洗濯性提高。 此處之鹼性水溶液可舉例如荷性鈉水溶液、荷性鉀水 溶液等，其荷性鹼濃度依所使用的低取代度纖維素醚的種 類或取代度而異，適當的指定即可。通常鹼濃度爲2〜25 -9- (7) 1359892 酸鈉、苯酸鈉等的鹽水溶液浸漬將附著液凝固的鹽析凝固 法。倂用鹽析凝固法時，將最初附著的溶液中和凝固後， 接著進行鹽析凝固亦可，鹽析凝固後進行中和凝固亦可。 又，亦可於含鹽與酸的水溶液中凝固。 於本發明所使用的交聯劑，可使用任一與低取代度纖 維素醚分子中殘留的羥基反應之交聯反應者。如此之交聯 劑，可列舉如交聯劑手冊（日本昭和56年1 0月20日， # 曰本大成社發行）所記載的與羥基進行反應之交聯劑。具 體的如乙二醇二環氧丙基醚、丙二醇二環氧丙基醚、甘油 聚環氧丙基醚二甘油聚環氧丙基醚、山梨糖醇聚環氧丙基 醚、烯丙基環氧丙基醚、丁基環氧丙基醍、苯基環氧丙基 醚、烷基酚環氧丙基醚、聚乙二醇二環氧丙基醚、三丙二 醇二環氧丙基醚、新戊基環氧丙基醚、1，6-己二醇、環氧 丙基醚、甘油聚環氧丙基醚、二甘油聚環氧丙基醚、甲苯 基環氧丙基醚、碳數3〜15的脂肪族環氧丙基醚、單環氧 ®丙基醚、環氧丙烯酸酯、雙酚A、丙基環氧丙基醚丙烯酸 酯、乙二醇二環氧丙基醚丙烯酸酯、三羥甲基丙烷聚環氧 丙基醚聚丙烯酸酯、對苯二甲酸二環氧丙基酯丙烯酸酯、 鄰苯二甲酸二環氧丙基酯、螺二醇二環氧丙基醚等的環氧 化合物，或乙二醛等的二醛、尿素甲醛等的甲醛葯交聯劑 ’甲苯胺異氰酸酯、2,4-甲苯胺異氰酸酯的二量物，伸萘 基-1，5-二拱氰酸酯、〇-甲苯胺異氰酸酯、二苯基甲烷二異 氰酸酯、三苯基甲烷三異氰酸酯、三- (p-氰酸酯苯基）硫 代磷酸酯、聚伸甲基聚苯基異氰酸酯、多官能芳香族異氰 -11 - (8) 1359892 酸酯、芳香族聚異氰酸酯、六伸甲基二異氰酸酯、三甲基 六伸甲基二異氰酸酯、異富爾酮二異氰酸酯、嵌段型聚異 氰酸酯、伸甲苯基二異氰酸酯、含有醚或含胺基甲酸酯嵌 段型異氰酸酯預聚物、聚異氰酸酯預聚物、嵌段異氰酸酯 、聚異氰酸酯、二液型聚異氰酸酯、無變黃性二液型用聚 異氰酸酯、熱硬化型聚異氰酸酯等的異氰酸酯系交聯劑， 又’ 一般式Si R1 R2 R3 R4(式中，R1爲碳數1或2的烷 φ基、烷氧基或醯氧基。又，R2、R3及R4分別爲相互獨立 之碳數1或2之烷氧基或醯氧基）所示之矽烷。 又鹸性水溶液中此等交聯劑濃度無特別的限制，1〜3 0 質量％，特別以5〜1 0質量％爲理想，未達1質量％時耐洗 濯性的提高效果不充分，超過30質量％時不能見到耐濯性 相稱的提高。 有關上述第1方法低取代度纖維素醚的交聯方法，可 採用溶解低取代度纖維素醚與交聯的鹼性水溶液附著於纖 #維，該纖維以酸水溶液處理將低取代度纖維素醚凝固，經 水洗淨再乾燥，接著於100〜170 °c加熱交聯反應的方法。 又，加熱時間無特別限制，以1 ~2 0分鐘爲理想。 有關上述第2方法低取代度纖維素醚的交聯方法，可 採用溶解低取代度纖維素醚與交聯的鹼性水溶液附著於纖 維，該纖維以酸水溶液處理將低取代度纖維素醚凝固，將 該纖維於100〜170°C加熱交聯反應後，以浸漬法等將纖維 於酸水溶液中處理中和殘留鹼，依必要經水洗後乾燥即可 。此時，加熱時間無特別限制，以1〜2 0分鐘爲理想。又 -12- (9) 1359892 ，乾燥後依必要可再進行再加熱處理。 於第2方法以酸中和時之酸，可使用如第1方法 之酸同樣者，水溶液濃度亦相同。 第1方法及第2方法任一者爲能容易浸漬交聯劑 同時添加0.5〜1質量％的比例的丙二醇或乙二醇等的 醚浸透劑或丙二醇與乙二醇的嵌段共聚物浸透劑等的 活性劑類與交聯劑溶液。 • 本發明的水系樹脂乳膠，在上述第1方法於凝固 代度纖維素醚之過程，水系樹脂乳膠與低取代度纖維 同時固定於纖維，接著於進行之加熱步驟將水系樹脂 硬化皮膜化，在第2方法於加熱步驟固定於纖維，經 化與低取代度纖維素醚成爲一體，由被覆於纖維表面 高耐洗濯性等纖維物性。因此，所使用的水性樹脂乳 加熱可硬化皮膜化，提高纖維與低取代度纖維素醚的 性者即可，可列舉一般纖維的樹脂加工所使用的水系 #甲酸酯樹脂乳膠、水系丙烯酸樹脂乳膠、水系醋酸乙 脂乳膠、水系乙烯/醋酸乙烯乳膠、水系環氧樹脂乳 反應性有機聚矽氧烷的0/W型乳膠、SBR乳膠等， 以水系胺基甲酸酯樹脂乳膠、反應性有機聚矽氧烷的 型乳膠爲合適。 水系胺基甲酸酯樹脂乳膠可舉例如自聚羥基乙二 聚羥基丙二醇、聚羥基丁二醇等的聚醚，與伸甲苯二 酸酯，3,3’-雙伸甲苯基-4,4’-二異氰酸酯、二苯基甲 氰酸酯、3,3-二甲基二苯基甲烷二異氰酸酯、4,4，_二 所舉 ，可 院基 界面 低取 素醚 乳膠 皮膜 ，提 膠由 附著 胺基 烯樹 膠、 特別 0/W 醇' 異氰 烷異 異氰 -13- (11) 1359892 等的各種金屬鹽亦無妨，特別以日本特公昭34-4 1 99號公 報記載之醋酸锆或日本特公昭5 1 -9440號公報記載之氯化 鉑酸等爲有用。此等的觸媒之使用量無特別的限定，可促 進交聯反應之合理量爲對100.質量份所使用之乳膠中的反 應性有機聚矽氧烷而言爲 0.001〜120質量份，特別以 0.005〜1 1 0質量份爲理想。0/W型膠的粒子徑無特別的限 定，自乳膠的安定性觀點以0.01〜100//m，特別以0.1~80 _ m爲理想。 又’使用反應性有機聚矽氧烷的0/W型乳膠，亦可 依上述水系胺基甲酸酯乳膠同樣的硬化皮膜化條件進行。 由本發明改質之纖維所得之紗所製之布或胚其通氣性 提高’成爲具清爽感或撓性之纖維，又於低取代度纖維素 醚的鹼性溶液中添加二氧化鈦1〜2 0質量％程度可成爲具有 光觸媒功能的纖維或布，亦可於低取代度纖維素醚的鹼性 溶液中添加染料或顔料加以著色。此外，在不妨碍達成本 •發明目的之範圍可在低取代度纖維素醚的鹼性溶液中添加 各種無機材料、有機材料得到改質的纖維。 【實施方式】 以下以實施例及比較例具體說明本發明，本發明不限 於實施例。 〔實施例1〜1 1〕 於如表1所示分散1 0質量份低取代度纖維素醚之水 -15- (12) 1359892 溶液5 0質量份添加1 8質量％荷性鈉水溶液5 0質量份將低 取代度纖維素醚溶解後，添加9質量份二苯基甲烷二異氰 酸酯溶解，調整溶解交聯劑之低取代度纖維素醚的鹼性溶 液，調製試料液。其次，將OOMIKENSI (股）製KNIT COMA棉紗30/1號或日本ASAHI熊（股）製聚酯紗30號 於日本KAKINOKI (股）製之KHS Universal Sizer裝置浸 漬該試料液，將吸液率爲2 00〜3 00質量％後，以同裝置立 φ即浸漬於10質量％之犠酸水溶液，凝固低取代度纖維素醚 。接著以充分的水洗淨後乾燥，其次於145 °C加熱處理5 分鐘，得到試料纖維紗。 如此所得之試料依下述試驗法，評價起毛性、拉伸強 度、耐摩耗性、抗電性、吸水性、耐洗濯性。結果如表1 〔實例]2〜18〕 使用聚經基乙二醇與二苯基甲烷二異氰酸酯的交聯物 之交聯構造型的水系胺基甲酸酯樹脂乳膠化替二苯基甲烷 二異氰酸酯’纖維使用日本OOMIKENSI (股）製KNIT COMA棉紗30/1號以外，與實施例1〜〗丨同樣得到試料纖 維紗’評價之。結果如表1。 〔實施例1 9〕 於如表1所示分散丨〇質量份低取代度纖維素醚之水 溶液50質量份添加丨8質量％荷性鈉水溶液5〇質量份將低 -16- (14) 1359892 以充分的水洗淨後乾燥，其次於〗45°C加熱處理5分鐘， 得到試料纖維紗。 如此所得之試料依下述試驗法’評價起毛性、拉伸強 度、耐摩耗性、抗電性、吸水性、耐洗濯性。結果如表1 〔比較例1〕 # 由曰本製紙（股）製的粉末纖維素KC BLOCKW 1〇〇 ，調製纖維素換算濃度8質量％、荷性鈉濃度6質量％、 二硫化碳2.5質量％所成之黏液100質量份作爲試料液以 外，與實施1〜7同樣製作試料評價。結果如表1。 〔實施例24~27〕 於如表2所示分散1 〇質量份低取代度纖維素醚之水 溶液50質量份添加1 8質量％荷性鈉水溶液50質量份將低 Φ取代度纖維素醚溶解後，添加9質量份二苯基甲烷二異氰 酸酯溶解’調整溶解交聯劑之低取代度纖維素醚的鹼性溶 液，調製試料液。其次，將OOMIKENSI (股）製KNIT COMA棉紗30/1號於日本KAKINOKI (股）製之KHS Universal Sizer裝置浸漬該試料液，將吸液率爲2〇〇〜300 質量％後’於1 4 5 °C加熱處理5分鐘，加熱處理之纖維以 1 〇質量％之蟻酸水溶液漬漬，中和殘留之荷性鈉。接著以 充分的水洗淨後乾燥，得到試料纖維紗。 如此所得之試料依下述試驗法，評價起毛性、拉伸強 -18- (15) 1359892 度、耐摩耗性 '抗電性、吸水性、耐洗濯性。結果如表2 〔實施例28〜3 1〕 使用聚羥基乙二醇與二苯基甲烷二異氰酸酯的交聯物 之交聯構造型的水系胺基甲酸酯樹脂乳膠化替二苯基甲烷 二異氰酸酯以外，與實施例24〜27同樣得到試料纖維紗， φ經評價其結果如表2。 〔實施例3 2〕 於如表2所示分散1〇質量份低取代度纖維素醚之水 溶液50質量份添加18質量％荷性鈉水溶液50質量份將低 取代度纖維素醚溶解後，添加3.2質量份甲基氫聚矽氧烷 ，3 g作爲交聯劑的醋酸锆，調製溶液。其次，將 OOMIKENSI (股）製KNIT COMA棉紗30/1號或日本 隹ASAHI熊（股）製聚酯紗30號於日本KAKINOKI (股） 製之KHS Universa】 Sizer裝置浸漬該試料液，將吸液率爲 200〜300質量％後，於145。(：加熱處理5分鐘，經加熱處理 之纖維浸漬於1 〇質量％之蟻酸水溶液，中和殘留的荷性鈉 。接著以充分的水洗淨後乾燥，得到試料纖維紗。 如此所得之試料依下述試驗法，評價起毛性、拉伸強 度、耐摩耗性、抗電性、吸水性、耐洗濯性。結果如表2 -19- (18)13598921359892 (1) Description of the Invention [Technical Field of the Invention] The present invention relates to a method for modifying a fiber and a modified fiber. [Prior Art] In order to prevent the fluffing of fibers, increase the tensile strength and abrasion resistance, and impart electric resistance or water absorption, and to create a fiber feel, it is proposed to adhere to the fiber viscous fibers and then solidify and regenerate. A method in which the surface of the fiber is coated with regenerated fibers by water washing and drying. However, the fiber modification method of the regenerated fiber coated with the fiber mucus contains a solution of the cellulose xanthate prepared by converting the cellulose into a toxic aqueous carbon disulfide solution, that is, after the fiber mucus adheres to the fiber. The step of solidifying and regenerating the cellulose is carried out by the manufacturer in the production step of the cellulose flavonate and the solidification and regeneration steps, and the manufacturer is exposed to the problem of exposure to carbon disulfide. Further, in the fiber upgrading method, since the water repellent property of the coated regenerated fiber itself is insufficient, the effect of improving the electric resistance, water absorption, shrinkage resistance, and the like is not good. In order to solve the fiber reforming method of the regenerated cellulose which is coated with the fiber mucilage, it is proposed that the cellulose is dissolved in the aqueous sodium solution and adhered to the fiber, and then solidified and regenerated to regenerate the surface of the cellulose-coated fiber. (Patent Document 1: JP-A-61-252369) However, this method is necessary to dissolve cellulose at a low temperature to dissolve the cellulose outside the aqueous sodium solution, and the cellulose of the raw material itself is hydrolyzed by wood pulp. , Yuqiu-5- (2) 1359892 Refining cellulose produced by mill pulverization or fiber slime, etc. 'Reducing the crystal structure to improve the solubility of cellulose is a necessary limitation. [Patent Document 1] JP-A-61-252369 SUMMARY OF INVENTION [Problem to be Solved by the Invention] The present invention has been made in view of the above-described facts, and provides carbon-free carbon dioxide as a basic toxic problem, and the manufacturing steps are simple. It can improve the modification of fibers with low alkali resistance and prevent fluffing, tensile strength, abrasion resistance, electrical resistance and water absorption. [Problem to solve the problems] The present inventors propose (see Japanese Patent Laid-Open Publication No. 2004-2 1 8 1 02). The fibers are adhered to a fiber having a low degree of substitution of cellulose ether dissolved in an alkali such as sodium, and the washing resistance thereof is concerned. After intensively improving the results of the improvement, it was found that a crosslinking agent and/or an aqueous resin latex was added to the aqueous solution of the low-substituted cellulose ether having a degree of substitution of the alkyl group and/or the hydroxyalkyl group having a degree of substitution of 0.05 to 1.3. After adhering to the fiber, the adhered solution is subjected to heat treatment by acid neutralization and heat treatment, or a low-degree-substituted cellulose ether aqueous solution is added to the crosslinking agent and/or the aqueous resin latex, and the solution is attached to the fiber, and the adhered solution is passed through After the heat treatment, the resin is neutralized and solidified to improve the washing resistance, and there is no problem of carbon disulfide. The fiber reforming process which can prevent fluffing, increase tensile strength, abrasion resistance, electric resistance, and water absorption is found, and the present invention has been completed. Therefore, the present invention provides a modification method of the following fibers and a modified fiber-6-(3) (3) 1359892. Application 1: The molar substitution degree of the alkyl group and/or the hydroxyalkyl group is 0.05 to 1.3. A degree of substitution of a cellulose ether is carried out by adding a crosslinking agent and/or an aqueous resin emulsion to the dissolved alkaline aqueous solution, and attaching the solution to the fiber, and then adhering the solution to acid neutralization, followed by heat treatment. Application 2: adding a crosslinking agent and/or a water-based resin emulsion to an alkali aqueous solution obtained by dissolving a low-degree-substituted cellulose ether having a molar substitution degree of 0.05 to 1.3 in an alkyl group and/or a hydroxyalkyl group, After the solution is attached to the fiber, it is heat treated, followed by a modification of the acid-neutralized fiber. Application 3: A method for upgrading a fiber according to the first or second aspect of the isocyanate crosslinking agent. Application 4: The aqueous resin emulsion is a fiber upgrading method of the first or second aspect of the 0/W type latex of the aqueous urethane latex or the reactive organic polyoxyalkylene. Item 5: Low-degree-substituted cellulose ether is a method of fiber upgrading according to any one of items 1 to 4, which is a low degree of substitution of a molar substitution degree of from 1 to 0.7. Item 6: A method for upgrading a fiber according to any one of items 1 to 5, wherein the alkaline aqueous solution is an aqueous sodium solution, wherein the aqueous alkaline solution is an aqueous sodium solution. Item 7: (4) 1359892 A modified fiber characterized by a low degree of substitution of a cellulose ether and a crosslinking agent having a molar substitution degree of the alkyl group and/or a hydroxyalkyl group of 〇·〇5 to 1.3 and/or Or water-based resin latex. [Effect of the Invention] According to the present invention, the fiber can be modified without using a toxic solvent such as carbon disulfide, and the manufacturing process is high and the manufacturing process is not complicated, and the occurrence of abrasion resistance, abrasion resistance, abrasion resistance, electric resistance, and water absorption can be obtained. Excellent quality fiber. Further, the modified fiber obtained by the present invention has improved air permeability, refreshing feeling, and firm and soft touch. [Best Mode for Carrying Out the Invention] The fibers used in the present invention are not particularly limited, and specific examples thereof include polyethylene fibers, polypropylene fibers, polyester fibers, nylon fibers, acrylic fibers, and nylon fibers. Synthetic fiber of silk fiber, polyethylene fiber, polyvinylidene chloride fiber, or natural fiber of cotton, cellulose, hemp, animal fiber such as wool, silk, wool and the like. According to the present invention, it is also suitable for use in animal fibers such as wool, silk, wool, and the like which are poor in alkali resistance. Here, the fiber is a woven fabric of yarn-containing fibers or a non-woven fabric of yarn-like fibers. The low-degree-substituted cellulose ether of the present invention is a cellulose ether in which the hydrogen of the hydroxyl group constituting the glucose ring of the fiber is substituted with an alkyl group or a hydroxyalkyl group, and the molar ratio is 0.05 to 1.3, preferably 0.1 to 0.7. , insoluble in water, soluble in alkaline aqueous solution. When the molar substitution degree is less than 0.05, it is hardly soluble in an alkaline aqueous solution, and when it exceeds 1.3, the solubility of water is improved, and the solubility of the alkaline aqueous solution is deteriorated by the solubility of -8 - (5) 1359892. Such a low degree of substitution cellulose ether may, for example, be a low degree of substitution methyl cellulose, a low degree of substitution ethyl cellulose, or the like, a low degree of substitution alkyl cellulose, a low degree of substitution with ethyl cellulose, a low degree of substitution. Hydroxyalkylcellulose such as hydroxypropylcellulose, low-substituted hydroxypropylmethylcellulose, low-substituted hydroxyethylmethylcellulose, low-substituted hydroxyethylethylcellulose, etc. Cellulose and the like are particularly desirable for low-substituted hydroxypropylcellulose. The fiber modification of the present invention is carried out by the following two methods. In the first method, a crosslinking agent and/or an aqueous resin latex are added to the alkaline aqueous solution in which the low-substituted cellulose ether is dissolved, and the solution is coated or impregnated. After adhering to the fiber, the excess adhering liquid is removed by using a centrifugal dehydrator, a rolling mill, a knife coater, etc., and then the adherent liquid is neutralized by acid neutralization, washed with water, dried, and then treated. method. In the second method, a crosslinking agent and/or an aqueous resin latex is added to the alkaline aqueous solution in which the low-substituted cellulose ether is dissolved, and the solution is coated or impregnated with β and attached to the fiber, and a centrifugal dehydrator or a rolling liquid is used as necessary. After removing the excess adhering liquid by a machine or a knife coater, the mixture is subjected to heat treatment, and then the residue is neutralized by acid neutralization and then dried. The cross-linking reaction of any of the methods and the hardening of the #-resin latex are carried out in a heating step, and the cross-linking reaction and the hardening of the aqueous resin latex all increase the adhesion amount of the low-substituted cellulose ether, and the result is resistant. The washing performance is improved. In the alkaline aqueous solution, for example, a sodium-saturated aqueous solution or a potassium-containing aqueous solution may be used. The concentration of the alkalinity to be used may be appropriately determined depending on the type or degree of substitution of the low-substituted cellulose ether to be used. Usually, a salt solution having a base concentration of 2 to 25 -9-(7) 1359892 sodium or sodium benzoate is immersed in a salting-out method for solidifying the adhering liquid. When the salting-out solidification method is used, the solution to be adhered to the first time is neutralized, and then the salting-out solidification may be carried out, and the salting-out solidification may be followed by neutralization and solidification. Further, it can also be solidified in an aqueous solution containing a salt and an acid. As the crosslinking agent used in the present invention, any crosslinking reaction which reacts with a hydroxyl group remaining in a molecule of a low-substituted cellulose ether can be used. The cross-linking agent may be a crosslinking agent which reacts with a hydroxyl group as described in the Handbook of Crosslinking Agents (issued by Sakamoto Daisaku Co., Ltd. on October 20, 2015, Japan). Specific examples include ethylene glycol diepoxypropyl ether, propylene glycol diepoxypropyl ether, glycerol polyepoxypropyl ether diglycerol polyepoxypropyl ether, sorbitol polyepoxypropyl ether, allyl Epoxypropyl ether, butyl epoxypropyl hydrazine, phenyl epoxidized propyl ether, alkyl phenol epoxidized propyl ether, polyethylene glycol diepoxypropyl ether, tripropylene glycol diepoxypropyl ether , neopentyl epoxypropyl ether, 1,6-hexanediol, epoxypropyl ether, glycerol polyepoxypropyl ether, diglycerol polyepoxypropyl ether, tolyl epoxidized ether, carbon 3 to 15 aliphatic epoxy propyl ether, monoepoxy propyl ether, epoxy acrylate, bisphenol A, propyl epoxy propyl ether acrylate, ethylene glycol diepoxypropyl ether acrylic acid Ester, trimethylolpropane polyepoxypropyl ether polyacrylate, diepoxypropyl terephthalate acrylate, diepoxypropyl phthalate, spirodiol diepoxypropyl ether Epoxide compounds, or dialdehydes such as glyoxal, formaldehyde-based cross-linkers such as urea formaldehyde, toluidine isocyanate, 2,4-toluidine isocyanate, and naphthyl-1,5-di Archa Cyanate, 〇-toluidine isocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, tris-(p-cyanate phenyl) thiophosphate, polymethyl methyl phenyl isocyanate, Polyfunctional aromatic isocyanide-11 - (8) 1359892 acid ester, aromatic polyisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, block polyisocyanate , tolyl diisocyanate, ether or urethane block isocyanate prepolymer, polyisocyanate prepolymer, blocked isocyanate, polyisocyanate, two-liquid polyisocyanate, non-yellowing two-liquid type An isocyanate crosslinking agent such as a polyisocyanate or a thermosetting polyisocyanate is used, and a general formula of Si R1 R2 R3 R4 (wherein R1 is an alkyllyl group having 1 or 2 carbon atoms, an alkoxy group or a decyloxy group). Further, R2, R3 and R4 are each a decane represented by an alkoxy group having 1 or 2 carbon atoms or a decyloxy group. Further, the concentration of the crosslinking agent in the aqueous alkaline solution is not particularly limited, and is preferably 1 to 30% by mass, particularly preferably 5 to 10% by mass, and when the amount is less than 1% by mass, the effect of improving the washing resistance is insufficient. At 30% by mass, a commensurate increase in resistance to sputum cannot be seen. The crosslinking method of the low-degree-substituted cellulose ether according to the above first method can be carried out by dissolving a low-substituted cellulose ether and a cross-linked aqueous alkaline solution, and the fiber is treated with an aqueous acid solution to treat a low-substituted cellulose. The ether is solidified, washed with water and then dried, followed by heating the crosslinking reaction at 100 to 170 ° C. Further, the heating time is not particularly limited, and it is preferably 1 to 20 minutes. The crosslinking method of the low-degree-substituted cellulose ether according to the above second method can be carried out by dissolving a low-substituted cellulose ether and a cross-linked alkaline aqueous solution, and the fiber is treated with an aqueous acid solution to coagulate the low-substituted cellulose ether. After the fiber is heated and crosslinked at 100 to 170 ° C, the fiber is treated with an aqueous acid solution by a dipping method or the like to neutralize the residual alkali, and if necessary, washed with water and dried. At this time, the heating time is not particularly limited, and it is preferably 1 to 20 minutes. Also -12- (9) 1359892, after drying, reheating may be carried out as necessary. In the second method, when the acid is neutralized with an acid, the same acid as in the first method can be used, and the concentration of the aqueous solution is also the same. Any one of the first method and the second method is an ether impregnating agent such as propylene glycol or ethylene glycol or a block copolymer penetrating agent of propylene glycol and ethylene glycol in which a ratio of 0.5 to 1% by mass can be easily added to the crosslinking agent. The active agent and crosslinker solution. In the aqueous resin emulsion of the present invention, in the process of coagulating the cellulose ether in the first method, the aqueous resin latex and the low-replacement fiber are simultaneously fixed to the fiber, and then the water-based resin is cured and cured in the heating step. The second method is fixed to the fiber in the heating step, and is chemically integrated with the low-substituted cellulose ether, and has high fiber properties such as washing resistance on the surface of the fiber. Therefore, the water-based resin emulsion to be used can be hardened and cured, and the fiber and the low-substituted cellulose ether can be improved. Examples of the water-based resin emulsion used in the resin processing of general fibers and water-based acrylic resin can be mentioned. Latex, water-based ethyl acetate latex, water-based ethylene/vinyl acetate latex, water-based epoxy resin emulsion reactive organic polyoxane 0/W latex, SBR latex, etc., water-based urethane resin latex, reactivity A latex of an organic polyoxane is suitable. The aqueous urethane resin emulsion may, for example, be a polyether such as polyhydroxyethylenedimer hydroxypropanediol or polyhydroxybutanediol, and an extended toluene diester, 3,3'-bis-tolyl-4,4. '-Diisocyanate, diphenylcyanate, 3,3-dimethyldiphenylmethane diisocyanate, 4,4, _ 2, can be used as a low-yield ether latex film at the hospital-based interface, It is also possible to attach a metal olefinic gum, particularly a 0/W alcohol, an isocyanatoisocyanide-13-(11) 1359892, etc., in particular, zirconium acetate or the zirconium acetate described in Japanese Patent Publication No. Sho 34-4 1 99 or Chlorinated platinum acid or the like described in Japanese Patent Publication No. 5 1-9440 is useful. The amount of the catalyst to be used is not particularly limited, and the amount of the crosslinking reaction can be promoted to be 0.001 to 120 parts by mass based on 100 parts by mass of the reactive organopolysiloxane in the latex used, particularly It is preferably 0.005 to 1 10 parts by mass. The particle diameter of the 0/W type gel is not particularly limited, and is preferably 0.01 to 100/m from the viewpoint of stability of the latex, and particularly preferably 0.1 to 80 _ m. Further, the 0/W type latex which uses a reactive organic polyoxyalkylene may be subjected to the same hardening conditions as the above aqueous urethane latex. The cloth or the embryo made of the yarn obtained by the modified fiber of the present invention has improved air permeability, and becomes a fiber having a refreshing feeling or flexibility, and is added with a titanium oxide 1 to 20 mass in an alkaline solution of a low-substituted cellulose ether. The % can be a fiber or cloth having a photocatalytic function, and can be colored by adding a dye or a pigment to an alkaline solution of a low-substituted cellulose ether. Further, various inorganic materials and organic materials may be added to the alkaline solution of the low-substituted cellulose ether to prevent the achievement of the object of the present invention. [Embodiment] Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples, but the present invention is not limited to the examples. [Examples 1 to 1 1] Dissolve 10 parts by mass of water of low-substituted cellulose ether as shown in Table 1 - 15 - (12) 1359892 Solution 50 parts by mass Add 1 8 % by mass of aqueous sodium solution 5 0 After dissolving the low-substituted cellulose ether in a mass portion, 9 parts by mass of diphenylmethane diisocyanate was added and dissolved, and an alkaline solution of a low-substituted cellulose ether in which a crosslinking agent was dissolved was adjusted to prepare a sample liquid. Next, the KNIT COMA cotton yarn No. 30/1 manufactured by OOMIKENSI Co., Ltd. or the Japanese ASAHI bear polyester yarn No. 30 was immersed in the KHS Universal Sizer device manufactured by KAKINOKI Co., Ltd., Japan, and the liquid absorption rate was obtained. After 2 to 00% by mass of 00% by mass, the solution was immersed in a 10% by mass aqueous solution of citric acid to form a low-substituted cellulose ether. Then, it was washed with sufficient water, dried, and then heat-treated at 145 ° C for 5 minutes to obtain a sample fiber yarn. The sample thus obtained was evaluated for the fuzzing property, the tensile strength, the abrasion resistance, the electric resistance, the water absorption property, and the washing resistance according to the following test method. The results are shown in Table 1 [Examples 2 to 18] Crosslinking of a crosslinked product of a polyethylene glycol and a diphenylmethane diisocyanate, a hydrous urethane resin of a crosslinked structure, and a diphenylmethane methane. The test fiber yarns were evaluated in the same manner as in Examples 1 to 以外, except that the isocyanate 'fibers were KNIT COMA cotton yarn No. 30/1 manufactured by Nippon OOMIKENSI Co., Ltd. The results are shown in Table 1. [Example 1 9] 50 parts by mass of an aqueous solution of a low-substituted cellulose ether dispersed as shown in Table 1 was added with 丨8 mass% aqueous solution of sodium carbonate 5 parts by mass, which was low - 16 - (14) 1359892 After washing with sufficient water, it was dried, followed by heat treatment at 45 ° C for 5 minutes to obtain a sample fiber yarn. The sample thus obtained was evaluated for the fluffing property, the tensile strength, the abrasion resistance, the electric resistance, the water absorbability, and the washing resistance according to the following test method. The results are shown in Table 1 [Comparative Example 1] # Powdered cellulose KC BLOCKW 1 manufactured by the paper making method, adjusted to a cellulose concentration of 8 mass%, a sodium concentration of 6 mass%, and 2.5% by mass of carbon disulfide. A sample evaluation was carried out in the same manner as in the first to seventh embodiments except that 100 parts by mass of the formed mucilage was used as the sample liquid. The results are shown in Table 1. [Examples 24 to 27] Dissolving 50 parts by mass of an aqueous solution of 1 part by mass of a low-substituted cellulose ether as shown in Table 2, and adding 50 parts by mass of a sodium hydroxide aqueous solution of 18% by mass to dissolve a low Φ substitution degree cellulose ether Thereafter, 9 parts by mass of diphenylmethane diisocyanate was added to dissolve an alkaline solution of the low-substituted cellulose ether which adjusted the dissolved crosslinking agent to prepare a sample solution. Next, the KNIT COMA cotton yarn 30/1 manufactured by OOMIKENSI Co., Ltd. was immersed in the KHS Universal Sizer device manufactured by KAKINOKI Co., Ltd., Japan, and the liquid absorption rate was 2 〇〇 to 300% by mass. The mixture was heat-treated at ° C for 5 minutes, and the heat-treated fiber was stained with a 1% by mass aqueous solution of formic acid to neutralize the residual sodium. Then, it was washed with sufficient water and dried to obtain a sample fiber yarn. The sample thus obtained was evaluated for the hairiness and tensile strength by the following test method: -18-(15) 1359892 degrees, abrasion resistance, electric resistance, water absorption, and washing resistance. The results are shown in Table 2 [Examples 28 to 3 1] Crosslinked structure of polyhydroxyethylene glycol and diphenylmethane diisocyanate. Crosslinked structural type aqueous urethane resin latexed diphenylmethane methane Sample fiber yarns were obtained in the same manner as in Examples 24 to 27 except for the isocyanate, and the results of the evaluation of φ are shown in Table 2. [Example 3 2] 50 parts by mass of an aqueous solution of a low-substituted cellulose ether dispersed in 1 part by mass as shown in Table 2, 50 parts by mass of an aqueous solution of 18% by mass of sodium carbonate was added, and the low-substituted cellulose ether was dissolved, and then added. 3.2 parts by mass of methylhydrogenpolysiloxane, 3 g of zirconium acetate as a crosslinking agent, and a solution was prepared. Next, OOMIKENSI (share) KNIT COMA cotton yarn 30/1 or Japanese 隹ASAHI bear (stock) polyester yarn No. 30 in Japan KAKOKI (KHS Universa) Sizer device is immersed in the sample solution, aspirating The ratio is 200 to 300% by mass after 145. (: Heat treatment for 5 minutes, the heat-treated fiber was immersed in a 1% by mass aqueous solution of formic acid to neutralize the residual sodium, and then washed with sufficient water and dried to obtain a sample fiber yarn. The following test methods were used to evaluate the fuzzing, tensile strength, abrasion resistance, electrical resistance, water absorption, and washing resistance. The results are shown in Table 2 -19-(18)1359892.
〔表1〕 低取代度纖維素醚的名稱與莫耳取 代度 評價 對 象 名稱 甲基 羥丙 起毛 拉伸 耐摩 抗電 吸水 耐洗 纖 基 性比 強度 耗性 性比 速度 濯性 維 比 比 比 實施例1 低取代度 0.18 0.03 ].] 38 0.05 】.1 〇 實施例2 羥丙基 0.26 0.04 1.1 40 0.08 1.1 〇 實施例3 纖維素 0.35 0.02 1.1 35 0.07 】.1 〇 實施例4 棉 0*5 0.06 1.1 38 0.07 1.1 〇 實施例5 紗 低取代度羥丙基 0.7 0.14 0.03 1.1 37 0.05 1.1 〇 實施例6 甲基纖維素 1.1 0.10 0.04 1.1 42 0.07 1.1 〇 實施例7 低取代度甲基纖維素 0.21 0.1 1.2 33 0.07 1.4 〇 實施例8 0.18 0.2 1.1 28 0.03 1.3 〇 實施例9 聚 0.26 0.3 1.1 25 0.02 1.7 〇 實施例10 酯 0.35 0.2 1.1 21 0.01 1.8 〇 實施例11 紗 低取代度 0.5 0.1 1.1 20 0.02 1.8 〇 實施例12 羥丙基 0_】8 0.03 ]·3 40 0.08 1.2 〇 實施例】3 纖維素 0.26 0.03 1.4 38 0.07 1.5 〇 實施例14 0.35 0.04 1.4 52 0.06 1.5 〇 實施例15 0.50 0.05 1.5 38 0.08 ].5 〇 實施例16 低取代度羥丙基 0.7 0.14 0.03 1.3 45 0.08 1.2 〇 實施例Π 甲基纖維素 1.1 0.10 0.03 1.3 41 0.06 】·5 〇 實施例18 棉 低取代度甲基纖維素 0.21 0.08 1.2 38 0.07 1.2 〇 實施例19 紗 0.26 0.08 1.1 45 0.09 0.9 〇 實施例20 低取代度 0.18 0.02 1.3 53 0.08 1.2 〇 實施例2] 羥丙基 0.26 0.02 1.3 62 0.08 1.2 〇 實施例22 纖維素 0.35 0.01 1.2 60 0.08 1.3 〇 實施例23 0.5 0.03 1.2 59 0.07 1.1 〇 比較例1 • 0.7 1.1 10 0.1 1 X -22-[Table 1] The name of the low-degree-substituted cellulose ether and the molar substitution degree of the evaluation object name methyl hydroxypropyl pilling tensile anti-wearing resistance water-absorbing and washing-resistant fiber-based specific strength strength loss ratio speed 濯 维 维 维 实施 实施 实施1 low substitution degree 0.18 0.03 ].] 38 0.05 】.1 〇 Example 2 Hydroxypropyl 0.26 0.04 1.1 40 0.08 1.1 〇 Example 3 Cellulose 0.35 0.02 1.1 35 0.07 】.1 〇 Example 4 Cotton 0*5 0.06 1.1 38 0.07 1.1 〇 Example 5 Yarn low substitution hydroxypropyl 0.7 0.14 0.03 1.1 37 0.05 1.1 〇 Example 6 Methylcellulose 1.1 0.10 0.04 1.1 42 0.07 1.1 〇 Example 7 Low-substituted methylcellulose 0.21 0.1 1.2 33 0.07 1.4 〇 Example 8 0.18 0.2 1.1 28 0.03 1.3 〇 Example 9 Poly 0.26 0.3 1.1 25 0.02 1.7 〇 Example 10 Ester 0.35 0.2 1.1 21 0.01 1.8 〇 Example 11 Low degree of substitution of yarn 0.5 0.1 1.1 20 0.02 1.8 〇Example 12 Hydroxypropyl 0_]8 0.03 ]·3 40 0.08 1.2 〇Example] 3 Cellulose 0.26 0.03 1.4 38 0.07 1.5 〇Example 14 0.35 0.04 1.4 52 0.06 1.5 〇Example 15 0.50 0.05 1.5 38 0.08 ].5 〇Example 16 Low degree of substitution Hydroxypropyl 0.7 0.14 0.03 1.3 45 0.08 1.2 〇Example Π Methylcellulose 1.1 0.10 0.03 1.3 41 0.06 】·5 〇 Example 18 Cotton Low Degree of Substitution Methyl Cellulose 0.21 0.08 1.2 38 0.07 1.2 〇 Example 19 Yarn 0.26 0.08 1.1 45 0.09 0.9 〇 Example 20 Low Substitution Degree 0.18 0.02 1.3 53 0.08 1.2 〇 Example 2] Hydroxypropyl 0.26 0.02 1.3 62 0.08 1.2 〇 Example 22 Cellulose 0.35 0.01 1.2 60 0.08 1.3 〇 Example 23 0.5 0.03 1.2 59 0.07 1.1 〇Comparative Example 1 • 0.7 1.1 10 0.1 1 X -22-