201107556 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種係可以酸性染料進行染色且具有吸 濕性之纖維及其製造方法。 【先前技術】 交聯丙烯酸系纖維係已知具有pH緩衝性、抗靜電性、 保水性等調和機能或高吸濕率、高吸濕速度、高吸濕率差 或者因此產生之調溫、調濕機能等，並利用在服裝領域或 產業資材領域。然而，交聯丙烯酸系纖維係有對於其染色 性之課題，成爲阻礙其用途擴展之要因。 交聯丙烯酸系纖維因係具有作爲陽離子性染料之染色 位之機能之羧基，原理上係可用陽離子性染料著色。但因 陽離子性染料與羧基間形成之離子鍵爲弱，容易因pH之變 化等使陽離子性染料游離，加以因該纖維之水膨潤性爲 高，使得游離之陽離子性染料容易溶出。因此，僅以一般 之處方作染色，係無法得到實用之耐性水準之染色堅牢度。 爲了解決關於如此之染色性的問題，於專利文獻1、2 中係提案了交聯丙烯酸纖維之藉由反應性染料之染色方 法。在此等方法雖係藉由使用反應性染料改善染色堅牢 度，但有染色時pH須爲強酸性條件，混用纖維的限制或腐 蝕對策等之設備對應成爲必需之問題。又，將與賽璐蘇系 纖維混用之纖維構造體染色之情況中，有產生與賽璐蘇系 纖維不同之色相之情形，於實用上之合色有困難。 又，於專利文獻3係提案了將具有羧基之原料纖維以 201107556 具有磺酸基之單體含浸、聚合導入磺酸基之纖維。此纖維 因係具有多量之作爲陽離子性染料之染著位之機能之磺酸 基，可以陽離子性染料著色，但要得到充分之發色性或染 色堅牢度或色相安定性係爲困難。又，爲了採用將原料纖 維以具有磺酸基之單體含浸、聚合導入磺酸基如此之手 段，有複雜之操作成爲必要、費用變高之問題。 [先前技術文獻] [專利文獻] [專利文獻1]特開2003 -27 8 0 79號公報 [專利文獻2]特開2006-70421號公報 [專利文獻3]特開2008- 1 74849號公報 【發明内容】 [發明欲解決之課題] 如上，以往之交聯丙烯酸系纖維係具有pH緩衝性、抗 靜電性、保水性等調和機能或高吸濕率、高吸濕速度、.高 吸濕率差或者因此產生之調溫、調濕機能等者，但爲留有 關於染色性之課題者。本發明係基於關聯先前技術之現況 而完成者，以提供保持高吸濕性、高吸濕率差等交聯丙烯 酸系纖維之特徵的同時，可藉由酸性染料進行實用之染色 的纖維爲目的。 [解決課題之手段] 本發明者們係爲達成上述目的而進行致力檢討之結 果，達到以下所示之本發明。 (1) 一種酸性染料可染性吸濕性纖維，其特徵爲由具有成 201107556 爲酸性染料染著位之官能基之聚合物之區域與具有交 聯構造與羧基之聚合物之區域所構成之纖維，且相對纖 維重量而言，酸性染料之飽和染著量係爲3.5〜1〇重量 %，竣基量係爲1.0〜10mmol/g。 (2) 如（1)的酸性染料可染性吸濕性纖維，其中具有成爲酸性 染料染著位之官能基之聚合物係以丙烯腈爲主成分，且 將至少含有陽離子性基之乙烯系單體作爲共聚合成分 之聚合物。 (3) 如（1)的酸性染料可染性吸濕性纖維，其中具有成爲酸性 染料染著位之官能基之聚合物係對以丙烯腈爲主成分 之聚合物施以藉由1分子中含有2個以上之氮原子之含 氮化合物之處理而得者。 (4) 如（1)的酸性染料可染性吸濕性纖維，其中具有交聯構造 與羧基之聚合物係對以丙烯腈爲主成分之聚合物施以 藉由1分子中含有2個以上之氮原子之含氮化合物之處 理以及水解處理而得者。 (5) —種如（1)的酸性染料可染性吸濕性纖維之製造方法，其 特徵爲：對由以丙烯腈爲主成分，且將至少含有陽離子 性基之乙烯系單體作爲共聚合成分之聚合物所構成之 纖維表層施以藉由1分子中含有2個以上之氮原子之含 氮化合物之交聯處理以及水解處理。 (6) —種如（1)的酸性染料可染性吸濕性纖維之製造方法，其 特徵爲：係對以丙烯腈爲主成分之聚合物所構成之纖維 施以藉由1分子中含有2個以上之氮原子之含氮化合物 201107556 之交聯處理後施以水解處理之方法，其中施以前述水解 處理之範圍較施以前述交聯處理之範圍爲小。 [發明之效果] 本發明的酸性染料可染性吸濕性纖維係由具有成爲酸 性染料染著位之官能基之聚合物之區域與具有交聯構造與 羧基之聚合物之區域所構成，因而可藉由酸性染料進行實 用之染色，吸濕性能亦爲高。因此，本發明的酸性染料可 染性吸濕性纖維關於顏色之制約爲小，對於重視顔色之用 途等在以往之交聯丙烯酸系纖維爲難以擴展之用途亦能擴 展。 【實施方式】 以下將詳細說明本發明。本發明的酸性染料可染性吸 濕性纖維係爲由具有成爲酸性染料染著位之官能基之聚合 物之區域與具有交聯構造與羧基之聚合物之區域所構成之 纖維。 本發明的酸性染料可染性吸濕性纖維中具有交聯構造 與羧基之聚合物之區域係該纖維的一個大特徵之主要負責 吸濕性能之部分。如上所述，存在於關聯區域之羧基係可 與陽離子染料形成離子鍵，但爲了容易離子交換而使染色 堅牢度不佳無法進行實用之染色。於本發明之纖維中，與 上述區域一同’以關聯區域與設有別的具有成爲酸性染料 染著位之官能基之聚合物之區域，作爲可以酸性染料進行 實用等級之染色者。 以具有成爲酸性染料染著位之官能基之聚合物而言， 201107556 可列舉以丙烯腈作爲主成分且將至少含有陽離子性基之乙 烯系單體作爲共聚合成分之聚合物或對以丙烯腈爲主成分 之聚合物施以藉由1分子中含有2個以上之氮原子之含氮 化合物之處理而得者。另外於本發明中，將以丙烯腈作爲 主成分且將至少含有陽離子性基之乙烯系單體作爲共聚合 成分之聚合物以「具有陽離子性基之丙烯腈系聚合物」、 將以丙烯腈作爲主成分之聚合物以「丙烯腈系聚合物」表 示。 於此處以成爲酸性染料染著位之官能基而言，係無特 別限定，但可列舉1級胺基、2級胺基、3級胺基、4級銨 基等陽離子性基。 又’以丙烯腈爲主成分而言，上述任一情形中皆可說 丙烯腈以40~ 100重量％結合含有於聚合物中。以丙烯腈以 外之單體成分而言’係無特別限制，可列舉（甲基）丙烯酸 甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸丁酯等之（甲基）丙 烯酸酯化合物’甲基烯丙磺酸、對-苯乙烯磺酸等含磺酸基 單體及其鹽：苯乙烯、乙酸乙烯酯等單體。於此處將具有 陽離子性基之乙稀系單體做爲共聚合成分的情況，該單體 之陽離子性基係爲作爲酸性染料之染著位之機能^ 以關聯具有陽離子性基之乙烯系單體而言，可例舉如 以式[I]、式[II]及式[III]表示之單體。於此處之式π]、式 [II]及式[III]中，R1係表示氫或C4以下之烷基，R2、R3 及R4係各自表示C4以下之烷基，R5係表示C4以下之烯 基或經嫌基’ R6係表示C4以下之烯基，X係表示c卜Br、 201107556 I ' CH3COO、CH3S04或SCN ’ m係表示2〜4之整數，n係 表示〇或1之整數。201107556 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a fiber which is dyeable by an acid dye and which is hygroscopic and a method for producing the same. [Prior Art] The crosslinked acrylic fiber system is known to have a pH-buffering property, an antistatic property, a water retention property, a blending function, a high moisture absorption rate, a high moisture absorption rate, a high moisture absorption rate, or a temperature adjustment and adjustment. Wet functions, etc., and use in the field of clothing or industrial materials. However, the crosslinked acrylic fiber has a problem of dyeability, and it is a factor that hinders the expansion of its use. The crosslinked acrylic fiber has a carboxyl group as a function of the dyeing position of the cationic dye, and in principle, it can be colored with a cationic dye. However, since the ionic bond formed between the cationic dye and the carboxyl group is weak, the cationic dye is easily released due to changes in pH, and the water swellability of the fiber is high, so that the free cationic dye is easily eluted. Therefore, the dyeing fastness of practical patience is not obtained by dyeing only in a general prescription. In order to solve the problem of such dyeability, Patent Literatures 1 and 2 propose a method of dyeing a crosslinked acrylic fiber by a reactive dye. In these methods, the dyeing fastness is improved by using a reactive dye, but the pH must be strongly acidic when dyeing, and the equipment corresponding to the restriction of the mixed fiber or the countermeasure against corrosion becomes a necessary problem. Further, in the case where the fiber structure mixed with the celluloid fiber is dyed, there is a case where a hue different from that of the celluloid fiber is produced, and it is difficult to combine the color in practical use. Further, in Patent Document 3, a fiber in which a raw material fiber having a carboxyl group is impregnated with a monomer having a sulfonic acid group in 201107556, and a polymer is introduced into a sulfonic acid group is proposed. This fiber has a large amount of a sulfonic acid group which functions as a dyeing site of a cationic dye, and can be colored by a cationic dye, but it is difficult to obtain sufficient color developability or color fastness or hue stability. Further, in order to impregnate the raw material fibers with a monomer having a sulfonic acid group and to polymerize and introduce a sulfonic acid group, a complicated operation is required and the cost is increased. [PATENT DOCUMENT] [Patent Document 1] JP-A-2006-70421 (Patent Document 3) JP-A-2006-70421 (Patent Document 3) JP-A-2008- 1 74849 DISCLOSURE OF THE INVENTION [Problems to be Solved by the Invention] As described above, the conventional crosslinked acrylic fiber has a blending function such as pH buffering property, antistatic property, water retention property, high moisture absorption rate, high moisture absorption rate, and high moisture absorption rate. Poor or the resulting temperature control, humidity control, etc., but for those who have questions about dyeability. The present invention has been completed based on the state of the art in connection with the prior art to provide a fiber which is dyed by an acid dye while maintaining the characteristics of a crosslinked acrylic fiber such as a high hygroscopicity and a high moisture absorption rate. . [Means for Solving the Problems] The present inventors have made efforts to review the above-mentioned objects, and have achieved the present invention as described below. (1) An acid dye-dyeable hygroscopic fiber characterized by comprising a region of a polymer having a functional group in which an acid dye is dyed at 201107556 and a region having a polymer having a crosslinked structure and a carboxyl group. The fiber, and the relative dyeing weight of the acid dye is 3.5 to 1% by weight, and the amount of the thiol group is 1.0 to 10 mmol/g. (2) The acid dye-dyeable hygroscopic fiber according to (1), wherein the polymer having a functional group which is a dyed site of the acid dye is mainly composed of acrylonitrile, and the vinyl group containing at least a cationic group A monomer as a polymer of a copolymerization component. (3) The acid dye-dyeable hygroscopic fiber according to (1), wherein the polymer having a functional group which becomes a dyed position of the acid dye is applied to the polymer containing acrylonitrile as a main component by one molecule A treatment of a nitrogen-containing compound containing two or more nitrogen atoms. (4) The acid dye-dyeable hygroscopic fiber according to (1), wherein the polymer having a crosslinked structure and a carboxyl group is applied to a polymer containing acrylonitrile as a main component, and two or more molecules are contained in one molecule. The treatment of the nitrogen-containing compound of the nitrogen atom and the hydrolysis treatment are obtained. (5) A method for producing an acid dye-dyeable hygroscopic fiber according to (1), which is characterized in that a vinyl monomer containing at least a cationic group and having a cationic group as a main component is used as a total The surface layer of the fiber composed of the polymer of the polymerization component is subjected to a crosslinking treatment and a hydrolysis treatment by a nitrogen-containing compound having two or more nitrogen atoms in one molecule. (6) A method for producing an acid dye-dyeable hygroscopic fiber according to (1), which is characterized in that a fiber composed of a polymer containing acrylonitrile as a main component is contained in one molecule A method of hydrolyzing the cross-linking treatment of two or more nitrogen-containing nitrogen-containing compounds 201107556, wherein the range of the hydrolysis treatment is smaller than the range in which the cross-linking treatment is applied. [Effects of the Invention] The acid dye-dyeable hygroscopic fiber of the present invention is composed of a region having a polymer which is a functional group which is a dyed site of an acid dye, and a region having a polymer having a crosslinked structure and a carboxyl group. The dyeing performance can also be high by practical dyeing with an acid dye. Therefore, the acid dye-dyeable hygroscopic fiber of the present invention has a small color restriction, and can be used for the purpose of using a crosslinked acrylic fiber which is difficult to expand in the conventional use of color. [Embodiment] Hereinafter, the present invention will be described in detail. The acid dye-dyeable absorbent fiber of the present invention is a fiber composed of a region having a polymer which becomes a functional group of a dyed site of an acid dye and a region having a polymer having a crosslinked structure and a carboxyl group. The region of the acid dye-dyeable absorbent fiber of the present invention having a crosslinked structure and a polymer of a carboxyl group is a portion of the fiber which is mainly responsible for the moisture absorption property. As described above, the carboxyl group present in the associated region can form an ionic bond with the cationic dye, but the dyeing fastness is poor for easy ion exchange, and practical dyeing cannot be performed. In the fiber of the present invention, a region in which an associated region and a polymer having a functional group having an acid dye-dyeing site are provided together with the above-mentioned region is used as an acid dye for practical grade dyeing. In the case of a polymer having a functional group which is a dyed site of an acid dye, 201107556 may be a polymer having acrylonitrile as a main component and a vinyl monomer containing at least a cationic group as a copolymer component or acrylonitrile. The polymer of the main component is obtained by a treatment of a nitrogen-containing compound containing two or more nitrogen atoms in one molecule. In the present invention, a polymer having a propylene-acrylic acid as a main component and a vinyl monomer having at least a cationic group as a copolymerization component is referred to as a "cationic-based acrylonitrile-based polymer", and acrylonitrile is used. The polymer as a main component is represented by "acrylonitrile-based polymer". Here, the functional group to be dyed in the acid dye is not particularly limited, and examples thereof include a cationic group such as a primary amino group, a secondary amino group, a tertiary amino group, and a tertiary ammonium group. Further, in the case of acrylonitrile as a main component, in any of the above cases, acrylonitrile may be contained in the polymer in an amount of 40 to 100% by weight. The monomer component other than acrylonitrile is not particularly limited, and examples thereof include (meth)acrylic acid ester compounds such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate. A sulfonic acid group-containing monomer such as methallylsulfonic acid or p-styrenesulfonic acid or a salt thereof: a monomer such as styrene or vinyl acetate. Here, when the ethylenic monomer having a cationic group is used as a copolymerization component, the cationic group of the monomer is a function as a dyeing site of the acid dye to associate a vinyl group having a cationic group. The monomer may, for example, be a monomer represented by the formula [I], the formula [II] and the formula [III]. In the formula π], the formula [II] and the formula [III] herein, R1 represents hydrogen or an alkyl group of C4 or lower, R2, R3 and R4 each represent an alkyl group of C4 or less, and R5 represents a C4 or lower. The alkenyl group or the deuterated group 'R6 group represents an alkenyl group of C4 or less, and the X system represents c, Br, 201107556 I 'CH3COO, CH3S04 or SCN 'm represents an integer of 2 to 4, and n represents an integer of 〇 or 1.
以此等具有陽離子性基之乙烯系單體之具體例而言， 可列舉（甲基）丙烯酸二甲胺乙酯、（甲基）丙烯酸二乙胺乙酯 等。 又’於對丙稀腈系聚合物施以藉由1分子中含有2個 以上之氮原子之含氮化合物之處理的情況，係考慮關於含 氮化合物與由丙烯腈而來之腈基反應形成聚合物中之交聯 構造，但此時沒有與腈基反應之官能基或不完全與腈基反 應形成交聯構造而副產生之官能基等當作作爲酸性染料染 201107556 著位之官能基之機能。 以1分子中含有2個以上之氮原子之含氮化合物而 言，以具有2個以上之1級胺基之胺化合物或肼系化合物 爲佳。1分子中之氮原子數上限係無特別限制，但以1 2個 以下爲佳，6個以下爲更佳，4個以下爲最佳。若1分子中 的氮原子數超過上述上限則交聯劑分子變大，有難以將交 聯導入聚合物中地情況。 以具有2個以上之1級胺基之胺化合物而言，例示有 乙二胺 '六亞甲二胺等之二胺化合物，二伸乙三胺、3, 3’-亞胺基雙（丙胺）、N-甲基-3, 3’-亞胺基雙（丙胺）等三胺系化 合物，三伸乙四胺、N，N’-雙（3-胺丙基）-1，4-丁二胺等四胺 系化合物，聚乙烯胺、聚烯丙胺等具有2個以上之1級胺 基之聚氨系化合物。 又，以肼系化合物而言，例示有水合肼、硫酸肼、鹽 酸肼、溴化氫酸肼、肼碳酸鹽等。 另一方面，以具有交聯構造與羧基之聚合物而言，可 列舉對丙烯腈系聚合物施以藉由1分子中含有2個以上之 氮原子之含氮化合物之處理，及水解處理而得者。前者之 處理中係含氮化合物與由丙烯腈而來之腈基反應，形成聚 合物中之交聯構造，後者之處理中係將腈基水解形成羧 基。藉此得到具有交聯構造與羧基之聚合物。 以關聯丙烯腈系聚合物及1分子中含有2個以上之氮 原子之含氮化合物而言，可例示與上述者同樣者。又’關 於水解處理’係可使用鹼金屬氫氧化物、鹼土類金屬氫氧 201107556 化物、鹼金屬碳酸鹽等之鹼性金屬鹽化合物。 另外’關於此處例示之具有交聯構造與羧基之聚合 物’係與以具有成爲酸性染料染著位之官能基之聚合物作 爲例示之聚合物同樣地，對丙烯腈系聚合物施以藉由丨分 子中含有2個以上之氮原子之含氮化合物之處理，但無法 以酸性染料進行實用之染色。此應係由於雖以交聯處理— 時形成有作爲酸性染料染著位之官能基，但藉由其後之水 解處理變化了關連官能基，使失去作爲酸性染料染著位之 機能之故。 又，本發明之酸性染料可染性吸濕性纖維係也可僅以 上述具有成爲酸性染料染著位之官能基之聚合物之區域與 具有交聯構造與羧基之聚合物之區域所構成，也可存在此 等區域以外之構成此等區域之聚合物混合的區域或以構成 此等區域之聚合物與不同之聚合物構成的區域。以此等區 域之配置代表例而言，可列舉以具有成爲酸性染料染著位 之官能基之聚合物之區域爲中心部、以具有交聯構造與羧 基之聚合物之區域爲表層部之芯鞘構造、具有成爲酸性染 料染著位之官能基之聚合物之區域與具有交聯構造與羧基 之聚合物之區域交互積層之多層構造、或以具有成爲酸性 染料染著位之官能基之聚合物之區域與具有交聯構造與羧 基之聚合物之區域之一方爲海部，另一方爲島部之海島構 造等。 關於具有成爲酸性染料染著位之官能基之聚合物之區 域與具有交聯構造與羧基之聚合物之區域之比率，係具有 -10- 201107556 交聯構造與羧基之聚合物之區域之比例較高則可得高吸濕 率之纖維，但在另一方面具有成爲酸性染料染著位之官能 基之聚合物之區域之比例變低，成爲發色性下降之傾向。 於得到吸濕性及發色性兩方兼顧之纖維，係以乾燥狀態下 之纖維截面積的20~80%，較佳爲30〜70%之面積被具有成 爲酸性染料染著位之官能基之聚合物之區域所佔有之方式 爲理想。 於此處之上述面積比率係可藉由以酸性染料染色處理 後切斷乾燥過之纖維，將其纖維斷面以光學顯微鏡觀察而 算出。亦即被染色之區域爲具有成爲酸性染料染著位之官 能基之聚合物之區域，而未被染色或無法確認之區域爲具 有交聯構造與羧基之聚合物之區域。 又，以於本發明之羧基量而言，相對於纖維重量而言 較佳爲1.0〜l〇mmol/g，更佳爲2.0〜6.0mmol/g爲理想。羧 基量較1.0 mmol/g爲少之情況係爲無法得到充分之吸濕性 能之情況，又較10 mmol/g爲多之情況係具有交聯構造與 羧基之聚合物之區域在吸濕或吸水時變爲脆弱，引起聚合 物之脫落，無法維持纖維形狀或吸濕性能之情況。 又，羧基係亦可爲Η型羧基亦可爲鹽型羧基，該等爲 混合也沒關係，在纖維製造後的階段，係爲了易於進行紡 織等加工而採用Η型羧基，在染色後或最終製品的階段， 係爲了得到高吸濕率而以羧基量的50%以上爲鹽型羧基爲 理想。 作爲關聯構成鹽型羧基之陽離子之例可列舉Li、Na、 -11- 201107556 K等之鹼金屬，Be、Mg、Ca、Ba等之鹼土金屬，Cu、Zn、 Al、Μη、Ag、Fe、Co、Ni等之金屬，NH4、胺等陽離子等， 複數種之陽離子混合亦可。 以於本發明之酸性染料之飽和染著量而言，相對於纖 維重量而言較佳爲3. 5〜10重量％，更佳爲4〜9重量％爲理 想。於關聯飽和染著量爲小於3 · 5之情況係不能染色至濃 色，係爲不適於實用之情況，於超過1 〇%之情況係染色速 度變快，容易引起染色不均。另外，關聯飽和染著量係藉 由後述方法求得者。 又，本發明之酸性染料可染性吸濕性纖維係相對於以 往之交聯丙烯酸系纖維爲改善了染色堅牢度者，用以下記 載之評估方法評估出染色堅牢度爲3級以上者爲理想。（評 估方法）將試料投入加入相對於該試料之重量爲5重量％之 酸性染料Supranol Black VLG(DyStar公司製）之浴中，以 乙酸調整至pH爲4以後，以100 °C浸漬30分鐘以後，進 行皂洗、水洗、乾燥。對於所得之纖維，藉由JIS-L-084 8 評估汗染色堅牢度。 本發明之酸性染料可染性吸濕性纖維於溫度20°C、相 對濕度65%大氣環境的飽和吸濕率係因視用途所必須之吸 濕率不同而一律不規定，但以15重量％以上爲佳，20重量 %以上爲更佳。 又’本發明之酸性染料可染性吸濕性纖維係膨潤度較 佳爲以2g/g以下，更佳爲1 .8g/g以下爲理想。於膨潤度爲 超過2g/g之情況，係爲纖維物性降低，且操作性成爲不良。 -12- 201107556 以由上述之本發明之酸性染料可染性吸濕性纖維的製 造方法而言，係可列舉幾個方法。例如，可舉出將由具有 陽離子性基之丙烯腈系聚合物所構成之丙烯腈系纖維作爲 原料纖維，對於該纖維施以部份交聯處理及水解處理之方 法。於相關方法中，具有陽離子性基之丙烯腈系聚合物的 一部份藉由交聯處理或水解處理變換至具有交聯構造與羧 基之聚合物之區域，未變換之部分成爲具有成爲酸性染料 染著位之官能基之聚合物之區域。 於此處，於由具有陽離子性基之丙烯腈系聚合物所構 成之丙烯腈系纖維中，以具有相對於纖維重量爲 0.15 mmol/g以上，較佳爲0.17 mmol/g以上之陽離子性基爲 理想。陽離子性基小於0.1 5mmol/g的情況，係爲了得到充 分之發色性，須使具有交聯構造與羧基之聚合物之區域爲 小之情況。另外，關於上限係無特別限制，但從染色的均 —性之觀點來看的情況，以0.40mmol/g以下爲理想。 又，以由丙烯腈系聚合物所構成之丙烯腈系纖維作爲 原料纖維，對於該纖維施以藉由1分子中含有2個以上之 氮原子之含氮化合物之處理之交聯處理後，施以水解處理 之方法，亦可採用前述施以水解處理之範圍較前述施以交 聯處理之範圍爲小的方法。於相關方法中，係首先藉由交 聯處理，與交聯構造一起形成具有成爲酸性染料染著位之 官能基之聚合物之區域，藉由其後之水解處理使該區域的 一部分變換至具有交聯構造與羧基之聚合物之區域。另 外’於相關方法中，並無言及作爲丙烯腈系聚合物，亦可 -13- 201107556 使用具有陽離子性基之丙烯腈系聚合物。 更甚者，亦可採用以由不具有成爲酸性染料染著位之 官能基之丙烯腈系聚合物所構成之丙烯腈系纖維作爲原料 纖維，於此導入具有成爲酸性染料染著位之官能基後施以 部份交聯處理及水解處理之方法，或以丙烯腈系聚合物以 外之含有具有成爲酸性染料染著位之官能基之聚合物之丙 烯腈系纖維，於此施以部份交聯處理及水解處理之方法。 另外，於上述列舉之製造方法中，關於成爲原料纖維 之丙烯酸系纖維中的丙烯腈系聚合物的比例係與成爲酸性 染料染著位之官能基之有無無關，以80〜100重量％爲理想。 又，成爲原料纖維之丙烯腈系纖維，至少係由丙烯腈 之含有率不同的2種丙烯腈系聚合物所構成，關於含有率 之差爲2重量％以上爲佳。藉此產生於進行交聯、水解之 容易度之差別，變得容易形成具有成爲酸性染料染著位之 官能基之聚合物之區域與具有交聯構造與羧基之聚合物之 區域。 關聯丙烯腈系纖維，雖係2種之丙烯腈系聚合物側對 側接合而成者，隨機混合而成者亦沒有關係，但以A-B-A 層所構成之3層構造而成者或芯鞘構造者爲佳，B層或芯 的部份爲丙烯腈的含有率高且具有多陽離子基者爲佳。具 體而言係B層或芯的部份的丙烯腈含有率爲82重量％以 上，較佳爲85重量％以上，更佳爲90重量％以上爲理想’ 陽離子性基的含有量爲0.15 mmol/g以上，較佳爲〇·17 mmol/g以上爲理想。 -14- .201107556 另外’以得到由A-B-A層所構成之三層構造的丙烯腈 系纖維之方法而言’可採用日本特開2000-45126號公報上 記載之方法等，此時’以A成分的原液濃度較B成分的原 液濃度爲低的方式，使B成分較少露出纖維表面爲理想。 以以上說明的之本發明的酸性染料可染性吸濕性纖維 之製造方法而言’係將由具有陽離子性基的丙烯腈系聚合 物所構成之丙烯腈系纖維藉由1分子中含有2個以上之氮 原子之含氮化合物進行交聯處理後，藉由鹼性金屬鹽水溶 液進行水解處理，或者係藉由同時進行此等之處理而在纖 維之表層部形成交聯構造與具有羧基之聚合物之區域，在 芯部留下具有陽離子性基之丙烯腈系聚合物之區域的方 法，由製造設備或費用方面爲理想。關於關聯方法在以下 作詳述。 於關聯方法中，係將上述由具有陽離子性基的丙烯腈 系聚合物所構成之丙烯腈系纖維藉由含有上述1分子中含 有2個以上之氮原子之含氮化合物之水溶液進行交聯導入 處理及藉由含有鹼性金屬鹽化合物之水溶液施以水解處 理。此等之處理係亦可於交聯處理後施以水解處理，如此 進行之個別處理；亦可以使用共存有1分子中含有2個以 上之氮原子之含氮化合物與鹼性金屬鹽化合物之水溶液進 行同時處理。任一情況皆以1分子中含有2個以上之氮原 子之含氮化合物與丙烯腈系纖維之表層部之丙烯腈系聚合 物所具有之腈基反應而形成交聯構造，或以鹼性金屬鹽化 合物水溶液與腈基反應而形成羧基，使其被變換爲具有交 -15- 201107556 聯構造與羧基之聚合物。 以上述交聯處理及水解處理具體之方法而言，係採用 在將纖維浸漬於用於處理之水溶液中之狀態下使其反應之 方法。又，個別處理、同時處理任一之情況中，以1分子 中含有2個以上之氮原子之含氮化合物的濃度而言，係皆 以0.1〜5重量％爲佳，0.1〜3重量％爲更佳。此濃度若過低 則會有無法得到具有交聯構造與羧基之聚合物的溶出抑制 效果之狀況。另一方面，於將交聯構造之導入止於纖維的 表層部，係此濃度爲5重量％以下爲理想。又，關於鹼性 金屬鹽化合物之濃度，係以〇 . 5〜5重量％爲佳，以0.5〜4重 量％爲更佳。鹼性金屬鹽化合物濃度若過低則會有產生之 羧基量不充分之狀況。另一方面，以將此濃度控制在5重 量％以下，可使羧基之導入止於纖維之表層部，可於芯部 留下具有陽離子性基之丙烯腈系聚合物之區域。 又關於反應溫度及時間，其適當之範圍係相應於1分 子中含有2個以上之氮原子之含氮化合物及/或鹼性金屬鹽 化合物的濃度而有不同。在同時處理之情況下，若係1分 子中含有2個以上之氮原子之含氮化合物之濃度爲〇.5~2 重量％之程度，鹼性金屬鹽化合物之濃度爲1~2重量％之程 度，所建議之條件爲於90〜100 °C下進行2小時之程度。 上述之個別處理的情況，經過交聯處理之纖維係於水 解處理前施以酸處理亦可。藉由關聯酸處理，可淡色化纖 維之著色。以於此處所使用之酸而言，可列舉硝酸、硫酸、 鹽酸等無機酸水溶液，有機酸等，但無特別限定。又以處 -16- 201107556 理條件而言，係可舉出將被處理纖維以溫度50〜120°C浸漬 於酸濃度5〜20重量％’較佳爲7〜15重量％之水溶液〇.5~10 小時之例。但，關聯酸處理係進於水解，爲了要有減少最 終所得纖維中應殘留之之丙烯腈系聚合物，亦即具有成爲 酸性染料染著位之官能基之聚合物之區域之效果，酌量此 事而設定條件係至爲必要。 如上而行所得之水解或交聯、水解同時處理後之纖維 係爲原樣亦可作爲本發明之酸性染料可染性吸濕性纖維利 用，但進一步藉由酸性水溶液洗淨亦可。藉此，可得較高 白度之纖維。以關聯酸性水溶液而言，可列舉硝酸、硫酸、 鹽酸等無機酸水溶液，有機酸等，但無特別限定。 又，於如上述之纖維製造後的階段中，係爲了容易進 行紡織等加工採用Η型羧基，於染色後或最終製品的階段 中，變換至所欲之鹽型羧基或Η型羧基，將不同種之鹽型 混合而行爲理想。關聯羧基型之調整係可藉由以硝酸鹽、 硫酸鹽、鹽酸鹽等之金屬鹽施以離子交換處理、藉由緩衝 液等施以pH調整處理而實施。另外，得到高吸濕率之情形 係羧基量之5 0 %以上爲鹽型羧基爲理想。 又，以上述丙烯腈系聚合體所構成之丙烯腈系纖維作 爲原料纖維，對該纖維施以藉由1分子中含有2個以上之 氮原子之含氮化合物之交聯處理後施以水解處理之方法， 亦以施以前述交聯處理之範圍較施以前述水解處理之範圍 爲小之方法爲佳。於關聯方法中，係爲了使施以水解處理 之範圍較施以交聯處理之範圍爲廣，首先以將1分子中含 -17- 201107556 有2個以上之氮原子之含氮化合物之濃度設定爲高的溶液 施以交聯處理’其後進行水解處理。例如，若爲以芯鞘構 造而行之情況，爲了對纖維整體施以交聯處理，含氮化合 物之濃度較佳係爲7~20重量％，更佳係爲1〇〜20重量·％。 關於關聯處理後之纖維表層部之水解處理之條件係若採用 上述條件爲可，若應其需要亦同樣可進行酸處理或羧基型 之調整。 [實施例] 藉由以下實施例具體說明本發明，但本發明係不爲以 下實施例所限定者。另外，實施例中的部及百分比係限於 無斷定時以重量基準表示。實施例中的特性之評估方法係 如以下所述。 (1) 羧基量 精秤充分乾燥之試料約1 g(A[g])，將之加於200 ml 之水中後，一邊加溫至50 °C —邊添加1 mo 1/L鹽酸水溶液 至pH2，接下來以常用方法以〇.1 m〇l/L氫氧化鈉水溶液求 得滴定曲線。從該滴定曲線求得被消耗於羧基之氫氧化鈉 水溶液消耗量（B[ml])，藉由下式算出羧基量。 翔基量[mmol/g] = 〇·1χΒ/Α (2) 原料纖維之陽離子性基量 精秤充分乾燥之試料約0.5g(C[g])，浸漬於裝有可充 分進行離子交換之量的0.1 m〇l/L鹽酸水溶液（D[ml])的燒 杯中。過濾試料，濾液作爲指示藥品添加於酚酞溶液中。 將此濾液以0.1 mm〇l/L之氫氧化鈉水溶液滴定，定量出殘 -18- 201107556 留之鹽酸。將此時之氫氧化鈉水溶液的滴定量作爲E [ml]， 藉由下式算出陽離子性基量。Specific examples of the vinyl monomer having a cationic group include dimethylaminoethyl (meth)acrylate and diethylamine ethyl (meth)acrylate. Further, in the case of treating a acrylonitrile-based polymer with a nitrogen-containing compound having two or more nitrogen atoms in one molecule, it is considered that a nitrogen-containing compound is formed by reacting a nitrile group derived from acrylonitrile. a cross-linking structure in a polymer, but at this time, there is no functional group reactive with a nitrile group or a functional group which is not completely reacted with a nitrile group to form a cross-linking structure, and a by-product is used as a functional group which is dyed as an acid dye in 201107556. function. The nitrogen-containing compound having two or more nitrogen atoms in one molecule is preferably an amine compound or an anthracene compound having two or more primary amino groups. The upper limit of the number of nitrogen atoms in one molecule is not particularly limited, but is preferably 12 or less, more preferably 6 or less, and most preferably 4 or less. When the number of nitrogen atoms in one molecule exceeds the above upper limit, the crosslinking agent molecule becomes large, and it is difficult to introduce crosslinking into the polymer. In the case of an amine compound having two or more amine groups, a diamine compound such as ethylenediamine 'hexamethylenediamine, diethylenetriamine, 3,3'-iminobis(propylamine) is exemplified. , a triamine compound such as N-methyl-3,3'-iminobis(propylamine), triamethylenetetramine, N,N'-bis(3-aminopropyl)-1,4-butyl A tetraamine compound such as a diamine, or a polyamine compound having two or more primary amine groups such as polyvinylamine or polyallylamine. Further, examples of the lanthanoid compound include hydrazine hydrate, barium sulfate, barium hydrochloride, barium hydrogen bromide, and barium carbonate. On the other hand, the polymer having a cross-linking structure and a carboxyl group may be subjected to a treatment of a nitrogen-containing compound containing two or more nitrogen atoms in one molecule, and a hydrolysis treatment. Winner. In the former treatment, a nitrogen-containing compound reacts with a nitrile group derived from acrylonitrile to form a crosslinked structure in the polymer, and in the latter treatment, the nitrile group is hydrolyzed to form a carboxyl group. Thereby, a polymer having a crosslinked structure and a carboxyl group was obtained. The same applies to the above-mentioned acrylonitrile-based polymer and a nitrogen-containing compound containing two or more nitrogen atoms in one molecule. Further, as the "hydrolysis treatment", an alkali metal salt compound such as an alkali metal hydroxide, an alkaline earth metal hydroxide, and a base metal carbonate can be used. In addition, the "polymer having a crosslinked structure and a carboxyl group exemplified here" is similar to the polymer having a functional group which is a dyed site of an acid dye, and the acrylic polymer is borrowed. It is treated by a nitrogen-containing compound containing two or more nitrogen atoms in the molecule, but it is not practically dyed with an acid dye. This is because the functional group which is dyed as an acid dye is formed by crosslinking treatment, but the related functional group is changed by the subsequent hydrolysis treatment, so that the function of dyeing the acid dye is lost. Further, the acid dye-dyeable hygroscopic fiber system of the present invention may be composed only of a region having a polymer having a functional group which is a dyed site of an acid dye and a region having a polymer having a crosslinked structure and a carboxyl group. It is also possible to have regions other than the regions in which the polymers constituting the regions are mixed or a region in which the polymers constituting the regions are composed of different polymers. In the example of the arrangement of the regions, the core of the surface layer is a region having a polymer having a functional group which is a functional group of an acid dye, and a region having a polymer having a crosslinked structure and a carboxyl group. a sheath structure, a multilayer structure in which a region of a polymer which becomes a functional group of an acid dye dyed site is alternately laminated with a region having a polymer having a crosslinked structure and a carboxyl group, or a polymerization having a functional group which becomes a dyed site of an acid dye One of the regions of the object and the polymer having the crosslinked structure and the carboxyl group is the sea portion, and the other is the island structure of the island. The ratio of the region of the polymer having the functional group which becomes the acid dye dyeing site to the region of the polymer having the crosslinked structure and the carboxyl group is a ratio of the region of the polymer having a crosslinked structure and a carboxyl group of -10-201107556. When the fiber has a high moisture absorption rate, the ratio of the polymer having a functional group which becomes a functional group of the acid dye is lowered, and the color developability tends to be lowered. The fiber which has both hygroscopicity and color developability is a functional group having a dye dyeing site in an area of 20 to 80%, preferably 30 to 70%, of the fiber cross-sectional area in a dry state. The area occupied by the polymer is ideal. The above area ratio here can be calculated by cutting the dried fiber with an acid dye, and cutting the fiber cross section by an optical microscope. That is, the dyed region is a region having a polymer which becomes a functional group of the acid dye dyeing site, and the region which is not dyed or unidentified is a region having a polymer having a crosslinked structure and a carboxyl group. Further, the amount of the carboxyl group in the present invention is preferably 1.0 to 1 mmol/g, more preferably 2.0 to 6.0 mmol/g, based on the weight of the fiber. When the amount of the carboxyl group is less than 1.0 mmol/g, the sufficient moisture absorption property cannot be obtained, and when it is more than 10 mmol/g, the region having the polymer of the crosslinked structure and the carboxyl group is hygroscopic or absorbent. It becomes fragile, causing the polymer to fall off and failing to maintain fiber shape or moisture absorption properties. Further, the carboxyl group may be a quinone type carboxyl group or a salt type carboxyl group, and these may be mixed. In the stage after the fiber production, a quinone type carboxyl group is used for easy processing such as weaving, and after dyeing or final product. In order to obtain a high moisture absorption rate, it is preferable that 50% or more of the carboxyl group amount is a salt type carboxyl group. Examples of the cation constituting the salt type carboxyl group include an alkali metal such as Li, Na, -11-201107556 K, an alkaline earth metal such as Be, Mg, Ca, or Ba, Cu, Zn, Al, Μη, Ag, Fe, or the like. A metal such as Co or Ni, a cation such as NH4 or an amine, or a plurality of cations may be mixed. 5〜10重量百分比, more preferably 4 to 9重量%, is preferable with respect to the fiber weight, in terms of the saturated dyeing amount of the acid dye of the present invention. In the case where the amount of saturated dyeing is less than 3 · 5 , it is not possible to dye to a dark color, which is unsuitable for practical use. In the case of more than 1%, the dyeing speed is fast, and uneven dyeing is likely to occur. Further, the correlation saturation amount is obtained by the method described later. Further, the acid dye-dyeable hygroscopic fiber of the present invention is excellent in dyeing fastness compared to the conventional crosslinked acrylic fiber, and it is preferable to evaluate the dye fastness to 3 or more by the evaluation method described below. . (Evaluation method) The sample was placed in a bath of an acid dye Supranol Black VLG (manufactured by DyStar Co., Ltd.) having a weight of 5% by weight based on the sample, adjusted to pH 4 with acetic acid, and immersed at 100 ° C for 30 minutes. , soaping, washing, and drying. For the obtained fiber, the sweat staining fastness was evaluated by JIS-L-084 8 . The acid dye-dyeable hygroscopic fiber of the present invention has a saturated moisture absorption rate at a temperature of 20 ° C and a relative humidity of 65% in an atmospheric environment, and is not required to be different depending on the moisture absorption rate necessary for the use, but is 15% by weight. The above is preferred, and 20% by weight or more is more preferred. Further, the acid dye-dyeable hygroscopic fiber of the present invention preferably has a degree of swelling of 2 g/g or less, more preferably 1.8 g/g or less. When the degree of swelling is more than 2 g/g, the physical properties of the fiber are lowered, and the workability is poor. -12-201107556 The method for producing the acid dye-dyeable hygroscopic fiber of the present invention described above is exemplified by several methods. For example, an acrylic fiber composed of an acrylonitrile-based polymer having a cationic group is used as a raw material fiber, and a partial crosslinking treatment and a hydrolysis treatment are applied to the fiber. In the related method, a part of the acrylonitrile-based polymer having a cationic group is converted into a region having a polymer having a crosslinked structure and a carboxyl group by a crosslinking treatment or a hydrolysis treatment, and the unaltered portion becomes an acid dye. The area of the polymer that is dyed with a functional group. Here, the acrylic fiber composed of the acrylonitrile-based polymer having a cationic group has a cationic group of 0.15 mmol/g or more, preferably 0.17 mmol/g or more, based on the weight of the fiber. Ideal. In the case where the cationic group is less than 0.15 mmol/g, in order to obtain sufficient color developability, the region of the polymer having a crosslinked structure and a carboxyl group must be made small. In addition, the upper limit is not particularly limited, but from the viewpoint of the uniformity of dyeing, it is preferably 0.40 mmol/g or less. In addition, an acrylic fiber composed of an acrylonitrile-based polymer is used as a raw material fiber, and the fiber is subjected to a crosslinking treatment by a treatment of a nitrogen-containing compound containing two or more nitrogen atoms in one molecule. The method of hydrolyzing treatment may also employ a method in which the range of the hydrolysis treatment described above is smaller than the range in which the crosslinking treatment is applied. In a related method, a cross-linking treatment is first performed to form a region of a polymer having a functional group which becomes a dyed site of an acid dye, and a part of the region is converted to have a hydrolysis treatment thereafter. A region of a polymer that crosslinks the structure with a carboxyl group. Further, in the related method, it is not mentioned that it is an acrylonitrile-based polymer, and an acrylonitrile-based polymer having a cationic group may be used in the same manner. Further, an acrylic fiber composed of an acrylonitrile-based polymer having no functional group dyed with an acid dye may be used as a raw material fiber, and a functional group having an acid dye dyeing site may be introduced here. Thereafter, a partial crosslinking treatment and a hydrolysis treatment method, or an acrylic fiber containing a polymer having a functional group which becomes an acid dye dyed site other than the acrylonitrile-based polymer, is partially applied thereto. Combined treatment and hydrolysis treatment methods. In addition, in the above-mentioned production method, the ratio of the acrylonitrile-based polymer in the acrylic fiber to be the raw material fiber is preferably 80 to 100% by weight irrespective of the presence or absence of the functional group which is the dyeing position of the acid dye. . In addition, the acrylic fiber to be a raw material fiber is composed of at least two types of acrylonitrile-based polymers having different acrylonitrile contents, and the difference in content ratio is preferably 2% by weight or more. This is caused by the difference in easiness of crosslinking and hydrolysis, and it is easy to form a region having a polymer which becomes a functional group of the acid dye dyeing site and a region having a polymer having a crosslinked structure and a carboxyl group. The related acrylic fiber is a combination of two types of acrylonitrile-based polymers. The three-layer structure or core-sheath structure consisting of the ABA layer is not involved. Preferably, the portion of the B layer or the core is preferably one having a high content of acrylonitrile and having a polycation base. Specifically, the acrylonitrile content of the portion of the B layer or the core is 82% by weight or more, preferably 85% by weight or more, more preferably 90% by weight or more, and the content of the cationic group is 0.15 mmol/ Above g, preferably 〇17 mmol/g or more is desirable. -14-.201107556 In addition, in the method of obtaining an acrylic fiber having a three-layer structure composed of an ABA layer, the method described in JP-A-2000-45126 can be used. The concentration of the stock solution is lower than the concentration of the stock solution of the component B, and it is preferable that the component B is less exposed to the surface of the fiber. In the method for producing an acid dye-dyeable hygroscopic fiber of the present invention described above, the acrylic fiber composed of the acrylonitrile-based polymer having a cationic group contains two molecules in one molecule. After the nitrogen-containing compound of the above nitrogen atom is subjected to a crosslinking treatment, the hydrolysis treatment is carried out by an aqueous solution of an alkali metal salt, or a crosslinking structure and a polymerization having a carboxyl group are formed in the surface layer portion of the fiber by simultaneously performing such treatment. The method of leaving a region of the acrylonitrile-based polymer having a cationic group in the core region is preferable from the viewpoint of manufacturing equipment or cost. The method of association is detailed below. In the related method, the acrylic fiber composed of the acrylonitrile-based polymer having a cationic group is crosslinked by an aqueous solution containing a nitrogen-containing compound having two or more nitrogen atoms in the above-mentioned one molecule. The treatment and hydrolysis treatment are carried out by an aqueous solution containing a basic metal salt compound. The treatment may be carried out by a hydrolysis treatment after the crosslinking treatment, and the individual treatment may be carried out as described above. An aqueous solution containing a nitrogen-containing compound having two or more nitrogen atoms and an alkali metal salt compound in one molecule may also be used. Simultaneous processing. In either case, a nitrogen-containing compound containing two or more nitrogen atoms in one molecule reacts with a nitrile group of an acrylic polymer in a surface layer portion of an acrylic fiber to form a crosslinked structure, or an alkali metal. The aqueous salt compound reacts with the nitrile group to form a carboxyl group, which is converted into a polymer having a bonded structure of -15-201107556 and a carboxyl group. In the above specific method of the crosslinking treatment and the hydrolysis treatment, a method of reacting the fibers in a state of being immersed in an aqueous solution for treatment is employed. Further, in the case of the individual treatment or the simultaneous treatment, the concentration of the nitrogen-containing compound containing two or more nitrogen atoms in one molecule is preferably 0.1 to 5% by weight, and 0.1 to 3% by weight. Better. If the concentration is too low, the effect of suppressing the dissolution of the polymer having a crosslinked structure and a carboxyl group cannot be obtained. On the other hand, it is preferable that the introduction of the crosslinked structure is stopped at the surface layer portion of the fiber, and the concentration is preferably 5% by weight or less. Further, the concentration of the basic metal salt compound is preferably 5 to 5 % by weight, more preferably 0.5 to 4 % by weight. If the concentration of the basic metal salt compound is too low, the amount of carboxyl groups generated may be insufficient. On the other hand, when the concentration is controlled to 5% by weight or less, the introduction of the carboxyl group can be stopped in the surface layer portion of the fiber, and the region of the acrylonitrile-based polymer having a cationic group can be left in the core portion. Further, regarding the reaction temperature and time, the appropriate range differs depending on the concentration of the nitrogen-containing compound and/or the basic metal salt compound containing two or more nitrogen atoms in the molecule. In the case of simultaneous treatment, if the concentration of the nitrogen-containing compound containing two or more nitrogen atoms in one molecule is 0.5 to 2% by weight, the concentration of the basic metal salt compound is 1 to 2% by weight. The degree is recommended to be carried out at 90 to 100 ° C for 2 hours. In the case of the above individual treatment, the fiber subjected to the crosslinking treatment may be subjected to an acid treatment before the hydrolysis treatment. By correlating the acid treatment, the color of the fiber can be lightened. The acid used herein may, for example, be an aqueous solution of an inorganic acid such as nitric acid, sulfuric acid or hydrochloric acid, or an organic acid, but is not particularly limited. Further, in the case of the condition of -16 to 201107556, the treated fiber is immersed in an aqueous solution having an acid concentration of 5 to 20% by weight, preferably 7 to 15% by weight, at a temperature of 50 to 120 ° C. ~10 hours. However, the associated acid treatment is carried out by hydrolysis, in order to reduce the effect of the acrylonitrile-based polymer which should remain in the finally obtained fiber, that is, the region of the polymer which becomes a functional group in which the acid dye is dyed. It is necessary to set conditions for things. The fiber obtained by the hydrolysis or cross-linking and the simultaneous hydrolysis treatment as described above may be used as the acid dye-dyeable hygroscopic fiber of the present invention as it is, but it may be further washed with an acidic aqueous solution. Thereby, a fiber having a higher whiteness can be obtained. Examples of the acidic aqueous solution to be used include an aqueous solution of an inorganic acid such as nitric acid, sulfuric acid or hydrochloric acid, an organic acid or the like, but are not particularly limited. Further, in the stage after the production of the above-mentioned fiber, in order to facilitate the processing such as weaving, a quinone type carboxyl group is used, and after the dyeing or the final product, the desired salt type carboxyl group or the quinone type carboxyl group is changed. The salt type is mixed and the behavior is ideal. The adjustment of the associated carboxyl group can be carried out by subjecting a metal salt such as a nitrate, a sulfate or a hydrochloride to ion exchange treatment or a pH adjustment treatment by a buffer or the like. Further, in the case where a high moisture absorption rate is obtained, it is preferable that 50% or more of the carboxyl group amount is a salt type carboxyl group. In addition, the acrylic fiber composed of the acrylonitrile-based polymer is used as a raw material fiber, and the fiber is subjected to a crosslinking treatment by a nitrogen-containing compound containing two or more nitrogen atoms in one molecule, followed by hydrolysis treatment. The method of applying the cross-linking treatment described above is preferably smaller than the range in which the hydrolysis treatment is applied. In the related method, in order to make the range of the hydrolysis treatment to be wider than the range of the crosslinking treatment, first, the concentration of the nitrogen-containing compound having two or more nitrogen atoms in -17-201107556 in one molecule is set. A high solution is subjected to a crosslinking treatment, which is followed by a hydrolysis treatment. For example, in the case of a core-sheath structure, in order to apply a crosslinking treatment to the entire fiber, the concentration of the nitrogen-containing compound is preferably 7 to 20% by weight, more preferably 1 to 20% by weight. The conditions for the hydrolysis treatment of the surface layer portion of the fiber after the treatment may be carried out under the above conditions, and the acid treatment or the carboxyl group may be adjusted in the same manner as needed. [Examples] The present invention will be specifically described by the following examples, but the present invention is not limited by the following examples. Further, the parts and percentages in the examples are limited to the uninterrupted timing and are expressed on a weight basis. The evaluation method of the characteristics in the examples is as follows. (1) About 1 g (A[g]) of the sample which is sufficiently dried by the carboxyl group, add it to 200 ml of water, and then add 1 mol of 1/L hydrochloric acid solution to pH 2 while heating to 50 °C. Then, the titration curve is obtained by a usual method using 〇.1 m〇l/L sodium hydroxide aqueous solution. From the titration curve, the consumption amount of sodium hydroxide aqueous solution (B [ml]) consumed in the carboxyl group was determined, and the amount of carboxyl groups was calculated by the following formula.翔基量 [mmol/g] = 〇·1χΒ/Α (2) The cationic base of the raw material fiber is about 0.5g (C[g]) of the sample which is sufficiently dried, and is immersed in the ion exchange. A quantity of 0.1 m〇l/L aqueous hydrochloric acid solution (D [ml]) in a beaker. The sample was filtered, and the filtrate was added as an indicator drug to the phenolphthalein solution. The filtrate was titrated with a 0.1 mm 〇l/L aqueous solution of sodium hydroxide to quantify the residual hydrochloric acid of -18-201107556. The titer of the aqueous sodium hydroxide solution at this time was taken as E [ml], and the cationic base amount was calculated by the following formula.
陽離子性基量[mmol/g] = (0.1xD-0.1xE)/C (3) 飽和吸濕率 將試料浸漬於5.0g之水中，添加相對於羧基之中和 度成爲如70%之氫氧化鈉溶液，於70 °C浸漬處理1小時後， 水洗、脫水、風乾24小時。將經中和處理之該試料以熱風 乾燥機於l〇5°C乾燥16小時測定其重量（F[g])。接著將該試 料調整至20 °C、相對濕度65%之條件，放入恆溫恆濕器中 24小時。測定如此進行吸溼之試料的重量。（G[g])。從以 上的測定結果，藉由下式算出。Cationic base amount [mmol/g] = (0.1xD-0.1xE)/C (3) Saturated moisture absorption rate The sample was immersed in 5.0 g of water, and a degree of neutralization with respect to the carboxyl group was 70%. The sodium solution was immersed at 70 ° C for 1 hour, washed with water, dehydrated, and air-dried for 24 hours. The sample subjected to the neutralization treatment was dried in a hot air dryer at 10 ° C for 16 hours to determine its weight (F [g]). Then, the sample was adjusted to a condition of 20 ° C and a relative humidity of 65%, and placed in a thermo-hygrostat for 24 hours. The weight of the sample thus subjected to moisture absorption was measured. (G[g]). From the above measurement results, the following formula was calculated.
飽和吸濕率[%] = (G- F) / FxlOO (4) 膨潤度 將試料約3 g以熱風乾燥機於70°C乾燥3小時測定其 重量（H[g])。接著將該試料浸漬於裝有300 ml水之燒杯中 30分鐘後，將膨潤之試料以桌上離心脫水機（160GX5分鐘） 脫水，測定試料之重量（J[g])。從以上的測定結果，藉由下 式算出。 膨潤度（g/g) = (J— Η)/ Η (5) 染色性 將試料投入裝有相對於該試料之重量爲5 %之酸性染 料81^以11〇181&。1{乂1^(0丫81&1'公司製）之浴中，並以乙酸 調整至ρΗ3.5後於100 °C浸漬30分鐘後進行皂洗、水洗、 乾燥。對所得之纖維，基於以下之判斷基準，藉由目視評 -19- 201107556 估。 〇：可充分染色 △:可淡色染色 X:幾乎不能染色，或色相異常 (6) 汗染色堅牢度 對以與「（5)染色性」同樣之方法染色之纖維，以 JIS-L-0848評估汗染色堅牢度。 (7) 丙烯腈系聚合物之區域之剖面積比率 將與「（5)染色性」同樣之方法染色之纖維切斷，藉由 以光學顯微鏡觀察纖維斷面算出。 (8) 飽和染色量 將含有相對於投入之試料重量爲 20%之酸性染料 Sandolan Fast Blue P-L 12 5% (Sandoz 公司製），並以乙酸 調整至pH3之染色母液以浴比1 :200作成，測定相關染色 母液之對於波長590nm之光之吸光度。接著，將試料投入 該染色母液中，於100 °C處理30分鐘。漸冷後以碳酸鈉將 染色浴調整至pH7,於70°C處理30分鐘。接著補充於處理 中蒸發掉之水分，再度將浴比調整爲1:200，測定染色殘液 之對於波長5 90 nm之光之吸光度。藉由以上的測定結果， 使用下述之式算出相對於纖維重量之飽和染著量。 飽和染著量(％)=(染色母液之吸光度-染色殘液之吸光度)/染色母液之吸光度χ20 另外，染色母液及染色殘液之吸光度係各自稀釋20倍後使 用U-1100 Spectrophotometer(日立製作所製造）測定。 -20- 201107556 [實施例1] 將由丙烯腈86%、丙烯酸甲酯11%及（甲基）丙烯酸二 甲胺乙酯3%所構成之丙烯腈系聚合物（在30°C二甲基甲醯 胺中之極限黏度[η] = 1.2)10部溶解於48%之硫氰酸鈉水溶 液90部之紡紗原液，以常用方法紡紗、延伸（總延伸倍率： 10倍）後，在乾球/溼球=120°C/60°C的空氣下乾燥後進行濕 熱處理得到單纖維纖度 2.2dtex之原料纖維（纖維長 51mm)。在含有水合肼0.4%及氫氧化鈉2%之水溶液中對該 纖維進行90°C χ2小時之處理，藉由以pH2以下之硝酸水溶 液洗淨、水洗、乾燥得到實施例1之纖維。所得纖維之評 估結果表示於表1。 [實施例2] 在含有水合肼0.4%及氫氧化鈉2%之水溶液中對實施 例1的原料纖維進行90°C X 1 .5小時之處理’藉由以pH2以 下之硝酸水溶液洗淨、水洗、乾燥得到實施例2之纖維。 所得纖維之評估結果表示於表1。 [實施例3] 將由丙烯腈90%、丙烯酸甲酯9.7 %及甲基烯丙基磺酸 鈉0.3%所構成之丙烯腈系聚合物（在30°C二甲基甲醯胺中 之極限黏度[η] = 1.2)10部溶解於48%之硫氰酸鈉水溶液90 部之紡紗原液，以常用方法紡紗、延伸（總延伸倍率：10 倍）後，在乾球/溼球=120°c/60°c的空氣下乾燥後進行濕熱 處理得到單纖維纖度2.2dtex之原料纖維（纖維長51mm)。 在含有水合肼10%之水溶液中對該纖維進行ll〇°Cxl小時 -21- 201107556 之處理，其後，在含有氫氧化鈉1.6%之水溶液進行100°Cxl 小時之處理，藉由以pH2以下之硝酸水溶液洗淨、水洗、 乾燥得到實施例3之纖維。所得纖維之評估結果表示於表 [實施例4] 在含有水合肼15%之水溶液中對實施例1的原料纖維 進行1 10°C X 1.5小時之處理，其後，在含有氫氧化鈉2%之 水溶液進行100 °C xl小時之處理，藉由以PH2以下之硝酸 水溶液洗淨、水洗、乾燥得到實施例4之纖維。所得纖維 之評估結果表示於表1。 [比較例1 ] 在含有水合肼1 5%之水溶液中對實施例1的原料纖維 進行110°Cx3小時之處理並洗淨。將所得之纖維浸漬於8% 硝酸水溶液中並進行l〇〇°C xl小時之處理。接續在含有氫 氧化鈉5%之水溶液進行100°C xl小時之處理，藉由以PH2 以下之硝酸水溶液洗淨、水洗、乾燥得到比較例1之纖維。 所得纖維之評估結果表示於表1。 [比較例2] 於實施例1中’使用實施例3之原料纖維作爲原料纖 維以外係相同而行，得到比較例2之纖維。所得纖維之評 估結果表示於表1。 -22- 201107556 [表1] 實施例1 實施例2 實施例3 實施例4 比較例1 比較例2 原料纖維之 陽離子性基量 mmol/g 0.18 0.18 0 0.18 0.18 0 羧基量 nunol/g 3.4 2.8 4.1 5.3 5.8 3.0 丙烯腈系聚合 物區域之比例 % 52 62 44 40 — — 飽和吸溼率 % 24 18 29 34 38 21 膨潤度 g/g 1.5 1.2 1.9 1.9 2.3 1.3 染色性 〇 〇 〇 〇 X X 汗染色堅牢度 級 5 5 4 4-5 1 — 飽和染著量 % 4.0 5.1 5.0 7.2 3.1 3.3 在實施例1係藉由酸性染料得到對染色具有良好之染 色性與染色堅牢度，且具有良好吸溼性能之纖維。實施例 2之吸溼性纖維係與實施例1之吸溼性纖維比較丙烯腈系 聚合物之區域較廣，但作爲吸溼性纖維具有充分之吸溼性 能，同時爲具有良好染色性與染色堅牢度者。在實施例3 係以由不具有成爲酸性染料染著位之官能基之丙烯腈系聚 合物所構成之丙烯腈系纖維爲出發原料，但得到具有良好 之染色性與染色堅牢度之吸溼性纖維。此應係因爲交聯處 理條件爲強而於纖維內層導入了從交聯劑而來之成爲酸性 染料染著位之官能基而造成者。在實施例4應係以由具有 陽離子性基之丙烯腈系聚合物所構成之丙烯腈系纖維作爲 原料纖維’進一步藉由交聯處理條件亦爲強而使對染色有 -23- .201107556 效之成爲酸性染料染著位之官能基變多，得到飽和染著量 爲高之吸溼性纖維。 另一方面，比較例1之纖維係成爲飽和染著量爲低， 不能以所意圖之色相進行染色，染色堅牢度亦爲低者。此 應係將水解條件增加之故而在纖維整體引起水解，失去多 數原料纖維所具有之陽離子性基之故。另外，關於由交聯 劑而來之成爲酸性染料染著位之官能基，應係亦藉由水解 變化爲其他的官能基，或該官能基之週邊因水解形成多量 之羧基，成爲容易吸水膨潤之構造，即使染劑染著，與水 接觸亦容易流出而使其作爲酸性染料染著位之機能充分地 失去者。又，比較例2之纖維應係因對不具有成爲酸性染 料染著位之官能基之原料纖維，使交聯處理與水解處理僅 止於纖維表層部，於芯部不存在成爲酸性染料染著位之官 能基，表層部係與比較例1之纖維爲同樣之構造，染色性 亦成爲劣者。另外，關於此等之比較例之纖維，係因不能 適當地染色，無法求得丙烯腈系聚合物之區域之剖面積比 率。 [產業上之利用可能性] 本發明之酸性染料可染性吸溼性纖維係因具有高吸溼 性能，且藉由酸性染料染色性爲優良之故，可實用地染色。 其故，因於先前之交聯丙烯酸系纖維之實用地染色爲困難 之故而限制了的使用用途亦可擴展。 【圖式簡單說明】 無。 -24- 201107556 【主要元件符號說明】Saturated moisture absorption rate [%] = (G-F) / FxlOO (4) Swelling degree Approximately 3 g of the sample was dried at 70 ° C for 3 hours in a hot air dryer to measure its weight (H [g]). Next, the sample was immersed in a beaker containing 300 ml of water for 30 minutes, and then the swollen sample was dehydrated by a table centrifugal dehydrator (160 GX for 5 minutes), and the weight (J [g]) of the sample was measured. From the above measurement results, it was calculated by the following formula. Degree of swelling (g/g) = (J - Η) / Η (5) Dyeing property The sample was charged with an acid dye 81 of 〇 181 & 5% with respect to the weight of the sample. In a bath of 1{乂1^(0丫81&1'), adjusted to pH Η3.5 with acetic acid, immersed at 100 °C for 30 minutes, then soaped, washed with water, and dried. The obtained fiber was estimated by visual evaluation -19-201107556 based on the following judgment criteria. 〇: Fully dyeable △: Can be dyed lightly X: Hardly dyed, or abnormal hue (6) Khan dye fastness The fiber dyed in the same way as "(5) dyeability", evaluated by JIS-L-0848 Sweat stain fastness. (7) Cross-sectional area ratio of the area of the acrylonitrile-based polymer The fiber dyed by the method similar to the "(5) dyeability" was cut, and the fiber cross-section was observed by an optical microscope. (8) The saturated dyeing amount will contain an acid dye Sandolan Fast Blue PL 125% (manufactured by Sandoz Co., Ltd.) of 20% by weight of the input sample, and a dyeing mother liquor adjusted to pH 3 with acetic acid at a bath ratio of 1:200. The absorbance of the relevant dyeing mother liquor for light having a wavelength of 590 nm was measured. Next, the sample was placed in the dyeing mother liquid and treated at 100 ° C for 30 minutes. After gradually cooling, the dye bath was adjusted to pH 7 with sodium carbonate and treated at 70 ° C for 30 minutes. Then, the water evaporated in the treatment was added, and the bath ratio was again adjusted to 1:200, and the absorbance of the dyed residue for light having a wavelength of 5 90 nm was measured. From the above measurement results, the saturated dyeing amount with respect to the fiber weight was calculated using the following formula. Saturated dyeing amount (%) = (absorbance of dyeing mother liquor - absorbance of dyeing residue) / absorbance of dyeing mother liquor χ 20 In addition, the absorbance of dyeing mother liquor and dyeing residue was diluted 20 times each, and then U-1100 Spectrophotometer was used (Hitachi Manufacturing Co., Ltd.) Manufacture) measurement. -20-201107556 [Example 1] An acrylonitrile-based polymer composed of acrylonitrile 86%, methyl acrylate 11%, and dimethyl (meth) methacrylate 3% (dimethyl group at 30 ° C) The ultimate viscosity [η] = 1.2) 10 parts of the spinning stock solution dissolved in 48% of sodium thiocyanate aqueous solution, spun and extended by the usual method (total stretching ratio: 10 times), after drying The ball/wet bulb = 120 ° C / 60 ° C was dried under air and then subjected to a wet heat treatment to obtain a raw material fiber (fiber length: 51 mm) having a single fiber fineness of 2.2 dtex. The fiber was treated at 90 ° C for 2 hours in an aqueous solution containing 0.4% hydrazine hydrate and 2% sodium hydroxide, and the fiber of Example 1 was obtained by washing with an aqueous solution of nitric acid having a pH of 2 or less, washing with water, and drying. The evaluation results of the obtained fibers are shown in Table 1. [Example 2] The raw material fiber of Example 1 was subjected to a treatment at 90 ° C for 1.5 hours in an aqueous solution containing 0.4% hydrazine hydrate and 2% sodium hydroxide by washing with water having a pH of 2 or less and washing with water. The fiber of Example 2 was obtained by drying. The evaluation results of the obtained fibers are shown in Table 1. [Example 3] An acrylic acid-based polymer composed of 90% acrylonitrile, 9.7% methyl acrylate, and 0.3% sodium methallylsulfonate (limit viscosity in dimethylformamide at 30 ° C) [η] = 1.2) 10 spinning stock solutions dissolved in 48% of a 48% sodium thiocyanate aqueous solution, spun and extended by a usual method (total stretching ratio: 10 times), after dry bulb/wet bulb = 120 The mixture was dried under air at °c/60 °c and then subjected to a wet heat treatment to obtain a raw material fiber (fiber length: 51 mm) having a single fiber fineness of 2.2 dtex. The fiber is treated in an aqueous solution containing 10% hydrazine hydrate in a period of ll 〇 C x 1 hour-21-201107556, and then treated in an aqueous solution containing 1.6% sodium hydroxide at 100 ° C for 1 hour, with a pH of 2 or less. The aqueous solution of nitric acid was washed, washed with water, and dried to obtain the fiber of Example 3. The evaluation results of the obtained fibers are shown in the table [Example 4] The raw material fibers of Example 1 were treated at 110 ° C for 1.5 hours in an aqueous solution containing 15% hydrazine hydrate, and thereafter, 2% of sodium hydroxide was contained. The aqueous solution was treated at 100 ° C for 1 hour, and the fiber of Example 4 was obtained by washing with an aqueous solution of nitric acid of pH 2 or less, washing with water, and drying. The evaluation results of the obtained fibers are shown in Table 1. [Comparative Example 1] The raw material fiber of Example 1 was treated at 110 ° C for 3 hours in an aqueous solution containing 5% hydrazine hydrate and washed. The obtained fiber was immersed in an 8% aqueous solution of nitric acid and treated at 10 ° C for 1 hour. Subsequently, the solution containing 100% of sodium hydroxide was subjected to treatment at 100 ° C for 1 hour, and the fiber of Comparative Example 1 was obtained by washing with an aqueous solution of nitric acid having a pH of 2 or less, washing with water, and drying. The evaluation results of the obtained fibers are shown in Table 1. [Comparative Example 2] The fibers of Comparative Example 2 were obtained in the same manner as in Example 1 except that the raw material fibers of Example 3 were used as the raw material fibers. The evaluation results of the obtained fibers are shown in Table 1. -22-201107556 [Table 1] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Cationic base amount of raw material fiber mmol/g 0.18 0.18 0 0.18 0.18 0 Carboxyl group nunol/g 3.4 2.8 4.1 5.3 5.8 3.0 Proportion of acrylonitrile-based polymer area 52 62 44 40 40 — — Saturated moisture absorption rate 24 18 29 34 38 21 Swelling degree g/g 1.5 1.2 1.9 1.9 2.3 1.3 Dyeing 〇〇〇〇 XX Khan dyeing is strong Degree 5 5 4 4-5 1 - Saturated dyeing % 4.0 5.1 5.0 7.2 3.1 3.3 In Example 1, the acid dye has good dyeability and dye fastness, and has good hygroscopic properties. fiber. The hygroscopic fiber of Example 2 has a wider area of the acrylic fiber than the hygroscopic fiber of Example 1, but has sufficient moisture absorption properties as the hygroscopic fiber, and has good dyeability and dyeing. Faster. In Example 3, an acrylic fiber composed of an acrylonitrile-based polymer having no functional group capable of dyeing an acid dye was used as a starting material, but moisture absorption with good dyeability and dye fastness was obtained. fiber. This is caused by the introduction of a functional group derived from a crosslinking agent into an acid dye dyed site in the inner layer of the fiber because the crosslinking treatment conditions are strong. In the fourth embodiment, the acrylic fiber composed of the acrylonitrile-based polymer having a cationic group is used as the raw material fiber', and the crosslinking treatment condition is also strong, so that the dyeing is -23-.201107556 The functional group which becomes the acid dye dyeing site is increased, and the hygroscopic fiber having a high saturated dyeing amount is obtained. On the other hand, in the fiber system of Comparative Example 1, the amount of saturated dyeing was low, and it was not possible to dye in the intended hue, and the dyeing fastness was also low. This is because the hydrolysis condition is increased to cause hydrolysis in the entire fiber, and the cationic group of most of the raw material fibers is lost. Further, the functional group which is a dyed site of the acid dye by the crosslinking agent is also changed to another functional group by hydrolysis, or a peripheral group is formed by hydrolysis to form a large amount of carboxyl groups, thereby becoming easily swelled and swelled. The structure is such that even if the dye is dyed, it is easy to flow out in contact with water, so that it is sufficiently lost as a function of dyeing the acid dye. Further, in the fiber of Comparative Example 2, the raw material fiber having no functional group to be dyed in the acid dye was used, and the crosslinking treatment and the hydrolysis treatment were stopped only at the surface layer of the fiber, and the acid dye was not present in the core portion. The functional group at the surface was the same structure as the fiber of Comparative Example 1, and the dyeability was also inferior. Further, in the fibers of the comparative examples, the cross-sectional area ratio of the region of the acrylonitrile-based polymer could not be obtained because the dye could not be properly dyed. [Industrial Applicability] The acid dye-dyeable hygroscopic fiber of the present invention has high hygroscopicity and is excellent in dyeability by an acid dye, and can be practically dyed. Therefore, the use of the previously crosslinked acrylic fiber which is practically dyed is difficult to expand and the use can be expanded. [Simple description of the diagram] None. -24- 201107556 [Description of main component symbols]