1338069 (1) 九、發明說明 【發明所屬之技術領域】 本發明爲關於纖維用濃色化劑及使用其之纖維製 濃色化法。更詳言之，本發明爲關於含有酸性條件下 有胺基之矽烷偶合劑處理之矽石微粒子和聚醚改質聚 烷的濃色化劑’及使用其染色之纖維製品的濃色化法 發明之纖維用濃色化劑爲提供染料固黏性優良，且改 色物的帶深色、吸水性優良。且不會損害此染色物本 洗滌堅年度、水堅牢度等的染色纖維加工物。 【先前技術】 關於經染色纖維製品的濃色化方法，已於20年 被提案’且至目前已提案各種濃色化劑、濃色化方法 且亦具有已實用化的技術。經染色之纖維製品的濃色 術爲對經染色的纖維表面賦予微細的凹凸，且以光的 、折射等改善顏色的帶深色，賦予凹凸之藥劑已提案 微粒子、胺基甲酸酯系樹脂乳化劑、丙烯酸系樹脂乳 等。 矽石微粒子系之濃色化劑爲記載於例如專利文獻 專利文獻2、專利文獻3、專利文獻4、專利文獻5等 如其中之專利文獻1所記載般，矽石微粒子系之濃色 基本上爲由含有矽石微粒子的水性懸浮液所構成。專 獻6中，提案將矽石微粒子的懸浮液以具有胺基的矽 合劑處理，於纖維上附著後再予以低溫電漿處理使用 品的 經具 矽氧 。本 善染 來的 以前 ，並 化技 反射 矽石 化劑 ，但 化劑 利文 院偶 的濃 -5- (2) (2)1338069 色化劑，但此濃色化劑爲以使用於聚酯纖維爲目的，於應 用在纖維素纖維的情形中則引起吸水性的降低。更且，專 利文獻7及專利文獻8所記載之濃色化劑，爲對於預先經 環氧化合物處理之聚酯纖維所用的濃色化劑，爲以具有胺 基之矽烷偶合劑處理之矽石微粒子所構成的濃色化劑。但 是，將此濃色化劑應用於纖維素纖維之情形中，則無法期 待確保充分的吸水性。更且，專利文獻9中，提案由矽石 微粒子和聚矽氧烷化合物所構成的濃色化劑，但此濃色化 劑爲被應用於聚酯纖維及羊毛，但關於對於重視吸水性之 纖維素纖維的應用則無任何記載。 更且，於專利文獻1 0中，提案不僅於聚酯纖維，且 於聚醯胺、丙烯酸、人、造絲等之合成纖維或再生纖維亦可 應用的濃色化劑：樹脂乳化劑。但是，此樹脂乳化劑由樹 脂的構造上而言並無法期待賦予充分的吸水性，又，以濃 色化劑處理時之處理浴安定性有問題，難應用浸漬處理法 等之簡單的處理法 如上述’先前所提案的濃色化劑爲以聚酯纖維等斥水 性纖維用爲主體’因此於羊毛、纖維素纖維等之較具親水 性的纖維染色物中若進行濃色化處理，則對纖維造成濃色 效果且同時賦予撥水性，多損害親水性或吸水性。 如此’迄今並未發現應用斥水性纖維及親水性纖維兩 者且賦予充分效果的濃色化劑。 [專利文獻1 ]特開昭5 6 - Π 2 5 8 3號公報 [專利文獻2]特開平2_2 5 9 1 60號公報 6 - (3) (3)1338069 [專利文獻3 ]特開平3 -2 6 9 1 7 1號公報 [專利文獻4]特開平4-214482號公報 [專利文獻5]特開平9-256280號公報 [專利文獻6 ]特開昭5 6 - 1 1 2 5 8 3號公報 [專利文獻7 ]特開平2 - 2 5 9 1 6 0號公報 [專利文獻8]特開平3-269171號公報 [專利文獻9]特開平3-4214482號公報 [專利文獻10]特開平9-256280號公報 [專利文獻1 1]特開平9-3 774號公報 【發明內容】 [發明之揭示] (發明所欲解決之課題） 本發明之課題爲在於開發出濃色化處理中之安定性優 良，且對於經染色加工之纖維製品' 濃色效果優良，且同 時於濃色化處理所得之纖維製品中的吸水性優良，且重複 洗滌耐性優良的濃色化劑’以及使用此類纖維用濃色化劑 經染色加工的纖維製品予以濃色化的方法。 (解決課題之手段） . 本發明者等人爲了解決上述課題致力硏究，結果發現 件.下’將具有胺基之矽烷偶合劑所處理的矽石微 粒子懸浮液與聚醚改雩聚矽氧烷混合所得之混合物，可提 供濃色效果優4 H時〜翠水丨生，生優良的纖維 (4) (4)1338069 製品’以及此混合物爲於濃色化處理中的安定性優良，並 且達到完成本發明。 即，本發明爲關於 (1 ) 一種纖維用濃色化劑，其特徵爲含有於酸性條 件下以具有胺基之矽烷偶合劑處理的矽石微粒子與聚醚改 質矽氧烷； (2 )如（1 )記載之纖維用濃色化劑，其中聚醚改質 聚矽氧烷的含量爲相對於矽石微粒子以5〜20重量。； (3 )如（1 )或（2 )記載之纖維用濃色化劑，其爲 令矽石微粒子之懸浮液於酸性條件下，以具有胺基之矽烷 偶合劑處理，其次混合聚醚改質聚矽氧烷則可取得； (4 ) 一種經染色加工之纖維的濃色化方法，其特徵 爲令經染色加工之纖維，以上述（1 )至（3 )中任一項記 載之纖維用濃色化劑予以處理； (5 )如（4 )記載之纖維的濃色化方法，其中經染色 加工的纖維爲纖維素纖維； (6 )如（4 )記載之纖維的濃色化方法，其中經染色 加工的纖維爲聚酯纖維： (7 )—種纖維染色加工物，其特徵爲根據如上述（4 )至（6 )中任一項記載之濃色化方法則可取得。 (發明之效果） 經由以本發明之濃色化劑，處理經染色的纖維製品， 則可取得濃色性、吸水性、耐洗滌堅牢度等優良的纖維染 -8- (5) (5)1338069 色加工物。不僅對於已被廣泛實施濃色化處理的聚酯織維 ，且對於先前困難之經染色的木棉、人造絲等之纖維素纖 維，亦可繼續保持吸水性且取得濃色化之效果。特別，應 用於禮服等之染色成濃黒色之染色物時的效果極大。本發 明之濃色化劑爲對於聚酯纖維爲首之斥水性纖維和木棉、 人造絲、羊毛等之親水性纖維的混紡纖維製品，提供親水 性、斥水性之兩纖維高的濃色化並且同時提高此些纖維所 具有之吸水性的效果。 如此，本發明之濃色化劑爲以提供附加價値極高之纖 維製品之染色物的理由而言，於染色加工產業中爲極高價 値的發明。 (實施發明之最佳形態） 本發明之濃色化劑爲含有於酸性條件下以具有胺基之 矽烷偶合劑處理的矽石微粒子和聚醚改質聚矽氧烷’較佳 ，令矽石微粒子之懸浮液於酸性條件下，以具有胺基之矽 烷偶合劑處理，其次混合聚醚改質矽氧烷則可取得。 於本發明中，於酸性條件下以具有胺基之矽烷偶合劑 處理所用之矽石微粒子’其粒徑通常爲使用30~85nm者’ 且可使用已以懸浮液形態販售者。懸浮液之介質以水爲佳 〇 具有胺基之矽烷偶合劑可使用α ·胺丙基三乙氧基砂 烷、Ν-(胺醚基）_胺丙基三甲氧基矽烷等一般販售的较 烷偶合劑（例如’ κ ΒΕ 9 0 3 (信越化學（股）製）° (6) (6)1338069 於酸性條件下以具有胺基之矽烷偶合劑處理時，相對 於矽石微粒子之具有胺基之矽烷偶合劑的使用比例通常爲 5〜2 0重量％，具有胺基之矽烷偶合劑的使用比例若少於此 範圍，則所得濃色化劑的耐洗滌堅牢度降低，相反地，使 用比例若大於此範圍則恐令濃色化劑的安定性降低。 將矽石微粒子，以具有胺基之矽烷偶合劑於酸性條件 下處理時，所使用之酸性物質可列舉無機酸、有機酸、較 佳爲甲酸、醋酸、乙醇酸、琥珀酸、順丁烯二酸等之一價 或二價之有機酸。於酸性條件下處理時之pH若爲6以下 即可，特別若爲pH 3〜5則濃色化劑之經時安定性提高，故 爲佳。於酸性條件下處理時矽石微粒子懸浮液中之矽石微 粒子濃度通常爲5〜20電暈％。濃度若低於此範圍則處理時 間變長，濃度若高於此範圍則恐溶液的安定性降低。矽石 微粒子於酸性條件下以具有胺基之矽烷偶合劑處理時的各 藥劑混合順序並無特別限制，但以在如前述酸性條件所調 製之矽石微粒子懸浮液中，加入矽烷偶合劑之水性懸浮液 或醇溶液爲佳。如此混合後，通常以5〜3 0 t ，較佳爲 15〜25°C混合，且較佳爲熟化至安定化爲止爲佳。 其次，本發明所用之聚醚改質聚矽氧烷爲於含有矽烷 基之聚矽氧烷中，附加烯丙醇的環氧乙烷、環氧丙烷、或 彼等之無規或分段共聚物所構成的聚醚。可使用一般已販 售者（例如，SII 190，東雷Dowcorning (股）製）。 經由混合具有親水性之聚醚改質聚矽氧烷，則可大幅 提高所得濃色化劑的吸水性，且重複洗滌耐性優良。聚醚 -10- (7) (7)1338069 改質聚矽氧烷的使用比例爲相對於該處理後之矽石微粒子 通常以3〜3 0重量％，5 ~ 2 0重量％爲佳。 對於酸性條件下以具有胺基之矽烷偶合劑處理之矽石 微粒子的懸浮液，將聚醚改質聚矽氧烷混合的方法並無特 別限定，但爲了取得更均勻的分散狀態，將聚醚改質聚矽 氧烷溶解於醇等中予以混合爲佳。 於本發明中，視需要將界面活性劑、柔軟劑等本身公 知的添加劑於調製本發明之濃色化劑時，或者於處理經本 發明之濃色化劑所染色之纖維製品的浴中添加亦可。 其次，說明關於使用本發明之濃色化劑所染色之纖維 製品的濃色化處理法。 適於應用本發明之濃色化劑染色之纖維製品中的纖維 可列舉木棉、麻、銅氨纖維（人造絲）、黏膠人造絲、波 里諾西克（polynosic)纖維等之天然或再生的纖維素纖維 、羊毛、絹等之蛋白質纖維、醋酸纖維等之半合成纖維、 聚酯纖維（包含CDP纖維（陽離子可染性聚酯纖維）） 聚丙烯腈纖維、尼龍等之聚醯胺纖維等之合成纖維等及此 些纖維之二種以上纖維所構成的混紡纖維。其中較佳之纖 維爲纖維素纖維、聚酯纖維、蛋白質纖維、聚醯胺醯胺、 及此些纖維與其他纖維的混紡纖維。 經染色之纖維製品的形狀可爲織物、編物、纖維狀等 任何形態均可。 本發明之濃色化法可根據軋染處理法、浸漬法等之通 常方法進行。 -11 - (8) (8)1338069 以軋染處理法的濃色化法爲於濃色化劑3 0 ~ 7 0重量份 中加水製作全量1 〇 〇 〇重量份左右的軋染浴，並於此軋染 浴中將前述經染色之纖維製品予以浸染後，以軋液機以擰 擠率約8 0重量％予以擰擠，且擰擠布通常以9 〇〜丨丨〇七乾 燥約3分鐘後’通常以1 3 〇〜1 7 0。(：進行乾熱處理1〜3分鐘 爲佳。1338069 (1) Description of the Invention [Technical Field of the Invention] The present invention relates to a color concentrate for fibers and a method for coloring a fiber using the same. More specifically, the present invention relates to a coloring agent for a vermiculite particle and a polyether modified polyalkane which are treated with an amine group-containing decane coupling agent under acidic conditions, and a coloring method for a fiber product using the same. In the fiber for coloring agent of the invention, the dye is excellent in adhesion, and the color-changing substance has a dark color and excellent water absorbability. It does not impair the dyed fiber processed product such as the dyeing year and the water fastness. [Prior Art] A method of coloring a dyed fiber product has been proposed in the past 20 years. Various coloring agents and coloring methods have been proposed so far, and a practical technique has also been proposed. The concentrated color of the dyed fiber product is a fine-grained surface which imparts fine irregularities to the surface of the dyed fiber, and is darkened by light, refraction, etc., and a fine-grained, urethane-based resin has been proposed. An emulsifier, an acrylic resin, or the like. The thick coloring agent of the vermiculite microparticle system is described in, for example, Patent Document 1, Patent Document 3, Patent Document 4, Patent Document 5, and the like, as described in Patent Document 1, the solid color of the vermiculite microparticle system is basically It consists of an aqueous suspension containing vermiculite particles. In the special proposal 6, it is proposed to treat the suspension of vermiculite particles with an amine-based chelating agent, and attach it to the fiber and then treat it with low-temperature plasma. Before the good dyeing, the chemical technology reflected the petrochemical agent, but the chemical agent Liwenyuan even concentrated 5-(2) (2) 1338069 coloring agent, but the concentrated coloring agent was used for polyester fiber. The object is to cause a decrease in water absorption in the case of application to cellulose fibers. Further, the coloring agent described in Patent Document 7 and Patent Document 8 is a coloring agent for a polyester fiber treated with an epoxy compound in advance, and is a vermiculite treated with an amine group-containing decane coupling agent. A coloring agent composed of microparticles. However, in the case where the concentrated coloring agent is applied to the cellulose fiber, sufficient water absorption cannot be expected. Further, Patent Document 9 proposes a coloring agent composed of vermiculite fine particles and a polyoxyalkylene compound. However, this concentrated coloring agent is applied to polyester fibers and wool, but regarding the importance of water absorption. There are no records for the application of cellulose fibers. Further, Patent Document 10 proposes a coloring agent: a resin emulsifier which can be applied not only to polyester fibers but also to synthetic fibers or recycled fibers of polyamine, acrylic, human, or silk. However, this resin emulsifier is not expected to impart sufficient water absorbability by the structure of the resin, and has a problem in the stability of the treatment bath when it is treated with a coloring agent, and it is difficult to apply a simple treatment method such as an immersion treatment method. As described above, the previously proposed thick coloring agent is mainly used for water repellent fibers such as polyester fibers. Therefore, if it is concentrated in a relatively hydrophilic fiber dye such as wool or cellulose fiber, It gives a strong color effect to the fiber and at the same time imparts water repellency, which is more damaging to hydrophilicity or water absorption. Thus, a concentrated coloring agent which uses both water-repellent fibers and hydrophilic fibers and imparts sufficient effects has not been found so far. [Patent Document 1] Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. 5-6 - No. 5, No. 5, No. 5, No. 5, No. 5, No. 2, No. Japanese Patent Publication No. Hei 9-256280 (Patent Document 5) Japanese Patent Publication No. Hei 9-256280 (Patent Document 6) [Patent Document 7] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 1 1] Japanese Patent Laid-Open Publication No. Hei 9-3 774. SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] An object of the present invention is to develop stability in a color-developing process. It is excellent in color, and is excellent in the color effect of the dyed fiber product, and at the same time, it is excellent in water absorption in the fiber product obtained by the coloring treatment, and the coloring agent excellent in repeated washing resistance' and the use of such fiber A method of coloring a fiber product dyed by a coloring agent. (Means for Solving the Problem) The inventors of the present invention have made efforts to solve the above problems, and as a result, found that the lower part of the meteorite fine particle suspension treated with the amine-based decane coupling agent and the polyether are modified to form polyoxyl The mixture obtained by mixing the alkane can provide a strong color effect when the excellent color is 4 H~ the water is produced, and the excellent fiber (4) (4) 1338069 product 'and the mixture is excellent in stability in the color processing, and The completion of the present invention is achieved. That is, the present invention relates to (1) a color concentrate for fibers characterized by containing vermiculite particles treated with an amine group-containing decane coupling agent under acidic conditions and a polyether-modified oxirane; (2) The coloring agent for fibers according to (1), wherein the content of the polyether modified polyoxyalkylene is 5 to 20 by weight based on the fine particles of the vermiculite. (3) The coloring agent for fibers according to (1) or (2), which is a suspension of vermiculite microparticles under acidic conditions, treated with an amine-based decane coupling agent, and secondly mixed polyether modified (1) A method for coloring a dyed fiber, characterized in that the dyed fiber is a fiber according to any one of (1) to (3) above. (5) The coloring method of the fiber according to (4), wherein the dyed fiber is a cellulose fiber; (6) the coloring method of the fiber according to (4) The dyed fiber is a polyester fiber: (7) A fiber dyed product, which is obtained by the coloring method according to any one of the above (4) to (6). (Effects of the Invention) By treating the dyed fibrous product with the concentrated coloring agent of the present invention, it is possible to obtain excellent dyeing of color, water absorption, washing fastness, etc. 8-(5) (5) 1338069 Color processed material. Not only the polyester woven fabric which has been widely subjected to the coloring treatment, but also the cellulose fibers of the previously difficult dyed kapok, rayon, etc., can maintain the water absorbing property and obtain the effect of rich coloring. In particular, it is extremely effective when applied to dyeing of a dress or the like to a colored tinge. The coloring agent of the present invention is a blended fiber product of a water-repellent fiber such as a polyester fiber and a hydrophilic fiber such as kapok, rayon, wool, or the like, and provides a high-density color of two fibers which are hydrophilic and water-repellent and At the same time, the effect of the water absorption of these fibers is enhanced. As described above, the coloring agent of the present invention is an extremely expensive invention in the dyeing processing industry for the purpose of providing a dyed product of a fiber product having an extremely high price. (Best Mode for Carrying Out the Invention) The rich coloring agent of the present invention is preferably a vermiculite microparticle and a polyether modified polyoxyalkylene which are treated with an amine group-containing decane coupling agent under acidic conditions. The suspension of the microparticles is treated under acidic conditions with a decane coupling agent having an amine group, and the second polyether modified oxirane is obtained. In the present invention, the fine particles of the vermiculite used for the treatment with an amine group-containing decane coupling agent under acidic conditions are usually used in a particle size of 30 to 85 nm and can be used in the form of a suspension. The medium of the suspension is preferably water. The decane coupling agent having an amine group can be generally sold as α-aminopropyl triethoxy sane, hydrazine-(amino ether group)-aminopropyltrimethoxy decane. Compared with an alkane coupling agent (for example, ' κ ΒΕ 903 (manufactured by Shin-Etsu Chemical Co., Ltd.) ° (6) (6) 1338069, when treated with an amine-based decane coupling agent under acidic conditions, with respect to vermiculite particles The ratio of the amine-based decane coupling agent is usually 5 to 20% by weight, and if the ratio of the decane coupling agent having an amine group is less than this range, the washing fastness of the obtained concentrated coloring agent is lowered, and conversely, If the use ratio is larger than this range, the stability of the coloring agent may be lowered. When the vermiculite particles are treated under acidic conditions with an amine-based decane coupling agent, the acidic substances used may be inorganic acids or organic acids. Preferably, it is a monovalent or divalent organic acid such as formic acid, acetic acid, glycolic acid, succinic acid or maleic acid, and the pH when the treatment is under acidic conditions is 6 or less, especially if it is pH 3 ~5, the stability of the coloring agent is improved over time, so Preferably, the concentration of the vermiculite particles in the suspension of the vermiculite particles in the suspension under acidic conditions is usually 5 to 20% of the corona. If the concentration is lower than the range, the treatment time becomes longer, and if the concentration is higher than the range, the concentration of the solution is feared. The stability is lowered. The mixing order of the respective particles when the vermiculite particles are treated under the acidic condition with the amine group-containing decane coupling agent is not particularly limited, but decane is added to the suspension of the fine particles of the fine particles prepared by the acidic conditions as described above. An aqueous suspension or an alcohol solution of the coupling agent is preferred. After mixing, it is usually mixed at 5 to 30 t, preferably 15 to 25 ° C, and preferably matured to stability. The polyether modified polyoxyalkylene used is composed of an alkylene group-containing polyoxyalkylene oxide, an allyl alcohol-added ethylene oxide, propylene oxide, or a random or segmented copolymer thereof. Polyether. It can be used by a generally sold person (for example, SII 190, manufactured by Toray Corning Co., Ltd.). By mixing a hydrophilic polyether modified polyoxyalkylene, the resulting concentrated coloring agent can be greatly improved. Water absorption and repeated washing resistance Excellent in nature. Polyether-10-(7) (7)1338069 The modified polyoxane is used in a proportion of 3 to 30% by weight, and 5 to 20% by weight, relative to the treated vermiculite particles. Preferably, the method of mixing the polyether modified polyoxane with a suspension of the fine particles of the vermiculite treated with the amine-based decane coupling agent under acidic conditions is not particularly limited, but in order to obtain a more uniform dispersion state, It is preferred that the polyether modified polyoxyalkylene is dissolved in an alcohol or the like and mixed. In the present invention, if necessary, an additive known per se such as a surfactant or a softening agent may be used to prepare the coloring agent of the present invention, or The addition of the fiber product dyed by the coloring agent of the present invention may be carried out. Next, a coloring treatment method for the fiber product dyed using the coloring agent of the present invention will be described. The fibers in the fiber product dyed by the rich coloring agent to which the present invention is applied may be natural or regenerated such as kapok, hemp, cuprammonium fiber (rayon), viscose rayon, polynosic fiber or the like. Cellulose fiber, protein fiber such as wool or sputum, semi-synthetic fiber such as acetate fiber, polyester fiber (including CDP fiber (cationic dyeable polyester fiber)) polyacrylonitrile fiber, polyamide fiber such as nylon, etc. A blended fiber composed of a synthetic fiber or the like and two or more kinds of fibers of the fibers. Among the preferred fibers are cellulosic fibers, polyester fibers, protein fibers, polyamidoamines, and blended fibers of such fibers with other fibers. The shape of the dyed fibrous product may be any form such as woven fabric, knitted fabric, fibrous or the like. The coloring method of the present invention can be carried out according to a usual method such as a pad dyeing treatment method or a dipping method. -11 - (8) (8) 1338069 In the thickening method of the pad dyeing method, water is added to the thick coloring agent from 30 to 70 parts by weight to prepare a full-calendering bath of about 1 part by weight. The dyed fiber product is impregnated in the padding bath, and then squeezed by a rolling machine at a screwing rate of about 80% by weight, and the twisted cloth is usually dried at 9 〇 丨丨〇 丨丨〇 7 After a minute 'usually 1 3 〇~1 7 0. (: Dry heat treatment for 1 to 3 minutes is preferred.
以浸漬法的濃色化方法爲相對於該經染色之纖維製品 100重量份’本發明之濃色化劑通常爲使用2〜20重量份' 較佳爲5~10重量份，且以水做爲介質，通常以30~70°C 通常處理10〜60分鐘即可。浴比通常爲調整至1 : 20〜50 〇 於本發明之濃色化法中’相對於本發明之濃色化劑施 以染色之纖維製品1 0 0重量份，濃色化劑以賦予〇 . 5〜9 0 重量份、較佳爲5〜30重量份、更佳爲3〜6重量份處理爲 佳。賦予量爲經由測定實施濃色化法前和後之各乾燥重量 而決定。 經染色之前述纖維製品爲根據本身公知的染色方法將 前述纖維製品予以染色則可調製，以下例示性敘述關於取 得經染色之纖維素纖維及聚酯纖維。 纖維素纖維的染色方法，可根據以反應染料之染色方 法，直接以染料之染色方法等之公知方法進行。以反應染 料之染色方法中，於染色步驟終了後，水洗、熱水洗後， 以含有市售的皂洗劑通常〇· 1〜5克/升的皂洗浴進行洗淨即 可。以反應染料之染色方法例如於木棉等之纖維素纖維的 -12- 1338069 Ο) 染色中，於染浴中加入反應染料，且將公知的無機中性鹽 ，例如，無水芒硝 '食鹽等與酸結合劑，例如，碳酸鈉、 重碳酸鈉、苛性鹼、第三磷酸鈉等單獨或倂用進行染色。 經染色的聚酯纖維製品爲例如經由將聚酯纖維布帛， 於調整至p H4.5之含有分散染料的水性介質中浸漬，且於 加壓下進行1 3 0 °C，6 0分鐘染色則可取得。染色終了後， 水洗、熱水洗後，於含有亞硫酸氫鹽2克/升和苛性蘇打2 克/升之鹼還原浴中以約8 0 °C進行洗淨，令染色步驟終了 。經染色之陽離子可染型聚酯纖維製品爲將陽離子可染型 聚酯纖維等，在調整至pH4.5之含有指定量陽離子染料的 水性介質中浸漬，且於加壓下進行1 2 (TC，3 0分鐘染色。 本發明之濃色化劑爲對於經染色加工的纖維，顯示胃 的濃色化效果，且對於斥水性纖維賦予高吸水性且同時胃 於纖維素纖維等之較親水性的纖維具有不損害吸水性@ # 微，更且不會損害所得染色加工物中所使用之各染料固有 的耐光性、洗滌性、水堅牢度、摩擦堅牢度並爲良好。 【實施方式】 以下，根據實施例、參考例及試驗例更加詳細說明本 發明，但本發明不被限定於此。實施例中之％及份爲重量 基準。 參考例1 試驗布之製作 -13- (10) (10)1338069 於]克反應染料（C . I · R e a c t i V e B丨a c k 5 )、無水芒硝 1 6份、水1 8 0份所調製之染浴中投入纖維素纖維（木、棉、） 纖維1 〇份，並升溫至6 0，以此溫度下維持1 〇分鐘後，加 入2 0 %蘇打灰溶液2 0份，進行6 0分鐘染色，其後，將所 得之染布水洗並進行2 0分鐘煮沸皂浴、水洗、乾燥取得 木棉染色物之試驗布。 實施例1 濃色化劑之調製及經染色之纖維素纖維製品的濃色化 處理 於粒徑40〜5 Onm之矽石微粒子的20%水懸浮液中，加 入甲酸及r-胺丙基三乙氧基砂院之水溶液並於pH4之酸 性條件下以25 °C處理後，混合聚醚改質聚矽氧烷（SII 190東雷- Dowcorning Silicone (股）製），取得本發明之 濃色化劑。此濃色化劑爲具有2 0 %矽石微粒子水懸浮液 4 1 % '甲酸1 . 9 %、7 -胺丙基三乙氧基矽烷0.6 °/〇、聚醚改 質聚矽氧烷1 .5%及水5 5.0%的組成。 於此濃色化劑50份中加水製作全量1 000份的軋染浴 。於此軋染浴中將前述所得之經染色的參考例1試驗布予 以軋染後，並以軋液機以擰擠率80%予以擰擠。將擰擠之 布以100°C乾燥3分鐘後，以l5〇aC進行乾熱處理3分鐘 ，取得經濃色化處理的染色纖維素纖維製品。 實施例2 -14· (11) (11)1338069 經染色之纖維素纖維製品以浸染處理法的濃色化處理 於實施例1所得之濃色化劑1 0份中加水9 0份作成處 理浴，於其中投入參考例1之試驗布1 0 0份，並以6 0 °c進 行3 0分鐘處理，取得經濃色化處理的染色纖維素纖維製 品。 比較例1 使用Sunotec OL (日產化學公司製）40份做爲矽石 微粒子、KBE903 (信越化學工業公司製）0.8份做爲具有 胺基的矽烷偶合劑，並以甲酸調整至PH4處理矽石微粒子 ，取得不含有聚醚改質聚矽氧烷之比較用的濃色化劑A。 使用此濃色化劑，同實施例〗處理並以軋染處理法進 行濃色化處理，取得經濃色化處理之比較用的纖維素纖維 製品。 比較例2 除了使用比較例1所製作之比較用的濃色化劑以外， 同實施例2處理並以浸染處理法進行濃色化處理，取得比 較用之纖維素纖維製品。 比較例3 使用 Sunotec OL (日產化學公司製）40份做爲矽石 微粒子、KBE 903 (信越化學工業公司製）〇.8份做爲具有 胺基之矽烷偶合劑，並以甲酸調整至PH4處理矽石微粒子 -15- (12) (12)1338069 後’加入P 〇丨Ο η M F - ] 8 (信越化學工業公司製，環氧改質 聚矽氧院）2份取得比較用的濃色化劑β。 除了使用此濃色化劑Β以外，同實施例1處理並以乳 染處理法進行濃色化處理’取得比較用的纖維素纖維製品 比較例4 除了使用比較例3所製作之比較用的濃色化劑β以外 ，同實施例2處理並以浸染處理法進行濃色化處理，取得 比較用的織維素纖維製品。 比較例5 對於參考例1之染色纖維素纖維製品的試驗布，未施 以濃色化處理，取得比較用的纖維素纖維製品》 試驗例1 使用實施例1及2所得之經濃色化處理的染色纖維素 纖維製品，比較例1至4所得之經濃色化處理的染色纖維 素纖維製品，及比較例5之未經濃色化處理的染色纖維素 纖維製品，根據下述方法，進行濃色化度、吸水性、耐光 堅牢度、汗耐光堅牢度 '洗滌堅牢度、氯堅牢度、氮氣（ NOx )堅牢度之各試驗。 (a )濃色化度之測定 -16 - (13) (13)1338069 試驗布之濃色化度爲使用根據反射率所計算之Qtotal 値以未處理布視爲1 00%表示濃度。所謂Qtota!値爲考慮 視感特性之表面濃度的代用値（K/S値的積分値）。 (b )吸水性之判定 於試驗布上滴下水滴（0.5毫升），測定水滴的吸水 時間，並根據下列基準判定。 〇：立即吸收。 △ : 1〜6 0秒鐘吸收。 X : 1分鐘以上未吸收。 (c )耐光堅牢度之判定 根據耐光試驗法（Π S L 0 8 4 2碳照射2 0、4 0小時）， 以：(I S B 1 u e S c a 1 e判定變褪色。 (d)汗耐光（Alkali JIS 5倍法）堅牢度之判定 根據耐光試驗法（JIS L08 8 8碳照射10小時），以 •HS變褪色用Gray Scale判定變褪色。 (e )洗滌堅牢度之判定 根據洗漉試驗法（JIS L0844 A-2法），以JIS污染用 Gray Scale判定附上絹（白布）的污染。 (f )氯堅牢度之判定 根據氯堅牢度（〗IS L0884 JIS強），以J1S變褪色用 -17- (14) (14)1338069 G r a y S c a 1 e判定變極色。 (g )氮氣（NOx )堅牢度之判定 根據氯試驗法（JIS L0 8 5 5 (單位），以JIS變褪色用 Gray Scale判定變植色。 根據上述（a )至（g )之各判定所得之結果示於表1 及表2。 表 1 試驗項目 實施例1 比較例1 比較例3 比較例5 濃色化度 1 5 5 115 116 1 00 吸水性 〇 X X 〇 耐光堅牢度 4-5 4-5 4-5 4-5 汗耐光堅牢度 4 4 4 4 洗滌堅牢度 4-5 4-5 4-5 4-5 氯堅牢度 3-4 3-4 3-4 3-4 氮氣堅牢度 4 4 4 4 -18- (15)1338069 表 2 試驗項目 實施例2 比較例2 比較例4 比較例5 濃色化度 13 5 1 20 116 1 00 吸水性 〇 X X 〇 耐光堅牢度 4-5 4-5 4-5 4-5 汗耐光堅牢度 4 4 4 4 洗滌堅牢度 4-5 4-5 4-5 4-5 氯堅牢度 3-4 3-4 3-4 3-4 氮氣堅牢度 4 4 4 4 由表1可知，實施例1之經濃色化處理的染色纖維素 纖維製品爲較比較例1 ' 3、5之濃色化度高，且吸水性爲 與未進行濃色化處理之比較例5同水準，比使用比較用之 濃色化劑A及同B的比較例1及3更高。關於耐光堅牢度 、汗耐光堅牢度、洗滌堅牢度、氯堅牢度、氮氣耐性、與 未進行濃色化處理之比較例5同水準，可確認經由濃色處 理並未令其耐性降低。關於表2亦進行與表1相同趣旨之 考察。 參考例2 聚酯試驗布之作成 將分散染料（Caya丨on Po丨yester B丨ack ECX 300;日 本化藥公司製）相對於斥水性纖維布帛使用5 %，且以浴 比1 : 20，pH4.5進行1 30°C ’ 60分鐘之染色，並以常法 -19- (16) (16)1338069 進行還原洗淨’取得經染色的聚酯纖維製品。 實施例3 經染色之聚酯纖維製品的濃色化處理 於實施例1所得之濃色化劑5份中加水2000份，其 次加入參考例2所染色之聚酯纖維製品〗00份（浴比！ ·· 2 0 )，並於4 0 °C下處理3 0分鐘’取得經濃色化處理的染 色聚酯纖維製品。 比較例6 使用比較例1之濃色化劑A，同實施例3處理予以濃 色化處理’取得經濃色化處理的染色聚酯纖維製品。 比較例7 使用比較例3之濃色化劑B，同實施例3處理予以濃 色化處理’取得經濃色化處理的染色聚酯纖維製品。 比較例8 將分散染料（Cayalon Dolyester Black ECX 300;日 本化藥公司製）相對於聚酯纖維布帛使用5 %且以公知公 用之方法予以染色加工，未進行以濃色化劑的處理，作成 經染色的聚酯纖維製品。 試驗例2 -20- (17) (17)1338069 對於實施例3之經濃色化處理的染色纖維素織維製品 、比較例6及7所得之經濃色化處理的染色纖維素纖維製 品，及比較例8之未經濃色化處理的染色纖維素纖維製品 ，根據下述記載之試驗方法’評價濃色化度、吸水性、耐 光堅牢度、汗耐光堅牢度、洗滌堅牢度、水堅牢度、摩擦 堅牢度等。 (1 )濃色化度之判定 試驗布之反射率（L値）以濃度表示。數値愈小，則 濃度愈高，具有濃色效果。 (2 )吸水性之判定 於試驗布上滴下水滴（〇 · 5毫升），判定水滴的吸水 時間，並根據下列基準判定。 〇：立即吸收。 △ : 1〜60秒鐘吸收。 X : 1分鐘以上未吸收。 (3 )耐光堅牢度之判定 根據耐光試驗法UIS L0 84 2碳照射20、40小時）， 以JIS Blue Scale判定變褪色。 (4 )洗滌堅牢度之判定 根據洗滌試驗法U I S L 0 8 4 4 A - 2法），以J I S污染用 G r a y S c a 1 e判定附上棉白布的污染。 -21 - (18) (18)1338069 (5 )水堅牢度之判定 根據水試驗法（J I S L 0 8 4 6 )，以 J I S污染用 G r a y Scale判定附上棉白布的污染。 (6 )摩擦堅牢度之判定 根據水試驗法（JIS L0 8 49 )，以 JIS污染用 Gray Scale判定附上棉白布的污染。以乾燥狀態和濕潤狀態之 兩者或任一者適當進行。 根據上述（】）至（6 )之各判定所得之結果示於表3 表 3 試驗項目 實施例3 比較例6 比較例7 比較例8 濃色化度 8.5 10.6 10.9 12.3 吸水性 〇 X X 〇 耐光堅牢度 4-5 4-5 4-5 4-5 洗滌堅牢度 4 4 4 4 水堅牢度 4-S 4-5 4-5 4-5 摩擦堅牢度 (乾燥） 4 4 4 4 如表3之結果所判定般，實施例3所得之經濃色化處 理的染色聚酯纖維製品，較比較例6及比較例7之經濃色 -22 - (19) (19)1338069 化處理的染色聚酯纖維製品無撥水性且爲不損害聚酯系纖 維之特性的品質。又，濃色效果亦優良。更且，實施例3 所得之經濃色化處理的染色聚酯纖維製品爲在耐光堅丰度 '洗滌堅牢度、水堅牢度、摩擦堅牢度對於所使用之染料 的固有特性不會造成任何不良影響。 參考例3 經染色之陽離子可染型聚酯試驗布的作成 將陽離子染料（Kayacryl Black BS-ED;日本化藥公 司製）相對於陽離子可染型聚酯纖維（CDP )布帛使用8% 並以120 °C進行60分鐘染色，作成試驗布。 實施例4 經染色之C D P纖維以浸染處理法的濃色化處理 將參考例3之經染色CDP纖維製品的試驗布1 〇〇份 加至水2 0 0 0份中（浴比1 : 2 0 )，其次加入實施例1之濃 色化劑5份，並於40°C下處理3 0分鐘，取得經濃色化處 理的C D P纖維製品。 比較例9 使用比較例1之濃色化劑A，同實施例4處理進行濃 色化處理，取得經濃色化處理的CDP纖維製品。 比較例1 0 •23- (20)1338069 使用比較例3之濃色化劑B，同實施例4處理進行@ 色化處理，取得經濃色化處理的CDP纖維製品。 比較例1 1The coloring method by the dipping method is 100 parts by weight relative to the dyed fiber product. The thick coloring agent of the present invention is usually used in an amount of 2 to 20 parts by weight, preferably 5 to 10 parts by weight, and is made of water. For the medium, it is usually treated at 30~70 °C for 10~60 minutes. The bath ratio is usually adjusted to 1: 20 to 50. In the coloring method of the present invention, '100 parts by weight of the dyed fibrous product is applied to the concentrated coloring agent of the present invention, and the coloring agent is used to impart hydrazine. 5 to 90 parts by weight, preferably 5 to 30 parts by weight, more preferably 3 to 6 parts by weight, are preferred. The amount of application is determined by measuring the respective dry weights before and after the coloring method. The dyed fibrous product is prepared by dyeing the above-mentioned fibrous product according to a dyeing method known per se, and the following description is directed to obtaining the dyed cellulose fiber and polyester fiber. The method of dyeing the cellulose fibers can be carried out by a known method such as dyeing by a reactive dye, directly by a dyeing method of a dye. In the dyeing method of the reaction dye, after the dyeing step is finished, after washing with water and hot water, it may be washed with a soap bath containing a commercially available soaping agent of usually 1 to 5 g/liter. In the dyeing method of a reactive dye such as -12-1338069 纤维素 of cellulose fibers of kapok or the like, a reactive dye is added to the dyebath, and a known inorganic neutral salt such as anhydrous sodium salt, salt and the like are mixed with an acid. The binding agent, for example, sodium carbonate, sodium bicarbonate, caustic, sodium triphosphate or the like is dyed alone or in combination. The dyed polyester fiber product is immersed, for example, by a polyester fiber cloth, in an aqueous medium containing a disperse dye adjusted to p H4.5, and subjected to dyeing at 130 ° C for 60 minutes. Available. After the dyeing is finished, after washing with water and hot water, it is washed at about 80 ° C in an alkali reduction bath containing 2 g/liter of bisulfite and 2 g/liter of caustic soda to complete the dyeing step. The dyed cationic dyeable polyester fiber product is prepared by immersing a cationic dyeable polyester fiber or the like in an aqueous medium containing a specified amount of cationic dye adjusted to pH 4.5, and performing 1 2 (TC) under pressure. The coloring agent of the present invention exhibits a rich coloring effect on the dyed fiber, and imparts high water absorption to the water repellent fiber and at the same time, hydrophilicity of the stomach fiber or the like. The fiber is excellent in light resistance, washing property, water fastness, and friction fastness inherent to each dye used in the obtained dyed product without impairing the water absorption@# micro. The present invention will be described in more detail based on examples, reference examples and test examples, but the present invention is not limited thereto. The % and parts in the examples are based on the weight. Reference Example 1 Production of test cloth-13- (10) ( 10) 1338069 Into the dyeing dye (C. I · R eacti V e B丨ack 5 ), 16 parts of anhydrous thenardite, and 180 parts of water, the dyeing bath is filled with cellulose fiber (wood, cotton,) Fiber 1 〇, and warmed up to 60, after maintaining at this temperature for 1 〇 minutes, add 20% of 20% soda ash solution, and dye for 60 minutes. Thereafter, the obtained dyed cloth is washed with water and boiled for 20 minutes, bathed with water, and washed with water. Drying to obtain a test cloth of kapok dyed matter. Example 1 Preparation of concentrated coloring agent and coloring treatment of dyed cellulose fiber product in a 20% aqueous suspension of vermiculite particles having a particle size of 40 to 5 Onm, Adding an aqueous solution of formic acid and r-aminopropyltriethoxylate and treating it at 25 °C under acidic conditions of pH 4, mixing polyether modified polyoxyalkylene (SII 190 Donglei - Dowcorning Silicone (share) The coloring agent of the present invention is obtained. The concentrated coloring agent is an aqueous suspension of 20% vermiculite microparticles, 4 1% 'formic acid, 0.9%, 7-aminopropyltriethoxydecane 0.6 ° /〇, polyether modified polyoxane 1.5% and water 5 5.0% composition. Add 50 parts of this concentrated coloring agent to make a full amount of 1 000 padding bath. In this padding bath The dyed reference test cloth 1 obtained in the foregoing was pad-dyed, and was screwed at a screwing rate of 80% with a rolling mill. The cloth to be squeezed was 100 ° C. After drying for 3 minutes, dry heat treatment was carried out for 1 minute at 15 ° C to obtain a dyed cellulose fiber product which was subjected to rich coloration. Example 2 -14· (11) (11) 1338069 Dyeing of cellulose fiber products by dyeing The coloring treatment of the treatment method was carried out by adding 90 parts of water to 10 parts of the coloring agent obtained in Example 1 to prepare a treatment bath, and 100 parts of the test cloth of Reference Example 1 was put therein, and was carried out at 60 ° C. After 30 minutes of treatment, the dyed cellulose fiber product obtained by the coloration treatment was obtained. Comparative Example 1 40 parts of Sunotec OL (manufactured by Nissan Chemical Co., Ltd.) were used as the gangue fine particles, and KBE903 (manufactured by Shin-Etsu Chemical Co., Ltd.) was used as a decane coupling agent having an amine group, and the formic acid was adjusted to pH 4 to treat the gangue fine particles. A coloring agent A for comparison which does not contain a polyether modified polyoxyalkylene is obtained. Using this concentrated coloring agent, it was treated in the same manner as in the Example and subjected to a coloring treatment by a pad dyeing method to obtain a cellulose fiber product for comparison which was subjected to a coloring treatment. Comparative Example 2 In the same manner as in Example 2 except that the coloring agent for comparison prepared in Comparative Example 1 was used, the coloring treatment was carried out by the dip dyeing treatment to obtain a cellulose fiber product for comparison. Comparative Example 3 40 parts of Sunotec OL (manufactured by Nissan Chemical Co., Ltd.) were used as the gangue fine particles, and KBE 903 (manufactured by Shin-Etsu Chemical Co., Ltd.) was used as an amine-based decane coupling agent, and adjusted to pH 4 with formic acid. Vermiculite fine particles -15- (12) (12) 1338069 After 'P P 〇丨Ο η MF - 8 (Xin Yue Chemical Industry Co., Ltd., epoxy modified polyoxan) 2 copies for comparison Agent β. In the same manner as in Example 1, except that the coloring agent was used, the coloring treatment was carried out by the emulsion dyeing method. [Comparative Example 4 of Comparative Cellulose Fiber Products] In addition to the comparative use of Comparative Example 3, In addition to the coloring agent β, it was treated in the same manner as in Example 2, and subjected to a coloring treatment by a dip dyeing treatment method to obtain a comparative weaving fiber product. Comparative Example 5 The test cloth of the dyed cellulose fiber product of Reference Example 1 was subjected to a coloring treatment to obtain a cellulose fiber product for comparison. Test Example 1 The coloring treatment obtained by using Examples 1 and 2 was carried out. The dyed cellulose fiber product, the dyed cellulose fiber product obtained by the coloring treatment of Comparative Examples 1 to 4, and the dyed cellulose fiber product of Comparative Example 5 which was not subjected to the coloration treatment were subjected to the following methods. Various tests for coloration, water absorption, light fastness, sweat fastness, 'fastness to wash, chlorine fastness, and nitrogen (NOx) fastness. (a) Determination of richness of color -16 - (13) (13) 1338069 The degree of coloration of the test cloth was expressed by using Qtotal 根据 calculated from the reflectance, and the untreated cloth was regarded as 100%. The so-called Qtota! is a substitute for the surface concentration of the visual characteristics (K/S値 integral 値). (b) Determination of water absorption Water droplets (0.5 ml) were dropped on the test cloth, and the water absorption time of the water droplets was measured and judged based on the following criteria. 〇: Absorb immediately. △ : 1 to 6 seconds absorption. X : Not absorbed for more than 1 minute. (c) Determination of light fastness according to the light resistance test method (Π SL 0 8 4 2 carbon irradiation for 20, 40 hours), with: (ISB 1 ue S ca 1 e judged to fade. (d) Khan light (Alkali JIS 5x method) The determination of the fastness is judged by the light resistance test method (JIS L08 8 8 carbon irradiation for 10 hours), and the fading of the HS is determined by Gray Scale. (e) The determination of the fastness of washing is based on the washing test method ( JIS L0844 A-2 method), the JIS contamination is determined by Gray Scale, and the contamination of the enamel (white cloth) is determined. (f) The determination of the fastness of chlorine is based on the fastness of chlorine (〗 IS L0884 JIS), which is faded with J1S - 17- (14) (14) 1338069 G ray S ca 1 e judges the color change. (g) Determination of the fastness of nitrogen (NOx) according to the chlorine test method (JIS L0 8 5 5 (unit), used for JIS fading Gray Scale determines the coloration. The results obtained by the respective judgments of (a) to (g) above are shown in Table 1 and Table 2. Table 1 Test item Example 1 Comparative Example 1 Comparative Example 3 Comparative Example 5 Thickness degree 1 5 5 115 116 1 00 Water absorption 〇 XX 〇 Light fastness 4-5 4-5 4-5 4-5 Sweat fastness 4 4 4 4 Wash fast 4-5 4-5 4-5 4-5 Chlorine fastness 3-4 3-4 3-4 3-4 Nitrogen fastness 4 4 4 4 -18- (15) 1338069 Table 2 Test item Example 2 Comparative example 2 Comparative Example 4 Comparative Example 5 Concentration degree 13 5 1 20 116 1 00 Water absorption 〇 XX 〇 Light fastness 4-5 4-5 4-5 4-5 Sweat fastness 4 4 4 4 Wash fastness 4 -5 4-5 4-5 4-5 Chlorine fastness 3-4 3-4 3-4 3-4 Nitrogen fastness 4 4 4 4 As shown in Table 1, the colored dyed fiber of Example 1 was obtained. The plain fiber product has a higher degree of coloration than the comparative example 1 '3, 5, and the water absorption is the same level as that of the comparative example 5 which is not subjected to the coloring treatment, and the thicker coloring agent A and the same B than the comparative use. Comparative Examples 1 and 3 were higher. With respect to light fastness, sweat fastness, washing fastness, chlorine fastness, nitrogen resistance, and the same level as Comparative Example 5 in which no coloring treatment was performed, it was confirmed that the color treatment was performed by dark color. The resistance was not lowered. Table 2 also carried out the same considerations as in Table 1. Reference Example 2 Preparation of polyester test cloth Disperse dye (Caya丨on Po丨yester B丨ack ECX 300; manufactured by Nippon Kayaku Co., Ltd. Relative to repulsion The water-based fiber cloth is 5% dyed and dyed at a bath ratio of 1:20, pH 4.5 at 1 30 ° C for 60 minutes, and washed with a conventional method of -19-(16) (16) 1338069. Dyed polyester fiber products. Example 3 The coloring treatment of the dyed polyester fiber product was carried out by adding 2000 parts of water to 5 parts of the coloring agent obtained in Example 1, and then adding 00 parts of the polyester fiber product dyed in Reference Example 2 (bath ratio) ··· 2 0 ), and treated at 40 ° C for 30 minutes to obtain a dyed polyester fiber product that has been subjected to intense coloration. Comparative Example 6 Using the rich coloring agent A of Comparative Example 1, the coloring treatment was carried out in the same manner as in Example 3, and the dyed polyester fiber product subjected to the coloring treatment was obtained. Comparative Example 7 Using the rich coloring agent B of Comparative Example 3, the coloring treatment was carried out in the same manner as in Example 3, and the dyed polyester fiber product subjected to the coloring treatment was obtained. Comparative Example 8 A disperse dye (Cayalon Dolyester Black ECX 300; manufactured by Nippon Kayaku Co., Ltd.) was dyed with 5% by weight using a polyester fiber cloth, and was processed by a known method. Dyed polyester fiber products. Test Example 2 -20-(17) (17) 1338069 For the dyed cellulose-woven fabric of Example 3, the dyed cellulose fiber product obtained by the coloring treatment of Comparative Examples 6 and 7, And the dyed cellulose fiber product of Comparative Example 8 which was not subjected to the coloration treatment, evaluated for the degree of coloration, water absorption, light fastness, sweat fastness, washing fastness, and water fastness according to the test method described below. Degree, friction fastness, etc. (1) Determination of rich coloring degree The reflectance (L値) of the test cloth is expressed by concentration. The smaller the number, the higher the concentration and the richer color effect. (2) Determination of water absorption Drops of water (〇 · 5 ml) were dropped on the test cloth, and the water absorption time of the water droplets was judged and judged based on the following criteria. 〇: Absorb immediately. △ : 1 to 60 seconds of absorption. X : Not absorbed for more than 1 minute. (3) Determination of light fastness According to the light resistance test method UIS L0 84 2 carbon irradiation for 20 or 40 hours), it was judged to be faded by JIS Blue Scale. (4) Determination of the fastness of washing According to the washing test method U I S L 0 8 4 4 A - 2), the pollution of the cotton cloth was judged by the pollution of J I S with G r a y S c a 1 e . -21 - (18) (18)1338069 (5) Determination of water fastness According to the water test method (J I S L 0 8 4 6), the contamination of the cotton cloth is judged by the G r a y Scale for J I S pollution. (6) Determination of the rubbing fastness According to the water test method (JIS L0 8 49), the contamination of the cotton cloth was judged by Gray Scale using JIS contamination. It is suitably carried out in either or both of a dry state and a wet state. The results obtained from the respective judgments of ()) to (6) are shown in Table 3. Table 3 Test item Example 3 Comparative Example 6 Comparative Example 7 Comparative Example 8 Concentration degree 8.5 10.6 10.9 12.3 Water absorption 〇 〇 〇 Light fast Degree 4-5 4-5 4-5 4-5 Wash fastness 4 4 4 4 Water fastness 4-S 4-5 4-5 4-5 Friction fastness (dry) 4 4 4 4 As shown in Table 3 As judged, the dyed polyester fiber product obtained by the coloring treatment obtained in Example 3 was dyed with the dyed polyester fiber of Comparative Example 6 and Comparative Example 7 by the concentrated color -22 - (19) (19) 1338069. The product has no water repellency and is of a quality that does not impair the properties of the polyester fiber. Also, the rich color effect is also excellent. Moreover, the dyed polyester fiber product obtained by the coloring treatment of Example 3 is such that the light fastness abundance 'wash fastness, water fastness, and friction fastness do not cause any defects to the inherent characteristics of the dye used. influences. Reference Example 3 Preparation of dyed cationic dyeable polyester test cloth cation dye (Kayacryl Black BS-ED; manufactured by Nippon Kayaku Co., Ltd.) was used with respect to the cationic dyeable polyester fiber (CDP) fabric by 8% and Dyeing was carried out at 120 ° C for 60 minutes to prepare a test cloth. Example 4 Dyeing treatment of dyed CDP fibers by dip dyeing treatment The test cloth 1 portion of the dyed CDP fiber product of Reference Example 3 was added to 200 parts of water (bath ratio 1: 2 0) Then, 5 parts of the coloring agent of Example 1 was added, and it was treated at 40 ° C for 30 minutes to obtain a CDP fiber product which was subjected to rich coloring treatment. Comparative Example 9 Using the rich coloring agent A of Comparative Example 1, the coloring treatment was carried out in the same manner as in Example 4 to obtain a CDP fiber product subjected to a coloration treatment. Comparative Example 1 0 • 23- (20) 1338069 Using the rich coloring agent B of Comparative Example 3, the color treatment was carried out in the same manner as in Example 4 to obtain a CDP fiber product subjected to a coloration treatment. Comparative Example 1 1
將陽離子染料（Kayacrgl Black BS-ED;日本化學公 司製）相對於CDP纖維布帛使用8%並以公知公用之方法 予以染色加工，且未以濃色化劑進行處理，作成經染色的 CDP纖維製品。 試驗例3 對於實施例4之經濃色化處理的CDP纖維製品、比 較例9及1 〇之經濃色處理的CDP纖維製品 '及比較例1 1 之未經濃色化處理的C D P纖維製品，根據試驗例2同樣 之試驗方法、評價濃色化度、吸水性、耐光堅牢度、洗滌 堅牢度、水堅牢度、摩擦堅牢度等。所得之各評價結果示 於表4。 -24· (21)1338069 表 4 試驗項目 實施例4 比較例9 比較例1 0 ------ 比較例1 1 濃色化度 10.2 11.9 11.5 13.4 吸水性 〇 X X 〇 耐光堅牢度 5以上 5以上 5以上 5以上 洗滌堅牢度 4-5 4-5 4-5 4-5 水堅牢度 4-5 4-5 4-5 4-5 摩擦 (乾燥） 4 4-5 4-5 4-5 摩擦 (濕潤） 4-5 4-5 4-5 4-5 如表4之結果所判定般’實施例4之方法所處理的 CDP纖維製品爲較比較例9〜1 1所得之CDP纖維製品，濃 色效果優良，吸水性亦大，且對於其他CDP織維製品所 使用之染料的固有特性不會造成損傷。 參考例4 經染色之尼龍纖維製品及羊毛纖維製品（試驗布）的 作成 將酸性染料（Kayacalan Black 2RL;日本化藥公司製 )相對於尼龍纖維布帛及羊毛纖維布帛分別使用3.5%， 並以p Η 5.5 ’溶比1 : 2 0，染色溫度1 〇 〇 t，染色時間6 〇 分鐘之條件染色，進行水洗，熱水洗，分別取得經染色的 -25- (22) (22)1338069 尼龍纖維製品及羊毛纖維製品。 實施例5 經染色加工之尼龍纖維製品以浸染處理法的濃色化處 理 於水2 0 0 0份中，投入參考例4所得之經染色的尼龍 纖維製品1 0 0份（浴比1 : 2 0 ) ’其次加入實施例1之濃 色化劑1 〇份’並於4 0 °C下處理3 0分鐘，取得經濃色化處 理的尼龍纖維製品。 比較例1 3 使用比較例1之濃色化劑A，同實施例5處理進行濃 色化處理’取得經濃色化處理的尼龍纖維製品。 比較例1 4 使用比較例3之濃色化劑B，同實施例5處理進行濃 色化處理’取得經濃色化處理的尼龍纖維製品。 比較例1 5 將酸性染料（Kayacalan Black 2RL;曰本化學公司製 )相對於參考例4所得之尼龍纖維製品使用3.5%並以公 知公用之方法予以染色加工，且未以濃色化劑進行處理’ 作成經染色的尼龍纖維製品。 -26- (23)1338069 試驗例4 對於實施例5之經濃色化處理的尼龍纖維製品、比較 例1 3及1 4之經濃色處理的尼龍纖維製品、及比較例i 5 之未經濃色化處理的尼龍織維製品，根據試驗例2同樣之 試驗方法、評價濃色化度、吸水性、耐光堅牢度、洗滌堅 牢度 '水堅牢度' 摩擦堅牢度等。所得之各評價結果示於 表5。 表 5 試驗項目 實施例5 比較例1 3 比較例1 4 比較例1 5 濃色化度 9.5 11.0 10.9 12.7 吸水性 〇 X X △〜〇 耐光堅牢度 5以上 5以上 5以上 5以上 洗滌堅牢度 3-4 3-4 3-4 3-4 水堅牢度 4-5 4-5 4-5 4-5 摩擦堅牢度 5 5 5 5 (乾燥） 摩擦堅牢度 4-5 4-5 4-5 4-5 (濕潤） 如表5之結果所判定般，實施例5所得之經濃色化處 理的染色尼龍纖維製品，較比較例1 3至1 5的染色尼龍纖 維製品’濃色效果、吸水性優良，且亦不損害尼龍纖維染 色物固有的特性。 -27- (24) (24)1338069 實施例1 6 經染色加工之羊毛纖維製品以浸染處理法的濃色化處 使用參考例4所得之經染色的羊毛纖維製品，同實施 例5處理，取得經濃色化處理的羊毛纖維製品。 比較例1 6 使用比較例1之濃色化劑A，同實施例6處理進行濃 色化處理，取得經濃色化處理的羊毛纖維製品。 比較例1 7 使用比較例3之濃色化劑B，同實施例6處理進行濃 色化處理，取得經濃色化處理的羊毛纖維製品。 比較例1 8 將酸性染料（Kayacalan Black 2RL;日本化學公司製 )相對於參考例4所得之羊毛纖維製品使用3 · 5 %並以公 知公用之方法予以染色加工’且未以濃色化劑進行處理， 作成經染色的羊毛纖維製品。 試驗例5 對於貫施例5之經濃色化處理的羊毛纖維製品、比較 例1 ό及1 7之經濃色處理的羊毛纖維製品、及比較例！ 8 之未經濃色化處理的羊毛纖維製品，根據試驗例2同樣之 -28- (25) (25)1338069 試驗方法、評價濃色化度、吸水性 '耐光堅牢度、洗滌堅 牢度、水堅牢度、摩擦堅牢度等。所得之各評價結果示於 表6。 表 6 試驗項目 實施例6 比較例1 6 比較例1 7 比較例1 8 濃色化度 9.6 12.0 11.6 12.8 吸水性 Δ XX X X X 耐光堅牢度 5以上 5以上 5以上 5以上 洗滌堅牢度 3-4 3-4 3-4 3-4 水試驗堅牢度 4-5 4-5 4-5 4-5 摩擦堅牢度 (乾燥） 3-4 3-4 3-4 3-4 摩擦堅牢度 (濕潤） 3-4 4 4 4 如表6之結果所判定般，實施例6所得之經濃色化處 理的染色羊毛纖維製品，較比較例]6至1 8之染色羊毛纖 維製品，濃色效果、吸水性優良，且亦不損害羊毛纖維製 品染色物固有的特性。 [產業上之可利用性] 對於經染色加工之纖維素纖維、聚酯纖維、蛋白質纖 維、聚醯胺纖維等，經由以本發明之濃色化劑處理，則可 -29- (26) - (26) -1338069 取得濃色化、吸水性優良的染色物。更且，所得染色纖維 製品之耐光性、汗耐光性、洗滌堅牢性、氯耐性亦均不會 損害所使用染料的特性且爲良好。 本發明之濃色化劑，對於經染色加工的纖維’顯示高 的濃色化效果’且對斥水性纖維賦予高的吸水性且同時對 於纖維素纖維等之較親水性的纖維具有不損害吸水性的特 徵，更且不會損害所得染色加工物中所使用之各染料固有 的耐光性、洗滌性、水堅牢度、摩擦堅牢度且爲良好》A cationic dye (Kayacrgl Black BS-ED; manufactured by Nippon Chemical Co., Ltd.) was dyed with 8% of the CDP fiber fabric and dyed by a known method, and was not treated with a coloring agent to prepare a dyed CDP fiber product. . Test Example 3 CDD fiber products of the color-developed CDP fiber product of Example 4, the color-treated CDP fiber product of Comparative Examples 9 and 1 and the non-concentrated CDD fiber product of Comparative Example 1 According to the same test method as in Test Example 2, the degree of coloration, water absorption, light fastness, washing fastness, water fastness, friction fastness, and the like were evaluated. The evaluation results obtained are shown in Table 4. -24· (21) 1338069 Table 4 Test item Example 4 Comparative Example 9 Comparative Example 1 0 ------ Comparative Example 1 1 Concentration degree 10.2 11.9 11.5 13.4 Water absorption 〇 XX 〇 Light fastness 5 or more 5 Above 5 or more 5 or more washing fastness 4-5 4-5 4-5 4-5 Water fastness 4-5 4-5 4-5 4-5 Friction (dry) 4 4-5 4-5 4-5 Friction (wet) 4-5 4-5 4-5 4-5 As determined by the results of Table 4, the CDP fiber product treated by the method of Example 4 was a CDP fiber product obtained in Comparative Example 9 to 11. The color effect is excellent, the water absorption is also large, and the inherent characteristics of the dye used in other CDP woven products are not damaged. Reference Example 4 Preparation of dyed nylon fiber product and wool fiber product (test cloth) Acid dye (Kayacalan Black 2RL; manufactured by Nippon Kayaku Co., Ltd.) was used in an amount of 3.5% with respect to nylon fiber cloth and wool fiber cloth, respectively. Η 5.5 'Dissolution ratio 1: 2 0, dyeing temperature 1 〇〇t, dyeing time 6 〇 minutes of dyeing, washing with water, hot water washing, respectively obtained dyed -25- (22) (22) 1338069 nylon fiber products And wool fiber products. Example 5 The dyed nylon fiber product was subjected to a coloring treatment by dip dyeing treatment in water 200 parts, and 100 parts of the dyed nylon fiber product obtained in Reference Example 4 was put (bath ratio 1: 2). 0) 'Secondly added to the concentrated coloring agent 1 ' part of Example 1 and treated at 40 ° C for 30 minutes to obtain a nylon product having a darkened color. Comparative Example 1 3 The coloring agent A of Comparative Example 1 was used, and the coloring treatment was carried out in the same manner as in Example 5, and the nylon fiber product subjected to the coloring treatment was obtained. Comparative Example 1 4 The coloring agent B of Comparative Example 3 was used, and the coloring treatment was carried out in the same manner as in Example 5, and the nylon fiber product subjected to the coloring treatment was obtained. Comparative Example 1 5 An acid dye (Kayacalan Black 2RL; manufactured by Sakamoto Chemical Co., Ltd.) was used in 3.5% with respect to the nylon fiber product obtained in Reference Example 4, and was dyed by a publicly known method, and was not treated with a coloring agent. ' Made into dyed nylon fiber products. -26- (23) 1338069 Test Example 4 For the nylon product of the color-treated nylon of Example 5, the nylon fiber product of Comparative Example 13 and 14 and the comparative example i 5 The nylon-woven fabric of the concentrated color treatment was evaluated for the degree of coloration, water absorption, light fastness, washing fastness, 'water fastness', friction fastness, and the like according to the same test method as in Test Example 2. The results of the respective evaluations obtained are shown in Table 5. Table 5 Test item Example 5 Comparative Example 1 3 Comparative Example 1 4 Comparative Example 1 5 Concentration degree 9.5 11.0 10.9 12.7 Water absorption 〇 XX △ ~ 〇 Light fastness 5 or more 5 or more 5 or more 5 or more Wash fastness 3 - 4 3-4 3-4 3-4 Water fastness 4-5 4-5 4-5 4-5 Friction fastness 5 5 5 5 (dry) Friction fastness 4-5 4-5 4-5 4-5 (wetting) As judged by the results of Table 5, the dyed nylon fiber product obtained by the coloring process obtained in Example 5 was superior in color effect and water absorption to the dyed nylon fiber product of Comparative Example 13 to 15. It also does not impair the inherent properties of nylon fiber dyes. -27- (24) (24) 1338069 Example 1 6 The dyed wool fiber product was dyed by the dip dyeing method. The dyed wool fiber product obtained in Reference Example 4 was used, and treated in the same manner as in Example 5, Wool fiber products treated with concentrated coloration. Comparative Example 1 6 The coloring agent A of Comparative Example 1 was used, and the coloring treatment was carried out in the same manner as in Example 6 to obtain a colored fiber treated wool fiber product. Comparative Example 1 7 Using the rich coloring agent B of Comparative Example 3, the coloring treatment was carried out in the same manner as in Example 6 to obtain a colored fiber treated wool fiber product. Comparative Example 1 8 An acid dye (Kayacalan Black 2RL; manufactured by Nippon Chemical Co., Ltd.) was used in an amount of 3.6 % with respect to the wool fiber product obtained in Reference Example 4, and was dyed by a publicly known method' and was not subjected to a coloring agent. Treatment, making dyed wool fiber products. Test Example 5 For the dyed wool fabrics of Example 5, the comparatively colored wool fabrics of Comparative Examples 1 and 17 and comparative examples! 8 wool fiber products without coloring treatment, according to test method 2, -28-(25) (25) 1338069 test method, evaluation of coloration degree, water absorption, light fastness, washing fastness, water Fastness, friction fastness, etc. The results of the respective evaluations obtained are shown in Table 6. Table 6 Test item Example 6 Comparative Example 1 6 Comparative Example 1 7 Comparative Example 1 8 Concentration degree 9.6 12.0 11.6 12.8 Water absorption Δ XX XXX Light fastness 5 or more 5 or more 5 or more 5 or more Wash fastness 3-4 3 -4 3-4 3-4 Water test fastness 4-5 4-5 4-5 4-5 Friction fastness (dry) 3-4 3-4 3-4 3-4 Friction fastness (wet) 3- 4 4 4 4 As judged by the results of Table 6, the dyed wool fiber product obtained by the coloring process obtained in Example 6 is superior to the dyed wool fiber product of Comparative Example 6 to 18 in coloring effect and water absorption. And does not damage the inherent characteristics of the dyeing of wool fiber products. [Industrial Applicability] For dyed cellulose fibers, polyester fibers, protein fibers, polyamide fibers, etc., by treatment with the coloring agent of the present invention, -29-(26) - (26) -1338069 A dyed product excellent in coloration and water absorption. Further, the obtained dyed fiber product also exhibited good light resistance, sweat light resistance, washing fastness, and chlorine resistance without impairing the characteristics of the dye used. The coloring agent of the present invention exhibits a high darkening effect on the dye-processed fiber 'and imparts high water absorption to the water repellent fiber and at the same time does not impair the water absorption to the more hydrophilic fiber such as cellulose fiber. Sexual characteristics, and will not damage the inherent light fastness, washing power, water fastness, and friction fastness of each dye used in the dyeing process obtained.
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