201120151 六、發明說明： 【發明所屬之技術領域】 本發明係有關於一種染料墨水組成物及使用此墨水組 成物之纖維的印染方法，更詳言之，係有關於一種纖維素 系纖維及聚酿胺系纖維的印染方法。 【先前技術】 使用喷墨印刷機來進行之纖維的喷墨印染，相較於網 版印染、滾琦（roller)印染、輪轉（r〇tary)印染等的印染方 法’具有以下等許多的優點， (1) 不需要製版製程，能夠縮短製程， (2) 能夠透過電腦將經數位化的圖案直接印花， (3) 即便每次少量亦能夠生產多品種的製品， (4) 能夠大幅度地削減染料色糊的廢液。 另一方面’相較於先前的製版印染’有印花加工速度 慢且難以重現深色等之課題，所以多半使用於製造樣品布 或少量生產的範圍。 近年來’由於電腦的畫像處理或印刷頭（亦稱為喷墨 頭等）製造的技術性進步，噴墨印刷機的印花速度大幅度 地k升而且在市場要求印花圖案的數位化、印花加工的 多樣化及小批量化等之背景，喷墨印染的普及正在進展 中。 作為喷墨印染用的染料墨水，銷售中的有絲綢、耐綸 201120151 等的聚醢胺系纖維用酸性染料墓.取卜^ 针墨水，聚酯系纖維用分散染 料墨水；棉、嫘縈等的纖維素奉鏞缺H = + I糸纖維用反應染料墨水等。 該等嘴墨印染用染料墨水，通當β + 士 * N通常疋在水中使染料溶解 或分散而成之水性墨水，為了抑制k八 j押制水分蒸發引起墨水的乾 燥且為了調整墨水的黏度之目的，而在墨水中添加乙二 醇、二伸乙甘醇、三伸乙甘醇等的二醇類或該等二醇類的 一烷基醚等的化合物、或是甘油等的有機溶劑。 但是，反應染料，係藉由存在於其染料分子中之可與 纖維反應的反應性基，與存在於纖維中的羥基等反應，來 固著於該纖維。因此，若添加上述物來作為有機溶劑而被 包含於含有反應染料之墨水中，則在墨水的保存中或是印 钯後，為了染料固著之目的而進行之利用熱的反應固著製 程，在此製程中，上述有機溶劑等所具有之羥基及/或羧 基等’會與染料進行反應’會有容易產生染料對纖維的固 著率低落之問題。因此’在反應染料墨水中所添加的有機 溶劑必須選擇與反應染料的反應性低者，或是必須添加與 染料的反應性低者來抑制染料與該溶劑的反應，已有提案 揭示此種有機溶劑。 作為其具體例’已知在墨水中添加硫二甘醇（專利文 獻1)、丙二醇（專利文獻2)、1，3-丁二醇（專利文獻3)、甘 油的EO加成物（專利文獻4)、聚丙二醇（專利文獻5)等》 在此*’作為一種含有反應染料以外的染料或顏料來作 為著色劑之，墨水組成物，亦已知有一種含有聚氧伸烷基二 甘油基醚者。該等的墨水組成物，由於未使用反應染料以 4 201120151 及其著色對象不是纖維或其構造物也就是布帛等之理 由，其用途不同’而作為此種墨水的例子’可舉出專利文 獻6至8所揭示的筆記器具用的水性墨水組成物及噴墨用 墨水組成物。 又’不管該墨水組成物的用途，一般而言，會在墨水 組成物中，作為添加劑之一而含有界面活性劑。例如含有 聚氧伸烷基二甘油基醚，同時在上述專利文獻6及7係各 自含有非離子界面活性劑，在專利文獻8係含有陰離子界 面活性劑。又，在專利文獻9中，實質上揭示—種併用非 離子界面活性劑及陰離子界面活性劑而成之喷墨印染用 墨水組成物》 已知界面活性劑具有降低墨水的表面張力之功能 等。例如喷墨用途時，係將提升墨水的吐出性能或印花物 等的效果設作目的而使用。 另一方面，近年來，為了確保吐出安定性之墨水的物 性’一般認為8〜20mPa.s左右的黏度是必要的，並且正 在開發工業用的高耐久性喷墨頭及搭載其之高速印刷機。 又，作為提升印花物品質的方法之一，已知有一種藉 由添加界面活性劑而調整墨水的表面張力，能夠控制墨水 對纖維等的記錄媒體之滲透或滲色，來改良印花物的畫質 之方法。通常藉由將表面張力下降’能夠提高對纖維等的 記錄媒體之渗透性，來降低印花物的粒狀感，但是將表面 張力過度下降時，會有印花物的細線部分產生渗色，致使 印花畫像雜亂之問題。 201120151 如此，因為墨水的表面張力太高、或是反過來太低時 畫像品質都會產生問題，有必要依照記錄媒體的種類而調 整在適當範圍》 在專利文獻5,揭示一種含有反應染料、非離子界面 活性劑、水及多元醇而成之喷墨印染用墨水組成物。 在專利文獻10,揭示一種含有反應染料、特定化學 式所表示的化合物、非離子界面活性劑及水而成之喷墨印 染用墨水級成物。 而且，喷墨印染用墨水組成物，被要求不會受到氣溫 變動的影響而能夠得到良好的吐出性及良好的印花物； 像品質。例如在夏季與冬季氣溫差異大的環境下使用時: 夏季顯示良好的吐出性能之墨水，在冬季變為吐出不良等 而成為-個問題。若改善該冬季之吐出性能，則反而會時 常產生染色性能不充分等之問題，市場大多要求提供一種 反應染料墨水，不會受到氣溫變動的影響而能夠兼備吐出 性與染色性能兩者。 但是’目前尚無法得到一種反應染料墨水，其能夠滿 足工業用的高速喷墨印刷機所要求之在高驅動頻率中的 不會受到氣溫變動影響的連續吐出性能及印花物的 品質。 [先前技術文獻] (專利文獻） 專利文獻1 .曰本特許第3323549號（實施例〇 專利文獻2 :日本特開2⑼2·241639號公報(實施例3) 201120151 專利文獻3 :曰本特開2〇〇3_3〇6627號公報（實施例2) 專利文獻4:日本特許第3582434號 專利文獻5 :日本特表2〇〇5_520015號公報 專利文獻6:日本特開平4_36362號公報 專利文獻7:日本特開2004-346134號公報 專利文獻8:曰本特開2004-155869號公報 專利文獻9 :曰本特開2007-238687號公報（製造例4至9) 專利文獻10 :國際公開第2009/104547號 【發明内容】 〔發明所欲解決之問題〕 本發明之目的在於提供一種纖維素系纖維及聚酿胺 系纖維染色用的反應染料墨水組成物，該反應染料墨水組 成物’對於搭載有工業喷墨頭之印刷機（工業用喷墨印刷 機）而言’具有適當的黏度，且在25°C的通常室溫下及在 10 C低溫環境下之任一種情況，不會受到溫度變化的影響 而在高驅動頻率下的連續吐出安定性優良且具有良好的 染色性能。 〔解決問題之技術手段〕 為了解決上述課題，本發明人專心研討的結果，發現 以下的水系墨水組成物，能夠解決上述課題，而完成了本 發明’該水系墨水組成物至少含有：1種類的反應染料、 下述式（1)所表示的特定化合物、以及非離子界面活性劑 和陰離子界面活性劑之2種類的界面活性劑。 201120151 亦即’本發明係 1}種墨水組成物，其至少含有：1種類的反應染料、 具有以環氧乙烷及/或環氧丙烷在二甘油（diglycerin)加成 成的構ie之化合物、非離子界面活性劑、陰離子界 面活性劑及水。 )如上述1)之墨水組成物，其中上述具有以環氧乙烷及 或環氧丙烷在二甘油加成聚合而成的構造之化合物，係 下述式（1)所表示的化合物， Η十 k ο ο ch2201120151 VI. Description of the Invention: [Technical Field] The present invention relates to a dye ink composition and a printing method for fibers using the ink composition, and more particularly, to a cellulose fiber and a poly Printing and dyeing method of brewing amine fiber. [Prior Art] Inkjet printing of fibers using an ink jet printer has many advantages over the printing and dyeing methods of screen printing, roller printing, and rotary printing. (1) It can shorten the process without the plate making process, (2) It can directly print the digitalized pattern through the computer, (3) It can produce a wide variety of products even in small quantities, (4) It can greatly Reduce the waste of dye paste. On the other hand, the printing speed of printing is slower than that of the previous plate making printing, and it is difficult to reproduce the dark color. Therefore, it is mostly used in the production of sample cloth or a small amount of production. In recent years, due to the technical progress of computer image processing or the manufacture of print heads (also known as inkjet heads, etc.), the printing speed of inkjet printers has been greatly increased by k, and digital printing and printing processing of printing patterns is required in the market. With the background of diversification and small batches, the popularity of inkjet printing and dyeing is progressing. As a dye ink for inkjet printing, there are silk dyes, such as silk and nylon 201120151, which are used for acid dyes, toluene inks, polyester dyes for disperse dyes, cotton, enamel, etc. The cellulose is deficient in H = + I 糸 fiber with reactive dye ink and the like. These dye inks for ink printing are used as an aqueous ink which is usually dissolved in or dispersed in water by β + 士*N, in order to suppress the drying of the ink caused by evaporation of water and to adjust the viscosity of the ink. For the purpose of adding a glycol such as ethylene glycol, diethylene glycol or triethylene glycol, or a monoalkyl ether of the glycol, or an organic solvent such as glycerin to the ink. . However, the reactive dye is fixed to the fiber by reacting with a reactive group capable of reacting with the fiber in the dye molecule, reacting with a hydroxyl group or the like present in the fiber. Therefore, when the above-mentioned substance is added as an organic solvent and contained in the ink containing the reactive dye, the reaction fixing process using heat is performed for the purpose of dye fixing after the ink is stored or after the palladium is adhered. In this process, the hydroxyl group and/or the carboxyl group which the organic solvent or the like has reacted with the dye may cause a problem that the fixing rate of the dye to the fiber is lowered. Therefore, 'the organic solvent added to the reactive dye ink must be selected to have a lower reactivity with the reactive dye, or the reactivity with the dye must be added to suppress the reaction of the dye with the solvent. It has been proposed to disclose such an organic Solvent. As a specific example, it is known to add thiodiglycol (Patent Document 1), propylene glycol (Patent Document 2), 1,3-butanediol (Patent Document 3), and EO adduct of glycerin to ink (Patent Literature) 4), polypropylene glycol (Patent Document 5), etc. Here, as a coloring agent containing a dye or a pigment other than a reactive dye, an ink composition is also known which contains a polyoxyalkylene diglyceride group. Ether. The ink composition is not used for the reaction dye 4 201120151 and its coloring target is not a fiber or a structure thereof, that is, a fabric, etc., and its use is different. As an example of such an ink, Patent Document 6 is exemplified. The aqueous ink composition for an instrument for reading and the ink composition for inkjet according to 8. Further, regardless of the use of the ink composition, in general, a surfactant is contained in the ink composition as one of the additives. For example, the polyoxyalkylene diglyceryl ether is contained, and the above-mentioned Patent Documents 6 and 7 each contain a nonionic surfactant, and Patent Document 8 contains an anionic surfactant. Further, Patent Document 9 discloses a liquid inkjet printing ink composition in which a nonionic surfactant and an anionic surfactant are used in combination, and a surfactant is known to have a function of lowering the surface tension of the ink. For example, in the case of inkjet use, the effect of improving the discharge performance of ink or the printed matter is used for the purpose. On the other hand, in recent years, it is necessary to develop a high-endurance inkjet head for industrial use and a high-speed printing machine equipped therewith in order to ensure the physical properties of the ink which is stable in the discharge. . Further, as one of methods for improving the quality of printed matter, it is known to adjust the surface tension of the ink by adding a surfactant, and it is possible to control the penetration or bleeding of the ink on a recording medium such as a fiber to improve the drawing of the printed matter. Quality method. Usually, by lowering the surface tension, the permeability of the recording medium such as fibers can be improved, and the graininess of the printed matter can be reduced. However, when the surface tension is excessively lowered, the fine line portion of the printed matter is bleed, resulting in printing. The problem of portrait confusion. 201120151 In this case, since the surface tension of the ink is too high or the image quality is too low, the image quality may cause problems, and it is necessary to adjust the appropriate range according to the type of the recording medium. In Patent Document 5, a reactive dye, nonionic is disclosed. An ink composition for inkjet printing made of a surfactant, water and a polyol. Patent Document 10 discloses an ink composition for inkjet printing comprising a reactive dye, a compound represented by a specific chemical formula, a nonionic surfactant, and water. Further, the ink composition for inkjet printing is required to be able to obtain good discharge property and good printed matter without being affected by temperature fluctuations; image quality. For example, when it is used in an environment where the temperature difference between summer and winter is large: In the summer, the ink exhibiting good discharge performance becomes a problem in the case of poor discharge in the winter. If the discharge performance in winter is improved, there is a problem that the dyeing performance is insufficient, and the like, and it is required to provide a reactive dye ink in the market, and it is possible to provide both the discharge property and the dyeing performance without being affected by the temperature fluctuation. However, it has not been possible to obtain a reactive dye ink which is capable of satisfying the continuous discharge performance and the quality of printed matter which are not affected by temperature fluctuations at high driving frequencies required by industrial high-speed ink jet printers. [Prior Art Document] (Patent Document) Patent Document 1. Japanese Patent No. 3323549 (Embodiment 〇 Patent Document 2: Japanese Patent Laid-Open No. Hei 2 (9) No. 2,241,639 (Embodiment 3) 201120151 Patent Document 3: Sakamoto Special 2 〇〇 _ _ 627 627 627 627 627 627 627 627 627 627 627 358 358 358 358 358 358 358 358 358 358 358 358 358 358 358 358 358 358 358 358 358 358 358 358 358 358 358 358 358 358 358 358 358 358 358 358 358 358 358 358 358 358 358 358 358 358 358 358 Japanese Laid-Open Patent Publication No. 2004-355869 (Patent Document No. 2007- 158 869) (Patent Documents 4 to 9) Patent Document 10: International Publication No. 2009/104547 [Problem to be Solved by the Invention] An object of the present invention is to provide a reactive dye ink composition for dyeing cellulose fibers and polyamine fibers, which is equipped with an industrial spray. The ink head printer (industrial inkjet printer) has 'appropriate viscosity, and is not affected by temperature changes at any room temperature of 25 ° C and at 10 C low temperature.The continuous discharge stability at a high driving frequency is excellent and the dyeing performance is excellent. [Means for Solving the Problem] In order to solve the above problems, the present inventors have found that the following water-based ink compositions can solve the above problems. In the present invention, the aqueous ink composition contains at least one type of reactive dye, a specific compound represented by the following formula (1), and two kinds of interface activities of a nonionic surfactant and an anionic surfactant. 201120151 That is, the ink composition of the present invention contains at least one type of reactive dye having a composition of ethylene oxide and/or propylene oxide added to diglycerin. The ink composition according to the above 1), wherein the above has a structure in which ethylene oxide and propylene oxide are added and polymerized in diglycerin. The compound is a compound represented by the following formula (1), Η10k ο ο ch2
HC—X2 OHC-X2 O
H CH2 I 2 HC-X3 oH CH2 I 2 HC-X3 o
H m (1) [式中，x丨、X2、X3及x4係各自獨立地表示氫原子或甲 土 j k m及n係表示總和為4以上、4 〇以下的數目]〇 )如上述1)或2)之墨水組成物，其中上述非離子界面活 性劑係炔二醇系界面活性劑或炔醇系界面活性劑，且陰離 子界面活性劑係磺酸基琥珀酸系界面活性劑。 4) 如上述2)之墨水組成物，其中上述式（1)中之Χι、χ2、 I及X4 ’全部係曱基β 5) 如上述1)之墨水組成物，其中相對於墨水組成物的總 質量，各自含有〇·5〜35質量〇/〇的反應染料、3〜5〇質量 201120151 %的具有以環氧乙烷及/或環氧丙烷在二甘油加成聚合而 成的構造之化合物、0.05〜2質量％的非離子界面活性 劑、0.05〜2質量％的陰離子界面活性劑，且剩餘部分為 水。 6) 如上述1)之墨水組成物’其中更含有水溶性有機溶劑。 7) 如上述1)之墨水組成物，其中相對於墨水組成物的總 質量’更含有0.05〜3質量％的pH調整劑》 8) —種纖維的印染方法，包含以下製程：使用上述丨）至 7)之墨水組成物作為墨水’並使該墨水的墨水滴藉由喷墨 印刷機吐出而賦予至纖維之製程；將藉由該製程所賦予的 墨水組成物中的染料，利用熱使其反應而固著於上述纖維 之製程；及洗淨殘留在上述纖維中的未固著染料之製程。 9) 如上述8)之纖維的印染方法，其中吏包含纖維的前處 理製程’其係使含有1種類以上的糊劑、前處理用的pH 調整劑及水溶助長性劑（hydrotropy agent)之水溶液，含浸 於要賦予墨水組成物之前的前述纖維中。 10) —種印染物’其係藉由如上述8)之纖維的印染方法 印染而成。 〔功效〕 藉由使用本發明之墨水組成物及使用此墨水組成物 之印染方法，能夠提供一種纖維素系纖維及聚醯胺系纖維 染色用的反應染料墨水組成物，該反應染料墨水組成物， 對於搭載有將高黏度墨水設-作必要的工業喷墨頭之印刷 機而言，在25°C的通常室溫下及在10°C低溫環境下之任 201120151 一種情況’不會受到溫度變化的影響而在高驅動頻率下的 連續吐出安定性優良且具有良好的染色性能。 【實施方式】 本發明的墨水組成物，含有反應染料作為色素，而且 是一種實質上為溶液的水性墨水組成物，其含有：以具有 環氧乙烧及/或環氧丙烧在二甘油加成聚合而成的構造之 化合物、非離子界面活性劑及陰離子界面活性劑。 作為纖維素系纖維的染色用染料，通常係使用反應染 料’作為聚酿胺系纖維的染色用染料，通常係使用酸性染 料，但是聚醯胺系纖維的染色亦可使用反應染料。 使用反應染料將纖維素系纖維染色時，反應染料在其 分子中具有反應性的基會與纖維素系纖維的羥基等反應 而產生共價鍵’藉此’將該纖維染色。相對地，聚酿胺系 纖維係在纖維中具有胺基，藉由該胺基與染料分子中的項 酸基等的酸性官能基產生離子鍵，來將該纖維染色。因 此’若是具有酸性官能基（較佳是磺酸基）的反應染料時， 能夠作為在本發明的墨水組成物中所含有的色素來加以 使用。 因為本發明的墨水組成物係以全彩色的印染作為目 的’能夠調製具有黃色、橙色、棕色、紅色、紫色、藍色、 綠色、黑色等各種色相之墨水組成物，並將該等併用作為 墨水組。 在本發明的墨水組成物中所使用的染料，只要是反應 10 201120151 染料’沒有特別限制，較佳是一種染料，其會與纖維反應 的反應性基是一氣三。并基，亦即是一種一氯三^系的反應 染料《反應染料的具體例，可舉出例如C. I. Reactive Yellow 2、3、18、81、84、85、95、99、102 等的黃色系 染料，C. I. Reactive Orange 5、9、12、13、35、45、99 等的橙色系染料；C.I. Reactive Brown 2、8、9、17、33 等的標色系染料；C. I. Reactive Red 3、3:1、4、13、24、 29、31、33、125、151、206、218、226、245 等的紅色 系染料；C. I. Reactive Violet 1、24等的紫色系染料；c. I. Reactive Blue 2、5、10、13、14、15、15:1、49、63、 7卜 72、75、162、176 等的藍色系染料；C· l Reactive Green 5、8、19 等的綠色系染料；c. I. Reactive Black 1、8、 23、39等的黑色系染料等。該等可單獨使用亦可併用2 種以上。 在上述反應染料中，將藍色系染料設作主體且調配橙 色系染料及紅色系染料而成的混合染料，亦能夠作為専色 系染料來使用…該黑色系染料，$了微調整而成為、高 品質的非淺色色調之目的’亦可更調配其他反應染料。 作為上述的反應染料，能夠使用粉末狀或塊狀的乾燥 或是濕餅塊（贈ealce)狀態等的染料。市售的反應染料有 工業染料用粉末、印染用液狀品、噴墨印染用等的各種品 質’且製造方法、純度等各不相同。因為保存安定性及對 從喷墨頭的吐出精細度之影響較少’本發明的墨水組成 物，較佳是盡可能使用不純物較少的染料來調製。通常， 201120151 在。成反應染料時’常有氣化納等的無機鹽混人的情況。 又，特別是沒有進行精製操作之水等，因為含有鈣離子、 鎂離子等的金屬離子，使用將此種水等來調製該墨水組成 物時’雖然微里但是該離子等亦會混入。以下，在本說明 書包a上述的無機鹽及金屬離子，在方便上記載為「無 機不純物」。該等無機不純物，不僅會使墨水中的染料的 溶解度及墨水的保存安定性顯著地惡化，亦成為喷墨印刷 機的喷墨頭發生腐敍、磨耗、喷嘴堵塞等之原因。為了除 去該等無機不純物’較佳是利用超濾法、逆滲透膜法、離 子交換法等眾所周釦的士 4 β 门夫的方法，盡可能地除去墨水組成物中 所含有的無機不純物。在墨水組成物的總質量中，無機不 純物的含量通常為1質量％以下，以0.1質量％以下為佳， 以〇.01質量％以下為更佳。下限係檢測機器的檢測界限 、下亦即可以疋〇%。而且’除去無機不純物後，亦可 適當地進行藉由稀釋或澧 义晨縮調整為需要的染料濃度，來 得到墨水組成物。 在本發明的墨水組成物 作為色素而含有的反應染 料之總含量，相對於累士 4 墨水組成物的總質量，通常為0.5〜 35質量％，以i〜2〇質 c 為佳，以5〜20質量〇/〇為較佳， 以5〜15質量％為更佳。 具有以環氧乙烷及/或環氧 ,.^ 衣氧丙烷在二甘油加成聚合而 成的構ia之化合物，只要是 ,,,,-^ 、有該構造者，並沒有特別限 制作為較佳者，可舉出上述 1八U)所表示的化合物。 上述式（1)所表示的化合物 你十均分子量為340至 201120151 2200的化合物，且χ 心、1及X4係各自獨 氫原子或甲基U、k、m乃〆 獨立地表不 m及η係表示總和為 以下的數目。 ~ 以上、40 X,至Χ*係可相同亦可 f不冋，以相同為佳。又， k以全部為氫原子或甲基 &至 ,* _ 人狂从全邠為甲基為特佳。 式（1)所表不的化合物， 付住 係以環氧丙烷或環氧 二甘油加成聚合而得到的化人 . 在 合的平均值。 tD物，k、”…係加成聚 式二）所表示的化合物，係以環氧丙燒在二甘油加成 聚合而付到的化合物，亦即1 m击 即式⑴中’在X丨至x4全部传 表示甲基之化合物中，k · 4主㈣ 及11係表示其總和為大致 上、24以下。各k、j、m及η之各自的值，因為該等 係平均值而難以特定，但是 ° 相同程度的值為佳。具體 上，k、j、m及η的任一者， m ^ 々疋以1左右至6左右的範 圍為佳。此時，上述式⑴所表示的化合物之平均分子量， 大約通常為340至2200’以38〇至2〇〇〇為佳 1600為更佳。 上述式⑴所表示的化合物，係以環氧乙院在二甘油 加成聚合而得到的化合物’亦即式⑴中，在全 部係表示氣之化合物中，k、h及η係表示其總和為大 致6以上、4〇以下。之各自的值，係與上述 同樣地’以相同程度的值為佳。具體上，卜^^的 任-者’均是以K5左右至1〇左右的範圍為佳。此時， 上遂式⑴所表示的化合物之平均分子量，大約通常為39〇 201120151 至2200,以430至2000為佳，以450至2〇〇〇為更佳。 上述式（1)所表示的化合物’通常是以聚氧丙稀二甘 油基趟或聚氧乙稀二甘油基驗而被知道，亦能夠市場取 得。作為其具體例，可舉出例如任一者均是阪本藥品工業 股份公司製的商品名SC_P4〇〇[在上述式⑴， k+j + m+n=4、平均分子量為4〇〇的化合物]、SC p75〇[在 上述式（1)，k+j+m+n=9、平均分子量為75〇的化合物]、 sc-piooo[在上述式（1)’ k+j+m+n=14、平均分子量為1〇〇〇 的化合物]、SC-P1200[在上述式⑴’ k+j + m+n=18、平均 分子量為1200的化合物]、SC_P16〇〇[在上述式（丨）， k+j+m+n=24、平均分子量為16〇〇的化合物]等的聚氧丙 烯二甘油基醚；SC_E450[在上述式（1)，k+j + m+n=6、平均 分子量為450的化合物]、SC- E750 [在上述式（1)， k+j + m+n==13、平均分子量為750的化合物]、SC_ E1000 [在 上述式（1)，k+j+m+n=2〇、平均分子量為1〇〇〇的化合物]、 SC- E15000 [在上述式〇)，k+j + m+n=3〇、平均分子量為 1500 的化合物]、sc_ E2000 [在上述式（1)，k+j + m+n=4〇、 平均为子量為2000的化合物]等的聚氧乙烯二甘油基趟。 該等具體例之中，平均分子量為大約34〇〜22〇〇，以 400〜2000者為佳。又，該平均分子量能夠使用GPC(凝 膠滲透色譜儀）來測定β 上述式（1)所表示的化合物’係以調整本發明的墨水 組成物的黏度作為目的.而使用。該化合物能夠將該墨水組 成物的黏度調整為適合於工業用喷墨頭（被要求在高速的 201120151 吐出應答性）的值之範圍内，特別是調整成在高黏度側。 上述式（1)所表示的化合物之含量，相對於本發明的 墨水組成物之總質量，通常為3〜5〇質量％，以4〜4〇質 量％為佳，以5〜30質量％為更佳。 本發明的墨水組成物，使用於搭载有工業用喷墨頭之 印刷機中的時候，以改善在高速時的吐出應答性作為目 的，在25°C的黏度，當使用E型黏度計來測定時，通常 為3〜20mPa.s，以8〜20mPa.s的範圍為佳。 本發明的墨水組成物，其特徵在於含有非離子界面活 性劑及陰離子|面活&劑兩者。ϋ由含有該㈣，能夠得 到種噴墨印染用墨水組成物，其不會受到溫度變化的影 響而在高驅動頻率下的連續吐出安定性優良且具有良好 的染色性能。 作為非離子界面活性劑，可舉出聚氧乙烯壬基苯基 醚聚氧乙烯辛基苯基醚、聚氧乙烯十二烧基苯基醚、聚 氧乙烯油醯基苯基醚、聚氧乙烯月桂基醚、聚氧乙烯烷基 醚等的醚系；聚氧乙烯油酸酯、聚氧乙烯二硬脂酸酯、山 梨糖醇酐月桂酸酯、山梨糖醇酐一硬脂酸酯、山梨糖醇酐 一油酸酯、山梨糖醇酐倍半油酸酯、聚氧乙烯一油酸酯、 聚氧乙烯硬脂酸酯等的酯系；3,5_二曱基_丨_己炔_3_醇等 的炔醇系；2,4,7,9-四甲基-5-癸炔-4,7-二醇、3,6-二曱基 -4-辛炔·3,6-二醇、AIR PR0DUCTS公司製的商品名 SURFYNOL104、SURFYNOL104PG50、SURFYNOL82、 SURFYNOL420、SURFYNOL440、SURFYNOL465、H m (1) [wherein, x 丨, X 2 , X 3 and x 4 each independently represent a hydrogen atom or a clay jkm and an n system represents a total of 4 or more and 4 〇 or less] 〇) as described above 1) or 2) The ink composition, wherein the nonionic surfactant is an acetylene glycol surfactant or an acetylene surfactant, and the anionic surfactant is a sulfonic acid succinic acid surfactant. 4) The ink composition according to the above 2), wherein Χ, χ2, I, and X4' in the above formula (1) are all thiol groups β 5), and the ink composition of the above 1), wherein the ink composition is relative to the ink composition Total mass, each containing 〇·5 to 35 mass 〇/〇 of reactive dye, 3 to 5 〇 mass 20112015% of a compound having a structure in which ethylene oxide and/or propylene oxide are added and polymerized in diglycerin 0.05 to 2% by mass of a nonionic surfactant, 0.05 to 2% by mass of an anionic surfactant, and the balance being water. 6) The ink composition of the above 1) which further contains a water-soluble organic solvent. 7) The ink composition according to the above 1), wherein the pH adjuster is further contained in an amount of 0.05 to 3% by mass based on the total mass of the ink composition. 8) A method for printing and dyeing a fiber, comprising the following process: using the above 丨) The ink composition of 7) is used as an ink and the ink droplets of the ink are discharged to the fiber by an inkjet printer; the dye in the ink composition imparted by the process is heated by heat The process of reacting and fixing the fiber; and the process of washing the unfixed dye remaining in the fiber. 9) The method for printing a fiber according to the above 8), wherein the ruthenium-containing fiber pretreatment process is an aqueous solution containing one or more types of paste, a pH adjuster for pretreatment, and a hydrotropy agent. Immersed in the aforementioned fibers before the ink composition is to be imparted. 10) A type of printed matter' which is printed by a printing method of the fiber of the above 8). [Effects] By using the ink composition of the present invention and the printing method using the ink composition, it is possible to provide a reactive dye ink composition for dyeing cellulose fibers and polyamide fibers, and the reactive dye ink composition For a printer equipped with an industrial inkjet head that is designed to make high-viscosity inks, a case of '201120151' at a normal room temperature of 25 ° C and a low temperature environment of 10 ° C 'will not be exposed to temperature The effect of the change is excellent in continuous discharge stability at a high driving frequency and good dyeing performance. [Embodiment] The ink composition of the present invention contains a reactive dye as a pigment, and is a substantially aqueous solution of a solution comprising: having ethylene bromide and/or propylene oxide in diglycerin A compound having a structure formed by polymerization, a nonionic surfactant, and an anionic surfactant. As the dye for dyeing cellulose fibers, a dye for dyeing of the polyanilan fiber is usually used as the dye for dyeing, and an acid dye is usually used. However, a reactive dye can also be used for dyeing the polyamide fiber. When the cellulose-based fiber is dyed with a reactive dye, the reactive dye-reactive group in the molecule reacts with the hydroxyl group of the cellulose-based fiber to generate a covalent bond, thereby dyeing the fiber. In contrast, the polyamine-based fiber has an amine group in the fiber, and the fiber is dyed by an ionic bond between the amine group and an acidic functional group such as an acid group in the dye molecule. Therefore, when it is a reactive dye having an acidic functional group (preferably a sulfonic acid group), it can be used as a coloring matter contained in the ink composition of the present invention. Since the ink composition of the present invention is intended for full-color printing, it is possible to prepare an ink composition having various hue such as yellow, orange, brown, red, purple, blue, green, black, etc., and use these as an ink. group. The dye used in the ink composition of the present invention is not particularly limited as long as it is a reaction. The dye is preferably a dye which reacts with the fiber. A thiol group, that is, a reaction dye of a monochlorotriazine system. Specific examples of the reactive dye include a yellow system such as CI Reactive Yellow 2, 3, 18, 81, 84, 85, 95, 99, 102, and the like. Dye, orange dyes of CI Reactive Orange 5, 9, 12, 13, 35, 45, 99; CI Reactive Brown 2, 8, 9, 17, 33 and other color-coded dyes; CI Reactive Red 3, 3: Red dyes such as 1, 4, 13, 24, 29, 31, 33, 125, 151, 206, 218, 226, 245; purple dyes such as CI Reactive Violet 1, 24; c. I. Reactive Blue 2 , blue dyes of 5, 10, 13, 14, 15, 15: 1, 49, 63, 7 b 72, 75, 162, 176; C· l Reactive Green 5, 8, 19, etc. ;c. I. Reactive Black 1, 8, 23, 39, etc. black dyes. These may be used alone or in combination of two or more. Among the above-mentioned reactive dyes, a mixed dye obtained by disposing a blue dye as a main component and blending an orange dye and a red dye can also be used as a ochre dye... This black dye is slightly adjusted to become The purpose of high-quality non-light-colored tones can also be blended with other reactive dyes. As the above-mentioned reactive dye, a dye which is in the form of a powder or a block of a dry or wet cake or ealce can be used. The commercially available reactive dyes are various types such as powders for industrial dyes, liquid products for printing, and ink jet printing, and the production methods and purity thereof are different. Since the preservation stability and the effect on the fineness of discharge from the ink jet head are small, the ink composition of the present invention is preferably prepared by using a dye having less impurities as much as possible. Usually, 201120151 is at. When a reactive dye is formed, it is often the case that an inorganic salt such as a vaporized sodium is mixed. Further, in particular, water or the like which is not subjected to the refining operation contains metal ions such as calcium ions and magnesium ions, and the ink composition is prepared by using such water or the like. Hereinafter, the inorganic salt and the metal ion described above in the present specification a are conveniently referred to as "organic impurities". These inorganic impurities not only cause a significant deterioration in the solubility of the dye in the ink and the storage stability of the ink, but also cause rot, abrasion, nozzle clogging, and the like of the ink jet head of the ink jet printer. In order to remove the inorganic impurities, it is preferable to remove the inorganic impurities contained in the ink composition as much as possible by a method such as an ultrafiltration method, a reverse osmosis membrane method, or an ion exchange method. . The content of the inorganic impurities in the total mass of the ink composition is usually 1% by mass or less, preferably 0.1% by mass or less, more preferably 0.001% by mass or less. The lower limit is the detection limit of the machine, and the lower limit is 疋〇%. Further, after the inorganic impurities are removed, the ink composition can be obtained by appropriately adjusting the concentration of the dye to be necessary by dilution or entanglement. The total content of the reactive dye contained in the ink composition of the present invention as a coloring matter is usually 0.5 to 35 mass% with respect to the total mass of the ink composition of the ink, and is preferably 2 to 2 enamel c. 〜20质量〇/〇 is preferred, and 5 to 15% by mass is more preferred. A compound having a structure of ia, which is obtained by addition polymerization of ethylene oxide and/or epoxy, and acetophenone, is not particularly limited as long as it is a structure of the compound ia. Preferably, the compound represented by the above-mentioned 18(U) is mentioned. The compound represented by the above formula (1) has a compound having a molecular average molecular weight of 340 to 201120151 2200, and the respective hydrogen atoms or methyl groups U, k, and m of the ruthenium, 1 and X4 are independently represented by m and η. Indicates that the sum is the following number. ~ Above, 40 X, to Χ* can be the same or f is not the same, the same is better. Further, k is all hydrogen atoms or methyl groups; to, * _ human madness is particularly good for all methyl groups. The compound represented by the formula (1) is a compound obtained by addition polymerization of propylene oxide or epoxy diglycerin. The compound represented by the tD substance, k, "...additional polymerization formula II" is a compound obtained by addition polymerization of dipropylene glycol by propylene oxide, that is, 1 m hitting the formula (1) in 'X丨Among the compounds in which all of methyl groups are represented by x4, k · 4 main (four) and 11 series indicate that the sum is substantially equal to or less than 24. The respective values of k, j, m and η are difficult to be averaged by these average values. Specifically, the value of the same degree is preferably in the range of about k, j, m, and η, and m ^ 々疋 is preferably in the range of from about 1 to about 6. In this case, the formula (1) The average molecular weight of the compound is usually about 340 to 2200', preferably 38 to 2, preferably 1600. The compound represented by the above formula (1) is obtained by addition polymerization of diethylene glycol in the epoxy group. In the compound of the formula (1), in all the compounds which are represented by the gas, k, h and η are represented by a total of approximately 6 or more and 4 or less, and the respective values are the same as described above. The value is good. Specifically, it is better to use the range of K5 to about 1〇. The average molecular weight of the compound represented by the above formula (1) is usually about 39〇201120151 to 2200, preferably 430 to 2000, more preferably 450 to 2〇〇〇. The compound represented by the above formula (1) is usually It is known that it is a polyoxypropylene diglyceryl ruthenium or a polyoxyethylene di glycerol group, and it can also be obtained by the market. As a specific example, the product of the Sakamoto Pharmaceutical Industry Co., Ltd. The name SC_P4〇〇[in the above formula (1), k+j + m+n=4, the compound having an average molecular weight of 4〇〇], SC p75〇 [in the above formula (1), k+j+m+n=9 a compound having an average molecular weight of 75 Å], sc-piooo [a compound of the above formula (1) 'k+j+m+n=14, an average molecular weight of 1 ]], SC-P1200 [in the above formula (1) 'k+j + m+n=18, compound having an average molecular weight of 1200], SC_P16〇〇 [in the above formula (丨), k+j+m+n=24, compound having an average molecular weight of 16〇〇], etc. Polyoxypropylene diglyceryl ether; SC_E450 [in the above formula (1), k+j + m+n=6, compound having an average molecular weight of 450], SC-E750 [in the above formula (1), k+j + m+n==13, average numerator a compound of 750], SC_E1000 [a compound of the above formula (1), k+j+m+n=2〇, an average molecular weight of 1〇〇〇], SC-E15000 [in the above formula 〇), k+ a compound of j + m+n=3〇, a compound having an average molecular weight of 1500], sc_E2000 [a compound of the above formula (1), k+j + m+n=4〇, an average of a sub-quantity of 2000] Oxyethylene diglyceryl hydrazine. Among these specific examples, the average molecular weight is about 34 Å to 22 Å, and preferably 400 to 2,000. In addition, the average molecular weight can be measured by using GPC (gel permeation chromatograph) to detect β. The compound represented by the above formula (1) is used for the purpose of adjusting the viscosity of the ink composition of the present invention. This compound can adjust the viscosity of the ink composition to a value suitable for an industrial ink jet head (required at a high speed 201120151 discharge responsiveness), in particular, to a high viscosity side. The content of the compound represented by the above formula (1) is usually 3 to 5 % by mass based on the total mass of the ink composition of the present invention, preferably 4 to 4 % by mass, and preferably 5 to 30% by mass. Better. When the ink composition of the present invention is used in a printing machine equipped with an industrial inkjet head, it is intended to improve the discharge responsiveness at a high speed, and the viscosity at 25 ° C is measured by using an E-type viscometer. When it is usually 3 to 20 mPa.s, it is preferably in the range of 8 to 20 mPa.s. The ink composition of the present invention is characterized by comprising both a nonionic surfactant and an anionic | surface active & By containing the above (4), it is possible to obtain an ink composition for ink jet printing which is excellent in continuous discharge stability at a high driving frequency and has good dyeing performance without being affected by temperature change. Examples of the nonionic surfactant include polyoxyethylene nonylphenyl ether polyoxyethylene octylphenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene decyl phenyl ether, and polyoxygen. An ether system such as ethylene lauryl ether or polyoxyethylene alkyl ether; polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, Ester esters of sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate, etc.; 3,5_didecyl-丨_己An alkynyl alcohol such as an alkyne-3-alcohol; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimercapto-4-octyne·3, 6-diol, AIR PR0DUCTS company's trade name SURFYNOL104, SURFYNOL104PG50, SURFYNOL82, SURFYNOL420, SURFYNOL440, SURFYNOL465,
S 15 201120151 SURFYNOL485 ; OLFINE STG 等的炔二醇系等。 上述之中，以炔二醇（ACETYLENE GLYCOL)系或炔醇 (ACETYLENE ALCOHOL)系為佳，以炔二醇系為更佳，以AIR PRODUCTS公司製的商品名SURFYNOL系列為特佳。 上述非離子界面活性劑的含量，相對於本發明的墨水 組成物之總質量，通常為0.5〜2質量％，以0.05〜1.5質 量％為佳，以0.05〜1質量％為更佳，以0.1〜0,5質量％ 為特佳^ 作為陰離子界面活性劑，可舉出烷基磺酸基羧酸鹽； α-烯烴磺酸鹽；聚氧乙烯烷基醚乙酸鹽；N-醯基胺基酸 或其鹽；Ν-醢基曱基牛磺酸鹽；烷基硫酸鹽聚氧烷基醚硫 酸鹽；烷基硫酸鹽聚氧乙烯烷基醚磷酸鹽；香茅酸肥皂； 蓖麻油硫酸酯鹽；月桂醇硫酸酯鹽；烷基醇型磷酸酯；烷 基型磷酸酯；烷基醇磺酸鹽；二乙基磺酸基琥珀酸鹽、二 乙基己基磺酸基琥珀酸鹽、二辛基磺酸基琥珀酸鹽等的磺 酸基琥珀酸系等。以磺酸基琥珀酸系為佳，其市售的例 子，可舉出LION股份有限公司製的商品名RIPAL 8351、 RIPAL860K、RIPAL870P、RIPALNTD、RIPALMSC ; ADEKA股份有限公司製的商品名ADEKACOL EC8600 ; 花王股份有限公司製的商品名PELEX OT-P、PELEXCS、 PELEXTA、PELEXTR ;新日本理化（股）公司製的S 15 201120151 SURFYNOL485; acetylene glycols such as OLFINE STG. Among the above, ACETYLENE GLYCOL or ACETYLENE ALCOHOL is preferred, and acetylene glycol is more preferred, and the product name SURFYNOL is AIR PRODUCTS. The content of the above nonionic surfactant is usually 0.5 to 2% by mass, preferably 0.05 to 1.5% by mass, more preferably 0.05 to 1% by mass, based on the total mass of the ink composition of the present invention. ～0,5质量% is particularly good. Examples of the anionic surfactant include an alkyl sulfonate carboxylate; an α-olefin sulfonate; a polyoxyethylene alkyl ether acetate; and an N-mercaptoamine group. Acid or its salt; Ν-mercaptopurine taurate; alkyl sulfate polyoxyalkyl ether sulfate; alkyl sulfate polyoxyethylene alkyl ether phosphate; citronellyl soap; castor oil sulfate Salt; lauryl sulfate; alkyl alcohol phosphate; alkyl phosphate; alkyl alcohol sulfonate; diethyl sulfosuccinate, diethylhexyl sulfosuccinate, A sulfonic acid succinic acid system such as an octylsulfonyl succinate or the like. The sulfonic acid succinic acid system is preferred, and commercially available examples thereof include RIPAL 8351, RIPAL860K, RIPAL870P, RIPALNTD, and RIPALMSC manufactured by LION Co., Ltd.; ADEKACOL EC8600, manufactured by ADEKA Co., Ltd.; The product names of the company's products are PELEX OT-P, PELEXCS, PELEXTA, PELEXTR; New Japan Physical and Chemical Co., Ltd.
RIKAMILD ES-100、RIKAMILDES-200、RIKASURF P-10、RIKASURFM-30、RIKASURFM-75、 RIKASURFM-300 ' RIKASURFG-30 ' RIKASURFG-600 ； 16 201120151 東邦化學工業（股）公司製的KOHACOOL L-300、 KOHACOOLL-40、KOHACOOLL-400、KOHACOOLNL-400 等。該等市售品之中，以ADEKACOL EC8600及PELEX 系列（較佳是PELEX OT-P)為特佳。 上述陰離子界面活性劑的含量，相對於墨水組成物的 總質量’通常為0.05〜2質量％，以〇·〇5〜1.5質量％為佳， 以0.05〜1質量％為較佳，以〇.1〜〇 5質量％為特佳。 本發明的墨水組成物，係以在搭載有工業用喷墨頭之 印刷機中使用時提升晝像品質作為目的，在1(rc及25〇c 的表面張力’使用平板法（plate method)測定時，通常為 20〜40mN/m，以25〜35mN/m的範圍為佳。 本發明的墨水組成物，係以改善在搭載有工業用喷墨 頭之印刷機中使用時的連續吐出性來作為目的，該吐出是 在低溫環境下以高速進行，在1〇〇c及25。〇，於1〇Hz時 的動態表面張力，當使用最大泡壓法來測定時，通常為 25 〜45mN/m，以 30〜45mN/m 為佳.，以 30〜40mN/m 的 範圍為更佳。該動態表面張力及其測定，亦揭示在日本特 開2007-16200號公報等之中。 本發明的墨水組成物，含有上述的反應染料、式 所表示的化合物化合物、非離子界面活性及陰離子界面活 性劑’且剩餘部分為水。 除了該等以外，作為本發明的墨水組成物亦可含有的 添加劑，可舉出水溶性有機溶劑、墨水調製劑等。 作為本發明的墨水組成物亦可含有的水溶性有機溶 17 201120151 劑’可舉出多元醇類、n比略咬酮類等。 作為多元醇類’可舉出例如具有2或3個醇性羥基之 C2-C6醇、及具有重複單位為4以上且分子量為2〇〇〇〇 左右以下的聚C2-3伸烷基二醇，以液狀的伸烷基二醇等 為佳。其具體例，可舉出甘油、丨，3_新戊二醇、丨，5_戊二 醇等具有2或3個醇性羥基之C2_C6醇；乙二醇、二伸 乙甘醇、二伸乙甘醇、丙二醇、聚乙二醇等二或三C2_C3 伸院基二醇；聚丙二醇等的聚c2_C3伸烷基二醇等。 作為吡咯啶_類，可舉出2-吡咯啶酮、N-曱基-2·吡 咯啶酮等。 水溶性有機溶劑可單獨使用，但是以併用為佳。 又，水溶性有機溶劑，係期待以下的效果來加以使 用·防止墨水組成物的乾燥（濕潤）、調整黏度及/或表面 張力、消泡、促進對纖維的滲透等。本發明的墨水組成物， 較佳是含有水溶性有機溶劑。 上述水 >谷性有機溶劑的含量，相對於墨水組成物的總 質量通常合叶為丨〜5〇質量％，以5〜4〇質量％為佳， 、〇 35質$ %為較佳。但是，只含有1種類反應染料 為色素時’水溶性有機溶劑的含量，依照情況，以1 〇 〜20質量。/〇為更佳。 •作為墨水調製劑，可舉出防腐防霉劑、pH調整劑等。 ^水調製劑的含量，相對於墨水組成物的總質量，通常合 為1〜10 %左右，以〇 05〜5 %左右為佳。 作為防腐防霉劑，可舉出例如脫氫乙酸鈉、苯曱酸 201120151 鈉、吡啶硫酮鈉-1-氧化物、吡啶硫酮鋅氧化物、丨2_ 苯并噻唑-3-酮、1-笨并噻唑-3-酮的胺鹽、ARCH Chemicals 公司製的PROXEL GXL等’以PROXEL GXL為佳。 作為pH調整劑，可舉出例如氫氧化鈉、氫氧化卸、 氫氧化經等的驗土類金属的氫氧化物；三乙醇胺、二乙醇 胺、一甲基乙醇胺、二乙基乙醇胺、參（羥曱基）胺基曱炫 等的3級胺類、較佳是亦可被羥基取代之一、二或三ci_c4 烷基胺等。該等之中，以參（羥甲基）胺基曱烷為佳。 本發明的墨水組成物’以含有pH調整劑為佳，其含 量相對於墨水組成物的總質量’通常為〇. 〇 5〜3質量％， 以0.05〜2.5質量。/◦為佳，以（M〜2質量％為更佳。 本發明的墨水組成物’能夠藉由將染料、上述式（1) 所表示的化合物化合物、非離子界面活性及陰離子界面活 性劑添加於水，並且按照必要更添加上述的水溶性有機溶 劑及墨水調製劑並加以攪拌，且混合至染料等的固體成分 溶解為止來得到。 添加各成分的順序’並沒有特別限定，只要藉由授掉 實質上合至成為溶液，來調製本發明的墨水組成物即 可。在調製墨水組成物時所使用的水，係如上述，以使用 無機不純物少者，例如蒸餾水或離子交換水等為佳。 而且，將本發明的墨水組成物使用於喷墨印染時，較 佳是將濾液作為墨水來使用，該濾液是使用膜過濾器等， 將本發明的墨水組成物精密過遽且已除去失雜物後之遽 液進行精密過遽時之過渡器的孔徑，通常為i〜〇. _， 19 201120151 以0.8〜〇.ιμηι為佳。 本發明的印染方法，係藉 认审^ 节錯由使用膜過濾器等將本發明 的墨水組成物精密過滹來 慮來除去失雜物後，使用該墨水來對 纖維、較佳是纖維素李 & Λ I糸纖維或聚醯胺系纖維進行印花，隨 後進行加熱等的處理 P杂方法。關於在印花時所使用的 Γ頭或墨水喷嘴’並沒有特別限制，能夠按照目的而適 田土選擇。作為要進行印花之纖維，更具體地，較佳是對 以纖維素系纖維或$ ^ 醯胺系纖維作為主體之布帛進行印 染。 素系纖維’可舉出例如棉、麻等的天然纖 、，‘，螺繁等的再生纖維素纖維；及含#該等的混紡纖維等。 作為聚醯胺系纖維，可舉出例如絲綢、羊毛等的天然 聚酿胺系纖維，耐論等的合成聚醯胺系纖維；及含有該等 的混紡纖維等。 乍為使用本發明@墨水組成才勿而對纖維進行印染之 方法’可舉出依照順序進行以下3製程之方法。 [製程1 ] 使用本發明的墨水組成物作為墨水，並藉由嘴墨印刷 機’使該墨水的墨水滴吐出而賦予在纖維之製程(印花製 程）。 [製程2] 將藉由製程1所賦予墨水組成物中的染料，利用熱使 其反應而固著.於上述纖維之製程。RIKAMILD ES-100, RIKAMILDES-200, RIKASURF P-10, RIKASURFM-30, RIKASURFM-75, RIKASURFM-300 'RIKASURFG-30 ' RIKASURFG-600 ; 16 201120151 KOHACOOL L-300, manufactured by Toho Chemical Industry Co., Ltd. KOHACOOLL-40, KOHACOOLL-400, KOHACOOLNL-400, etc. Among these commercial products, the ADEKACOL EC8600 and PELEX series (preferably PELEX OT-P) are particularly preferred. The content of the anionic surfactant is usually 0.05 to 2% by mass based on the total mass of the ink composition, preferably 5 to 1.5% by mass, and preferably 0.05 to 1% by mass, preferably 〇. 1 to 〇 5 mass% is particularly good. In the ink composition of the present invention, the surface tension of 1 (rc and 25 〇c is measured by a plate method) for the purpose of improving the image quality when used in a printing machine equipped with an industrial inkjet head. In the case of 20 to 40 mN/m, it is preferably in the range of 25 to 35 mN/m. The ink composition of the present invention is improved in continuous discharge when used in a printing machine equipped with an industrial inkjet head. For the purpose, the discharge is performed at a high speed in a low temperature environment, and the dynamic surface tension at 1 〇 Hz at 1 〇 Hz is usually 25 to 45 mN when measured by the maximum bubble pressure method. m is preferably 30 to 45 mN/m, more preferably in the range of 30 to 40 mN/m. The dynamic surface tension and the measurement thereof are also disclosed in Japanese Laid-Open Patent Publication No. 2007-16200, etc. The ink composition contains the above-mentioned reactive dye, a compound compound represented by the formula, a nonionic surfactant, and an anionic surfactant, and the remainder is water. In addition to these, the ink composition of the present invention may contain an additive. , can be cited as water soluble The solvent of the solvent, the ink preparation agent, etc. The water-soluble organic solvent 17 201120151 agent which can also be contained in the ink composition of the present invention is exemplified by a polyol, a n-bit ketamine or the like. For example, a C2-C6 alcohol having 2 or 3 alcoholic hydroxyl groups, and a poly C2-3 alkylene glycol having a repeating unit of 4 or more and a molecular weight of about 2 Å or less, and a liquid alkyl group A diol or the like is preferred. Specific examples thereof include C2_C6 alcohol having 2 or 3 alcoholic hydroxyl groups such as glycerin, hydrazine, 3_neopentyl glycol, hydrazine, and 5-pentylene glycol; ethylene glycol; Two or three C2_C3 stretching diols such as ethylene glycol, diethylene glycol, propylene glycol, and polyethylene glycol; polyc2_C3 alkyl diols such as polypropylene glycol, etc. As the pyrrolidine group, 2 - pyrrolidone, N-fluorenyl-2, pyrrolidone, etc. The water-soluble organic solvent may be used singly, but it is preferably used in combination. Further, the water-soluble organic solvent is expected to be used in the following effects. Drying (wetting), adjusting viscosity and/or surface tension, defoaming, promoting penetration of fibers, etc. The ink composition of the present invention preferably contains a water-soluble organic solvent. The content of the water > glutenic organic solvent is usually 丨5 〇 mass% with respect to the total mass of the ink composition, and is 5 to 4 〇. The mass% is preferably 5%, and the 〇35 mass is preferably %. However, when only one type of reactive dye is used as the pigment, the content of the water-soluble organic solvent is preferably 1 〇 20-20 。. • Examples of the ink preparation agent include a preservative and antifungal agent, a pH adjuster, etc. The content of the water preparation agent is usually about 1 to 10% with respect to the total mass of the ink composition, and is 〇05 to 5%. The left and right are better. Examples of the antiseptic and antifungal agent include sodium dehydroacetate, sodium benzoate 201120151, sodium pyrithione-1-oxide, zinc pyrithione oxide, 丨2_benzothiazol-3-one, and 1- The amine salt of stupid thiazol-3-one, PROXEL GXL manufactured by ARCH Chemicals, etc. is preferably PROXEL GXL. Examples of the pH adjuster include hydroxides of soil-measuring metals such as sodium hydroxide, hydroxide, and hydroxide; triethanolamine, diethanolamine, monomethylethanolamine, diethylethanolamine, and hydroxy A tertiary amine such as a mercapto group, such as an amine group, may preferably be substituted with a hydroxyl group, a di- or tri-ci-c4 alkylamine or the like. Among these, ginsyl (hydroxymethyl) amino decane is preferred. The ink composition of the present invention is preferably contained in a pH adjusting agent, and its content is usually 〇. 5 to 3 mass%, and 0.05 to 2.5 mass based on the total mass of the ink composition. It is preferable that (M~2 mass% is more preferable. The ink composition of the present invention can be added by a dye, a compound compound represented by the above formula (1), a nonionic surfactant, and an anionic surfactant. In addition, the water-soluble organic solvent and the ink preparation agent are added to the water, and the mixture is stirred and mixed until the solid component such as a dye is dissolved. The order of adding the components is not particularly limited, as long as it is taught by The ink composition of the present invention may be prepared by substantially combining it with a solution. The water used in the preparation of the ink composition is as described above, and it is preferred to use less inorganic impurities such as distilled water or ion-exchanged water. Further, when the ink composition of the present invention is used for inkjet printing, it is preferred to use the filtrate as an ink which is subjected to a membrane filter or the like to precisely remove the ink composition of the present invention and has been removed. The pore size of the transition device after the mashing of the debris is precisely i~〇. _, 19 201120151 is preferably 0.8~〇.ιμηι. The printing method is based on the use of a membrane filter or the like to accurately remove the ink composition of the present invention to remove the impurities, and then use the ink to treat the fibers, preferably cellulose Li & The ΛI糸 fiber or the polyamide fiber is printed, and then the P-method is treated by heating, etc. The gutta or ink nozzle used in the printing is not particularly limited, and the soil can be selected according to the purpose. More specifically, it is preferable to carry out printing on a fabric mainly composed of cellulose fibers or oxime-based fibers. The prime fibers are, for example, natural fibers such as cotton and hemp. ', a regenerated cellulose fiber such as a snail, and the like, and a blended fiber containing the same. The polyamidated fiber may, for example, be a natural polyamine-based fiber such as silk or wool. The amide-based fiber; and the blended fiber containing the same. 乍 The method of printing the fiber by using the ink composition of the present invention ′ is a method of performing the following three processes in order. [Process 1] Use The ink composition of the present invention is used as an ink, and is supplied to the fiber process (printing process) by discharging the ink droplets of the ink by the nozzle ink printer. [Process 2] The ink composition to be imparted by Process 1 The dye is fixed by heat and reacted to the above fiber.
[製程3J 20 201120151 將殘留在上述纖維令的未固著的染料洗淨之製程。 作為在上述製程1中的將本發明的墨水組成物賦予 至纖維之方法，可舉出一種喷墨印花方法，該方法將填充 有本發明的墨水組成物之容器，裝配在喷墨印刷_ 位置，並使用該墨水組成物作為墨水，且按照記錄信號使 該墨水的墨水滴賦予至纖維。 作為在上述製程2中之將墨水組成物中的染料利用 熱使其反應而固著於纖維之製程，可舉出將被賦予本 的墨水組成物後之纖維，在常溫〜15代，放！ 〜Μ 分鐘使其預乾燥後，進而施行蒸烘處理之方法等 烘處理的條件，以在濕度8〇〜1〇〇%、溫度95〜1〇代的 環境下，將該纖維放置5〜4G分鐘之條件為佳。 作為在上述製程3中之洗淨殘留在纖維中的未固著 染枓之製程，以使用冷水洗淨該纖維為佳。在洗淨時，在 該水中亦可含有界面活性劑。 。藉由將已洗淨未固著染料後的該纖維，纟5〇〜⑶ °C ’乾燥5〜3〇分鐘，能夠得到作為目標之印染物。 作為纖維的印染方法’較佳是含有前處理製程之方 法’該前處理製程，是對在上述的3製程之前亦即賦予墨 水組成物之前的纖維’進行前處理的方法。作為前處理製 :二舉出-種製程’該製程將含有i種類以上的糊劑、 液中Λ含有的、阳調整劑及水溶助長性劑而成之 meth d、4為剛處理液並藉由例如壓染法(Padding 岣’而使該前處理液含2浸於要賦予墨水組成物之前 201120151 的纖維中。壓染的收縮率以40〜90%左右為佳，以60〜 80%左右為更佳。 雖然該前處理製程並非必要，但是因為在包含印花時 之印染的情況下’亦有能夠得到防止染料產生滲色的效果 之情況’所以較佳是依照順序進行包含前處理製程的4 個製程之印染方法。 又，在前處理液中所含有的pH調整劑，其使用目的 係與在本發明的墨水組成物中所含有的pH調整劑相同， 但疋其較佳的具體例等係不同。因此，在本說明書，在本 發明的墨水組成物中所含有的pH調整劑，只記载為「pH 調整劑」’而在前處理液令所含有的pI1調整劑，係記載 為「前處理用的pH調整劑」，來區別兩者。 作為上述糊劑，可舉出：瓜耳豆（guar)、刺槐豆（1〇cust bean)等的天然樹脂類、澱粉類 '海藻酸鈉鹼、海蘿等的 海藻類、果膠酸等的植物皮類、甲基纖維素、乙基纖維素、 羥乙基纖維素、羧甲基纖維素等的纖維素衍生物、羧甲基 澱粉等的加工殿粉、黃箸樹膠(shiraz gum)系、刺槐豆樹 膠等的加X天然樹膠類、聚乙稀醇、聚丙稀酸自旨等的合成 糊等。 該等之中’作為較佳糊齊卜在纖維素系纖、維中，可舉 出海躁酸納鹼；在聚酿胺系纖維中，可舉出瓜耳豆、刺槐 豆等的天然樹膠類；及/或黃蓍樹膠系、刺槐豆樹膠等的 加工天然樹膠類。 作為在纖維素系纖維的前處理製海φ + a老 心王教桎中之前處理用的 22 201120151 PH調整劑，較佳是在成為水溶液時顯示驗性者， 例如無機酸或有機酸的鹼金屬鹽；鹼土類金 . 熱時會游離驗之化合物。特別是以無機酸或有：酸 屬氫氧化物及驗金屬鹽為適合。具體例可舉出氫氧化納、 氫氧化卸、碳酸鈉、碳酸氫㉟、碳酸卸、甲酸鈉、鱗酸納 等，該等之中，以碳酸氫鈉為佳。 作為聚酿胺㈣維的前處理製程中之前處理用的pH 調整劑’較佳是在成為水溶液時顯示酸性者，可舉出例如 硫酸敍、酒石酸錄、乙酸録等的録鹽。該等之中，以硫酸 銨為佳。 作為在前處理之水溶助長性劑，可舉出尿素、二甲 脲、硫脲、-甲基硫脲、二甲基硫脲等的尿素衍生物，較 佳者可舉出尿素。 在前處理中之該等前處理劑，雖然亦可單獨使用，但 是以併用為佳。 相對於前處理液的總質量，糊劑、前處理用的{)11調 整劑及水溶助長性劑的含量’例如由於纖維素系纖維及聚 醯胺系纖維之各自的混紡比率等的不同，而難以一概而 定’作為標準’相對於前處理液的總質量，任一者以質量 基準來決定時，糊劑為0.5〜5%、前處理用的pH調整劑 為0.5〜5%、水溶助長性劑為1〜2〇質量。/。，剩餘部分為 水。 [實施例] 23 观20151 以下，藉由實施例 不被這些實施例所限定。在、：明本發明，但是本發明 係意味著重量份，「 中，若未事先告知，「份」 °」係意味著質量％。 在以下的本發明中 m 丙規在二甘油加成 乍為具有以核氧乙院及/或環氧 聚&而成的構造之化合物，俜使用上、+、 式⑴所表示的化合物 "使用上述 一者妁 乍為該式（1)所表示的化合物，任 者均倉b夠以市售〇从 得日4田 ，形式從阪本藥品工業股份公司取 得’且使用以下2系姑 、、，的化〇物。其中，「SC_Pj的化 。物係任-者均是聚氧丙烯：甘油㈣，「WE」的化 合物係任—者均是聚氧乙稀二甘油基趟。 商品名 1) SC-P400 :平均分子量4〇〇 2) SC-Pl〇〇〇:平均分子量1〇〇〇 3) SC_P1600:平均分子量16〇〇 4) SC_E450 :平均分子量45〇 5) SC-E2000 :平均分子量2〇〇〇 [實施例1〜6] 混合在下述各實施例中所記載的成分，並且藉由攪拌 大約1小時’至固體成分溶解為止，來得到各自的墨水組 成物後，使用〇.45μιη的膜過濾器（商品名CELLULOSE ACETATE系濾紙、ADVANTEC公司製）過濾，來調製試 驗用墨水。將該墨水的調製各自設作實施例〜6。 又，在各墨水中作為色素來使用之反應染料，任一者 均是日本化藥股份公司製的一氯三。井系，「C.I.」之後緊 24 201120151 ，係意味著 接著記載的「Reactive」的用語，如眾所周知 _反應染料」。 [實施例1(黃色墨水）] C. I. Reactive Yellow 2 10份 參(羥曱基)胺基曱烷 0.5份 SC-P400 25份 丙二醇 10份 2-β比嘻咬酮 5份 SURFYNOL 104PG50 0.1份 ADEKACOL EC8600 0.5份 PROXEL GXL 0.1份 離子交換水 48.8 份 [實施例2 (品紅墨水）] C. I. Reactive Red 3:1 10 份 參(羥甲基)胺基曱烷 0.5份 SC-P1000 15 份 丙二醇 10份 2-吡咯啶酮 3份 SURFYNOL 440 0.3 份 ADEKACOL EC8600 0.3 份 PROXEL GXL 0.1 份 離子交換水 60.8份 [實施例3(青藍色(cyan)墨水] C. I. Reactive Blue 15:1 10 份 參(羥甲基)胺基甲烷 0.5份 SC-P1600 25 份 丙二醇 10份 2-吡咯啶酮 3份 SURFYNOL 485 0.1 份 ADEKACOL EC8600 0.2 份 PROXEL GXL 0.1 份 離子交換水 51.1份 25 201120151 [實施例4(橙色墨水)] C. I. Reactive Orange 13 10 份 參(羥甲基)胺基曱烷 0.5份 SC-E450 25 份 丙二醇 10份 2-°比洛咬_ 3份 SURFYNOL 440 0.3 份 PELEXOT-P 0.1 份 PROXEL GXL 0.1 份 離子交換水 51份 [實施例5(青藍色(cyan)墨水)] C. I. Reactive Blue 49 10 份 參(羥甲基)胺基曱烷 〇.5份 SC-E2000 20 份 丙二醇 10份 2-吡咯啶酮 3份 SURFYNOL 485 0.5 份 PELEX OT-P 0.5 份 PROXEL GXL 0.1 份 離子交換水 55.4份 [實施例6(黑色墨水)] C. I. Reactive Blue 176 9 份 C. I. Reactive Red 3:1 3 份 C. I. Reactive Orange 12 3 份 參(羥曱基)胺基曱烷 0.5份 SC-E2000 5 份 乙二醇 15份 丙二醇 10份 2-吡咯啶酮 10份 SURFYNOL 485 0.5 份 ADEKACOL EC8600 0.1 份 PROXEL GXL 0.1 份 離子交換水 43.8份 26 201120151 [比較例1〜4] 除了未併用非離子界面活性劑及陰離子界面活性劑 而是各自單獨使用以外，係與實施例2同樣地進行來調製 比較用的墨水。將該比較用的墨水之調製，設作比較例^ 及2。 同樣地，除了單獨使用界面活性劑以外與實施例5同 樣地進行來調製比較用的墨水。並將該比較用的墨水之調 製’設作比較例3及4。 而且，比較例1及比較例3的墨水，係只有使用非離 子界面活性劑’並將離子交換水增量來代替陰離子界面活 性劑而成之墨水。比較例2及比較例4的墨水，係只有使 用陰離子界面活性劑’並將離子交換水增量來代替非離子 界面活性劑而成之墨水。 [比較例1] 10份 0.5份 15份 10份 3份 0.3份 〇·1份 61.1 份 C. I. Reactive Red 3:1 參(經甲基)胺基甲烷 SC-P1000 丙二醇 2·吡咯啶酮 SURFYNOL 440 PROXEL GXL 離子交換水 27 201120151 [比較例2] C. I. Reactive Red 3:1 10份 參(經甲基)胺基曱烷 0.5份 SC-P1000 15份 丙二醇 10份 2-0比!$•咬酿| 3份 ADEKACOL EC8600 〇_3份 PROXEL GXL 0.1份 離子交換水 61.1 份 [比較例3] C. I. Reactive Blue 49 10份 參(羥甲基)胺基甲烷 0.5份 SC-E2000 20份 丙二醇 10份 2-吡咯啶酮 3份 SURFYNOL 485 0.5份 PROXEL GXL 0.1份 離子交換水 55.9 份 [比較例4] C. I. Reactive Blue 49 10份 參(經曱基)胺基曱烷 0.5份 SC-E2000 20份 丙二醇 10份 2-°比略咬酮 3份 PELEX OT-P 0.5份 PROXEL GXL 0.1份 離子交換水 55.9 份 [比較例5〜7 ]在實施例4，除了使用各自25份以下所示的化合物 28 201120151 中U上述式⑴所表示的化合物 同樣地進行來調製比較例5〜7 來代替25份在實施例4 (SC-45〇)以外，與實施例4 的比較用墨水。 比較例5 :甘油 750的聚 比較例k P0LYGLYCERIN 75〇(平均分子量為 甘油、阪本藥品工業股份公司製） 比較例7 :丙二醇 使用如上述進行而得到之實施例卜5及比較例Η 的墨水’並如以下進行，來進行基礎物性值的測定、染布 的調製及評價。 [墨水的評價] 對在上述實施例1〜5及比較例1〜7中所調製之各自 的墨水，進行下述（1)至（7)的7種類試驗，來評價墨水的 性能。各試驗結果之中，墨水的基礎物性值的測定試驗亦 即（1)黏度試驗〜（3)動態表面張力，係如下述表1所示； 墨水的性能試驗亦即（4)連續吐出性試驗〜（7)染色性能試 驗’係如下述表2所示。 (1)黏度試驗 在10°C及25°C，使用Ε型黏度計（Rl 15型黏度計、 東機產業公司製）來測定各實施例及比較例的墨水之黏 度。又，下述表1中的數值之單位係mPa · s。 (2)表面張力 在1(TC及25°C，使用平板法（CBVP-Z型表面張力計、 協和界面科學公司製）來測定各實施例及比較例的墨水之 29 201120151 表面張力。又，下述表1中的數值之單位係mN/m。 (3) 動態表面張力 在l〇°C的10Hz及25°C的10Hz的情況，使用最大泡 壓法（SITA SCIENCE LINE 60型動態表面張力計、SITA Messtechnik GmbH公司製）來測定各實施例及各比較例的 動態表面張力。又，下述表1中的數值之單位係mN/m。 (4) 連續吐出性試驗 使用含有海藻酸鈉、尿素、碳酸氫鈉之溶液，並藉由 壓染法來進行前處理後的棉布，對此棉布各自單獨使用各 實施例及各比較例的墨水，並藉由搭載有工業用喷墨頭 (NOVA、FUJIFILM Dimatix 公司製）之 〇NDEMAND 型喷 墨印刷機（APOLLO 2 PRINTER SYSTEM、FUJIFILM Dimatix公司製），且在25°C的環境下進行印花，來評價 各墨水的吐出性。吐出性係使用m Web Transport(喷墨 印刷布搬運機、ITI Corporation公司製），並在7 5cm寬 卷物狀的棉布以單色花紋（Beta pattern)進行連續印花5 次，來得到印花棉布。依照所得到的印花畫像狀態並基於 以下的基準來評價試驗結果。 〇：到最後能夠良好地印花 △:在印花畫像能夠確認條紋缺損、或是雖然印花不安定 但是能夠印花至最後。 x ·印化畫像散亂且條紋缺損嚴重、或是印花不定定且無 法印花至最後》 ' (6)染色性試驗1 30 201120151 <在棉布的試驗> 將在：述(4)連續吐出性試驗中所得到的 棉布 :⑽部分30cm，於—進行中間乾燥後於 。103c進行蒸烘處理ίο分鐘。水洗後，使用95〜100 弗κ洗淨10分鐘，再藉由水洗、乾燥來得到試驗用 的經印染棉染布。 <在絲綢布的試驗> 、在使用含有瓜耳豆、硫酸銨及尿素之水溶液並藉由壓 染法來進行前處理而成之絲綢布’進行上述(4)連續吐出 性試驗’並將所得到的絲綢布的印花初期部分2〇咖，在 6〇〜8〇t進行中間乾燥後，於1〇〇〜1〇3χ：進行蒸烘處理 20分鐘。水洗後，藉由乾燥來得到試驗用的經印染絲綢 染布。依照所得到各染布的狀態且基於以下的基準來評 試驗結果。 而且，對比較例5及7，因為在前述（4)連續吐出性試 驗無法進行良好的印花，所以未進行該染色性試驗1。 〇.在印花晝像無粒狀感，而且在經印花的染布亦無氣泡。 X :在印花畫像有粒狀感，而且在經印花的染布有氣泡。 (7)染色性試驗2 為了調查式（1)所表示的化合物對反應染料固著於纖 維素纖維的影響之目的，對實施例4及比較例5〜7，將 在上述（5)低溫連續吐出性試驗所得到的印花棉布的印疒 初期部分20cm，在60〜80eC進行中間乾燥後，於1〇〇〜 103 C進行蒸烘處理1〇分鐘。水洗後，在95〜 31 201120151 水洗淨1 〇分鐘，並藉由水洗、乾燥來調製經印染棉染布。 使用測色機（SpectroEye GRETAG-MACBETH 公司 製）’並將上述進行所得到的經印染棉染布之MACBETh 反射濃度進行比色，且藉由下述式來求取各固著率。 固著率=(Α/Β)χΐ〇〇(〇/。） A:實施例4、或比較例5〜7的經印染棉染布的反射濃度。 B :實施例4的經印染棉染布的反射濃度。 〇：95°/。以上 △ : 90%以上 X :小於90% [表1] 黏 度 表面張力 動態表面張力 25〇C 10°c 25〇C 10°C 25〇C 10°C 實施例1 9.5 18.5 27 28 32 39 實施例2 8.5 18.0 29 30 31 36 實施例3 8.1 17.0 30 32 34 40 實施例4 8.9 18.3 32 34 37 39 實施例5 9.6 19.2 26 27 32 35 實施例6 9.3 18.5 31 33 33 36 比較例1 8.4 18.0 37 39 38 39 比較例2 8,5 18.1 29 30 33 45 比較例3 9.5 19.2 38 40 39 40 比較例4 9.5 19.2 27 28 33 45 比較例5 5.2 11.2 32 34 37 39 比較例6 7.3 15.5 32 34 37 39 比較例7 5.4 11.5 32 34 37 39 32 201120151 [表 2]_ 試驗結果 連續 _ 吐出性試驗 實施例1 實施例2 實施例3 實施例4 實施例5 .實施例6 ~~比較例ί 比較例2 比較例3 比較例4 比較例5 比較例6 比較例7[Process 3J 20 201120151 The process of washing the unfixed dye remaining in the above fiber order. As a method of imparting the ink composition of the present invention to a fiber in the above Process 1, there is exemplified an ink jet printing method which comprises a container filled with the ink composition of the present invention in an ink jet printing position And using the ink composition as an ink, and imparting ink droplets of the ink to the fibers in accordance with a recording signal. In the process of the above-mentioned process 2, the dye in the ink composition is reacted to be fixed to the fiber by heat, and the fiber to be imparted to the ink composition is placed at room temperature for 15 generations. After the pre-drying is carried out for a period of time, the conditions of the bake treatment such as the steaming and bake treatment are carried out, and the fiber is placed at 5 to 4 G in an environment of a humidity of 8 〇 to 1% by weight and a temperature of 95 to 1 〇. The condition of minutes is better. As a process for washing the unfixed enamel remaining in the fiber in the above process 3, it is preferred to wash the fiber with cold water. At the time of washing, a surfactant may also be contained in the water. . The target dye can be obtained by drying the fiber after washing the unfixed dye at 纟5 〇 to (3) °C for 5 to 3 minutes. The method of printing as a fiber is preferably a method comprising a pretreatment process. The pretreatment process is a method of pretreating the fiber before the above-mentioned three processes, i.e., before the ink composition is applied. As a pretreatment system: two methods - a process - the process will contain more than i kinds of paste, liquid yttrium, a positive modifier and a hydrotrope meth d, 4 is just the treatment liquid and borrowed For example, the pretreatment liquid containing 2 is immersed in the fiber to be applied to the ink composition before 201120151 by a pressure dyeing method (Padding 岣'. The shrinkage rate of the dyeing is preferably about 40 to 90%, and about 60 to 80%. It is more preferable. Although the pre-treatment process is not necessary, it is preferable to carry out the pre-treatment process in order to obtain the effect of preventing the dye from bleeding in the case of printing including printing. Further, the pH adjusting agent contained in the pretreatment liquid is used in the same manner as the pH adjusting agent contained in the ink composition of the present invention, but a preferred specific example thereof In the present specification, the pH adjuster contained in the ink composition of the present invention is only described as "pH adjuster" and the pI1 adjuster contained in the pretreatment liquid is described. For pre-processing p The above-mentioned pastes include natural resins such as guar and 〇cust bean, and starches such as sodium alginate and sea radish. Processed plants such as seaweed, pectic acid, plant cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, cellulose derivatives such as carboxymethyl cellulose, and carboxymethyl starch. Powder, shiraz gum, locust bean gum, and other synthetic natural pastes such as X natural gums, polyethylene glycols, and polyacrylic acid, etc. Examples of the cellulosic fiber and the sulphate may be sodium citrate; and the polyamine fiber may be a natural gum such as guar or locust bean; and/or a sassafras or locust bean. For the treatment of natural gums such as gums, it is preferred to use the 22 201120151 pH adjuster for the treatment of the cellulose fiber before the treatment of the sea φ + a old heart, and it is preferable to show the tester when it becomes an aqueous solution. For example, an alkali metal salt of an inorganic or organic acid; an alkaline earth gold. A compound which is freely tested when heated. The inorganic acid or the acid hydroxide and the metal salt are suitable, and specific examples thereof include sodium hydroxide, hydrogen hydroxide, sodium carbonate, hydrogencarbonate 35, carbonic acid unloading, sodium formate, sodium sulphate, and the like. Among these, sodium hydrogencarbonate is preferred. The pH adjuster used for the pretreatment in the pretreatment process of the polystyrene (tetra) dimension is preferably acidic when it is an aqueous solution, and examples thereof include sulphate and tartaric acid. Recorded salt, recorded in acetic acid, etc. Among them, ammonium sulfate is preferred. As the water-soluble extender in the pretreatment, urea, dimethyl urea, thiourea, methylthiourea, and dimethyl The urea derivative such as thiourea is preferably urea. The pretreatment agents in the pretreatment may be used singly or in combination. The content of the paste of the paste, the {1111 adjusting agent for the pretreatment, and the hydrotrope-based agent is different from the total blending ratio of the pretreatment liquid, for example, due to the blending ratio of the cellulose fibers and the polyamide fibers. It is difficult to determine the total mass of the pretreatment liquid as the standard as the standard, and the paste is 0.5 to 5%, the pH adjuster for the pretreatment is 0.5 to 5%, and the water is soluble. The growth promoting agent is 1 to 2 〇 mass. /. The rest is water. [Embodiment] 23 View 20151 Hereinafter, the embodiment is not limited by these examples. In the present invention, the present invention is in the form of parts by weight, and "parts" means "% by mass" unless otherwise notified. In the following invention, the m-propionate is a compound having a structure of a nucleus oxyethylene and/or an epoxy poly-amplifier, and the compound represented by the formula (1) is used. The above-mentioned one is used as the compound represented by the formula (1), and any of the two warehouses is commercially available, and the product is obtained from Sakamoto Pharmaceutical Co., Ltd. , chemical scorpion. Among them, "SC_Pj is a chemical system. All of the compounds are polyoxypropylene: glycerol (4), and all of the compounds of "WE" are polyoxyethylene diglyceryl hydrazine. Product name 1) SC-P400: average molecular weight 4〇〇2) SC-Pl〇〇〇: average molecular weight 1〇〇〇3) SC_P1600: average molecular weight 16〇〇4) SC_E450: average molecular weight 45〇5) SC-E2000 : average molecular weight: 2 〇〇〇 [Examples 1 to 6] The components described in the following examples were mixed, and the respective ink compositions were obtained by stirring for about 1 hour until the solid components were dissolved. A membrane filter (trade name: CELLULOSE ACETATE filter paper, manufactured by ADVANTEC Co., Ltd.) of 45.45 μm was filtered to prepare a test ink. The preparation of the ink was set as each of Examples 1-6. Further, any of the reactive dyes used as a dye in each ink is monochlorotrim manufactured by Nippon Kayaku Co., Ltd. The well system, "C.I." is followed by 24 201120151, which means the term "Reactive" as described below, such as the well-known "reactive dye". [Example 1 (yellow ink)] CI Reactive Yellow 2 10 parts of hydroxy(hydroxy)amino decane 0.5 part SC-P400 25 parts of propylene glycol 10 parts of 2-β specific biting ketone 5 parts SURFYNOL 104PG50 0.1 part ADEKACOL EC8600 0.5 parts PROXEL GXL 0.1 part ion exchange water 48.8 parts [Example 2 (magenta ink)] CI Reactive Red 3:1 10 parts ginseng (hydroxymethyl) amino decane 0.5 parts SC-P1000 15 parts propylene glycol 10 parts 2 - pyrrolidone 3 parts SURFYNOL 440 0.3 parts ADEKACOL EC8600 0.3 parts PROXEL GXL 0.1 parts ion exchange water 60.8 parts [Example 3 (cyan ink) CI Reactive Blue 15:1 10 parts ginseng (hydroxymethyl) Aminomethane 0.5 parts SC-P1600 25 parts propylene glycol 10 parts 2-pyrrolidone 3 parts SURFYNOL 485 0.1 parts ADEKACOL EC8600 0.2 parts PROXEL GXL 0.1 parts ion exchange water 51.1 parts 25 201120151 [Example 4 (orange ink)] CI Reactive Orange 13 10 parts ginseng (hydroxymethyl) amino decane 0.5 parts SC-E450 25 parts propylene glycol 10 parts 2-° bil _ 3 parts SURFYNOL 440 0.3 parts PELEXOT-P 0.1 parts PROXEL GXL 0.1 parts ion exchange water 51 [Example 5 (cyan ink)] CI Rea Ctive Blue 49 10 parts ginseng (hydroxymethyl) amino decane oxime. 5 parts SC-E2000 20 parts propylene glycol 10 parts 2-pyrrolidone 3 parts SURFYNOL 485 0.5 parts PELEX OT-P 0.5 parts PROXEL GXL 0.1 parts ion exchange 55.4 parts of water [Example 6 (black ink)] CI Reactive Blue 176 9 parts CI Reactive Red 3: 1 3 parts CI Reactive Orange 12 3 parts hydroxy(hydroxy) amino decane 0.5 parts SC-E2000 5 parts B Glycol 15 parts propylene glycol 10 parts 2-pyrrolidone 10 parts SURFYNOL 485 0.5 parts ADEKACOL EC8600 0.1 parts PROXEL GXL 0.1 parts ion exchange water 43.8 parts 26 201120151 [Comparative Examples 1 to 4] Except that non-ionic surfactants and anions are not used in combination The ink for comparison was prepared in the same manner as in Example 2 except that the surfactants were used alone. The modulation of the ink for comparison was set as Comparative Examples ^ and 2. Similarly, the ink for comparison was prepared in the same manner as in Example 5 except that the surfactant was used alone. The modulation of the ink for comparison was set as Comparative Examples 3 and 4. Further, the inks of Comparative Example 1 and Comparative Example 3 were inks obtained by using only a nonionic surfactant and increasing the amount of ion exchange water in place of the anionic surfactant. The inks of Comparative Example 2 and Comparative Example 4 were inks obtained by using only an anionic surfactant and increasing the amount of ion-exchanged water in place of the nonionic surfactant. [Comparative Example 1] 10 parts 0.5 parts 15 parts 10 parts 3 parts 0.3 parts 〇·1 part 61.1 parts CI Reactive Red 3:1 参(methyl)aminomethane SC-P1000 propylene glycol 2·pyrrolidone SURFYNOL 440 PROXEL GXL ion exchange water 27 201120151 [Comparative Example 2] CI Reactive Red 3:1 10 parts ginseng (methyl) amino decane 0.5 parts SC-P1000 15 parts propylene glycol 10 parts 2-0 ratio! $•biting | 3 ADEKACOL EC8600 〇3 parts PROXEL GXL 0.1 parts ion exchange water 61.1 parts [Comparative Example 3] CI Reactive Blue 49 10 parts ginseng (hydroxymethyl) aminomethane 0.5 parts SC-E2000 20 parts propylene glycol 10 parts 2-pyrrolidine Ketone 3 parts SURFYNOL 485 0.5 parts PROXEL GXL 0.1 parts ion exchange water 55.9 parts [Comparative Example 4] CI Reactive Blue 49 10 parts ginseng (fluorenyl) amino decane 0.5 parts SC-E2000 20 parts propylene glycol 10 parts 2-° 3 parts PELEX OT-P 0.5 parts PROXEL GXL 0.1 parts ion-exchanged water 55.9 parts [Comparative Examples 5 to 7] In Example 4, except for the use of each of the 25 parts of the compound shown below 28 201120151, the above formula (1) The compounds shown were similarly prepared to prepare Comparative Examples 5 to 7 instead of 25 parts. Except Example 4 (SC-45〇) Embodiment Comparative Example 4 ink. Comparative Example 5: Comparative Example of Glycerol 750 k P0LYGLYCERIN 75〇 (average molecular weight: glycerin, manufactured by Sakamoto Pharmaceutical Co., Ltd.) Comparative Example 7: Propylene glycol using the ink of Example 5 and Comparative Example obtained as described above The measurement of the basic physical property value, the preparation and evaluation of the dyed fabric were carried out as follows. [Evaluation of Ink] Each of the inks prepared in the above Examples 1 to 5 and Comparative Examples 1 to 7 was subjected to seven types of tests (1) to (7) below to evaluate the performance of the ink. Among the test results, the measurement test of the basic physical property value of the ink is (1) viscosity test ~ (3) dynamic surface tension, as shown in the following Table 1; ink performance test, that is, (4) continuous spit test The ~(7) dyeing performance test' is shown in Table 2 below. (1) Viscosity test The viscosity of the ink of each of the examples and the comparative examples was measured at 10 °C and 25 °C using a Ε-type viscometer (Rl 15 type viscometer, manufactured by Toki Sangyo Co., Ltd.). Further, the unit of the numerical value in Table 1 below is mPa·s. (2) Surface tension The surface tension of the ink of each of the examples and the comparative examples was measured by a flat plate method (CBVP-Z type surface tension meter, manufactured by Kyowa Interface Science Co., Ltd.) at 1 (TC and 25 ° C). The unit of the numerical values in Table 1 below is mN/m. (3) The dynamic surface tension is 10 Hz at 10 °C and 10 Hz at 25 °C, using the maximum bubble pressure method (SITA SCIENCE LINE 60 type dynamic surface tension) The dynamic surface tension of each of the examples and the comparative examples was measured by the method of SITA Messtechnik GmbH. The unit of the numerical values in Table 1 below is mN/m. (4) The continuous spit test is performed using sodium alginate. a solution of urea, sodium hydrogencarbonate, and pre-treated cotton cloth by a pressure dyeing method, each of which uses ink of each of the examples and the comparative examples, and is equipped with an industrial inkjet head ( NOVA, FUJIFILM Dimatix Co., Ltd.) NDEMAND type inkjet printer (APOLLO 2 PRINTER SYSTEM, manufactured by FUJIFILM Dimatix Co., Ltd.), and printed in an environment of 25 ° C to evaluate the dischargeability of each ink. m Web Transport (spray The printing cloth conveyer (manufactured by ITI Corporation) was continuously printed five times in a 7-cm-thick cotton fabric in a single-pattern (Beta pattern) to obtain a woven cotton cloth. The benchmark is used to evaluate the test results. 〇: It can be printed well at the end △: The streak defect can be confirmed in the printed image, or the print can be printed until the end. x · The printed image is scattered and the streak defect is serious, or The printing is not fixed and cannot be printed until the end. ' (6) Dyeing test 1 30 201120151 <Test on cotton> The cotton cloth obtained in the (4) continuous spit test: (10) part 30 cm, - After performing intermediate drying, steam drying is carried out at 103c for 0.25 minutes. After washing with water, it is washed with 95 to 100 volts for 10 minutes, and then washed and dried to obtain a dyed cotton dyed fabric for testing. Test of cloth> The above-mentioned (4) continuous spit test was carried out using a silk cloth made of an aqueous solution containing guar, ammonium sulfate and urea and pretreated by a pressure dyeing method. 'The initial part of the printing of the obtained silk cloth was dried in the middle of 6 〇 to 8 〇t, and then dried at 1 〇〇 to 1 〇 3 χ for 20 minutes. After washing, it was dried. The dyed silk dyed fabric for the test was obtained, and the test results were evaluated based on the state of each of the obtained dyed fabrics based on the following criteria. Further, in Comparative Examples 5 and 7, the continuous discharge test was impossible in the above (4). Good dyeing, so the dyeability test 1 was not carried out. 〇. There is no graininess in the printed image, and there is no bubble in the printed dyed fabric. X: There is a grainy feeling in the printed image, and there are bubbles in the printed dyed fabric. (7) Dyeing test 2 In order to investigate the effect of the compound represented by the formula (1) on the effect of fixing the reactive dye on the cellulose fiber, the low temperature continuous in the above (5) was carried out for Example 4 and Comparative Examples 5 to 7. In the initial stage of the printing of the printed cotton cloth obtained by the spouting test, 20 cm was dried in the middle at 60 to 80 eC, and then steamed and baked at 1 to 103 C for 1 minute. After washing, wash the water at 95~ 31 201120151 for 1 minute, and prepare the dyed cotton dyed cloth by washing with water and drying. The MACBETh reflection density of the obtained dyed cotton dyed fabric obtained by the above was colorimetrically measured using a color measuring machine (SpectroEye GRETAG-MACBETH Co., Ltd.), and each fixing ratio was determined by the following formula. Fixing rate = (Α / Β) χΐ〇〇 (〇 /.) A: The reflection density of the dyed cotton-dyed cloth of Example 4 or Comparative Examples 5 to 7. B: Reflected concentration of the dyed cotton-dyed cloth of Example 4. 〇: 95°/. Above △ : 90% or more X : less than 90% [Table 1] Viscosity Surface tension Dynamic surface tension 25 〇 C 10 ° c 25 〇 C 10 ° C 25 〇 C 10 ° C Example 1 9.5 18.5 27 28 32 39 Example 2 8.5 18.0 29 30 31 36 Example 3 8.1 17.0 30 32 34 40 Example 4 8.9 18.3 32 34 37 39 Example 5 9.6 19.2 26 27 32 35 Example 6 9.3 18.5 31 33 33 36 Comparative Example 1 8.4 18.0 37 39 38 39 Comparative Example 2 8,5 18.1 29 30 33 45 Comparative Example 3 9.5 19.2 38 40 39 40 Comparative Example 4 9.5 19.2 27 28 33 45 Comparative Example 5 5.2 11.2 32 34 37 39 Comparative Example 6 7.3 15.5 32 34 37 39 Comparison Example 7 5.4 11.5 32 34 37 39 32 201120151 [Table 2]_Test Results Continuous_Spitability Test Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 ~~Comparative Example 例 Comparative Example 2 Comparison Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7
〇〇〇〇〇〇〇〇〇〇X △ X 染| 〇〇〇〇〇〇 X ο X ο - ο 000000x0x0-0 布I 同 % |±- 低溫連續 染色性試g 2 吐出性試驗 〇 --- 〇 〇 〇 〇 〇 〇 〇 ---- X • 〇 一 X 〇 X 〇 X 〇 〇 從表1的結果可清楚明白，併用非離子界面活性劑及 陰離子界面活性劑而成之各實施例的墨水，在25。〇及 c之表面張力’在25〜35mN/m的職，同溫度條件之在 10Hz的動態表面張力，在3〇〜4〇mN/m的範圍。 又，在全部的試驗項目，各實施例係顯示最高的結果。 另一方面，得知只使用非離子界面活性劑的比較例i 及3,雖然吐出性良好，但是於（6)染色性試驗丨中在印 花畫像有粒狀感，又，在經印染的染布亦有氣泡，其品質 差又’得知只使用陰離子界面活性劑的比較例2及4， 於（5)低溫連續吐出性試驗中，無法得到良好的吐出性。 又代替式（1)所表示的化合物，使用甘油之比較例 5 ’使用聚甘油75〇之比較例6、及使用丙二醇之比較例7， 在25 C時之墨水黏度低，在（4)連續吐出性試驗中，任一 者均無法得到良好的吐出性。 33 201120151 又’比較例5〜 顯示良好的吐出性 7’雖然於（5)低溫連續吐出性試驗尹， ，但是於使用所得到的印花棉布之（7) 染色性試驗2中 比較例5及6的染色性能極差。 根據以上的結果’得知本發明的墨水組成物，是一種 不會又到/皿度變化的影響而連續吐出性優良且染色性亦 良好的印染用墨水，特別適合作為使用於工業用喷墨頭中 之纖維的印染用墨水。 (產業上之利用可能性） 本發明的墨水組成物，能夠適合作為纖維的印染用 較佳是喷墨印染用、特別是使用工業用喷墨頭之嘴墨印$ 用的墨水來使用。 【圖式簡單說明】 無 【主要元件符號說明】 無 34〇〇〇〇〇〇〇〇〇〇X △ X dyed| 〇〇〇〇〇〇X ο X ο - ο 000000x0x0-0 cloth I with % |±- low temperature continuous dyeing test g 2 spit test 〇-- - 〇〇〇〇〇〇〇---- X • 〇-X 〇X 〇X 〇〇 From the results of Table 1, it is clear that the non-ionic surfactant and anionic surfactant are used in the examples. Ink, at 25. The surface tension of 〇 and c is in the range of 25 to 35 mN/m, and the dynamic surface tension at 10 Hz is in the range of 3 〇 to 4 〇 mN/m. Moreover, in all the test items, each example showed the highest result. On the other hand, it was found that Comparative Examples i and 3 using only a nonionic surfactant had good spouting properties, but in the dyeing test, (6) the printed image had a grainy feeling, and was dyed by printing. The cloth also had air bubbles, and the quality was poor, and it was found that Comparative Examples 2 and 4 using only an anionic surfactant did not provide good dischargeability in the (5) low-temperature continuous discharge test. Further, in place of the compound represented by the formula (1), Comparative Example 5 using glycerin, Comparative Example 6 using polyglycerol 75 Å, and Comparative Example 7 using propylene glycol, the ink viscosity at 25 C was low, and (4) continuous In the spit test, neither of them had good spitability. 33 201120151 Further, 'Comparative Example 5 to show good discharge property 7' was compared with (5) low-temperature continuous discharge test Yin, but Comparative Example 5 and 6 in (7) Dyeing Test 2 using the obtained printed cotton cloth. The dyeing performance is extremely poor. According to the above results, it is found that the ink composition of the present invention is an ink for printing which is excellent in continuous discharge property and excellent in dyeability without being affected by changes in the degree of the dish, and is particularly suitable for use as an industrial inkjet. The ink for printing and dyeing the fibers in the head. (Industrial Applicability) The ink composition of the present invention can be suitably used as a dye for fibers, and is preferably used for ink jet printing, particularly ink for ink jet printing using an industrial ink jet head. [Simple diagram description] None [Main component symbol description] None 34