TW434297B - Water insoluble mono-azo dyes and the production thereof - Google Patents

Abstract

The present invention provides a blue mono-azo dye which can be used for dyeing even at high temperatures and under harsh conditions. The present invention is a water-insoluble mono-azo dye of the formula [I], characterized by a modified crystal form showing in an X-ray diffraction pattern (CuKΑ) at diffraction angles (2θ) 9.8 DEG and 21.7 DEG higher peak values and at 7.5 DEG, 13.6 DEG, 19.7 DEG, 22.6 DEG, 24.4 DEG and 25.8 DEG medium peak values and a process for preparing the dye by diazotizing 6-chloro-2,4-dinitroaniline followed by a condensation of the resultant diazotized compound the cake into an alcohol or ether and stirring at a temperature of 15 to 100 DEG C for 0.5 to 10 hours.

Description

d34297 A7 B7 五、發明説明（1 ) 本發明係爲一偶氮染料之發明，詳細而·言，係於高溫 且嚴苛條件下亦可使聚酯纖維等均勻染色之具有新穎結晶 變形之青色系一偶氮染料及其製造方法》 近年來，染色業界開始對染色法進行合理化之處理， 例如，使用分散染料對聚酯纖維進行染色時，布類使用液 流染色法，絲則使用筒子染色法或捲裝染色法等方式進行 0 此些染色法中，纖維係以層狀捲曲形成緻密纖維層之 靜止狀態，於該纖維層內染色分散液係以強制循環方式進 行染色，故至目前爲止，常要求染色浴中分散之染色粒子 應爲微粒子且染色浴需具優良之分散安定性·.。若染色粒子 過大則纖維層對染色粒子會形成過濾現象，使對纖維內部 之染料形成浸透不良，或因附著凝集物而使內外層染色不 均，或染料僅附著於纖維表面而產生耐摩擦堅固度等堅固 度降低等問題。 經濟部中央標準局員工消費合作社印製 (請先调讀背洒之注意事項再填寫本頁) 因此，此些染色法所使用之染料，必須具有於染色浴 中分散度良好，且由室溫至實際產生染著之髙溫之間廣大 溫度範圍中不會降低分散性之特性^ 但，一般而言，將染色浴提至高溫時 > 染料之分散性 往往容易降低，其結果常使染料凝集而於上述被染物之表 面以濾過之殘渣狀附著，又，對於數層疊覆之被染物，常 使外層部份與內層部份之染色濃度不均，而無法得到均勻 濃度之染色物。 特別是最近由節省資嫄，節約能源之觀點而言已有， 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 4 3 4 29 7 A7 B7 五、發明説明（2 ). 如（1 )染色浴之低浴比化（被染物：染色.液之比例由1 :30降至1:10) ， （2)分散劑使用比例之降低化 (染色餅：分散劑之比例由1 : 3降至1 : 1)，且（3 )染色條件更短時高溫化（由1 3 0 °C，1小時變爲 1 3 5°C，0 . 5小時）等使染色條件趨向更嚴苛之條件 ，無論上述任一條件，皆傾向不利於染料分散安定性方面 ，既使對以往染色法具較佳分散安性之染料，對目前逐漸 嚴苛之染色條件而言，大多皆算是分散安定性不佳之物質 〇 例如•申請專利範圍第1項記載之結構式〔I〕所示 之3 —二乙胺乙醯替苯胺系之一偁氮染料^依化審法（3 )一 3 6 6 2而爲公知物，該染料之製法可依一般方法· 將二偶氮成份與偶合成份進行偶合反應而製得。 此一偶氮染料可於以往溫和的染色條件下，對聚酯纖 維作均勻之染色，且具優良之堅固度•但若在上述般之髙 溫及嚴苛條件下進行染色時，其染料之分散性顯著降低· 而幾乎無法得到染色均勻之染色物。 經濟部中央標準局員工消费合作社印製 (請先调讀背面；之注意事項再填寫本頁) 又，此染料與各種染色助劑之相溶性亦爲問題之一， 例如於芒硝（N a 2S 04)存在下則其高溫分散安定性顯 著不佳，故併用反應性染料等之聚酯/綿混紡品在芒硝存 在下進行染色時則形成不均勻染色。 又，既使配合染料使用之時，由其與所配合染料之相 溶性點而言，易產生色斑、染色不均等缺點" 本發明爲解決上記缺點，而提出於高溫嚴苛條件下亦 本紙張尺度適用中國國家標準（CNS > A4规格（210X297公釐） -5 - 434297 A7 B7 五'發明説明（3 ) 可進行良好染色之 本發明者們， 前記結構式〔I〕 化合物至少存在2 染色條件下分散性 所製得之染料餅爲 嚴苛之染色條件下 形結晶。 且，染料組成 並非僅取決於染料 用上記具有新穎結 於高溫染色浴中達 本發明係爲一 (20)9. 8。 、1 3 6 0 、1 2 5· 8 °爲中間 染料。 . 對上記缺點經刻意深入檢討結果*得知 所示3 —二乙胺乙醯替苯胺系之一偶氮 種之變形結晶形態，其中一種爲高溫之 不佳之變形結晶，相對於以往合成反應 此變形結晶而言，發現了另一於高溫或 亦具有非常優良之分散安定性的新穎變 物於高溫染色浴中分散狀 粒子的大小而與結晶性有 晶性之結晶形態化合物可. 成其分散安定性，因而達 ，於X光衍射圖（CuK 及21· 7°爲較高峰值 9 . 7 ° '22. 6 ° 、 峰值，爲特徵的具變形結 態之安定性， 重大關係，使 使染料組成物 成本發明。 α )中衍射角 ，且 7 · 5 0 2 4 · 4 0 及 晶之下記結構 請 先 η 讀 背 注 意d34297 A7 B7 V. Description of the invention (1) The invention is an invention of an azo dye. In detail, it is a cyan with novel crystal deformation that can make polyester fibers and other materials uniformly dyed under high temperature and severe conditions. An azo dye and its manufacturing method "In recent years, the dyeing industry has begun to rationalize the dyeing method. For example, when dispersing dyes are used to dye polyester fibers, the cloth is dyed by liquid flow, and the silk is dyed by bobbin. In these dyeing methods, the fibers are curled in layers to form a stationary state of the dense fiber layer, and the dyeing dispersion in the fiber layer is dyed in a forced circulation method, so far. It is often required that the dyeing particles dispersed in the dyeing bath should be fine particles and the dyeing bath must have excellent dispersion stability .. If the dyed particles are too large, the fiber layer will filter the dyed particles, causing poor penetration of the dye inside the fiber, or uneven dyeing of the inner and outer layers due to the adhesion of agglomerates, or the dye only adheres to the surface of the fiber, resulting in strong and friction-resistant Such as reduced solidity. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions for back spray before filling this page). Therefore, the dyes used in these dyeing methods must have a good dispersion in the dyeing bath and be at room temperature. Dispersibility does not decrease in a wide temperature range from the temperature at which dyeing actually occurs ^ However, in general, when the dyeing bath is raised to a high temperature > the dispersibility of the dye tends to decrease, and as a result, the dye Agglutinated and adhered to the surface of the above-mentioned dyed matter as a filtered residue, and for several layers of dyed matter, the dyeing density of the outer layer part and the inner layer part is often uneven, and a dyed matter of uniform concentration cannot be obtained. Especially from the viewpoint of saving resources and energy recently, this paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 4 3 4 29 7 A7 B7 V. Description of the invention (2). For example, (1) the low bath ratio of the dyeing bath (the ratio of the dyed object: the dyeing solution is reduced from 1:30 to 1:10), (2) the use of the dispersant is reduced (the ratio of the dyeing cake: the dispersant is changed from 1: 3 to 1: 1), and (3) higher temperature when dyeing conditions are shorter (from 130 ° C, 1 hour to 1 3 5 ° C, 0.5 hours), etc. Strict conditions, regardless of any of the above conditions, tend to be detrimental to the stability of the dye dispersion. Even dyes that have better dispersion stability for the previous dyeing methods are mostly considered to be gradually harsher dyeing conditions. Substances with poor dispersion stability. For example, 3-diethylamine, acetanilide, and one of the nitrogen dyes shown in the structural formula [I] described in the first patent application scope. 6 6 2 It is a well-known thing. The dye can be prepared according to the general method. And prepared. This azo dye can uniformly dye polyester fibers under the past mild dyeing conditions, and has excellent solidity. But if dyeing under the above-mentioned temperature and severe conditions, the dye Dispersibility is remarkably reduced, and a uniformly dyed substance can hardly be obtained. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the back; please note this page before filling out this page) Also, the compatibility of this dye with various dyeing auxiliaries is also one of the problems, such as in thenardite (N a 2S 04) In the presence of high-temperature dispersion stability, the polyester / cotton blended product using reactive dyes and the like is dyed in the presence of thenardite to form uneven dyeing. In addition, even when the compound dye is used, from the point of compatibility with the compound dye, defects such as stains and uneven dyeing are easy to occur. The present invention proposes to solve the above-mentioned disadvantages under severe conditions of high temperature. This paper size applies Chinese national standard (CNS > A4 size (210X297mm) -5-434297 A7 B7 Five 'invention description (3) The inventors who can perform good dyeing, the compound of the above formula [I] exists at least 2 The dye cake prepared by dispersibility under dyeing conditions is crystallized under severe dyeing conditions. Moreover, the dye composition is not only dependent on the use of dyes. It has a novel knot in a high-temperature dyeing bath. The present invention is one (20) 9. 8. ， 1 360 ， 1 2 5 · 8 ° are intermediate dyes. After deliberate in-depth review of the shortcomings mentioned above, we know that the 3-diethylamine acetamidine is one of the azo species. Deformed crystal form, one of which is a bad deformed crystal at high temperature. Compared with the deformed crystal of the previous synthetic reaction, another novel variant that has high dispersion or excellent dispersion stability was found at high temperature. The size of the dispersed particles in the color bath can be crystalline in the form of crystalline compounds. Its dispersion stability is achieved, so that it reaches the X-ray diffraction pattern (CuK and 21.7 ° are the higher peaks of 9.7 ° '22. 6 °, the peak, which is characterized by the stability of the deformed junction state, has a significant relationship, which makes the dye composition cost invented. Α) The diffraction angle, and 7 · 5 0 2 4 · 4 0 and the crystal Please read the structure first.

I 费 經濟部中夬標準局貝工消費合作社印裝 式〔I〕所示水不溶性一偶氮染料及，將6 —氯—2 , 4 一二硝基苯胺經二偶氮化，再與3 —（Ν，Ν -二乙基胺 )-乙醯替苯胺縮合後’將濾得之濾拼於水媒體中分散， 於6 0〜1 3 0°C溫度下經〇 . 5〜3 0小時攪拌，或將 該濾餅於醇或醚中分散，並於1 5〜1 〇 〇°C溫度進行 0 . 5〜1 0小時攪拌而得之該染料的製造方法，及以含 有此染料之染料混合物爲發明目的〃 本紙張尺度適用中國國家標準（CNS〉Α4規格（210X297公釐） a 3 7 A7 B7 五、發明説明（4 ) 〇2nI The water-insoluble mono-azo dye shown in the formula [I] and printed by the China Industrial Standards Bureau Shellfish Consumer Cooperative of the Ministry of Economic Affairs, and 6-chloro-2, 4-dinitroaniline are diazotized, and then — (Ν, Ν -diethylamine) -acetamidine is condensed, and the filtered mixture is dispersed in an aqueous medium at a temperature of 60 to 130 ° C over 0.5 to 30 hours. A method for producing the dye by stirring, or dispersing the filter cake in alcohol or ether, and stirring at 0.5 to 100 ° C for 0.5 to 10 hours, and a dye containing the dye The mixture is for the purpose of the invention. 纸张 The paper size is applicable to the Chinese national standard (CNS> A4 specification (210X297 mm) a 3 7 A7 B7. V. Description of the invention (4) 〇2n

ill 以下將本發明作更詳細之說明。 本發明之如上記結構式〔I〕所示，且爲 晶（以下稱α型結晶）之一偶氮化合物係依以 。例如將6 —氯—2，4_二硝基苯胺以一般 經濟部中央標隼局員工消費合作社印製 化，其次•再將其 〜1 0°C溫度及0 ，N —二乙基胺） 示結構式〔I〕所 將偶合反應後 偶氮化合物之濾餅 變形結晶），本發 形成α型變形形態 此處理方法爲 )於水媒體中分散 合物，木質磺酸鈉 等分散劑之存在下 1 0 0 °C溫度作0 攪拌處理之方法* 等醇類，或二噁烷 於水媒體中以-5〜1 5小時 一乙醯替苯胺經 示之一偶氮化合 之反應混合物經 爲近乎無定型之 明係將此濾餅， 〇 ，例如，將沒型 ，依情形之不同 爲主成份之亞硫 ，以6 0〜1 3 -5〜3 0小時 或（2 )於甲醇 ，二***等醚類 5 〜1 5 °C 間，與偶-合 偶合反應， 物。 萃取，濾過 變形結晶（ 於特定條件 新穎變形結 下方法製得 方式二偶氮 ，較佳爲0 劑之3 ( N 即可合成前 後所得之一 以下稱沒型 下處理使其 變形結晶之濾餅以（1 ，可於棻磺酸之甲醛縮 酸鹽紙漿廢液之濃縮物 01，較佳爲80〜 ，較佳爲1〜10小時 、乙醇、丙醇、乙二醇 形成之有機溶媒中分散 (請先間讀背面‘之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） A7 B7 經濟部中央橾率扃負工消費舍作社印製 五、發明説明（5 ). ，以15〜100 °C，較佳爲20 〜3 0小時左右攪拌處理之方法| 氯—2，4一二硝基苯胺二偶氮化 二乙基胺）一乙醯替苯胺於0. 5 縮合後，將所得淤漿未經濾過下再 作0. 5〜10小時攪拌之方法。 以下，將以圖式說明前示結構 合物之型變形結晶與；S型變形結 爲粉體X線衍射法之C u Κ α線之 記錄而得之X線衍射圖，橫軸爲衍 衍射強度。圖1爲本發明之具新穎 ，特別是具有，衍射角（20) 9 有較高峰值，7. 5° *13.6 2 2. 6 ° ，24.40 及 25. 2爲目前之jS型變形結晶，與圖1 X光衍射法之衍射角，若爲同 在±0. 1°左右時雖可視爲相同 晶形態有.明顯不同。此結晶形態之 化合物之舉動亦有所不同，具有_本 化合物於高溫甚至嚴苛條件下之染 染色。 本發明之3 —二乙基胺乙醯替 予染色之纖維類，例如聚乙烯對苯 〜8 0 °C_溫度作〇 . 而製得。或採用將6 — ，再與 3 — ( N，N — 〜15%硫酸水溶液中 以5 0〜9 0 °C溫度下 式〔I〕所示一偶氮化 晶之關係 衍射狀態 射角（2 結晶型的. 請 閲 讀 背 ..面 之 注 意 事 項 -8 0及 0 ，1 9 8 °具有 之變形結 一結晶型 β圖1及圖2 以比例計數器 0 )，縱軸爲 α型變形結晶 2 1 · 7 ° 具 .7 ° ， 中間峰值。圖 晶明顯不同》 之物質時該差 圖式得知其結 ，但由此 差異導致 發明變形 色法，亦可得到良好的 染色時·一偶氮 結晶之一偶氦 、裝 頁 訂 與 苯胺系之一偁氮染料可 二甲酸酯，對苯二甲酸 4 -雙-（羥甲基）環己烷之聚縮合物等所形成之 本紙張尺度適用中國國家標準（CNS ) Α4規格（21〇><297公釐） 8 43429 7 A7 B7 五、發明説明（6 ) 聚酯纖維、三乙酸酯、二乙酸酯等乙酸酯纖.維、或木綿、 羊毛等天然纖維與上記聚酯纖維或乙酸酯纖維之混紡品、 混織品等等· 使用本發明之一偶氮染料對聚酯纖維等進行染色方法 中，一般常使用之分散劑例如菓磺酸與甲醛之縮合物、髙 級醇硫酸酯、高級烷基苯磺酸鹽等，可將染料於水性媒體 中分散製成染色浴或捺染糊以便進行浸染或捺染。又，浸 染時可使用上述之高溫染色法、載體染色法、恆溫染色法 等染色處理法，且，此些方法既使採用嚴苛染色條件時， 本發明之一偶氮染料仍具優良之分散安定性，故可對聚酯 纖維、乙酸酯纖維及其與他種纖維之混紡品··皆具良好之染 色力β具體而言，例如聚酯纖維等在染色染度1 2 5〜· 1 4 0°C，染浴比1 5倍以下，相對於染料分散劑之使用 比例爲3重量倍以下之嚴苛條件下，於水性媒體中，分散 劑之存在下亦可充分予以染色。 又，依情形之不同，染色浴可配合添加蟻酸、醋酸、 磷酸、硫酸銨等酸性物質，而得到更好的結果》 且，本發明之前示結構式〔I〕所示一偶氮染料亦可 與其他染料併用，可因染料相互配合而提高染色性之效果 9 例如，對本發明之前示結構式〔I〕所示之一偶氮染 料1重量份，配合下記結構式〔E〕所示染料〇. 5〜 1. 0重量份，'較佳爲〇 55〜0 8重量份經混合後 ，可得組合性、分散性良好之海軍藍色染料混合物。 本紙張尺度適用中國國家榇隼（CNS ) Α4規格（210 X 297公釐）_ 請 先 聞 讀 背 -面 之 注 Ϊ 經濟部中央標準局舅工消費合作社印製 A7 B7 五、發明説明（7 )The present invention will be described in more detail below. The azo compound of the present invention, which is represented by the above-mentioned structural formula [I] and is a crystal (hereinafter referred to as an α-type crystal), is based on. For example, 6-chloro-2,4-dinitroaniline is printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, followed by • ~ 10 ° C temperature and 0, N-diethylamine) The structural formula [I] shows that the azo compound filter cake is deformed and crystallized after the coupling reaction, and the α-shaped deformed form is formed. The treatment method is) the presence of a dispersant in an aqueous medium, and a dispersant such as sodium lignosulfonate. A method of stirring at a temperature of 100 ° C at 0 ° * and other alcohols, or dioxane in an aqueous medium at -5 to 15 hours. The reaction mixture of acetanilide is shown as The nearly amorphous type is the filter cake. For example, the sulfite, which is the main component depending on the situation, will be used for 60 ~ 1 3 -5 ~ 30 hours or (2) in methanol. Ethers, such as diethyl ether, react with the coupling-coupling reaction at 5 to 15 ° C. Extraction, filtration of deformed crystals (in a new method under specific conditions, a new method of making diazo, preferably 0 of 3 (N can be obtained before and after synthesis) (1, can be dispersed in the sulfonic acid formaldehyde condensation salt pulp waste liquid concentrate 01, preferably 80 ~, preferably 1 ~ 10 hours, in an organic solvent formed by ethanol, propanol, ethylene glycol (Please read the "Notes on the back" first and then fill out this page) This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) A7 B7 Description of the invention (5). Method of stirring treatment at 15 to 100 ° C, preferably about 20 to 30 hours | Chlorin-2,4-dinitroaniline diazonium diethylamine) -acetamidine After condensing fenaniline at 0.5, the obtained slurry was stirred for 0.5 to 10 hours without filtration. Hereinafter, the type-deformation crystals of the structural compound shown previously and the S-type deformation will be explained by diagrams. X-ray diffraction pattern obtained by recording the C u κ α line of powder X-ray diffraction method, horizontal axis To diffract the diffraction intensity. Figure 1 shows the novelness of the present invention, in particular, the diffraction angle (20) 9 has a higher peak, 7.5 ° * 13.6 22.6 °, 24.40 and 25.2 are the current jS Deformed crystals, and the diffraction angle of the X-ray diffraction method in Fig. 1 may be regarded as the same crystal form if they are the same at about ± 0.1 °. Obviously different. The behavior of the compound in this crystal form is also different, it has _The compound is dyed and dyed under high temperature or even severe conditions. 3-Diethylamine ethyl acetate of the present invention is used for dyeing fibers, such as polyethylene p-benzene ~ 8 0 ° C Or use the diffraction angle of 6—, and 3— (N, N— ~ 15% sulfuric acid aqueous solution at a temperature of 50 ~ 90 ° C for an azotite crystal as shown in formula [I]. 2 Crystal type. Please read the back .. Note on the surface -8 0 and 0, 198 ° deformation of a crystal type β (Figure 1 and Figure 2 with proportional counter 0), the vertical axis is α-type deformed crystal 2 1 · 7 ° with .7 °, with a middle peak. The difference in the crystals is obviously different. As a result of the invention of the discoloration method, good dyeing can also be obtained. One of the azo crystals is azo, one of the binding and aniline azo dyes can be diformates, terephthalic acid 4-bis- (hydroxy The paper size formed by the polycondensation products of methyl) cyclohexane is applicable to the Chinese National Standard (CNS) A4 specification (21〇 > < 297 mm) 8 43429 7 A7 B7 V. Description of the invention (6) Ester fiber, triacetate, diacetate, and other acetate fibers; natural fibers such as cotton, wool, wool, etc., and polyester fibers or acetate fiber blends, blended fabrics, etc. Examples of dispersants commonly used in dyeing polyester fibers with an azo dye include condensates of sulfonic acid and formaldehyde, thiol sulfate, higher alkylbenzene sulfonate, etc. Disperse in the media to make a dyeing bath or paste for dip or paste. In addition, the above-mentioned dyeing treatment methods such as the high-temperature dyeing method, the carrier dyeing method, and the constant temperature dyeing method can be used during the dip dyeing, and even when these methods are used under severe dyeing conditions, one of the azo dyes of the present invention has excellent dispersion. Stability, so it can have good dyeing power for polyester fiber, acetate fiber and its blended products with other kinds of fibers. Specifically, for example, polyester fiber has a dyeing degree of 1 2 5 ~ At 140 ° C, the dyeing bath ratio is 15 times or less, and under the severe conditions that the use ratio of the dye dispersant is 3 times or less by weight, it can be fully dyed in the presence of a dispersant in an aqueous medium. In addition, depending on the situation, a dyeing bath can be added with acidic substances such as formic acid, acetic acid, phosphoric acid, and ammonium sulfate to obtain better results. Moreover, an azo dye represented by the structural formula [I] shown in the present invention may also be used. When used in combination with other dyes, the dyeing effect can be improved due to the mutual cooperation of the dyes. For example, 1 part by weight of an azo dye represented by the structural formula [I] shown previously in the present invention is blended with a dye represented by the following structural formula [E]. 5 ~ 1.0 parts by weight, 'preferably 055 ~ 0 8 parts by weight after mixing, a navy blue dye mixture with good combination and dispersibility can be obtained. The size of this paper is applicable to China National Standard (CNS) A4 (210 X 297 mm) _ Please read the back-to-side note first. Printed by the Central Standards Bureau of the Ministry of Economic Affairs and the Consumer Cooperatives. A7 B7 V. Description of the invention (7 )

NHCOCH3 又，對此海軍藍色染料混合物1重量份；，配合下記式 (瓜〕所示橙色染料0. 6〜1. 0重量份，較隹爲 0. 7〜0· 9重量份經混合後，可得組合性、分散性良 好之黑色染料混合物。 μ1 /C2h5 〔III〕 一 \2h,cn (式中，X1及X2表示相同或相異之氫原子、氯原 子或溴原子。） 經濟部中央標準局員工消費合作社印製 (請先閱讀背面，之注意事項再填寫本頁) 〔實施例〕 以下，將本發明以實施例作更具體之說明，本發明於 未變更實質下不受下列實施例所限定。 實施例1 (染料結晶之製造例） 將3 — (N，N-二乙基胺）一乙醯替苯胺4. 1 g 於水2 0 0m文中分散而得偶合成份。其次將添加有4 3 本紙浪尺度適用中國國家標準（CNS ) A4規格{ 210X297公釐） 434297 Λ Λ. Α7 _______Β7_ 五、發明説明丨8 ). %亞硝基硫酸4. 3g之98%硫酸5. 8:g，於20〜. 3 0°C攪拌下，徐徐添加入6 —氯一 2，4 一二硝基苯胺 4. 3g中，進行二偶氮化而得二偶氮化溶液。此二偶氮 化溶液於前記偶合成份溶液中於0〜5 °C間滴下，經1 0 小時，同溫度下攪拌，將析出結晶濾過、水冼、乾燥，而 得前示結構式〔I〕所示化合物之綠色結畢6. 5g。此 反應所得一偶氮染料粉末以X光衍射法分析*得圖2之X 光衍射圖所示之jS型變形結晶。 其次，將所得；9型變形結晶於1 0倍容量之水中分散 ，並於8 5〜9 0eC攪拌3小時，以進行結晶之移轉。於 結晶移轉後，進行濾過、乾燥，將所得結晶„以X光衍射法 進行分析，得圚1之X光衍射圖所示之OE型變形結晶。 試驗例1 (染色例） 將前記實施例1所製得之具GE型變形結晶之一偶氮染 料0. 2g，置於含某磺酸—甲醛縮合物0. 2g及高級 醇硫酸酯0. 2g之1又水中，使之分散以調製染色浴。 經濟部中央標準局負工消費合作社印製 將此染色浴浸入聚酯纖維1 0 0 g，於1 3 5°C進行 3 0分鐘之染色後，進行皂洗、水洗及乾燥後，得染色分 散性良好，且均勻染色之染布。又，所得染布爲青紫龟、 耐光堅固度5〜6級、耐摩擦堅固度4〜5級之良好物品 〇 又，上記製造例之製造途中使用万型變形結晶之一偶 氮染料，並進行同樣之染色試驗，惟染浴中染料產生部份 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -11 - 經濟部中央標準局W；工消費合作社印製 Α7 Β7 五、發明説明（9 ). 凝聚現象，於染布上形成不均勻之染色，且·耐摩擦堅固度 爲1級之較劣物品。 試驗例2 (染色例） 於試驗例1中，除將某磺酸一甲醛縮合物及高級醇硫 酸酯之量各增加3倍而爲0. 6g，水增如3倍而爲35 ，染色條件設爲1 30 eC，60分鐘以外*其他皆與試驗 1相同。以半溫和染色法進行染色所得結果，於本發明之 α型變形結晶之具一偶氮染料，可得與試驗例1相同良好 的染色，所得染布之耐光堅固度爲5〜6級，耐摩擦堅固 度爲4 - 5級之良好程度。相對於此，使用J型變形結晶 物質之時，僅較試驗例1有些許提昇，但同樣得到染色不 均之染布，具耐摩擦堅固度爲3級。 實施例2 (染料結晶之製造例及染色例） 將3 —（Ν，Ν —二乙基胺）-乙醯替苯胺8. lg 分散於水1交中使成偶合成份。其次將添加有4 3 %亞硝 基硫酸12. 2g之98%硫酸13g，於20〜30°C 攪拌下，徐徐添加6 —氯—2，4 一二硝基苯胺8. 6 g 進行二偶氮化而得二偶氮化溶液。將此二偶氮化溶液於前 記偶合成份溶液中於0〜5 °C間滴下，經4小時，同溫度 下攪拌。隨後將此淤液於7 5 進行2小時熱處理，所析 出之結晶經濾過、水洗、乾燥得前示構造式〔I〕所示化 合物之綠色結晶13. lg。此反應所得一偶氮染料之粉 本紙張尺度適用中國國家標準（CNS > A4規格（210Χ297公釐）~ -12 -NHCOCH3 In addition, 1 part by weight of this navy blue dye mixture; 0.6% to 1.0% by weight of the orange dye represented by the following formula (melon), 7 to 0.9% by weight after mixing A black dye mixture with good combination and dispersibility can be obtained. Μ1 / C2h5 [III]-\ 2h, cn (where X1 and X2 represent the same or different hydrogen atom, chlorine atom, or bromine atom.) Ministry of Economic Affairs Printed by the Consumer Standards Cooperative of the Central Bureau of Standards (please read the notes on the back, and then fill out this page) [Examples] Hereinafter, the present invention will be described in more detail with examples. The present invention is not subject to the following changes without substantial changes. It is limited by the examples. Example 1 (manufacturing example of dye crystal) 3- (N, N-diethylamine) -acetamidine aniline 4. 1 g was dispersed in water 200 m to obtain an even part. Second 4 3 paper waves will be added to the Chinese National Standard (CNS) A4 specification {210X297 mm) 434297 Λ Λ. Α7 _______ Β7_ V. Description of the invention 丨 8).% Nitrosulphuric acid 4. 3g 98% sulfuric acid 5. 8: g, at 20 ~. 30 ° C, slowly add 6-chloro-1, 2-dinitrate Aniline 4. 3g, be diazotized diazo solution was obtained. This diazo solution was dripped at a temperature of 0 to 5 ° C in the former mixture solution, stirred for 10 hours at the same temperature, and the precipitated crystals were filtered, hydrolyzed, and dried to obtain the structural formula [I] shown above. 5g。 The green compound of the compound shown was 6.5 g. An azo dye powder obtained by this reaction was analyzed by X-ray diffraction * to obtain a jS-type deformed crystal as shown in the X-ray diffraction chart of FIG. 2. Next, the obtained 9-type deformed crystals were dispersed in water having a capacity of 10 times, and stirred at 85 to 90 eC for 3 hours to transfer the crystals. After the crystals were transferred, they were filtered and dried, and the obtained crystals were analyzed by X-ray diffraction to obtain OE-type deformed crystals shown in the X-ray diffraction pattern of 圚 1. Test Example 1 (Dyeing Example) The previous examples will be described. 1.2g of an azo dye with GE-type deformed crystals obtained was placed in 0.2g containing a certain sulfonic acid-formaldehyde condensate and 0.2g in higher alcohol sulfate, and dispersed in water for modulation Dyeing bath. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. This dyeing bath is immersed in 100 g of polyester fiber and dyed at 1 35 ° C for 30 minutes. After soaping, washing and drying, A dyed cloth with good dispersibility and uniform dyeing was obtained. In addition, the obtained dyed cloth was a good product with a purple tortoise, a light fastness of 5 to 6, and a frictional fastness of 4 to 5. Also, during the manufacturing process of the above-mentioned manufacturing example An azo dye, one of the 10,000-type deformed crystals, was used for the same dyeing test, except that the dye produced in the dyeing bath was in accordance with the Chinese National Standard (CNS) A4 specification (210X297 mm). -11-Central Standard of the Ministry of Economic Affairs Bureau W; printed by industrial and consumer cooperatives Α7 Β7 Explained clearly (9). Cohesion phenomenon, forming uneven dyeing on the dyed cloth, and inferior items with abrasion resistance and hardness of Class 1. Test Example 2 (Dyeing Example) In Test Example 1, except a The amount of acid-formaldehyde condensate and higher alcohol sulfate each increased by 3 times to 0.6g, the water was increased by 3 times to 35, the dyeing conditions were set to 1 30 eC, other than 60 minutes * the same as Test 1. As a result of dyeing by a semi-mild dyeing method, the azo dye having the α-type deformed crystal of the present invention can obtain the same good dyeing as in Test Example 1. The lightfastness and solidity of the obtained dyed cloth are grades 5 to 6, and The frictional firmness is a good level of 4-5. In contrast, when using J-shaped deformed crystalline material, it is only slightly improved compared to Test Example 1, but the dyed cloth with uneven dyeing is also obtained. The frictional firmness is Grade 3. Example 2 (manufacturing and dyeing examples of dye crystals) 3- (N, N-diethylamine) -acetamidine 8.18 lg was dispersed in water to make couples. Second, Added 13% 98% sulfuric acid with 4 2% nitrosylsulfuric acid 12.2g, slowly stirred at 20 ~ 30 ° C, Add 8.6 g of 6-chloro-2,4-dinitroaniline to diazotization to obtain a diazotization solution. This diazotization solution was added to the solution of the former coupling solution at a temperature between 0 and 5 ° C. Dropwise, after 4 hours, stir at the same temperature. The slurry was then heat treated at 7 5 for 2 hours. The precipitated crystals were filtered, washed with water, and dried to give the green crystals of the compound represented by the structural formula [I] 13. lg. The paper size of the azo dye obtained by this reaction is in accordance with Chinese national standards (CNS > A4 specification (210 × 297 mm) ~ -12-

^1- *^1· J H ^^^1 nn frlai HL 1-J 』"、v* (請先閲讀背面之注意事項再填寫本頁) -A 43429 7 A7 B7 五 '發明説明（l〇 ) 末以X光衍射法分析結果，爲圖1之X光衍射圖所示之α. 型變形結晶· 使用此方法製得之染料依試驗例2方法進行染色時， 得與試驗例2相同良好的染色。 實施例3 (染料混合物之製造例） 將前示結構式〔I〕所示染料56g與結構式〔Π〕 所示染料4 4 g所形成之染料混合物與木質磺酸一甲醛縮 合物1 5 0 g與水6 5 0 g混合，以砂磨機進行濕式粉碎 後噴霧乾燥，得粉末狀染料混合物》 請 -閲 讀 背 意 事 項 再 填 頁 經濟部中央標準局貝工消費合作社印製 試驗例 將前記 染劑載爾赛 )0.08 鈉系調整至 ，將染色浴 〇C，6 0 分 得海軍藍色 又，將 相同之染色 色調幾乎相 3 (染色例） 實施例3所得染料混合物0. (商標）LP — PSL (三菱 g及水1 5 Omj?形成染色浴 PH4. 5。於此染色浴中浸 之溫度中室溫以2 eC / ip i η 鐘吸收染色後•被染物經皂洗 之被染物。 染色浴添加C u++2 0 p pm ，其結果與未添加C u + +之情 同，得知C u + +離子幾乎不產 4 g與壬酮系均 化學（株）製品 ，以醋酸/醋酸 入聚酯材料5 g 昇溫，於1 3 0 、水洗及乾燥， 後，進行與上記 形下，被染物之 生影響。 實施例4〜8 (染料混合物之製造例及染色例） 本紙浪尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 訂 13 - 經濟部中央標準局員工消費合作社印製 434297 Μ Λ Α7 __Β7 五、發明説明(：II ) 使用表1所示染色進行與試驗例3相同·之染色方式。 所得到之被染物皆得均勻濃度之染色，又，C u + +離子幾 乎不具影響》 表一1 \染料使用 (g) 實施\ m \ 染料結構式 色 相 [I ] [Π ] [ΙΠ -1 ] [皿-2] 實施例4 46 28 58 — 黑色 實施例5 40 30 45 10 黑色 實施例6 50 3 0 — 60 黑色 實施例7 45 25 — — 海軍藍 實施例8 60 36 — 85 黑色 本紙張尺度適用中國國家榇準（CNS ) Α4規格（210X297公釐）， -14 - (請先鬩讀背面之注意事項再填寫本頁)^ 1- * ^ 1 · JH ^^^ 1 nn frlai HL 1-J "", v * (Please read the notes on the back before filling out this page) -A 43429 7 A7 B7 Five 'invention description (l〇 ) The results of the X-ray diffraction analysis showed that the α.-type deformed crystals shown in the X-ray diffraction chart of Fig.1. When the dye prepared by this method was dyed according to the method of Test Example 2, it was as good as Test Example 2. Of staining. Example 3 (Production Example of Dye Mixture) A dye mixture formed with 56 g of the dye represented by the structural formula [I] and 4 4 g of the dye represented by the structural formula [Π] and lignosulfonic acid monoformaldehyde condensate 1 50 g is mixed with water 650 g, wet-milled with a sand mill, and spray-dried to obtain a powdery dye mixture. Please-read the intent and then fill out the page. Printed test example by the Central Laboratories of the Ministry of Economic Affairs. (Previous dyestuff dyestuff) (0.08) Sodium system is adjusted so that the dyeing bath 〇C, 60 points are navy blue, and the same dyeing hue is almost phase 3 (dyeing example) The dye mixture obtained in Example 3 is 0. (Trademark ) LP — PSL (Mitsubishi g and water 1 5 Omj? Form a dyeing bath PH4.5. After immersing in this dyeing bath at room temperature at 2 eC / ip i η clock absorption dyeing • The dyed object was soaped The dyeing bath added Cu + + 2 0 p pm, the result is the same as that without adding Cu + +, it was learned that Cu + + ions hardly produce 4 g and nonanone series chemical products. Heat 5 g of polyester material with acetic acid / acetic acid, wash and dry at 130, water, and then The effects of the dyed matter are as described above. Example 4 ~ 8 (Manufacturing and dyeing examples of dye mixtures) The size of this paper applies to China National Standard (CNS) A4 (210X297 mm). Order 13-Central Standard of the Ministry of Economic Affairs Printed by the Bureau's Consumer Cooperatives 434297 Μ Λ Α7 __B7 V. Description of the invention (: II) The dyeing method shown in Table 1 is used to perform the same dyeing method as in Test Example 3. All the dyed objects obtained are dyed at a uniform concentration. C u + + ions have almost no effect. Table 1 1 \ Use of dyes (g) \ m \ Dye structure formula hue [I] [Π] [ΙΠ -1] [皿 -2] Example 4 46 28 58 — Black Example 5 40 30 45 10 Black Example 6 50 3 0 — 60 Black Example 7 45 25 — — Navy Example 8 60 36 — 85 Black This paper is sized for China National Standards (CNS) A4 (210X297) %), -14-(Please read the notes on the back before filling in this page)

43429 7 0 β Α7 _Β7 五、發明説明_( l2 ). 染料結構式 n〇2 OzN )N-N -N (C2H5) 2 'Cl / NHCOCHa43429 7 0 β Α7 _Β7 V. Description of the invention _ (l2). Dye structural formula n〇2 OzN) N-N -N (C2H5) 2 'Cl / NHCOCHa

爲 /〇CHj ΟϊΝ —^ N=N N(C2H5) z ^CI / NHC0CH3/ 〇CHj ΟϊΝ-^ N = N N (C2H5) z ^ CI / NHC0CH3

〔II〕〔II〕

,C1 02N N=N-^)-N, C1 02N N = N-^)-N

Cl 經濟部中央標準局員工消费合作社印製 "11-1〕 U I I -2〕~ 本發明之具〇£型變形結晶之水不溶性一偶氮染料，可 於高溫，及，例如被染物：染色液之比例爲1 : 10，染 料濾餅：分散劑之比例爲1 : 1，染色條件爲135°C’ 0. 5小時之嚴苛染色條件下，亦具有非常良好之分散安 定性，且所製得之染布亦具有優良的耐光堅固度’耐摩擦 堅固度等性質。故，本發明之染料，由節省資源及節約能 源觀/點/而言，爲非常有用之物質。 圖式簡單說明 〔圖1〕 爲本發明實施例所得一偶氮染料之α型變形結晶的X 本紙張尺度適用中囷國家標準（CNS>A4規格（ 210X297公釐）_15-Cl Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs " 11-1] UII -2] ~ The water-insoluble azo dye with 0 £ type deformable crystals of the present invention can be used at high temperature, and, for example, dyed: dyeing The ratio of the liquid is 1: 10, the ratio of the dye filter cake: the dispersant is 1: 1, and the dyeing conditions are 135 ° C '0.5 hours. Under the severe dyeing conditions, it also has very good dispersion stability, and The prepared dyed fabric also has excellent light fastness and abrasion resistance. Therefore, the dye of the present invention is a very useful substance from the viewpoint of saving resources and energy. Brief description of the drawing [Figure 1] This is the X-type deformed crystal of an azo dye obtained in the embodiment of the present invention. The paper size is applicable to the Chinese standard (CNS > A4 specification (210X297 mm) _15-

CzHXN c2iucn mu ^ftt i n^i n^i ml l^ln l·—— - - ^ i .' <請先閎讀背面之注意事項再填寫本頁) 4 3^297 ：- A7 B7 五、發明説明（13) 光衍射圖，圖中，橫軸爲衍射角（2 0 ) ，·縱軸爲衍射強 度。 〔圖2〕 爲本發明實施例所得一偶氮染料之js型變形結晶的X 光衍射圖，圖中，橫軸爲衍射角（20)，縱軸爲衍射強 度β (請先閱讀背面之注意事項再填寫本頁) 力装· 訂 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -16-CzHXN c2iucn mu ^ ftt in ^ in ^ i ml l ^ ln l · ——--^ i. '≪ Please read the notes on the back before filling out this page) 4 3 ^ 297 ：-A7 B7 V. Invention Explanation (13) A light diffraction diagram, where the horizontal axis is the diffraction angle (2 0) and the vertical axis is the diffraction intensity. [Figure 2] This is an X-ray diffraction pattern of a js-type deformed crystal of an azo dye obtained in an example of the present invention. In the figure, the horizontal axis is the diffraction angle (20), and the vertical axis is the diffraction intensity β (please read the note on the back first) Please fill in this page again for details) Printed on the paper printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, China Paper Standard Applicable to China National Standard (CNS) Α4 Specification (210 × 297 mm) -16-

Claims (1)

43429 7, Λ Α8 Η8 C8 1)8 弟 申請專利範圍 _ 1—« 第85 1 10 796號專利申請案 中文申請專利範圍修正本 民國8 9年11月修IE 種下式（I )所示之水不溶性一偶氮染料：43429 7, Λ Α8 Η8 C8 1) 8 brothers apply for patent scope _ 1— «85 1 10 796 Patent Application Chinese Patent Range Amendment November 1989 Revised IE as shown in the following formula (I) Water-insoluble azo dye: ~/~Vn(C2II5)2 v=/ NHCOCH3 . ⑴， (請先龄讀背面之注意事項再填寫本頁) 經濟郢智慧財產局員工消f合作钍印製 其特徵爲，結晶 9 . 8 0 與 2 1 在約7 . 5 ° 、 2 4 . 4 ° 及 2 2 .—種如 染料之製造方法 氮化，令重氮化 醢替苯胺偶合， 將該沈澱物分散 並將所得混合物 3 0小時，或將 混合物於1 5〜 3 .如申請 料之製造方法， 結構於X .7。之 13.6 5.8° 申請專利 ，包括將 產物與3 把反應混 在（a ) 於6 0〜 該沈澱物 10 0。。 專利範圍 α )中之約 對強峰，而 2.6°' 一光繞射圖（CliK 0 >呈相 7。、2 2 Θ )呈中間峰 繞射角（2 ° ' 1 9 . 之繞射角（ 範圍第1項所述水不溶性一偶氮 6_氯一 2，4_二硝基苯胺重 —(Ν，Ν —二乙基胺基）一乙 合物裡的沈 水性介質（ 1 3 0。<：之 分散在（b 下攪拌0 . 第2項所述 澱物分離 aqueous 溫度下攪 )醇或醚 5〜1 0 出來，以及 medium )中 拌0 5〜 裡並將所得 小時。 之水不溶性一偶氮染 係將6 -氯一 2，4 一二硝基苯胺重氮化 本紙張又度適用'^因國家標準（CNSU4規格（210 X 297公坌） 4 34 29 7 , Λ ΑΗ ΗΗ C8 1)8 ^、申請專利範圍 ，令重氮化產物與3_ (Ν，Ν —二乙基胺基）_乙醯替 苯胺偶合後，將所得淤液再於5 0〜9 0°C溫度攪拌 ο 5 得 製 而時 小 ο (請先陪讀背之注意事項再填寫本頁) ---'裝--------訂---------線 經-部智慧財產局員工消費合作社印製 本紙張尺度適用*國囤家標準（C>：S)A4規格（210 X 297公S ) -2 -~ / ~ Vn (C2II5) 2 v = / NHCOCH3. ⑴, (please read the precautions on the back before filling out this page) Economics, Intellectual Property Bureau, staff, cooperation, and printing. Its characteristics are crystallized 9. 8 0 Nitriding with 2 1 at about 7.5 °, 24.4 °, and 2 2 .—a method of manufacturing such as dyes, coupling diazonium dianiline, dispersing the precipitate and obtaining the resulting mixture for 30 hours , Or mix the mixture at 15 ~ 3. According to the manufacturing method of the application materials, the structure is at X.7. 13.6 5.8 ° Patent application, including mixing the product with 3 reactions (a) at 60 to the precipitate 100. . The patent range α) is about the strong peak, and the 2.6 ° 'light diffraction pattern (CliK 0 > phase 7., 2 2 Θ) is the middle peak diffraction angle (2 °' 1 9. Angle (the water-insoluble mono-azo-6-chloro-2,4-dinitroaniline as described in item 1 of the range—a sinking medium in a heavy- (N, N-diethylamino) -ethyl compound (1 3 0. <: Disperse (stir at 0 under b. Stir at aqueous temperature of the precipitate described in item 2) alcohol or ether 5 ~ 1 0 out, and medium) and stir for 5 ~ 5 hours. The water-insoluble monoazo dyeing system will again diazotize 6-chloro-2,4-dinitroaniline. This paper is applicable again due to the national standard (CNSU4 specification (210 X 297 cm) 4 34 29 7, Λ ΑΗ ΗΗ C8 1) 8 ^ The scope of the patent application, after coupling of the diazotized product with 3_ (N, N-diethylamino) _acetamidine, the resulting slurry was re-deposited at 50 ~ 90 ° C temperature stirring ο 5 can be made while small ο (please read the precautions before filling in this page) --- 'Installation -------- Order --------- Thread Sutra- Printed by the Ministry of Intellectual Property Bureau's Consumer Cooperative * Paper applicable national scale store house standard (C >: S) A4 size (210 X 297 well S) -2 -