TW476775B - Water-insoluble monoazo dye mixture - Google Patents

Abstract

To obtain a blue monoazo dye enabling desirable dyeing even under severe conditions at a high temperature, and a dye mixture compounded with the dye. The objective water-insoluble monoazo dye is expressed by the formula and has a crystal morphology characterized by an X-ray diffraction pattern (CuKΑ) having intense peaks at diffraction angles (2θ) of 9.8 deg. and 21.7 deg. and medium peaks at 7.5 deg. 13.6 deg., 19.7 deg., 22.6 deg., 24.4 deg. and 25.8 deg.. This invention also relates to a process for producing the dye, a dye mixture containing the dye and a product dyed with the dye or the dye mixture.

Description

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 476775 A7 B7 V. Description of the invention (1) This invention is an invention of an azo dye. In particular, it can make polyester fibers under high temperature and severe conditions. Uniformly dyed cyan-azo dye with novel crystal deformation and its manufacturing method. In recent years, the dyeing industry has begun to rationalize the dyeing method. For example, when disperse dyes are used to dye polyester fibers, the cloth is dyed by liquid flow, and the silk is dyed by package dyeing or package dyeing. In these dyeing methods, the fiber is curled in layers to form a stationary state of a dense fiber layer, and the dyeing dispersion liquid in the fiber layer is dyed in a forced circulation method. Therefore, until now, the dyeing particles dispersed in the dyeing bath are often required. It should be fine particles and the dyeing bath should 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. Therefore, the dyes used in these dyeing methods must have good dispersibility in the dyeing bath * and do not reduce dispersibility in a wide temperature range from room temperature to the high 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. As a result, the dye often aggregates and adheres to the surface of the dyed matter as a filtered residue. Dyeing materials often make the dyeing density of the outer layer part and the inner layer part uneven, and cannot obtain the dyeing matter with even sentence concentration. Especially from the viewpoint of saving resources and energy recently, this paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) --------- 一 — 装 --- -^ --- Order ------- line (please read the precautions on the back before filling this page) -4-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 476775 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) the dyeing conditions become hotter when the dyeing conditions are shorter (from 130 ° C, 1 hour to 13.5 ° 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 is one of the compounds shown in the structural formula [I] described in the first patent application scope. Dye, according to Law Concerning the Examination (3) is a known substance and 3662, the manufacturing method of the dye to follow the general procedure, the diazo component and a coupling component to a coupling reaction in the system. This azo dye can uniformly dye polyester fibers under the past mild dyeing conditions, and has excellent solidity. However, when dyeing under the above-mentioned high temperature and severe conditions, the dispersibility of the dye is significantly reduced, and a uniformly dyed dyed substance can hardly be obtained. In addition, the compatibility of this dye with various dyeing auxiliaries is also one of the problems. For example, in the presence of thenardite (N a 2 S 0 4), the high-temperature dispersion stability is significantly poor, so polyesters such as reactive dyes are also used in combination. When dyed in the presence of thenardite, cotton / cotton blends form uneven dyeing. Moreover, even when the compound dye is used, disadvantages such as discoloration and uneven dyeing are liable to occur from the point of compatibility with the compound dye. In order to solve the shortcomings mentioned above, the present invention proposes that the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 public love) under the severe conditions of high temperature. -------- Order —_------ line (please read the notes on the back before filling out this page) 5 Printed by the Consumers' Cooperative of Intellectual Property Bureau of the Ministry of Economy 476775 A7 ___B7 ___ V. Description of Invention (3) Dye that can be dyed well. The inventors have deliberately reviewed the shortcomings of the above, and have learned that there is at least two deformed crystal forms of one of the azo compounds of the 3-diethylamine acetanilide aniline shown in the structural formula [I], one of which It is a deformed crystal with poor dispersibility under high temperature dyeing conditions. Compared to the dye cake produced by previous synthetic reactions, this deformation crystal has found another excellent dispersion under high temperature or severe dyeing conditions. Stable new deformation crystal. Moreover, the stability of the dispersion state of the dye composition in the high-temperature dyeing bath does not only depend on the size of the dye particles, but has a significant relationship with the crystallinity. The use of the above-mentioned crystalline compound with novel crystallinity allows the dye composition to be dyed at high temperatures. Its dispersion stability is achieved in the bath, and thus the invention is achieved. The present invention is one. The diffraction angles (20) 9.8 ° and 2 1 ° in the X-ray diffraction pattern (CuKa) are higher peaks, and 7.5. , 1 3 · 6;, 1 9 · 7. , 2 2 · 6. , 2 4 · 4. And 25.8 ° is the middle peak, which is characterized by deformed crystals. The water-insoluble monoazo dye represented by the formula [Ϊ] is shown below, and 6-chloro-2,4-dinitroaniline is passed through diazo. And then condensed with 3- (N, N-diethylamine) -acetamidine, and the filtered cake is dispersed in an aqueous medium, and the temperature is from 0.5 to 30 at 60 to 130 ° C. Stirring for hours, or dispersing the filter cake in alcohol or ether, and stirring at a temperature of 15 to 100 ° C for 0.5 to 10 hours, a method for producing the dye, and a dye containing the dye The mixture is for the purpose of the invention β This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) '" " a 6------------- pack ----- Γ--Order --------- line (please read the precautions on the back before filling this page) 476775

〔Chem 1〕

02N N〇2 n = NN (C 2 Η 5) 2 C 1 NHCOCH3 cn Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs The following describes the present invention in more detail * The present invention has the structural formula [I] shown above An azo compound, which is a novel deformed crystal (hereinafter referred to as α-type crystal), is prepared according to the following method. For example, 6-chloro-2,4-dinitroaniline is diazotized in a general manner, and then, it is further immersed in an aqueous medium at a temperature of 5 to 15 ° C, preferably 0 to 10 ° C and From 0.5 to 15 hours, a coupling reaction with 3 (N, N-diethylamine) -acetamidine of coupling agent can synthesize an azo compound represented by the structural formula [I] shown above. The reaction mixture after the coupling reaction is extracted, and the filter cake of an azo compound obtained after filtration is a nearly amorphous deformed crystal (hereinafter referred to as an amorphous deformed crystal. The present invention is to treat the filter cake under specific conditions to make it Form α-type deformed morphology · This treatment method is "For example, disperse the / 3-type deformed crystal filter with (1) in water medium. Depending on the situation * it can be used in formaldehyde condensate of sulfonic acid, wood ~ basic In the presence of a dispersant such as a concentrate of a sulfite pulp waste liquid containing sodium as the main component, a temperature of 60 to 130 ° C, preferably 80 to 100, and a temperature of 0.5 to 30 Hours, preferably 1 to 10 hours, by stirring, or (2) methanol, ethanol, propanol, ethylene glycol and other alcohols, or two Dispersed in organic solvents formed by ethers such as alkane, diethyl ether, etc. -----------_ (Please read the precautions on the back before filling out this page) Binding ·! 4. This paper size applies to Chinese national standards (CNS) A4 specification (210x 297 public love) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 476775 A7 __B7_ V. Description of the invention (5), 15 ~ 10 0 ° C, preferably 20 ~ 8 0 It can be prepared by stirring at a temperature of 0.5 to 30 hours, or by using 6-chloro-2,4-dinitroaniline diazotization, and then reacting with 3- (N, N_diethyl). 5〜10Hours of stirring method after condensing acetanilide in a 0.5 ~ 15% sulfuric acid aqueous solution without filtering the resulting slurry at a temperature of 50 ~ 9 0 ° C In the following, the relationship between the α-type deformed crystal of an azo compound shown in the aforementioned structural formula [I] and the 3-type deformed crystal will be explained graphically. Figures 1 and 2 show the C u of the powder X-ray diffraction method. The diffraction pattern of the Kα line is an X-ray diffraction pattern obtained by recording a proportional counter. The horizontal axis is the diffraction angle (20) and the vertical axis is the diffraction intensity. Figure 1 is a novel aspect of the present invention. Crystalline α-type deformed crystals, in particular, have diffraction peaks (20) 9.8 ° and 21.7 ° with higher peaks, 7.5 °, 13.6 °, 19.7 °, 22.6. , 24.4, and 25.8 ° have intermediate peaks. Figure 2 is the current deformed crystal, which is significantly different from the deformed crystal of Figure 1. The diffraction angle of the X-ray diffraction method, if it is the same crystal form of the substance Although the difference can be regarded as the same when the difference is about ± 0.1 °, the crystal morphology is obviously different from this figure. This difference in crystal form causes the behavior of an azo compound to be different when dyeing. The dyeing method of the azo compound, which is one of the deformed crystals of the present invention, under high temperature and even severe conditions can also obtain good dyeing. Fibers that can be dyed in the 3-diethylamine acetanilide azo dyes of the present invention, such as polyethylene terephthalate, terephthalic acid and 1,4 one pair one (hydroxymethyl) Base) The paper size formed by the polycondensate of cyclohexane is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) ----------- pack ------- --Order --------- line (please read the precautions on the back before filling this page) 8 476775 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (6) Polyester fiber , Triacetate, diacetate and other acetate fibers, or cotton, wool and other natural fibers and polyester fibers or acetate fibers of the above-mentioned blended products, blended fabrics and so on. In the method for dyeing polyester fibers and the like using one of the azo dyes of the present invention, dispersants generally used such as a condensate of a sulfonic acid and formaldehyde, a higher alcohol sulfate, a higher alkylbenzene sulfonate, etc. The dye is dispersed in an aqueous medium to make a dyeing bath or dyeing paste for dipping or dyeing. 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 if 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 blends with other fibers. Specifically, for example, under severe conditions such as polyester fibers under a dyeing degree of 1 25 to 140 ° C, a dye bath ratio of 15 times or less, and a use ratio of 3 times or less by weight of the dye dispersant, In aqueous media, it can be fully dyed in the presence of a dispersant. In addition, depending on the situation, a dyeing bath can be added with formic acid, acetic acid, phosphoric acid, ammonium sulfate and other acidic substances to obtain better results. Moreover, the azo dye represented by the structural formula [I] shown previously in the present invention can also be used in combination with other dyes, and the dyeing effect can be improved due to the mutual cooperation of the dyes. For example, with respect to the structural formula [I] shown before the present invention, 1 parts by weight of an azo dye, in combination with the dye represented by the following structural formula [Π] 0.5 to 1. 0 parts by weight, preferably 0.55 to 0. 8 parts by weight after mixing, can be combined, dispersion Good navy blue dye mixture. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ----------- installation ----- 1--1T ---_--- r-- -Line (please read the precautions on the back before filling this page) 476775 Α7 Β7 Λ, .. ;; year month 〇2n

no2 N-N Cl

NHCOCHa 〔II〕 V. Description of the invention (OCH3 iN (C2H5) 2 In addition, 1 part by weight of this navy blue dye mixture, combined with the orange dye shown in the following formula [dish] 0. 6 ~ 1.0 parts by weight, preferably 7 ～ 0. 9 parts by weight After mixing, a black dye mixture with good combination and dispersibility can be obtained * (Please read the precautions on the back before filling in this page)

OzN

[III] Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

S (In the formula * X1 and X2 represent the same or different hydrogen atom, chlorine atom or bromine atom.). ;;, ;; [Examples] The following * The present invention will be described in more detail by way of examples. The invention is not changed in essence. Y is not limited by the following examples. Example 1 (Dye crystallization production example) 3- (N, N-diethylamine) -acetanilide 4. In water 2 0 0m ί Distribute evenly-combined parts in the middle. • 4 3 will be added. This paper size is applicable to China National Standard (CNS) A4 (210 X 297 public love). ___ V. Description of the invention (8)% nitrosylsulfuric acid 4. 3g, 98% sulfuric acid 5.8g, under stirring at 20 ~ 30 ° C, 6-chloro-1,2,4-dinitroaniline 4 is added slowly. In 3 g, diazotization was performed to obtain a diazotization solution. The second gasification solution was dropped in the solution of the former coupling solution at 0 to 5 ° C, and after stirring for 10 hours at the same temperature, the precipitated crystals were filtered, washed with water, and dried to obtain the structural formula [I] shown above. 5g。 Green crystals of the compound shown 6.5g. An azo dye powder obtained by this reaction was analyzed by an X-ray diffraction method, and a yS-type deformed crystal shown in the X-ray diffraction chart of Fig. 2 was obtained. Secondly, the obtained / 3-type deformed crystals were dispersed in water having a capacity of 10 times, and stirred at 85 to 90 ° C. 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 α-type deformed crystals as shown in the X-ray diffraction chart of Fig. 1. Test Example 1 (Dyeing Example) The azo dye with an α-type deformed crystal prepared in Example 1 0.2 g was placed in a sulfonic acid-formaldehyde condensate 0.2 g and a higher alcohol sulfate 0. 1 g of 2 g was dispersed in water to prepare a dyeing bath. This dyeing bath was immersed in 100 g of polyester fiber and dyed at 1 35 ° C for 30 minutes. After soaping, washing and drying, a dyeing cloth with good dispersibility and uniform dyeing was obtained. In addition, the obtained dyed cloth was a good product with a cyan color, a light fastness level of 5 to 6, and a frictional fastness level of 4 to 5.

P Also, the azo dye, one of the lingering deformed crystals, was used in the manufacturing process of the above-mentioned manufacturing example, and the same dyeing test was performed, except that the dye produced in the dyeing bath ------------ pack --- -, --- Order ---'------ line (please read the notes on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -11-476775 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (9) Cohesion phenomenon, which forms uneven sentences on the dyed fabrics, and is a relatively inferior item with a rubbing firmness of 1. Test Example 2 (Dyeing Example) In Test Example 1, except that the amounts of sulfonic acid-formaldehyde condensate and higher alcohol sulfate were each increased by 3 times to be 0.6 g, water was increased by 3 times to be 3 again, and the dyeing conditions Set to 130 ° C. Except for 60 minutes, everything else is 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 Friction firmness is a good level of 4-5. In contrast, when the 73-type deformed crystalline substance was used, it was only slightly improved compared to Test Example 1. However, a dyed cloth with uneven dyeing was also obtained. Example 2 (Production Example and Dyeing Example of Dye Crystal) 3- (N, N-diethylamine) -acetamidine 8.1 g was dispersed in water 1 to form a couple. Next, 13 g of 98% sulfuric acid with 12.3 g of 4% nitrosylsulfuric acid was added. With stirring at 20 ~ 30 ° C, 6-chloro-2,4-dinitroaniline 8.6 g was slowly added to perform the dicouple. Nitriding to obtain a diazo solution. This diazotization solution was dropped into the solution of the former coupling solution at 0 to 5 ° C, and stirred at the same temperature for 4 hours. This slurry was then heat-treated at 75 ° C for 2 hours, and the precipitated crystals were filtered, washed with water, and dried to obtain 13.lg of green crystals of the compound represented by the structural formula [I] shown previously. The paper size of the azo dye obtained from this reaction is in accordance with the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ------------ pack -----.--- Order ---.------ line (please read the precautions on the back before filling this page) ~ 12-476775 A7 B7 V. Description of the invention (1G) The analysis result by X-ray diffraction method is shown in Figure 1 An α-type deformed crystal as shown in the X-ray diffraction pattern. (Please read the precautions on the back before filling out this page.) When dyes prepared by this method are dyed according to the method of Test Example 2, the same good dyeing as Test Example 2 is obtained. Example 3 (manufacturing example of a dye mixture) A dye mixture formed with 5 6 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-formaldehyde condensate 1 5 O g was mixed with 650 g of water, wet-milled with a sand mill, and spray-dried to obtain a powdery dye mixture. Test Example 3 (Dyeing Example) 0.4 g of the dye mixture obtained in the previous Example 3 and a nonone-based leveling agent, Carsay (trademark) LP — PSL (Mitsubishi Chemical Co., Ltd.) 0.08 g and water 150 mj? 5。 Forming a dyeing bath, acetic acid / acetic acid, Intellectual Property Bureau of the Intellectual Property Bureau, the consumer cooperatives printed sodium system adjusted to PH4.5. Immerse 5g of polyester material in this dyeing bath, raise the temperature of the dyeing bath to 2 ° C / mi η at room temperature, and absorb and dye at 130 ° C for 60 minutes. The dyed objects are then soaped, washed and Dry to get navy blue dye. In addition, after adding Cu 2 + 0 0 ppm to the dyeing bath, the same dyeing as described above was performed. As a result, the color tone of the object to be dyed was almost the same as that in the case where Cu + + was not added. Make an impact. Examples 4 to 8 (manufacturing and dyeing examples of dye mixtures) This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy 476775 A7 B7_ V. Invention Explanation (11) The same dyeing method as in Test Example 3 was performed using the dyeing shown in Table 1. The obtained dyed objects were all dyed at a uniform concentration, and Cu + + ions were hardly affected. Table 1 1 Dye use 4 (g) Example Dye Structural Formula Hue [I] [π] [Dish-1] [Π -2] Example 4 46 28 58-Black Example 5 40 30 45 10 Black Example 6 50 30 one 60 black example 7 45 25 — navy blue example 8 60 36 — 85 black This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) --------- ,-Install ----- ^ --- order ---'------ line (please read the precautions on the back before filling this page) -14-476775 A7 _ B7 Staff of Intellectual Property Bureau, Ministry of Economic Affairs Printed by Consumer Cooperatives

V. Description of the invention (12) Structural formula of the dye II [II]. Ί [III-1] [II 1-2] _ The water-insoluble azo dye with α-type deformed crystals of the present invention can be used at high temperature, and, For example, the ratio of dyed: dyeing liquid is 1: 1, the ratio of dye filter cake: dispersant is 1: 1, the dyeing conditions are 135 t, and 0.5 hours under severe dyeing conditions, it is also very good. The dispersion stability, and the prepared dyed fabric also has excellent light fastness, rubbing fastness and other properties. 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 [Fig. 1] X o2n- N = N-/ NHCOCHa of α-type deformed crystal of an azo dye obtained in the embodiment of the present invention

/ Cl yCzHs

OzN \ C2H4CN CzHs

C21UCN ---------,-install ----- ^ --- order ---.------ line (Please read the precautions on the back before filling this page) This paper The scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm)-15-476775 A7 _B7 V. Description of the invention (13) Light diffraction pattern, the horizontal axis is the diffraction angle (2 0), and the vertical axis is Diffraction intensity. [Figure 2] This is an X-ray diffraction pattern of a / 3-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 0 ----- ----.-- install --------- order ---.------ line (please read the precautions on the back before filling this page) The paper size of the paper is applicable to China National Standard (CNS) A4 (210 X 297 mm) -16-

Claims (1)

476775 Printed by A8, B8, C8, D8, Consumer Cooperatives of the Ministry of Economic Affairs, Intellectual Property Co., Ltd. 6. Patent application _ ~ 1. A navy blue dye mixture, which uses the water-insoluble azo represented by the following formula [I] 1 part by weight of the dye, mixed with 0.5 to 1_ 0 parts by weight of the dye represented by the following formula [Π]; Ν〇2 ο2ν Ν = Ν Cl ~ ^ y ^ (c2H5) 2nhc〇ch3 in (the diffraction angle (2 0) 9.8 ^ and 2 1 · 7 ° in the X-ray diffraction pattern (Cu Ka)) are the higher peaks, And 7 · 5., 1 3 · 6 0, 19.7.70, 2 2 · 6., 2 4 · 4., And 2 5 8 ^ are intermediate peaks), NOz O21V -N = N Cl NHCOCH: OCII3 N (C2H5) 2 (I Π 2 · — a black dye mixture, which uses 1 part by weight of the navy blue dye mixture as claimed in the scope of the patent application No. 1 with the dye 0 shown in the following formula [m]. 6 ~ 1.0 parts by weight; ο- / C2Hs CzH ^ CN 〔III〕 This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm)-17---------- —— (Please read the precautions on the back before filling out this page) 476775 A8 B8 C8 D8 VI. Patent application scope (where X1 and X2 can be the same or different hydrogen atom, chlorine atom or bromine atom). ...... S (Please read the notes on the back before filling out this page) # 、 Yanxianyi Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is printed in accordance with Chinese National Standard (CNS) A4 (210X297) Mm) one 18 one