Black liquid reactive disperse dye, its preparation method and dyeing application

Abstract

The present invention belongs to the fields of dyes and textile printing and dyeing, and specifically relates to a black liquid reactive disperse dye, a preparation method thereof, and a dyeing application. The present invention discloses a black liquid reactive disperse dye, which is composed of the following components by mass content: 15% - 30% of a black dye composition, 5% - 10% of a dispersant, 5% - 10% of a fixing agent, 1.0 - 1.2% of an auxiliary agent, and the balance is water. The black dye composition is composed of dyes D1, D2, and D3, and the fixing agent is compound M. The present invention also simultaneously provides the use of the above black liquid reactive disperse dye: for dyeing spandex. The black liquid reactive disperse dye provided by the present invention has the characteristics of pure black shade for dyeing spandex, high fixation rate, high soaping fastness, rubbing fastness, and sublimation fastness.

Description

Technical Field

[0001] The present invention belongs to the fields of dyes and textile printing and dyeing, and particularly relates to a black liquid reactive disperse dye, a preparation method thereof, and a dyeing application thereof. Background Art

[0002] Spandex is a well-known elastic fiber and is widely used in the textile and clothing fields. Spandex can be dyed with disperse dyes or acid dyes. However, there are problems of poor depth and fastness of dyeing. When using acid dyes for dyeing, the dyes can form ionic bonds with the amino groups on spandex. However, the number of amino groups in the spandex structure is limited and cannot bind more acid dyes, so it is difficult to obtain a dark color. When using disperse dyes for dyeing, since the hydrophobicity of the dyes and the fibers is the same, spandex can adsorb a large amount of dye molecules. However, the flexible chain segments of the spandex fiber macromolecules are in a relaxed state, and the dye molecules are easily separated. Therefore, the soaping fastness of disperse dyes dyed on spandex is poor (reference: Dyeing and Finishing Technology, 2021, 43(07), 19-21+43).

[0003] Reactive disperse dyes refer to a class of dyes in which reactive groups are introduced into the molecular structure of conventional disperse dyes. Such dyes have both the hydrophobicity of disperse dyes and the reactivity of reactive dyes. Conventional reactive disperse dyes usually use triazine structure or vinyl sulfone sulfate structure as reactive groups, and the fixation rate of reacting with hydroxyl groups, amino groups, etc. on the fiber is only 50% - 70%. Since the number of primary amino groups in spandex fiber molecules is extremely small, the reactivity of conventional reactive disperse dyes with spandex is even worse.

[0004] Carbene dyes refer to a class of dyes containing carbene precursor structures in their molecular structures. Such dyes can form active carbene intermediates under high temperature or ultraviolet radiation conditions, and then can react with oxygen-hydrogen bonds, nitrogen-hydrogen bonds, and even carbon-hydrogen bonds on the fiber, thereby firmly binding the dyes to the fiber. Research shows that both diaziridine and diazo groups can be used as carbene precursors for the design of dye reactive groups. Among them, the diazo group has the characteristics of simple synthesis and low cost. Patents (CN117304711 and CN117402507) proposed a structural design scheme of carbene dyes based on diazo groups, and the fixation rate of the obtained dyes dyed on spandex reached more than 90%.

[0005] The patents (CN117304711 and CN117402507) have the following problems: only monochromatic dyes such as yellow, orange, red, purple, and blue are provided, and there is no black dye. It is common knowledge in the dye field that black dyes can usually be obtained by mixing monochromatic dyes. The difficulties are as follows: (1) The color light of the existing dyes may not match. For example, screening only from the dye types provided in the patents (CN117304711 and CN117402507), even if mixed, a satisfactory black color cannot be obtained. (2) The compatibility of the existing monochromatic dyes is unknown. Compatibility refers to whether parameters such as the dyeing rate, dye uptake rate, fixation rate, and dyeing depth of the dyes on the fiber are similar. Only dyes with good compatibility can have an ideal dyeing effect after compounding. (3) The color fastness of the dyed black spandex may not be guaranteed. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to provide a black liquid reactive disperse dye, its preparation method, and its application in dyeing spandex.

[0007] To solve the above technical problems, the present invention provides a black liquid reactive disperse dye, which is composed of the following components by mass content:

[0008] 15% - 30% of black dye composition, 5% - 10% of dispersant, 5% - 10% of fixing agent, 1.0 - 1.2% of auxiliary agent, and the balance is water.

[0009] As an improvement to the black liquid reactive disperse dye of the present invention: the auxiliary agent is composed of penetrant, wetting agent, defoamer, and bactericide with a mass ratio of 5:(2±0.2):(2±0.2):(2±0.2).

[0010] That is, the black liquid reactive disperse dye of the present invention is composed of the following components by mass content: 15% - 30% of black dye composition, 5% - 10% of dispersant, 5% - 10% of fixing agent, 0.5% of penetrant, 0.2% of wetting agent, 0.2% of defoamer, 0.2% of bactericide, and the rest is water.

[0011] As a further improvement to the black liquid reactive disperse dye of the present invention: the black dye composition is composed of dyes D1, D2, and D3:

[0012]

[0013] The mass ratio of dyes D1, D2, and D3 is 12 - 16:0.8 - 1.2:20.

[0014] As a further improvement to the black liquid reactive disperse dye of the present invention: the mass ratio of dyes D1, D2, and D3 is 14:1:20.

[0015] As a further improvement of the black liquid reactive disperse dye of the present invention: the fixing agent is a compound M having the following structure:

[0016]

[0017] As a further improvement of the black liquid reactive disperse dye of the present invention:

[0018] The dispersant is a mixture composed of an anionic dispersant and a non-ionic dispersant in a mass ratio of 2:1;

[0019] The anionic dispersant is dispersant MF, and the non-ionic dispersant is fatty alcohol polyoxyethylene ether AEO-9.

[0020] As a further improvement of the black liquid reactive disperse dye of the present invention:

[0021] The mass ratio of the black dye composition, the dispersant and the fixing agent is 3:1:1.

[0022] The present invention also simultaneously provides a preparation method of the above black liquid reactive disperse dye, including the following steps:

[0023] 1), Mix the black dye composition, the dispersant, the fixing agent and water and then grind them;

[0024] 2), Add auxiliaries (penetrant, wetting agent, defoamer, bactericide) to the mixture obtained in step 1) and stir evenly (continue stirring for 10 min), and then adjust the pH to 6.5 - 7.5 to obtain the black liquid reactive disperse dye.

[0025] Note: According to the acidity and alkalinity of the system, the present invention uses acetic acid or sodium bicarbonate to adjust the pH value of the system to 6.5 - 7.5.

[0026] The said step 1) is:

[0027] Mix the black dye composition, the dispersant, the fixing agent and water and then add them to a grinding machine pre-filled with zirconium beads for grinding;

[0028] The specification of the zirconium beads is 0.2 ± 0.05 mm; the dosage of the zirconium beads is 4 ± 0.5 times the total mass of the grinding materials; the grinding speed is 1500 ± 100 r / min; the grinding time is 2 ± 0.5 h; the ambient temperature during grinding is 25 ± 5 °C.

[0029] The present invention also simultaneously provides the use of the above black liquid reactive disperse dye: for dyeing spandex.

[0030] As an improvement of the use of the black liquid reactive disperse dye of the present invention, the dyeing steps are as follows:

[0031] 1. In a dyeing vat, prepare a dye solution by adding water to a black liquid reactive disperse dye, adjust the pH value of the dye solution to 5 - 6, put in spandex, seal the dyeing vat, heat up to the holding temperature, and carry out dyeing; the holding temperature is 95 ± 3 °C, and the holding time is 45 ± 5 min;

[0032] The mass ratio of the spandex to the black dye composition in the black liquid reactive disperse dye is 100:(3 ± 0.3);

[0033] 2. After dyeing, put the spandex obtained in step 1 into an oven for heat fixation; the fixation temperature is 130 ± 5 °C, and the fixation time is 30 ± 5 min;

[0034] 3. Take out the spandex obtained in step 2 and place it in a soap washing solution at 80 °C, carry out soap washing once, then rinse with clear water at room temperature and dry; the formula of the soap washing solution is 1 g / L of soap flakes and 1 g / L of sodium carbonate; the bath ratio of the soap washing solution is 1:50; the soap washing duration is 10 min.

[0035] The main inventive points and technical advantages of the present invention are as follows:

[0036] (1) The present invention first designs and synthesizes 3 diazo - type reactive dyes in orange, red, and blue with color matching. Mixing these 3 dyes in a specific ratio can make the dyed spandex obtain a very deep black color.

[0037] (2) In the structure of dye D1 of the present invention, 2 α - phenyl diazoester structures are used. The introduction of the double - diazo group greatly improves the reaction effect between the dye and spandex, improves the dye utilization rate, and reduces dye waste. In the structures of dyes D2 and D3, 1 α - phenyl diazoester structure is used, which can ensure a good reaction effect. In the black dye composition, the different designs of the number of diazo groups of each dye take into account both the reaction effect between the dye and the fiber and the synthesis cost of the dye, achieving an optimal choice.

[0038] (3) To further improve the fixation effect of the black dye, the present invention designs and synthesizes a fixing agent with 3 α - phenyl diazoester structures. Through the cross - linking and fixing form, this fixing agent can further firmly bind the dye molecules that have not reacted with spandex to the fiber, improve the fixation rate of the dyed spandex. At the same time, it can also reduce dye waste and reduce the post - treatment cost of dyeing.

[0039] In summary, the black liquid reactive disperse dye provided by the present invention has the characteristics of pure black color shade for dyed spandex, high fixation rate, high soaping, rubbing, and sublimation color fastness. Compared with traditional reactive disperse dyes, the reactive disperse dye of the present invention does not require additional alkali addition, and the dye molecules can be reacted onto the fiber through simple heat treatment. The treatment process is simple, efficient, and environmentally friendly. Description of the Drawings

[0040] The following further elaborates on the specific embodiments of the present invention in conjunction with the accompanying drawings.

[0041] Figure 1 For the 1 1H NMR spectrum of dye D1;

[0042] Figure 2 For the 13 13C NMR spectrum of dye D1;

[0043] Figure 3 For the 1 1H NMR spectrum of dye D3;

[0044] Figure 4 For the 13 13C NMR spectrum of dye D3;

[0045] Figure 5 For the 1 1H NMR spectrum of compound 3;

[0046] Figure 6 For the 13 13C NMR spectrum of compound 3;

[0047] Figure 7 For the 1 1H NMR spectrum of compound M;

[0048] Figure 8 For the 13 13C NMR spectrum of compound M;

[0049] Figure 9 For the UV-visible absorption spectra of dyes D1-D3 in DMF;

[0050] Figure 10 For the dyeing rate curves, dye uptake rates, color depths, and fixation rates of dyes D1-D3 when dyeing spandex alone;

[0051] Figure 11 For the K / S curve and physical photos of spandex dyed with black liquid reactive disperse dye 1;

[0052] Figure 12 For the K / S curve of spandex dyed with liquid reactive disperse dye 12 (Comparative Example 5). Specific Embodiments

[0053] The following further describes the present invention in conjunction with specific embodiments, but the protection scope of the present invention is not limited thereto:

[0054] In the present invention:

[0055] Compound 1, which is Compound A in CN117402507A;

[0056] Dye D2, which is the reactive dye corresponding to Structural Formula (V) in CN117304711A.

[0057] Compound 2, which is Compound D in CN117304711A.

[0058] Except as otherwise specially informed, the raw materials and reagents used in the remaining synthesis process can all be obtained commercially and are directly used except as otherwise specified. Dispersant MF, fatty alcohol polyoxyethylene ether AEO-9, penetrant JFC, wetting agent LCN407, defoamer DF830, bactericide BIT20, acetic acid, and sodium bicarbonate are all obtained commercially. Spandex filament (40D) is purchased from Huafeng Chongqing Spandex Co., Ltd. The oil agent on the fiber needs to be removed before the spandex is dyed, otherwise it will affect the dyeing effect of the dye (commercially available deoiling agent 5 g / L, 90 °C, 30 min).

[0059] I. Preparation of Dye D1:

[0060] The preparation of 2,6-dichloro-4-nitrobenzenediazonium salt can be referred to CN116876243A, and the preparation of Dye D1 can be referred to CN117402507A. Specifically, the following steps are carried out in sequence:

[0061]

[0062] Step (1): Add 2,6-dichloro-4-nitroaniline (5 mmol, 1.04 g) and 1,5-naphthalenedisulfonic acid (5 mmol, 1.44 g) to a 250 mL three-necked flask, and then add ethyl acetate (50 mL). Place the three-necked flask in a water bath at 50 °C and stir for 10 min to dissolve the solid. Then, take out the three-necked flask, and after cooling to room temperature, drop in tert-butyl nitrite (7.5 mmol, 0.77 g) within 2 min, and further stir at room temperature for 30 min. A large amount of solid can be seen to precipitate. After the reaction is completed, filter by suction, and dry the filter cake at room temperature to obtain orange solid powder, which is 2,6-dichloro-4-nitrobenzenediazonium salt, 2.28 g, with a yield of 92%.

[0063]

[0064] Step (2): Dissolve compound 1 (3 mmol) in methanol (10 mL), and add the 2,6-dichloro-4-nitrobenzenediazonium salt (5 mmol) obtained in step (1) in 3 - 5 portions at 0 - 5 °C, then stir the reaction at 0 - 5 °C. During the reaction, control the acidity of the reaction system by adding sodium carbonate powder to make the pH value within the range of 4 - 6. After reacting for 30 min, detect with 0.2 mm thin-layer chromatography. At this time, compound 1 is completely consumed. Add 10 mL of water, and filter to obtain a precipitate. This precipitate can be further purified by silica gel (200 - 300 mesh) column chromatography (eluent: V 石油醚 / V 二氯甲烷 = 1 / 1), the eluent flow rate is 20 - 30 mL / min, and collect the eluate containing the compound with a retention factor (R f ) of 0.3 - 0.4; The eluate is evaporated under reduced pressure using a rotary evaporator to remove the organic solvents (petroleum ether and dichloromethane) to obtain dye D1, an orange-red solid, 1.71 g, with a yield of 83%. 1 1H NMR (CDCl3, 400 MHz) δ 8.27 (s, 2H), 7.93 (d, J = 9.2 Hz, 2H), 7.43 (d, J = 7.2 Hz, 4H), 7.38 (dd, J 1 = 7.6 Hz, J 2 = 8.0 Hz, 4H), 7.20 (dd, J 1 = 7.2 Hz, J 2 = 7.2 Hz, 2H), 6.94 (d, J = 9.2 Hz, 2H), 4.52 (t, J = 6.0 Hz, 4H), 3.85 (t, J = 6.0 Hz, 4H). 13 13C NMR (CDCl3, 100 MHz) δ 165.00, 152.44, 145.46, 138.08, 129.05, 126.38, 126.26, 124.94, 124.26, 119.74, 111.83, 61.43, 49.79. HRMS (ESI + , m / z) calculated for C32H24Cl2N8O6: 687.1274 [M + H] + , found: 687.1256. The 1H NMR spectrum of dye D1 is as shown in Figure 1 . The 13C NMR spectrum of dye D1 is as shown in Figure 2 .

[0065] II. Synthesis example of dye D3:

[0066] Perform the following steps in sequence:

[0067] Step (1): Preparation of diazonium salt by diazotization reaction of 3-amino-5-nitro-2,1-benzisothiazole

[0068]

[0069] Sodium nitrite (5 mmol, 0.35 g) was slowly added to 3 mL of concentrated sulfuric acid at 0 °C (ice-water bath), and stirred until sodium nitrite was completely dissolved. A mixed acid of 6 mL of propionic acid and glacial acetic acid (V 丙酸 :V 冰乙酸 = 1:5) was added dropwise within 10 min, and after dropping, stirring was continued for 30 min while maintaining the temperature at 0 °C. Subsequently, a mixture of 6 mL of propionic acid and glacial acetic acid containing 3-amino-5-nitro-2,1-benzisothiazole (5 mmol) (V 丙酸 :V 冰乙酸 = 1:5) was slowly added dropwise within 10 min. After dropping, stirring was continued for 1 h to obtain a diazonium salt solution of 3-amino-5-nitro-2,1-benzisothiazole, which was stored at 0 °C for later use.

[0070] Step (2): Preparation of dye D3 by coupling reaction

[0071]

[0072] Compound 2 (3 mmol) was dissolved in methanol (10 mL), and all of the diazonium salt solution of 3-amino-5-nitro-2,1-benzisothiazole prepared in step (1) (5 mmol) was added in 3 - 5 portions at 0 - 5 °C and stirred for reaction. During the reaction, the acidity of the reaction system was controlled by adding sodium carbonate powder to keep the pH value within the range of 4 - 6. After reacting for 30 min, TLC with a thickness of 0.2 mm was used for detection. At this time, compound 2 was completely consumed, 10 mL of water was added, and the precipitate was filtered. The precipitate could be further purified by silica gel (200 - 300 mesh) column chromatography (eluent: V 石油醚 / V 二氯甲烷 = 1 / 1), the eluent flow rate was 20 - 30 mL / min, and the eluate containing the compound with a retention factor (R f ) of 0.3 - 0.4 was collected; the eluate was evaporated under reduced pressure using a rotary evaporator to remove organic solvents (petroleum ether and dichloromethane) to obtain dye D3, a blue solid, 1.16 g, with a yield of 75%.

[0073] 1 1H NMR (CDCl3, 400 MHz) δ 9.22 (d, J = 2.4 Hz, 1H), 8.22 (dd, J 1 = 9.6 Hz, J[[ID=3P6]] 2= 2.4 Hz, 1H), 8.00 (d, J = 9.2 Hz, 2H), 7.78 (d, J = 9.6 Hz, 1H), 7.46 (d, J = 7.6 Hz, 2H), 7.39 (dd, J 1 = 7.6 Hz, J 2 = 8.0 Hz, 2H), 7.21 (dd, J 1 = J 2 = 8.0 Hz, 1H), 6.88 (d, J = 9.2 Hz, 2H), 4.53 (t, J = 6.0 Hz, 2H), 3.83 (t, J = 6.0 Hz, 2H), 3.61 (q, J = 7.2 Hz, 2H), 1.32 (t, J = 7.2 Hz, 3H). 13 C NMR (CDCl3, 100 MHz) δ 180.83, 162.49, 152.65, 144.53, 144.09, 130.96, 129.09, 128.88, 127.87, 126.27, 124.92, 124.16, 123.11, 122.70, 119.91, 112.15, 61.68, 49.06, 45.96, 12.44. HRMS (ESI + , m / z) calculated for C25H21N7O4S: 516.1448 [M+H] + , found: 516.1466. The 1H NMR spectrum of dye D3 is as shown in Figure 3 Figure. The 13C NMR spectrum of dye D3 is as shown in Figure 4 Figure.

[0074] The UV-visible absorption spectra of dyes D1-D3 in DMF are shown in Figure 9 . The dyeing rate curves, dye uptake, color depth, and fixation rate data of dyes D1-D3 when dyeing spandex alone are shown in Figure 10 . From Figure 10 it can be seen that the three dyes provided by the present invention have similar dyeing rate curves, and the dye uptake, color depth values, and fixation rates of the three dyes when dyeing spandex alone are not very different. Thus, the three dyes have good dyeing compatibility.

[0075] Note: The detection methods for dye uptake, color depth value, and fixation rate are the following conventional methods:

[0076] Dye uptake: Use a pipette to take 1 mL each of the pre-dyeing solution and the post-dyeing solution, and dilute them to m mL and n mL respectively with acetone to bring their concentrations within the test range. Then, use a UV-visible spectrophotometer to measure the absorption spectra of the pre-dyeing solution and the post-dyeing solution, and record the absorbance values A0 (pre-dyeing solution) and A1 (post-dyeing solution) at the maximum absorption wavelength. Denote the calculated value of [1 - (n×A1) / (m×A0)] as the dye uptake.

[0077] Color depth value: Neatly wind the dyed spandex yarn around a cardboard with a length of 5 cm and a width of 1 cm for 3 layers to ensure light-tightness. Then, use a Datacolor colorimeter to measure the K / S data at intervals of 10 nm in the range of 360 nm - 700 nm under a D65 light source and a 10° viewing angle.

[0078] Fixation rate: Extract the dyed spandex with ethyl acetate at 60 °C for 10 min, measure the K / S values of the spandex before and after extraction, and denote the ratio of the K / S value of the spandex after extraction to the K / S value of the spandex before extraction as the fixation rate.

[0079] III. Synthesis example of compound M:

[0080] Perform the following steps in sequence:

[0081] Step (1): Synthesis of compound 3

[0082]

[0083] Step (1): Place a three-necked flask containing 1,1,1-trimethylol ethane (10 mmol) and dichloromethane (40 mL) in an ice-water bath, slowly add phenylacetyl chloride (35 mmol) dropwise to the reaction system, and then add triethylamine (45 mmol) dropwise. After the addition, remove the ice-water bath and allow the reaction to proceed at room temperature for 30 min. Add 60 mL of water to the flask for extraction, and collect the organic phase. The organic phase is further washed with saturated brine, dried with anhydrous magnesium sulfate, and the organic solvent (dichloromethane) is removed by rotary evaporation. The obtained crude product is separated and purified by silica gel column chromatography with 200 - 300 mesh silica gel (eluent: V 石油醚 / V 乙酸乙酯 = 10 / 1), the eluent flow rate is 20 - 30 mL / min, and collect the eluent containing the compound with a retention factor (R f ) of 0.2 - 0.3; the eluent is concentrated under reduced pressure by rotary evaporation to remove the organic solvent, obtaining compound 3, a yellow oil, 4.23 g, with a yield of 89%, 1 1H NMR (CDCl3, 400 MHz) δ 7.40 - 7.25 (m, 15H), 3.93 (s, 6H), 3.61 (s, 6H), 0.86 (s, 3H). 1313C NMR (CDCl3, 100 MHz) δ 171.00, 133.97, 129.35, 128.72, 127.27, 65.88, 41.32, 38.61, 16.89. The 1H NMR spectrum of Compound 3 is as shown in Figure 5 shown. The 13C NMR spectrum of Compound 3 is as shown in Figure 6 shown.

[0084] Step (2): Preparation of Compound M by diazotization transfer reaction

[0085]

[0086] Dissolve Compound 3 (3 mmol) in 10 mL of acetonitrile, add 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, 10.8 mmol). After stirring at room temperature for 10 minutes, add 4-acetamidobenzenesulfonyl azide (p-ABSA, 10.8 mmol), and continue the reaction for 20 hours. At this time, monitor using 0.2 mm thin-layer chromatography. After Compound 3 is completely consumed, add 100 mL of water and extract three times with ethyl acetate (100 mL × 3). Combine the organic phases, wash with saturated brine (30 mL), and dry using anhydrous magnesium sulfate. After evaporating the organic solvents under reduced pressure using a rotary evaporator, purify the residue by silica gel (200 - 300 mesh) column chromatography (the eluent is V 石油醚 / V 二氯甲烷 = 1 / 1), the eluent flow rate is 20 - 30 mL / min, and collect the eluate containing the compound with a retention factor (R f ) of 0.3 - 0.4; Evaporate the organic solvents from the eluate under reduced pressure using a rotary evaporator to obtain Compound M, a pale yellow solid, 1.30 g, with a yield of 78%. 1 1H NMR (CDCl3, 400 MHz) δ 7.45 (d, J = 7.6 Hz, 6H), 7.38 (dd, J 1 = 7.6 Hz, J 2 = 7.6 Hz, 6H), 7.19 (dd, J 1 = 7.6 Hz, J 2 = 7.6 Hz, 3H), 4.28 (s, 6H), 1.14 (s, 3H). 13 13C NMR (CDCl3, 100 MHz) δ 164.60, 129.03, 126.13, 125.06, 124.14, 66.07, 39.24, 17.35. The 1H NMR spectrum of Compound M is as shown in Figure 7 shown. The 13C NMR spectrum of Compound M is as shown in Figure 8 shown.

[0087] The formulation of the black dye composition is as follows in the table (taking blue dye D3 as the benchmark, and adjusting the dosages of dyes D1 and D2 to determine the optimal ratio):

[0088] Serial number Composition serial number Dye D1:D2:D3 (mass ratio) 1 Black dye composition 1 14:1:20 2 Black dye composition 2 12:1:20 3 Black dye composition 3 16:1:20 4 Black dye composition 4 14:0.8:20 5 Black dye composition 5 14:1.2:20 6 Black dye composition 6 8:1:20 7 Black dye composition 7 20:1:20 8 Black dye composition 8 14:0.5:20 9 Black dye composition 9 14:1.5:20

[0089] Example 1: Preparation of black liquid reactive disperse dye

[0090] (1) Add black dye composition 1 (21 g), dispersant (7 g, a mixture of dispersant MF and fatty alcohol polyoxyethylene ether AEO-9 with a mass ratio of 2:1), fixing agent (7 g, compound M), and water (63.9 g) into a grinding device pre-filled with zirconium beads (Φ0.2 mm, 395 g) (equipped with circulating cooling water, water temperature is 20 ± 5 °C) for grinding. Set the grinding speed to 1500 ± 100 r / min, and grind for 2 h at room temperature of 25 ± 5 °C.

[0091] (2) Add penetrant JFC (0.5 g), wetting agent LCN407 (0.2 g), defoamer DF830 (0.2 g), and fungicide BIT20 (0.2 g) to the ground liquid mixture obtained in step (1), and continue stirring for 10 min. Adjust the pH value of the system to 6.5 - 7.5 using acetic acid or sodium bicarbonate according to the acidity and alkalinity of the system, and thus obtain black liquid reactive disperse dye 1 (note: the mass ratio of the black dye composition in this black liquid reactive disperse dye 1 is 21%).

[0092] Examples 2 - 5

[0093] Use black dye compositions 2 - 5 (21 g) to replace black dye composition 1 (21 g) respectively, and the others are the same as in Example 1, to obtain black liquid reactive disperse dyes 2 - 5 (note: the mass ratio of the black dye composition in these black liquid reactive disperse dyes 2 - 5 is 21% for all).

[0094] Example 6

[0095] Replace black dye composition 1 (21 g), dispersant (7 g), fixing agent (7 g), and water (63.9 g) in step (1) of Example 1 with black dye composition 1 (15 g), dispersant (5 g), fixing agent (5 g), and water (73.9 g), and the others are the same as in Example 1, to obtain black liquid reactive disperse dye 6 (note: the mass ratio of the black dye composition in this black liquid reactive disperse dye 6 is 15%).

[0096] Example 7

[0097] The black dye composition 1 (21 g), dispersant (7 g), fixing agent (7 g) and water (63.9 g) in step (1) of Example 1 were replaced with black dye composition 1 (30 g), dispersant (10 g), fixing agent (10 g) and water (48.9 g), and the rest were as described in Example 1 to obtain black liquid reactive disperse dye 7 (Note: the mass proportion of the black dye composition in this black liquid reactive disperse dye 7 is 30%).

[0098] Application Example 1

[0099] (1) Accurately weigh black liquid reactive disperse dye 1 (286 mg), dilute with water to 100 mL, and prepare a dye solution with a dye content of 3% owf (owf, the mass ratio of dye to fabric, note: all based on the black dye composition). Use acetic acid to adjust the pH value of the dye solution to 5-6, add spandex (2 g), seal the dye vat, heat to 95°C, and keep warm for 45 minutes;

[0100] (2) After dyeing, the spandex obtained in step (1) is placed in an oven at 130° C. for heating and color fixing for 30 minutes;

[0101] (3) The spandex obtained in step (2) was taken out and placed in a soaping solution (soap flakes 1 g / L, sodium carbonate 1 g / L, bath ratio 1:50) at 80°C, and soaped once for 10 minutes. The remaining soaping solution was then rinsed with clean water at room temperature and dried to obtain dyed spandex for testing.

[0102] Application Examples 2 to 5

[0103] The black liquid reactive disperse dye 1 (286 mg) in Application Example 1 was replaced with black liquid reactive disperse dyes 2 to 5 (286 mg). Other preparations were the same as those described in Application Example 1.

[0104] Application Example 6

[0105] The black liquid reactive disperse dye 1 (286 mg) in Application Example 1 was replaced with black liquid reactive disperse dye 6 (400 mg), and the rest was the same as described in Application Effect Example 1 (Note: the change in dosage is to ensure that the black dye composition remains consistent relative to the amount of fabric, both being 3% owf).

[0106] Application Example 7

[0107] The black liquid reactive disperse dye 1 (286 mg) in Application Effect Example 1 was replaced with black liquid reactive disperse dye 7 (200 mg), and the rest was the same as described in Application Effect Example 1 (Note: the change in dosage is to ensure that the black dye composition relative to the fabric amount remains consistent, both being 3% owf).

[0108] Test method:

[0109] (1) Black light: Using the naked-eye observation method, observe the light of the spandex under a D65 light source with the naked eye, and compare it with the standard black color card to confirm whether the black light is pure.

[0110] (2) Color depth value: Neatly wind the spandex yarn around a cardboard with a length of 5 cm and a width of 1 cm for 3 layers to ensure light-tightness. Then, use a Datacolor colorimeter to measure the K / S data every 10 nm in the range of 360 nm to 700 nm under a D65 light source and a 10° viewing angle. Sum up all the obtained K / S values and record them as the Integ value (for reference, see: Dyeing and Finishing, 2006, (24), 30 - 33).

[0111] (3) Fixation rate: Extract the dyed spandex with ethyl acetate at 60 °C for 10 min, measure the Integ values of the spandex before and after extraction, and record the ratio of the Integ value of the spandex after extraction to the Integ value of the spandex before extraction as the fixation rate.

[0112] (4) Migration rate: Uniformly stack 1 g of dyed spandex and 1 g of undyed spandex as original samples together, clamp them with 2 pieces of white cotton cloth (5 cm × 5 cm), and sew the four sides of the cotton cloth with a needle and thread. Then, put the mixed fabric into a dye bath (bath ratio 1∶30, pH value 5.0, 130 °C, 1 h) for treatment; after cooling to room temperature, take out the spandex and dry it in an oven at 60 °C, and measure the Integ values of the two portions of spandex. Record the ratio of the Integ value of the dyed spandex after treatment to the Integ value of the undyed spandex as the original sample after treatment as the migration rate.

[0113] (5) Color fastness: The color fastness to soaping is tested with reference to GB / T 3921—2008 "Textiles - Tests for color fastness - Color fastness to soaping". The color fastness to rubbing is tested with reference to the national standard GB / T 3920—2008 "Textiles - Tests for color fastness - Color fastness to rubbing". The color fastness to sublimation is tested with reference to the national standard GB / T 5718—1997 "Textiles - Tests for color fastness - Color fastness to dry heat".

[0114] Table 1

[0115] Black color tone Integ value Fixation rate Migration rate Application Example 1 Deep black 688 90％ 3％ Application Example 2 Deep black 683 87％ 4％ Application Example 3 Deep black 670 88％ 3％ Application Example 4 Deep black 668 86％ 4％ Application Example 5 Deep black 672 85％ 4％ Application Example 6 Deep black 670 89％ 3％ Application Example 7 Deep black 680 88％ 4％

[0116] As can be seen from Table 1, the color of the spandex dyed with the black liquid reactive disperse dye provided by the present invention is deep black. Among them, the black observed by the naked eye in Application Example 1 is the purest (the K / S curve and physical photos of the spandex dyed with Black Liquid Reactive Disperse Dye 1 are shown in Figure 11) That is, when the mass ratio of dyes D1 - D3 is 14:1:20, the black shade is the best; when the dye dosage is 3% owf, the Integ value of the dyed spandex can reach over 660; the fixation rate of the dyed spandex reaches over 85%, and it has excellent resistance to organic solvent extraction; the dye migration rate is lower than 5%, and it has excellent resistance to migration characteristics. The above results show that the black liquid reactive disperse dye of the present invention can obtain a fast deep black color when dyeing spandex.

[0117] Table 2

[0118]

[0119] As can be seen from Table 2, when using the black liquid reactive disperse dye provided by the present invention to dye spandex, it has excellent soaping fastness, rubbing fastness and sublimation fastness.

[0120] Comparative Examples 1 - 4

[0121] Use black dye compositions 6 - 9 to prepare liquid reactive disperse dyes 8 - 11 according to Example 1. Specifically, that is, use black dye compositions 6 - 9 (21 g) to replace black dye composition 1 (21 g), and the others are as described in Example 1 to obtain liquid reactive disperse dyes 8 - 11.

[0122] Then use liquid reactive disperse dyes 8 - 11 to dye spandex according to Application Example 1 to obtain dyed spandex. Specifically, that is, use liquid reactive disperse dyes 8 - 11 (286 mg) to replace black liquid reactive disperse dye 1 (286 mg), and the others are as described in Application Example 1 to obtain dyed spandex.

[0123] Table 3

[0124] Black color tone Integ value Fixation rate Migration rate Comparative Example 1 Black, with severe lack of orange light 567 89％ 4％ Comparative Example 2 Black, with excessive orange light 724 86％ 4％ Comparative Example 3 Black, with severe lack of red light 589 88％ 2％ Comparative Example 4 Black, with excessive red light 708 85％ 4％

[0125] As can be seen from Table 3, the colors of the dyed spandex obtained in Comparative Examples 1 - 4 are all impure black, that is, when the mass ratio of dyes D1 - D3 is not within the range provided by the present invention, it will cause a change in the black shade; the fixation rate of the dyed spandex in Comparative Examples 1 - 4 can still be maintained above 85% and the migration rate is maintained below 5%.

[0126] Comparative Example 5

[0127] Replace dye D3 in black dye composition 1 with compound 4 to prepare black dye composition 10. The chemical structure of compound 4 is as follows, that is, dye VIII in patent (CN117304711):

[0128]

[0129] Further replace the black dye composition 1 (21 g) in Example 1 with black dye composition 10 (21 g), and prepare liquid reactive disperse dye 12 as described in Example 1 for other aspects.

[0130] Then, use liquid reactive disperse dye 12 to dye spandex according to Application Example 1 to obtain dyed spandex. Specifically, use liquid reactive disperse dye 12 (286 mg) to replace black liquid reactive disperse dye 1 (286 mg), and obtain dyed spandex as described in Application Example 1 for other aspects.

[0131] After testing, the dyed spandex shows a brownish-black shade and lacks blue-violet light. This is because although compound 4 is a blue dye, it lacks absorption ability in the 650 - 700 nm region of the absorption spectrum, resulting in insufficient blue-violet light in the dye composition prepared from compound 4, and ultimately the dyed spandex cannot obtain a pure black color. This result indicates that combining existing dyes cannot achieve the effect of the dyed spandex of the black liquid reactive disperse dye prepared from the dyes provided in the present invention. The K / S curve of the spandex dyed with liquid reactive disperse dye 12 is as Figure 12 shown.

[0132] Comparative Example 6

[0133] Replace dye D1 in black dye composition 1 with compound 5 to prepare black dye composition 11. The chemical structure of compound 5 is as follows, that is, dye III in patent (CN117402507).

[0134]

[0135] Further replace the black dye composition 1 (21 g) in Example 1 with black dye composition 11 (21 g), and prepare liquid reactive disperse dye 13 as described in Example 1 for other aspects.

[0136] Then, use liquid reactive disperse dye 13 to dye spandex according to Application Example 1 to obtain dyed spandex. Specifically, use liquid reactive disperse dye 13 (286 mg) to replace black liquid reactive disperse dye 1 (286 mg), and obtain dyed spandex as described in Application Example 1 for other aspects.

[0137] After testing, the dyed spandex shows a black-violet color and has a serious lack of orange light; this is because compared with dye D1, compound 5 has one less chlorine atom in its structure, and the color of compound 5 is red, which cannot match the colors of dyes D2 and D3, thus unable to obtain the black color as in the present invention.

[0138] Comparative Example 7

[0139] Replace the dye D1 in the black dye composition 1 with compound 6 to formulate the black dye composition 12. The chemical structure of compound 6 is as follows, namely Dye IV in the patent (CN117304711).

[0140]

[0141] Further replace the black dye composition 1 (21 g) in Example 1 with the black dye composition 12 (21 g), and the others are as described in Example 1 to prepare the liquid reactive disperse dye 14.

[0142] Then use the liquid reactive disperse dye 14 to dye spandex according to Application Example 1 to obtain dyed spandex. Specifically, use the liquid reactive disperse dye 14 (286 mg) to replace the black liquid reactive disperse dye 1 (286 mg), and the others are as described in Application Example 1 to obtain dyed spandex.

[0143] After testing, the dyed spandex is black, but the orange light is slightly missing; the Integ value of the dyed spandex is measured to be 642, slightly lower than the Integ value of the dyed spandex in Application Example 1, which is also caused by the lack of orange light; the fixation rate of the dyed spandex is measured to be 77%, and the migration rate is 12%, indicating that there are more dyes on the dyed spandex that fail to form covalent bonds with the fiber; the soaping color fastness of the dyed spandex is measured to be 3 - 4 grades (color change) and 3 grades (ammonia staining), and the sublimation color fastness is 3 - 4 grades (color change) and 3 grades (ammonia staining). The above results show that if the orange dye component in the black dye composition of the present invention is replaced with compound 6, that is, using an orange dye containing only one α - phenyl diazoester structure instead of the orange dye containing two α - phenyl diazoester structures of the present invention, and further using the dyeing method provided by the present invention, a fast deep black dyed spandex as in the present invention cannot be obtained.

[0144] Comparative Example 8 (Improvement of Comparative Example 7)

[0145] Replace the dye D1 in the black dye composition 1 with compound 6, and at the same time change the mass ratio of compound 6, dye D2 and dye D3 to 20:1:20 to formulate the black dye composition 13.

[0146] Further replace the black dye composition 1 (21 g) in Example 1 with the black dye composition 13 (21 g), and the others are as described in Example 1 to prepare the liquid reactive disperse dye 15.

[0147] The spandex was dyed with liquid reactive disperse dye 15 according to Application Example 1 to obtain dyed spandex. Specifically, liquid reactive disperse dye 15 (286 mg) was used to replace black liquid reactive disperse dye 1 (286 mg), and the soaping was changed from once to three times. Other conditions were the same as those described in Application Example 1, and dyed spandex was obtained.

[0148] After testing, the dyed spandex was dark black, and the Integ value of the dyed spandex was 663; the fixation rate of the dyed spandex was 82%, and the migration rate was 7%; the color fastness to soaping was 4 - 5 grades (color change) and 4 grades (spandex staining), and the color fastness to sublimation was 4 - 5 grades (color change) and 4 grades (spandex staining). By improving Comparative Example 7, on the one hand, the dosage ratio of Compound 6 was increased to supplement orange light, and on the other hand, by increasing the number of soaping times, the dyes that did not react with the fiber on the spandex were thoroughly washed away to improve the fixation rate, migration resistance, and color fastness of the dyed spandex. However, obviously, this improvement not only increased the dye consumption but also increased the complexity of the post - treatment and the application cost; in addition, the fixation rate, migration property, and color fastness of the dyed spandex were still slightly worse than the various properties of the dyed spandex of the present invention.

[0149] Comparative Example 9

[0150] Liquid disperse dye was prepared using C.I. Disperse Blue 79, C.I. Disperse Orange 44, and C.I. Disperse Violet 93 according to the patent (CN115678311). The specific process was as follows: First, water, Peregal O - 25, ethylene glycol, dispersant MF, coconut oil fatty acid diethanolamide, ethylene glycol monobutyl ether, penetrant JFC, isothiazolinone, and defoamer were sequentially added to the beating pot, and then Disperse Blue 79, Disperse Orange 44, and Disperse Violet 93 were added while stirring. Finally, beating, emulsification, and ultrasonic sanding were carried out. The ultrasonic sanding was carried out until the proportion of solid particles with a particle size less than 1 μm in the mixture was 97%, and then water was added to prepare to the required strength; the weight percentages of each component were: Disperse Blue 79: 20%, Disperse Orange 44: 10%, Disperse Violet 93: 30%, dispersant MF 6%, Peregal O - 25 0.5%, ethylene glycol 1%, coconut oil fatty acid diethanolamide 0.2%, penetrant JFC 1%, ethylene glycol monobutyl ether 0.2%, isothiazolinone 0.5%, defoamer 1.8%, and the balance was water; among them, when beating, the pH of the mixture was controlled at 6; when sanding, zirconium beads with a diameter of 0.5 mm were used, the zirconium bead filling rate was 40%, the rotation speed of the sand mill was 1300 r / min, and the ultrasonic frequency was 100 KHz.

[0151] The obtained liquid disperse dye was used to dye spandex in the application mode of Application Example 1 to obtain dyed spandex. After testing, the dyed spandex was dark brown, the fixation rate was less than 1%, and the migration rate was greater than 95%. The reason for the above results is that the dye raw materials used in the liquid disperse dye are all conventional disperse dyes, that is, the dye structure does not contain reactive groups, and the dye and the fiber cannot form covalent bonds, but only combine with weak forces such as hydrogen bonds and van der Waals forces. Therefore, numerous dyes can be washed off the dyed spandex by simple soaping, and more blue-violet dyes are washed off, resulting in a brownish color. In addition, the dyed spandex has no fixation effect, and the dye molecules can migrate freely. The above results show that only using conventional disperse dyes without a diazo group in the dye structure provided by the present invention as a reactive group to firmly bind the dye molecules to spandex cannot achieve a high color fastness black dyeing effect under the dyeing conditions provided by the present invention.

[0152] Comparative Example 10

[0153] A commercial reactive dye, Reactive Black KN-B (C.I. Reactive Black 5, a bis-azo bis-reactive dye with a vinyl sulfone type reactive group, and the fixation rate for cotton dyeing is about 70% - 80%) was used to replace Black Dye Composition 1, etc. to prepare a black reactive dye. Specifically as follows: Reactive Black KN-B (21 g), water (77.9 g), penetrant JFC (0.5 g), wetting agent LCN407 (0.2 g), defoamer DF830 (0.2 g), fungicide BIT20 (0.2 g) were mixed and stirred for 10 min. According to the acidity and alkalinity of the system, acetic acid or sodium bicarbonate was used to adjust the pH value of the system to 6.5 - 7.5 to obtain the black reactive dye.

[0154] The black reactive dye was used to dye spandex according to Application Example 1, that is, Black Liquid Reactive Disperse Dye 1 (286 mg) was replaced with the black reactive dye (286 mg), and the others were as described in Application Example 1 to obtain dyed spandex. After testing, the dyed spandex was light grayish black, and the fixation rate was less than 5%. This result shows that using conventional reactive dyes cannot dye spandex well under the dyeing conditions provided by the present invention. The reason is that conventional reactive dyes have insufficient affinity for spandex and poor dyeing depth. Secondly, the reactive groups of conventional reactive dyes (such as the vinyl sulfone reactive group in this example) need to add extra alkali in the dyeing system to form an alkaline environment to carry out the fixation reaction well, while the fixation conditions provided by the present invention only provide a high-temperature environment by heating, which is not applicable to the dyeing and fixation of conventional reactive dyes.

[0155] Comparative Example 11

[0156] Using commercially available reactive disperse yellow GR (21 g) instead of black dye composition 1 (21 g), and following the other procedures of Example 1, a yellow liquid reactive disperse yellow dye was prepared. (Note: Since there is no existing reactive disperse black dye for comparison, a commercial reactive disperse yellow dye was used in this example for comparison except for color).

[0157] Further, 286 mg of black liquid reactive disperse dye 1 was replaced with 286 mg of yellow reactive disperse dye, and following the other procedures of Application Example 1, dyed spandex was obtained. After testing, the dyed spandex was yellow, the fixation rate was less than 5%, the migration rate was greater than 90%, the color fastness to soaping was 3 - 4 grades (color change) and 2 - 3 grades (spandex staining), and the color fastness to sublimation was 3 - 4 grades (color change) and 2 - 3 grades (spandex staining).

[0158] Structure of reactive disperse yellow GR:

[0159]

[0160] The results show that using conventional reactive disperse dyes cannot well obtain dyed spandex with fast colors as provided by the present invention under the dyeing conditions of the present invention. The reason is that the reactive groups of conventional reactive disperse dyes are still conventional groups (such as the triazine reactive group in this example), and an additional base needs to be added to the dyeing system to form an alkaline environment for the fixation reaction to proceed well, while the fixation conditions provided by the present invention only provide a high - temperature environment by heating, which is not applicable to the dyeing and fixation of conventional reactive disperse dyes.

[0161] Comparative Example 12

[0162] 7 g of a fixing agent (Compound M) and 63.9 g of water were replaced with 70.9 g of water, and following the other procedures of Example 1, i.e., without adding the fixing agent of the present invention relative to Example 1, black liquid reactive disperse dye 16 was prepared. Further, the spandex was dyed according to Application Example 1 to obtain dyed spandex. After testing, the dyed spandex was black, the Integ value of the dyed spandex was 656; the fixation rate of the dyed spandex was 80%, and the migration rate was 10%; the color fastness to soaping was 4 grades (color change) and 4 grades (spandex staining), and the color fastness to sublimation was 4 grades (color change) and 4 grades (spandex staining). The above results show that if the fixing agent of the present invention is not used, dyed spandex with fast deep black color as provided by the present invention cannot be obtained.

[0163] Comparative Examples 13 - 15

[0164] 7 g of the fixing agent (Compound M) was replaced with 7 g of Compound N, 7 g of Compound P, or 7 g of Compound Q, and following the other procedures of Example 1, black liquid reactive disperse dye 17 was prepared. Further, the spandex was dyed according to Application Example 1 to obtain dyed spandex. The test results are shown in Table 4 below.

[0165] Among them, the structural formula of compound N (i.e., compound 1 of patent CN114478307) is as follows:

[0166]

[0167] The structural formula of compound P (i.e., compound 1-1 in patent CN114478306) is as follows:

[0168]

[0169] The structural formula of compound Q (i.e., compound 2 in patent CN114478306) is as follows:

[0170]

[0171] Table 4

[0172] Black color tone Integ value Fixation rate Migration rate Comparative Example 13 Deep black 667 82％ 8％ Comparative Example 14 682 87％ 6％ Deep black Comparative Example 15 Deep black 680 86％ 6％

[0173] After testing, the dyed spandex in Comparative Example 13 was black, the Integ value of the dyed spandex was 667; the color fixation rate of the dyed spandex was 82%, and the migration rate was 8%. The results of Comparative Example 13 show that if there are only two α-phenyl diazoester structures in the structure of the color fixing agent used, fast deep black dyed spandex as in the present invention cannot be obtained.

[0174] The results of Comparative Example 14 and Comparative Example 15 show that if the color fixing agent in the present invention is replaced by compound P or compound Q, deep black dyed spandex can finally be obtained, and it has good color fixation rate and migration resistance. However, compared with compound M provided by the present invention, the color fixation rate and migration resistance are slightly worse.

[0175] Comparative Examples 16 - 29

[0176] The dyeing temperature, dyeing time, color fixing temperature, and color fixing time in Application Example 1 were adjusted, and the corresponding results are shown in Table 5 below with the Integ value and color fixation rate as the test indicators.

[0177] Table 5

[0178]

[0179]

[0180] The results of Comparative Examples 16 - 19 show that as the dyeing temperature increases, the Integ value of the dyed spandex increases in turn, but the color fixation rate will decrease. Combining with the application results of Example 1, it is concluded that when the dyeing temperature is 95°C, the best color yield and color fixation effect are obtained.

[0181] The results of Comparative Examples 20 to 22 show that as the dyeing time increases, the Integ value of the dyed spandex first increases and then remains constant, and the color fixation rate data is not greatly affected. Combined with the application results of Example 1, it is concluded that the optimal dyeing time is 45 minutes.

[0182] The results of Comparative Examples 23 to 26 show that as the fixing temperature increases, the Integ value and the fixing rate of the dyed spandex both show a trend of first increasing and then leveling off. Combined with the application results of Example 1, it is concluded that the optimal fixing temperature is 130°C.

[0183] The results of Comparative Examples 27 to 29 show that as the fixing time increases, the Integ value and the fixing rate of the dyed spandex both show a trend of first increasing and then leveling off. Combined with the application results of Example 1, it is concluded that the optimal fixing time is 30 minutes.

[0184] Finally, it should be noted that the above examples are merely specific embodiments of the present invention. Obviously, the present invention is not limited to the above examples and is subject to numerous variations. All variations that can be directly derived or conceived by a person of ordinary skill in the art from the disclosure of the present invention are considered to be within the scope of protection of the present invention.

Claims

1. A black liquid reactive disperse dye, characterized in that It consists of components with the following mass percentages: 15% - 30% of the black dye composition, 5% - 10% of the dispersant, 5% - 10% of the color fixative, 1.0 - 1.2% of the auxiliary agent, and the balance is water; The black dye composition consists of dyes D1, D2, and D3: The mass ratio of dyes D1, D2, and D3 is 12 - 16:0.8 - 1.2:20; The auxiliary agent consists of a penetrant, a wetting agent, an antifoaming agent, and a bactericide with a mass ratio of 5:(2±0.2):(2±0.2):(2±0.2).

2. The black liquid reactive disperse dye according to claim 1, wherein: The mass ratio of dyes D1, D2, and D3 is 14:1:

20.

3. The black liquid reactive disperse dye according to claim 1 or 2, characterized in that The color fixative is compound M with the following structure:

4. The black liquid reactive disperse dye according to claim 3, characterized in that: The dispersant is a mixture composed of an anionic dispersant and a non-ionic dispersant in a mass ratio of 2:1; The anionic dispersant is dispersant MF, and the non-ionic dispersant is fatty alcohol polyoxyethylene ether AEO-9.

5. The black liquid reactive disperse dye according to claim 4, characterized in that: The mass ratio of the black dye composition, the dispersant, and the color fixative is 3:1:1.

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