Dyeing method capable of regulating and controlling in-situ assembly of dye molecules through cellulose fiber grafting modification

Abstract

The invention belongs to the field of textile dyeing and finishing, and relates to a dyeing method capable of regulating and controlling in-situ assembly of dye molecules through cellulose fiber graft modification. The dyeing method comprises the following steps: soaking a cellulosic fiber textile in a 4-beta-hydroxyethylsulfonyl sulfate aniline-2-sulfonic acid aqueous solution for reaction, washing with water, drying, soaking in a hydrochloric acid aqueous solution, adding a sodium nitrite aqueous solution for reaction, adding urea, washing with water, and drying to obtain the cellulosic fiber textile. Soaking in a coupling component aqueous solution containing a coupling component, sodium hydroxide and sodium carbonate for reaction, alternately washing with hot water and cold water, and drying to obtain the dyed textile. The dyeing method is mild in condition, dye hydrolysis is avoided, the dye uptake and the dyeing fastness are improved, and the dye utilization rate is high; high temperature and a large amount of inorganic salt or auxiliaries are not needed, the dye is directly generated and fixed in the fiber, energy consumption is remarkably reduced, and waste water treatment pressure is reduced.

Description

Technical Field

[0001] The invention belongs to the field of textile dyeing and finishing, and particularly relates to a dyeing method for graft-modified cellulose fibers with controllable in-situ assembly of dye molecules. Background Art

[0002] Cellulose fiber, rich in hydroxyl groups in its structure, exhibits excellent hydrophilicity, biodegradability, and comfort, making it one of the most widely used natural fiber materials in the textile industry. Currently, the dyeing of cellulose fibers relies primarily on reactive dyes, vat dyes, and direct dyes. Reactive dyes, which can form covalent bonds with the hydroxyl groups in the fibers and exhibit excellent wash fastness, have become the mainstream dyeing method. However, while reactive dyes covalently bond with cellulose fibers, their active groups are susceptible to hydrolysis, resulting in a low relative fixation rate after dyeing. While increasing dyeing temperature helps increase the reaction rate between reactive dyes and fibers, it also increases the hydrolysis rate of reactive dyes. Traditional reactive dyeing processes often rely on higher temperatures and large amounts of inorganic salts (such as NaCl and Na2SO4) to increase dye uptake, which not only increases dyeing and finishing costs but also increases the burden on wastewater treatment, limiting the promotion of green printing and dyeing processes.

[0003] To reduce environmental impact, efforts are underway to develop low-temperature, low-salt, green dyeing methods. One approach involves structurally modifying dye molecules to enhance their fiber affinity; another involves chemically modifying fibers, such as grafting cationic groups to enhance their adsorption capacity for anionic dyes. While these methods have achieved some progress, they still face challenges such as poor dye migration, insufficient color fastness, and high raw material costs. Summary of the Invention

[0004]

Technical Issues

[0005] The active groups of reactive dyes are susceptible to hydrolysis, resulting in a decrease in color fixation. This leads to significant pollution in the form of high-salt and colored wastewater produced during dyeing. There is a need to develop a salt-free dyeing method for cellulose fibers that offers high color fixation and excellent color fastness, while also reducing the difficulty of wastewater treatment.

[0006]

Technical solution

[0007] Vinylsulfone type active groups (-SO2CH2CH2-) are a type of nucleophilic substitution group with high reactivity and strong selectivity. They can react with hydroxyl groups on cellulose fibers under mild conditions to form stable covalent ether bonds with good bonding strength and process adaptability.

[0008] This invention utilizes vinylsulfone groups to graft intermediate molecules containing primary aromatic amine structures onto cellulose fibers, providing reaction sites for subsequent diazotization and azo coupling reactions, enabling in situ synthesis and fixation of dyes onto the fibers. During the coupling reaction, phenolic or aromatic amine coupling components can be flexibly selected according to actual needs, allowing the synthesis of azo dyes with a variety of structures and colors. This method addresses key issues inherent in traditional dyeing systems, such as harsh reaction conditions, severe dye hydrolysis, and the burden of wastewater treatment. It offers the advantages of high efficiency, environmental friendliness, and color-tuning capabilities.

[0009] The first object of the present invention is to provide a dyeing method for cellulose fiber graft-modified tunable dye molecules in situ assembly, comprising the steps of:

[0010] S1. Immersing a cellulose fiber textile in an aqueous solution of 4-β-hydroxyethylsulfonyl sulfate aniline-2-sulfonic acid for reaction, washing the textile with water, and drying to obtain a vinylsulfone-modified textile;

[0011] S2, immersing the vinyl sulfone modified textile in a hydrochloric acid aqueous solution, adding a sodium nitrite aqueous solution for reaction, adding urea, washing the textile with water, and drying to obtain a diazotized textile;

[0012] S3. Dissolving a coupling component, sodium hydroxide, and sodium carbonate in water to obtain a coupling component solution, immersing the diazotized textile in the coupling component solution for reaction, washing with hot water and cold water alternately, and drying to obtain a dyed textile.

[0013] In one embodiment of the present invention, in step S1, the cellulose fiber textile is cellulose fiber yarn or fabric.

[0014] In one embodiment of the present invention, in step S1, the mass ratio of the cellulose fiber textile to 4-β-hydroxyethylsulfonyl sulfate aniline-2-sulfonic acid is 1:0.3-0.8.

[0015] In one embodiment of the present invention, in step S1, the mass ratio of the cellulose fiber textile to 4-β-hydroxyethylsulfonyl sulfate aniline-2-sulfonic acid is preferably 1:0.5.

[0016] In one embodiment of the present invention, in step S1, the bath ratio (mass ratio of textile to aqueous solution) of the reaction is 1:4-8.

[0017] In one embodiment of the present invention, in step S1, the reaction temperature is 60-70° C., and the reaction time is 20-40 min.

[0018] In one embodiment of the present invention, in step S2, the bath ratio of the reaction is 1:5-10.

[0019] In one embodiment of the present invention, in step S2, the concentration of the hydrochloric acid aqueous solution is 0.5-0.8 mol / L; the concentration of the sodium nitrite aqueous solution is 8-12 mol / L; and the volume ratio of the hydrochloric acid aqueous solution to the sodium nitrite aqueous solution is 12-18:1.

[0020] In one embodiment of the present invention, in step S2, the reaction temperature is 15-30° C., and the reaction time is 5-15 min.

[0021] In one embodiment of the present invention, in step S2, the sodium nitrite aqueous solution is added by slowly dropping it into the hydrochloric acid aqueous solution; the slow dropwise addition means that the solution is dropped at a uniform speed over 4 to 8 minutes.

[0022] In one embodiment of the present invention, in step S2, urea is added to remove excess nitrous acid; urea is added until the reaction solution does not change color when dropped on potassium iodide test paper within 1 to 2 seconds.

[0023] The coupling component refers to a compound that can undergo a coupling reaction with a diazonium salt to form an azo group -N=N- to generate an azo dye.

[0024] In one embodiment of the present invention, the coupling component is selected from one or more of phenolic compounds, aromatic amine compounds, active methylene compounds, heterocyclic compounds, hydroxy naphthoic acid compounds, sulfonic acid-substituted phenols, sulfonic acid-substituted amines, and polycyclic aromatic hydrocarbon derivatives.

[0025] In one embodiment of the present invention, the coupling component is selected from one or more of phenols, naphthols, resorcinols, p-cresols, p-hydroxybenzoic acids, anilines, toluidines, naphthylamines, p-toluidines, N-substituted aromatic amines, benzidines, acetoacetic acid derivatives, pyrazolones, cyanoacetic acid derivatives, pyridones, indoles, thiophene derivatives, naphthoic acids, and anthraquinone compounds.

[0026] In one embodiment of the present invention, the coupling component is selected from phenol, o-cresol, p-cresol, p-methoxyphenol, 2,4-dichlorophenol, α-naphthol, β-naphthol, 2-hydroxy-3-naphthoic acid, resorcinol, 4-methylresorcinol, p-hydroxybenzoic acid, methyl p-hydroxybenzoate, aniline, p-aminobenzenesulfonic acid, N-methylaniline, 1-naphthylamine, 2-naphthylamine-1-sulfonic acid, p-toluidine, p-toluidine-4-sulfonic acid, 3,3'-dichlorobenzidine, N,N-dimethylaniline, 2-hydroxy-3-naphthoic acid anilide, ethyl acetoacetate, ethyl cyanoacetate, 1-phenyl-3-methyl-5-pyrazolone, 3-carboxy-1-(4- sulfonic acid phenyl)-5-pyrazolone, 3-methyl-1-(4-sulfonic acid phenyl)-5-pyrazolone, 1-(4'-sulfonic acid phenyl)-3-carboxy-5-pyrazolone, 3-carboxy-1-(4-sulfonic acid phenyl)-5-pyrazolone sodium salt, barbituric acid, H acid, J acid, γ acid, L acid, NW acid, perisulfonic acid, 1,5-naphthalene disulfonic acid, 1-amino-8-naphthol-3,6-disulfonic acid, 2-amino-8-naphthol-6-sulfonic acid, 1-hydroxy-6-naphthalenesulfonic acid, 2-hydroxy-6-naphthalenesulfonic acid, 2-hydroxy-3,6-naphthalene disulfonic acid, 2-hydroxypyridine, indole, 8-hydroxyquinoline, phloroglucinol, one of Chicago acids.

[0027] In one embodiment of the present invention, in step S3, in the coupling component solution, the concentration of the coupling component is 1-10 g / L; the concentration of sodium hydroxide is 0.1-0.6 g / L; and the concentration of sodium carbonate is 3-7 g / L.

[0028] In one embodiment of the present invention, in step S3, the bath ratio of the reaction is 1:5-30.

[0029] In one embodiment of the present invention, in step S3, the reaction temperature is 10-35° C.; and the reaction time is 5-30 min.

[0030] In one embodiment of the present invention, in step S3, the temperature of the hot water is 50-70°C, and the temperature of the cold water is 5-15°C.

[0031] In one embodiment of the present invention, in step S3, hot water washing and cold water washing are performed alternately 1 to 3 times.

[0032] In one embodiment of the present invention, in steps S1, S2, and S3, the drying is performed so that the moisture content of the textile is ≤2%.

[0033] The second object of the present invention is to provide dyed textiles prepared by the above dyeing method.

[0034] The third object of the present invention is to provide the use of the dyed textile in the textile field.

[0035] Beneficial effects:

[0036] Compared with the prior art, the present invention has the following beneficial effects:

[0037] 1. High reaction activity and excellent grafting efficiency: The present invention adopts vinylsulfone type active groups to graft and modify cellulose fibers. This group has strong nucleophilic substitution reaction activity and can covalently bond with the hydroxyl groups in the cellulose molecules under mild conditions. It has high reaction efficiency and controllable modification degree, which significantly improves the effective site density of subsequent coupling reactions.

[0038] 2. In-situ dye generation and good fixation fastness: The present invention directly constructs azo dye molecules on the fiber surface through diazotization and coupling reaction, so that the dye is generated and fixed, without the need for exogenous dye migration process, avoiding dye hydrolysis, improving dyeing rate and color fastness, and high dye utilization rate.

[0039] 3. Rich color types and adjustable structure: Since the diazo group can react with a variety of phenolic or aromatic amine coupling components to generate azo dyes with diverse structures and rich colors, it has good application flexibility and adjustable colors.

[0040] 4. Green and environmentally friendly, simplified process: The entire dyeing process does not rely on high temperature or large amounts of inorganic salts. The reaction conditions are mild, and the dye is directly generated and fixed inside the fiber, significantly reducing energy consumption and wastewater treatment pressure. The wastewater is salt-free, has few auxiliaries, and has low chroma, which meets the needs of sustainable green textile processing.

[0041] 5. Strong adaptability and easy industrial promotion: This method is applicable to common cellulose substrates, such as cotton, viscose, Tencel, etc., and the raw materials used are from a wide range of sources, the operation process is controllable, and it has a good industrialization foundation and process compatibility. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 K / S curve of the dyed cotton fabric prepared in Example 1 before and after DMF stripping.

[0043] Figure 2 The K / S curves of the dyed linen fabric prepared in Example 2 before and after DMF stripping are shown.

[0044] Figure 3 This is the K / S curve of the dyed fabric of Comparative Example 1.

[0045] Figure 4 This is the K / S curve of the dyed fabric of Comparative Example 2. DETAILED DESCRIPTION

[0046] Example 1

[0047] The in-situ assembly dyeing method of cotton fabric Y1 with controllable dye molecules comprises the following steps:

[0048] S1. Immerse 10 g of a cellulose fiber textile in an aqueous solution of 4-β-hydroxyethylsulfonyl sulfate aniline-2-sulfonic acid for reaction at 65° C. for 30 min, wash with water, and dry to obtain a vinylsulfone-modified textile; the mass ratio of the 4-β-hydroxyethylsulfonyl sulfate aniline-2-sulfonic acid compound to the mass of the cellulose fiber textile is 0.5:1, and the bath ratio of the reaction is 1:5;

[0049] S2. Mix 1.01 mL of concentrated hydrochloric acid containing 0.01 mol of HCl with 15 g of water to obtain a hydrochloric acid aqueous solution; mix 0.0101 mol of sodium nitrite with 1 g of water to obtain a sodium nitrite aqueous solution; immerse a vinyl sulfone-modified textile in the hydrochloric acid aqueous solution, slowly and uniformly add the sodium nitrite aqueous solution dropwise (over 5 minutes) to obtain a reaction solution, react at room temperature (25° C.) for 10 minutes, add urea until the reaction solution does not change color within 1 to 2 seconds when dropped on potassium iodide test paper, wash the textile with water, and dry it to obtain a diazotized textile;

[0050] S3. Dissolve the coupling component, sodium hydroxide and sodium carbonate in water to obtain 200 mL of a coupling component solution, wherein the coupling component concentration of the coupling component solution is 2 g / L, the concentration of sodium hydroxide is 0.3 g / L, and the concentration of sodium carbonate is 5 g / L. Immerse the diazotized textile in the coupling component solution and react at room temperature for 10 min. Wash the textile alternately with hot water at 60°C and cold water at 8°C twice, and dry the resulting fabric to obtain dyed cotton fabric Y1.

[0051] The coupling component is 3-carboxyl-1-(4-sulfonic acid phenyl)-5-pyrazolone, and its structural formula is:

[0052]

[0053] The resulting dyed cotton fabric Y1 was yellow in color and exhibited uniform dyeing. Dyed cotton fabric Y1 was tested according to the "Color Fastness to Washing (GB / T 3921-2008)", "Color Fastness to Rubbing (GB / T 3920-2008)", and "Color Fastness to Dry Heat (GB / T 5718-1997)". The results are shown in Table 1. The dyed cotton fabric Y1 had a dry rubbing fastness of 4-5, a wet rubbing fastness of 4-5, and a soaping fastness of 4-5. Fabrics dyed using this method exhibit excellent color fastness.

[0054] N,N-dimethylformamide (DMF) is a highly polar solvent and is often used to remove dyes adsorbed on the surface of fabrics that do not form covalent bonds with cellulose macromolecules. DMF is used to strip dyed cotton fabrics. The steps are: soak the dyed fabric in 25mL of DMF solution and strip for 50 minutes at 100℃. The K / S curve of dyed cotton fabric Y1 before and after DMF stripping is shown in Figure 2. Figure 1The wavelength corresponding to the maximum K / S value of the fabric sample in the curve is 460nm, the maximum K / S value during dyeing is 9.87, and the relative fixation rate (K / S value after stripping divided by K / S value before stripping) reaches 73.4%. The maximum K / S value does not decrease much after stripping, indicating that the dye forms a covalent bond with the fiber.

[0055] The use of 4-β-hydroxyethylsulfonyl sulfate aniline-2-sulfonic acid ensures the realization of in situ assembly dyeing. On the one hand, the vinyl sulfone type active group (-SO2CH2CH2OSO3Na) can efficiently undergo nucleophilic substitution reaction with the hydroxyl group in the cellulose molecule under mild conditions, achieving covalent grafting on the fiber. On the other hand, its molecular structure also contains the electron-withdrawing group sulfonate (-SO3H), which effectively reduces the electron cloud density of the aromatic primary amine (-NH2), increases steric hindrance, and reduces the reaction between the vinyl sulfone type active group and the aromatic primary amine in 4-β-hydroxyethylsulfonyl sulfate aniline-2-sulfonic acid.

[0056] If other molecules with similar structures but lacking the above-mentioned key functional group combinations (such as intermediates containing only aromatic amine or only vinyl sulfone structures) are used for the reaction, effective covalent grafting with cellulose cannot be completed, or further diazotization and coupling reactions cannot be carried out after grafting, resulting in the inability to generate azo dyes on the fiber surface, poor dyeing effect or no color development.

[0057] In addition, the presence of sulfonic acid groups (-SO3H) also gives the molecule good water solubility and fiber affinity, which helps to improve reaction uniformity and coloring uniformity.

[0058] The coupling component has a relatively simple structure and does not form a conjugated system that strongly absorbs visible light, resulting in a colorless or light-colored product. The coupling component reacts with the diazo component to form an azo dye, producing a conjugated system that strongly absorbs visible light, resulting in a rich, vibrant color. The coupling component solution used in the dyeing process of the present invention contains only the coupling component. During dyeing, the coupling component reacts with the diazo-treated textile to color the fabric. Compared to conventional dyeing methods, the dyeing wastewater is lighter in color and has a lower chroma than wastewater from dyeing with traditional reactive dyes.

[0059] Example 2

[0060] The method for in-situ assembly dyeing of linen fabric R1 with controllable dye molecules differs from that in Example 1 in that the cotton fabric is replaced with linen fabric, and the coupling component is replaced with 1-amino-8-naphthol-3,6-disulfonic acid, whose structural formula is:

[0061]

[0062] The resulting dyed linen fabric R1 was red and uniformly dyed. Dyed linen fabric R1 was tested according to the "Color Fastness to Washing" (GB / T 3921-2008), "Color Fastness to Rubbing" (GB / T 3920-2008), and "Color Fastness to Dry Heat" (GB / T 5718-1997). The results are shown in Table 1. The dyed linen fabric R1 had a dry rubbing fastness of 4-5, a wet rubbing fastness of 4-5, and a soaping fastness of 4-5, with a relative color fixation rate of 91.2%. Fabrics dyed using this method exhibit excellent color fastness.

[0063] The K / S curve of the dyed linen fabric R1 before and after DMF stripping is as follows: Figure 2 The wavelength corresponding to the maximum K / S value of the fabric sample in the curve is 510nm, and the maximum K / S value of the dyeing is 6.91. The maximum K / S value hardly decreases after stripping, indicating that the dye forms a covalent bond with the fiber.

[0064] Example 3

[0065] The invention discloses a method for dyeing bamboo fabric with controllable dye molecules in situ assembly, comprising the steps of:

[0066] S1. Immerse 10 g of a cellulose fiber textile in an aqueous solution of 4-β-hydroxyethylsulfonyl sulfate aniline-2-sulfonic acid for reaction at 65° C. for 32 min, wash with water, and dry to obtain a vinylsulfone-modified textile; the mass ratio of the 4-β-hydroxyethylsulfonyl sulfate aniline-2-sulfonic acid compound to the mass of the cellulose fiber textile is 0.6:1, and the bath ratio of the reaction is 1:7;

[0067] S2. Mix 1.01 mL of concentrated hydrochloric acid containing 0.01 mol of HCl with 13 g of water to obtain a hydrochloric acid aqueous solution; mix 0.0101 mol of sodium nitrite with 1 g of water to obtain a sodium nitrite aqueous solution; immerse a vinyl sulfone-modified textile in the hydrochloric acid aqueous solution, slowly and uniformly add the sodium nitrite aqueous solution dropwise (over 5 minutes) to obtain a reaction solution, react at 20° C. for 15 minutes, add urea until the reaction solution does not change color within 1 to 2 seconds when dropped on potassium iodide test paper, wash the textile with water, and dry it to obtain a diazotized textile;

[0068] S3. Dissolve the coupling component, sodium hydroxide and sodium carbonate in water to obtain 230 mL of a coupling component solution, wherein the coupling component concentration of the coupling component solution is 2.5 g / L, the concentration of sodium hydroxide is 0.5 g / L, and the concentration of sodium carbonate is 6 g / L. Immerse the diazotized textile in the coupling component solution and react at 20° C. for 20 min. Alternately wash the textile with hot water at 70° C. and with cold water at 10° C. twice, and dry the textile to obtain a dyed bamboo fabric.

[0069] The coupling component is 2-amino-8-naphthol-6-sulfonic acid, and its structural formula is:

[0070]

[0071] Comparative Example 1

[0072] Use reactive dyes to dye linen fabric (the same linen fabric used in Example 2) by conventional dyeing methods. The reactive dye selected is Reactive Red 24:1, and its structural formula is as follows:

[0073]

[0074] Dyeing is carried out according to the following process: dye mass concentration is 0.2g / L, sodium chloride is 70g / L, sodium carbonate is 10g / L, bath ratio is 1:100, dyeing is carried out at room temperature, heating to 70℃ at a heating rate of 1℃ / min and then keeping warm for 60min. After the insulation is completed, take out the linen fabric, wash it with water and soap it several times, and dry it.

[0075] The K / S curve of the linen fabric treated by the method described in Comparative Example 3 is as follows: Figure 3 The wavelength corresponding to the maximum K / S value of the fabric sample in the curve is 542nm, and the maximum K / S value of dyeing is 10.23. The dyed fabric has a dry friction fastness of 4 to 5, a wet friction fastness of 4, and a soaping fastness of 4 to 5, with a relative fixation rate of 68.5%.

[0076] The dye liquor in Comparative Example 1 contains not only dyes but also a large amount of electrolytes (NaCl and Na2CO3), which results in the discharge of colored saline wastewater and increases the difficulty of wastewater treatment.

[0077] Comparative Example 2

[0078] The flax fiber fabric (the same as the flax fiber fabric used in Example 2) was dyed using a conventional dyeing method using a reactive dye. The reactive dye used was Reactive Blue 49, which has the following structural formula:

[0079]

[0080] Dyeing was carried out according to the following process: the dye mass concentration was 0.2 g / L, sodium chloride was 70 g / L, sodium carbonate was 10 g / L, the bath ratio was 1:100, dyeing was carried out at room temperature, the temperature was raised to 70°C at a heating rate of 1°C / min, and then the temperature was kept for 60 minutes. After the temperature was kept at this temperature, the hemp fiber fabric was taken out, washed with water and soaped several times, and then dried.

[0081] The K / S curve of the hemp fiber fabric treated by the method described in Comparative Example 2 is as follows: Figure 4 The wavelength corresponding to the maximum K / S value of the fabric sample in the curve is 600nm, and the maximum K / S value of dyeing is 8.67. The dyed fabric has a dry friction fastness of 4 to 5, a wet friction fastness of 4, and a soaping fastness of 4. The relative color fastness reaches 69.5%.

[0082] The dye liquor in Comparative Example 2 contains not only dyes but also a large amount of electrolytes (NaCl and Na2CO3), which results in the discharge of colored saline wastewater and increases the difficulty of wastewater treatment.

[0083] The time, temperature and various data of the dyeing samples after dyeing used by different dyeing methods are summarized in Table 1. It can be seen that the present invention has good data performance under various indicators.

[0084] Table 1

[0085]

[0086]

[0087] The embodiments provided above are not intended to limit the scope of the present invention, nor are the steps described to limit their execution order. Any obvious improvements to the present invention made by those skilled in the art in combination with existing common knowledge shall fall within the scope of protection defined by the claims of the present invention.

Claims

1. A dyeing method for cellulose fiber graft modification with controllable in-situ assembly of dye molecules, characterized in that: Including steps: S1. Immersing a cellulose fiber textile in an aqueous solution of 4-β-hydroxyethylsulfonyl sulfate aniline-2-sulfonic acid for reaction, washing the textile with water, and drying to obtain a vinylsulfone-modified textile; S2, immersing the vinyl sulfone modified textile in a hydrochloric acid aqueous solution, adding a sodium nitrite aqueous solution for reaction, adding urea, washing the textile with water, and drying to obtain a diazotized textile; S3. Dissolving a coupling component, sodium hydroxide, and sodium carbonate in water to obtain a coupling component solution, immersing the diazotized textile in the coupling component solution for reaction, washing with hot water and cold water alternately, and drying to obtain a dyed textile.

2. The dyeing method according to claim 1, wherein In step S1, the mass ratio of the cellulose fiber textile to 4-β-hydroxyethylsulfonyl sulfate aniline-2-sulfonic acid is 1:0.3-0.

8.

3. The dyeing method according to claim 1, wherein In step S1, the bath ratio of the reaction is 1:4-8; the reaction temperature is 60-70° C.; and the reaction time is 20-40 min.

4. The dyeing method according to claim 1, wherein In step S2, the concentration of the hydrochloric acid aqueous solution is 0.5-0.8 mol / L; the concentration of the sodium nitrite aqueous solution is 8-12 mol / L; and the volume ratio of the hydrochloric acid aqueous solution to the sodium nitrite aqueous solution is 12-18:

1.

5. The dyeing method according to claim 1, wherein In step S2, the bath ratio of the reaction is 1:5-10; the reaction temperature is 15-30° C., and the reaction time is 5-15 min.

6. The dyeing method according to claim 1, wherein In step S3, the coupling component is selected from one or more of phenolic compounds, aromatic amine compounds, active methylene compounds, heterocyclic compounds, hydroxynaphthoic acid compounds, and polycyclic aromatic hydrocarbon derivatives.

7. The dyeing method according to claim 1, wherein In step S3, in the coupling component solution, the concentration of the coupling component is 1-10 g / L; the concentration of sodium hydroxide is 0.1-0.6 g / L; and the concentration of sodium carbonate is 3-7 g / L.

8. The dyeing method according to claim 1, wherein In step S3, the bath ratio of the reaction is 1:5-30; the reaction temperature is 10-35° C.; and the reaction time is 5-30 min.

9. Dyed textiles produced by the dyeing method according to any one of claims 1 to 8.

10. Use of the dyed textile according to claim 9 in the textile field.

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