A method for salt-free dyeing of plant protein cationic assistant modified cellulose textile

Abstract

The application provides a method for salt-free dyeing of plant protein cationic auxiliary modified cellulose textiles, and belongs to the technical field of dyeing chemicals.The method comprises the following steps: mixing a phosphated plant protein solution with a quaternary ammonium reagent and / or an amino-containing reagent solution, adding a crosslinking agent to react, and obtaining a cationic auxiliary; placing cellulose textiles in the cationic auxiliary for impregnation pretreatment, placing the treated textiles in an active dye bath for salt-free dip dyeing, and obtaining salt-free dyed cellulose textiles.The application uses phosphated plant protein as a skeleton, covalently crosslinks the phosphated plant protein with a quaternary ammonium reagent and / or an amino-containing reagent through a crosslinking agent to form a cationic auxiliary with a porous three-dimensional network structure, constructs a high-density positive charge layer on the surface of the fiber, changes the electrostatic repulsion between the active dye and the cellulose fiber into electrostatic attraction, and thus realizes salt-free dyeing.

Description

Technical Field

[0001] This invention relates to the field of dye chemical technology, specifically to a method for salt-free dyeing of cellulose textiles modified with plant protein cationic auxiliaries. Background Technology

[0002] Cotton possesses excellent hydrophilicity, biodegradability, breathability, and comfort, making it one of the main cellulose raw materials in the textile industry. Eco-friendly dyeing of cotton is one of the most significant challenges facing the textile industry. In the textile industry, reactive dyes (anionic dyes that can form covalent bonds with cellulose under alkaline conditions) offer a wide range of hues and vibrant colors, making them among the most commonly used dyes for cotton fabrics. However, reactive dyes are prone to hydrolysis when forming covalent bonds with cellulose, resulting in low dye uptake and fixation rates. In traditional dyeing processes, to overcome the repulsive forces between anionic dyes and the cellulose surface and to improve dye uptake and fixation rates, cotton textiles are typically dyed in high-concentration inorganic salt solutions (such as Na₂SO₄, NaCl, or Na₂CO₃). This method generates dyeing wastewater containing high concentrations of inorganic salts, which is environmentally harmful and has high treatment costs.

[0003] Reports indicate that textile dyeing wastewater accounts for approximately 17-20% of global industrial water pollution. Therefore, avoiding the use of high temperatures and inorganic salts in reactive dyeing processes, finding greener methods for dyeing cotton fabrics with reactive dyes, and developing more energy-sustainable processes are of paramount environmental and practical significance. Low-salt and salt-free reactive dyeing mainly involves four methods: developing low-salt reactive dyes, optimizing dyeing processes, developing salt-free dyeing auxiliaries, and cationization modification of cotton. Among these, cationization modification of cotton fabrics is an effective way to eliminate the electrostatic repulsion between cellulose and reactive dyes.

[0004] Different cationic reagents, such as 3-chloro-2-hydroxypropyltrimethylammonium chloride (CHPTAC), (3-acrylamidopropyl)trimethylammonium chloride (AAHTAPC), quaternary ammonium cationic groups and biopolymers, as well as combinations of epoxy polymers and biopolymers, all have different limitations. For example, high doses of CHPTAC lead to high costs and environmental problems. Furthermore, quaternary ammonium cationic groups require high concentrations of base during modification, while polymers containing primary amine groups (i.e., polyethyleneimine) suffer from low adsorption efficiency.

[0005] Glycols are a class of natural plant proteins with molecular chains rich in active groups such as hydroxyl and amino groups. They also possess good biocompatibility and biodegradability, making them ideal candidate materials for the backbone of cationic auxiliaries. However, the presence of numerous hydrophobic amino acids in the glycolic protein molecule results in low solubility in water, hindering its direct and uniform reaction with quaternizing agents and crosslinking agents in aqueous systems, thus limiting its application in the textile printing and dyeing industry. If glycolic proteins could be chemically modified into water-soluble proteins, their structural advantages could be fully utilized to construct high-performance cationic auxiliaries. Summary of the Invention

[0006] The technical problems to be solved: Existing reactive dyeing processes require the addition of large amounts of inorganic salts, leading to high-salt wastewater pollution. Furthermore, existing cationization modification of cotton fibers suffers from high costs, high alkali concentrations, and low adsorption efficiency due to the large amount of cationic reagents used. This invention provides a method for salt-free dyeing of cellulose textiles modified with plant protein cationic auxiliaries. Using plant protein as a framework, cationic auxiliaries are prepared through covalent cross-linking with quaternizing agents and / or amino-containing reagents. After modification of cellulose textiles, salt-free dyeing is achieved. This method has the advantages of low auxiliary dosage, good dyeing effect, and environmental friendliness.

[0007] Technical solution: A method for salt-free dyeing of cellulose textiles modified with plant protein cationic auxiliaries, comprising the following steps: S1. The plant protein is phosphorylated to obtain phosphorylated plant protein. The phosphorylated plant protein is dissolved in a good solvent to obtain a phosphorylated plant protein solution. The quaternizing reagent and / or amino-containing reagent are dissolved in a good solvent to obtain a cationic precursor solution. S2. Mix the phosphorylated plant protein solution and the cationic precursor solution in equal volumes, adjust the pH to 4.5, add the cross-linking agent, and stir at 20~70℃ for 30~120 min to obtain the cationic auxiliary agent; S3. Pre-treat the cellulose textiles in a cationic auxiliaries: impregnate, wash with cold water, and dry to obtain cationic auxiliaries modified cellulose textiles; S4. Prepare a dye bath for reactive dyes, place the cellulose textile modified with cationic auxiliaries in the dye bath, immerse and dye it, and dry it to obtain salt-free dyed cellulose textiles.

[0008] Preferably, the plant protein in step S1 is a prolysin, which is selected from one or more of corn prolysin, wheat prolysin, and sorghum prolysin.

[0009] Preferably, the phosphorylation modification includes the following steps: S11. Disperse alcohol-soluble protein in water, add phosphorylation reagent, wherein the mass ratio of phosphorylation reagent to alcohol-soluble protein is 1:1 to 1:4, adjust pH to 8 to 10, stir and react at 20 to 50°C for 0.5 to 3 hours to obtain phosphorylation reaction solution; S12. Ultrafilter the phosphorylation reaction solution to remove unreacted phosphorylation reagent; S13. Freeze-dry the ultrafiltration product to obtain phosphorylated modified prolysin.

[0010] Preferably, the phosphorylation reagent in step S11 is any one of sodium tripolyphosphate, phosphorus oxychloride, sodium pyrophosphate, or sodium trimetaphosphate.

[0011] Preferably, the quaternizing agent in step S1 includes one or more of 2,3-epoxypropyltrimethylammonium chloride, 3-chloro-2-hydroxypropyltrimethylammonium chloride, dodecyltrimethylammonium chloride, dimethyldiallylammonium chloride, dodecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, triethylamine hydrochloride, and 4-chloromethylpyridine hydrochloride, and the amino-containing agent includes one or more of ethylenediamine, diethylenetriamine, polyethyleneimine, cationic polyacrylamide, chitosan, and betaine.

[0012] Preferably, the good solvent in step S1 includes one or more of methanol, ethanol, water, isopropanol, and dilute acetic acid.

[0013] Preferably, the crosslinking agent in step S2 includes one or more of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide, ethylene glycol diglycidyl ether, glycerol triglycidyl ether, glutaraldehyde, genipin, citric acid, aldehyde-modified arabinoxylan, tea polyphenols, gallic acid, and sodium tripolyphosphate.

[0014] Preferably, in step S2, the mass ratio of phosphorylated plant protein to cationic precursor in the cationic adjuvant is 1:1 to 1:3, and the amount of crosslinking agent is 10% of the total amount of quaternizing agent and / or amino-containing agent.

[0015] Preferably, in step S3, the cellulose textile is cotton, hemp, ramie, jute, apocynum, viscose, Modal, Lyocell, cotton / linen blend, or cotton / viscose blend; the concentration of the cationic auxiliaries is 2–8 g / L; the pH of the pretreatment is 3–5; the bath ratio of the pretreatment is 1:10–1:40; the impregnation temperature is 20–60°C; and the impregnation time is 20–60 min.

[0016] Preferably, in step S4, the concentration of reactive dye in the dye bath is 1-5% (owf), the bath ratio is 1:10-1:50, the immersion time is 20-50 min, and the immersion temperature is 40-90℃.

[0017] Beneficial effects: The salt-free dyeing method for cellulose textiles modified with plant protein cationic auxiliaries of the present invention has the following advantages: This invention utilizes plant protein as a macromolecular structural framework, and covalently crosslinks it with quaternizing agents and / or amino-containing agents to form a cationic additive with a porous three-dimensional network structure. The plant protein molecular chain is rich in active groups such as hydroxyl, amino, and carboxyl groups, which have a natural affinity with cellulose fibers, enabling it to spread evenly and bind firmly. The quaternizing agents and amino-containing agents provide a source of cationic charge, giving the modified cellulose fiber surface a high density of positive charge.

[0018] In traditional reactive dyeing, there is electrostatic repulsion between anionic dyes and the negatively charged cellulose surface, requiring the addition of a large amount of inorganic salts to achieve effective dyeing. This invention introduces a high density of positive charges onto the fiber surface, transforming electrostatic repulsion into electrostatic attraction, enabling the dye to be efficiently applied and fully fixed without the addition of any inorganic salts. At the same time, it imparts excellent color fastness to the fabric, fundamentally reducing the discharge of high-salt dyeing wastewater.

[0019] In this invention, the cationic groups provided by the amino reagent or quaternizing reagent can interact electrostatically with the negatively charged lipopolysaccharides and proteins in the bacterial cell wall, thereby disrupting the integrity of the cell wall, causing leakage of intracellular substances and metabolic disorders, thus exerting an antibacterial and bactericidal effect. Through the covalent bond action of the cross-linking agent, these antibacterial active components are stably anchored on the plant protein skeleton and fiber surface, overcoming the problems of small molecule antibacterial agents being susceptible to washing and easy to be lost.

[0020] Plant protein molecules are rich in polar groups such as hydroxyl and amino groups, which have a natural affinity with cellulose fibers. They can spread evenly on the fiber surface and avoid local aggregation of cationic groups. At the same time, the porous three-dimensional network structure constructed by the cross-linking agent provides a moderate physical obstacle to the diffusion of dye molecules, exerting a slow dyeing effect and enabling the dye to be evenly adsorbed and dyed. The plant protein molecules themselves are flexible, and the hydrophilic groups such as phosphate introduced by phosphorylation further enhance the lubricity of the fiber surface, making the fabric feel soft and smooth. Attached Figure Description

[0021] Figure 1 This is a flowchart illustrating the preparation, modification, and salt-free staining process of the cationic auxiliaries of this invention. Figure 2 The dyeing process curve for the modified fabric; Figure 3The dyeing process curve for unmodified fabrics; Figure 4 This is a comparison chart of antibacterial performance tests against Escherichia coli. Figure 5 This is a comparison chart showing the antibacterial performance against Staphylococcus aureus. Detailed Implementation

[0022] The present invention will be further described below with reference to embodiments. These embodiments are illustrative of the present invention, but the present invention is not limited to these embodiments: Example 1

[0023] A method for salt-free dyeing of cellulose textiles modified with a plant protein cationic auxiliaries includes the following steps: S1. Disperse 5g of wheat gliadin in 100mL of water, add 2.5g of sodium tripolyphosphate, adjust the pH to 9 with NaOH solution, stir and react at 25℃ for 1.5h to obtain a phosphorylated reaction solution, ultrafilter the phosphorylated reaction solution, freeze-dry the ultrafiltered product to obtain phosphorylated wheat gliadin; dissolve the phosphorylated wheat gliadin in water to obtain a 1g / L phosphorylated wheat gliadin solution, and dissolve chitosan in 1% acetic acid solution to obtain a 1g / L cationic precursor solution; S2. Mix 10 mL of phosphorylated wheat gliadin solution with 10 mL of cationic precursor solution in equal volume, adjust the pH to 4.5, add 0.001 g of genipin, stir and react at 20℃ for 30 min to obtain a 2 g / L cationic adjuvant. S3. The cotton fabric is pretreated by immersing it in cationic auxiliaries at 20°C with a bath ratio of 1:10 for 20 min, then washed with cold water and dried to obtain cationic auxiliaries modified cotton textiles. S4. Prepare a 2% (owf) Reactive Red 24 dye bath. Place the cationic auxiliary modified cotton textiles from S3 into the dye bath at a bath ratio of 1:50, and proceed according to the dyeing temperature process curve ( Figure 2 The dyeing process involves immersion dyeing and drying to obtain salt-free dyed cellulose textiles.

[0024] K / S ratio and staining fastness were measured, and the results are shown in Table 1.

[0025] Table 1

[0026] Example 2

[0027] A method for salt-free dyeing of cellulose textiles modified with a plant protein cationic auxiliaries includes the following steps: S1. Disperse 5g of sorghum prolysin in 100mL of water, add 2.5g of sodium tripolyphosphate, adjust the pH to 9 with NaOH solution, stir and react at 25℃ for 1.5h to obtain a phosphorylated reaction solution, ultrafilter the phosphorylated reaction solution, freeze-dry the ultrafiltered product to obtain phosphorylated sorghum prolysin; dissolve the phosphorylated sorghum prolysin in water to obtain a 5g / L phosphorylated sorghum prolysin solution, and dissolve chitosan in 1% acetic acid solution to obtain a 10g / L cationic precursor solution; S2. Mix 10 mL of phosphorylated sorghum prolysin solution with 10 mL of cationic precursor solution in equal volume, adjust the pH to 4.5, add 0.005 g of citric acid, and stir at 70℃ for 120 min to obtain 8 g / L cationic adjuvant. S3. The cotton fabric is pretreated for 60 minutes by immersing it in cationic auxiliaries at 60°C with a bath ratio of 1:40, followed by cold water washing and drying to obtain cationic auxiliaries modified cotton textiles. S4. Prepare a 2% (owf) reactive yellow dye bath. Place the cationic auxiliary modified cotton textiles from S3 into the dye bath at a bath ratio of 1:50, and proceed according to the dyeing temperature process curve. Figure 2 The dyeing process involves immersion dyeing and drying to obtain salt-free dyed cellulose textiles.

[0028] K / S ratio and staining fastness were measured, and the results are shown in Table 2.

[0029] Table 2

[0030] Example 3

[0031] A method for salt-free dyeing of cellulose textiles modified with a plant protein cationic auxiliaries includes the following steps: S1. Disperse 5g of zein in 100mL of water, add 2.5g of sodium tripolyphosphate, adjust the pH to 9 with NaOH solution, stir and react at 25℃ for 1.5h to obtain a phosphorylated reaction solution, ultrafilter the phosphorylated reaction solution, freeze-dry the ultrafiltered product to obtain phosphorylated zein; dissolve the phosphorylated zein in water to obtain a 4g / L phosphorylated zein solution, and dissolve chitosan in 1% acetic acid solution to obtain a 12g / L cationic precursor solution; S2. Mix 10 mL of phosphorylated zein solution with 10 mL of cationic precursor solution in equal volume, adjust the pH to 4.5, add 0.004 g of aldehyde-modified arabinoxylan, and stir at 20 °C for 120 min to obtain 8 g / L cationic adjuvant. S3. The cotton fabric is pretreated by immersing it in cationic auxiliaries at 20°C with a bath ratio of 1:10 for 60 minutes, then washed with cold water and dried to obtain cationic auxiliaries modified cotton textiles. S4. Prepare a 2% (owf) reactive brilliant blue KN-G dye bath. Place the cationic auxiliary modified cotton textiles from S3 into the dye bath at a bath ratio of 1:50, and proceed according to the dyeing temperature process curve. Figure 2 The dyeing process involves immersion dyeing and drying to obtain salt-free dyed cellulose textiles.

[0032] K / S ratio and staining fastness were measured, and the results are shown in Table 3.

[0033] Table 3

[0034] Example 4

[0035] A method for salt-free dyeing of cellulose textiles modified with a plant protein cationic auxiliaries includes the following steps: S1. Disperse 5g of zein in 100mL of water, add 2.5g of sodium tripolyphosphate, adjust the pH to 9 with NaOH solution, stir and react at 25℃ for 1.5h to obtain a phosphorylated reaction solution, ultrafilter the phosphorylated reaction solution, freeze-dry the ultrafiltered product to obtain phosphorylated zein; dissolve the phosphorylated zein in water to obtain a 4g / L phosphorylated zein solution, and dissolve 2,3-epoxypropyltrimethylammonium chloride in 10% methanol solution to obtain a 12g / L cationic precursor solution; S2. Mix 10 mL of phosphorylated zein solution with 10 mL of cationic precursor solution in equal volume, adjust the pH to 4.5, add 0.004 g of sodium tripolyphosphate, and stir at 50 °C for 120 min to obtain 8 g / L cationic adjuvant. S3. The cotton fabric is pretreated for 30 minutes by immersing it in cationic auxiliaries at 30°C with a bath ratio of 1:20, followed by cold water washing and drying to obtain cationic auxiliaries modified cotton textiles. S4. Prepare a 2% (owf) Reactive Red 24 dye bath. Place the cationic auxiliary modified cotton textiles from S3 into the dye bath at a bath ratio of 1:50, and proceed according to the dyeing temperature process curve ( Figure 2 The dyeing process involves immersion dyeing and drying to obtain salt-free dyed cellulose textiles.

[0036] K / S ratio and staining fastness were measured, and the results are shown in Table 4.

[0037] Table 4

[0038] Example 5

[0039] A method for salt-free dyeing of cellulose textiles modified with a plant protein cationic auxiliaries includes the following steps: S1. Disperse 5g of zein in 100mL of water, add 2.5g of sodium tripolyphosphate, adjust the pH to 9 with NaOH solution, stir and react at 25℃ for 1.5h to obtain a phosphorylated reaction solution, ultrafilter the phosphorylated reaction solution, freeze-dry the ultrafiltered product to obtain phosphorylated zein; dissolve the phosphorylated zein in water to obtain an 8g / L phosphorylated zein solution, and dissolve chitosan in 1% acetic acid solution to obtain an 8g / L cationic precursor solution; S2. Mix 10 mL of phosphorylated zein solution with 10 mL of cationic precursor solution in equal volume, adjust the pH to 4.5, add 0.008 g of aldehyde-modified arabinoxylan, and stir at 50 °C for 120 min to obtain 8 g / L cationic adjuvant. S3. The cotton fabric is pretreated for 30 minutes by immersing it in cationic auxiliaries at 30°C with a bath ratio of 1:20, followed by cold water washing and drying to obtain cationic auxiliaries modified cotton textiles. S4. Prepare a 2% (owf) reactive yellow dye bath. Place the cationic auxiliary modified cotton textiles from S3 into the dye bath at a bath ratio of 1:50, and proceed according to the dyeing temperature process curve. Figure 2 The dyeing process involves immersion dyeing and drying to obtain salt-free dyed cellulose textiles.

[0040] K / S ratio and staining fastness were measured, and the results are shown in Table 5.

[0041] Table 5

[0042] Example 6

[0043] A method for salt-free dyeing of cellulose textiles modified with a plant protein cationic auxiliaries includes the following steps: S1. Disperse 5g of zein in 100mL of water, add 2.5g of sodium tripolyphosphate, adjust the pH to 9 with NaOH solution, stir and react at 25℃ for 1.5h to obtain a phosphorylated reaction solution, ultrafilter the phosphorylated reaction solution, freeze-dry the ultrafiltered product to obtain phosphorylated zein; dissolve the phosphorylated zein in water to obtain an 8g / L phosphorylated zein solution, and dissolve polyethyleneimine in water to obtain an 8g / L cationic precursor solution; S2. Mix 10 mL of phosphorylated zein solution with 10 mL of cationic precursor solution in equal volume, adjust the pH to 4.5, add 0.008 g of aldehyde-modified arabinoxylan, and stir at 50 °C for 120 min to obtain 8 g / L cationic adjuvant. S3. The cotton fabric is pretreated for 30 minutes by immersing it in cationic auxiliaries at 30°C with a bath ratio of 1:20, followed by cold water washing and drying to obtain cationic auxiliaries modified cotton textiles. S4. Prepare a 2% (owf) reactive brilliant blue KN-G dye bath. Place the cationic auxiliary modified cotton textiles from S3 into the dye bath at a bath ratio of 1:50, and proceed according to the dyeing temperature process curve. Figure 2 The dyeing process involves immersion dyeing and drying to obtain salt-free dyed cellulose textiles.

[0044] K / S ratio and staining fastness were measured, and the results are shown in Table 6.

[0045] Table 6

[0046] Example 7

[0047] A method for salt-free dyeing of cellulose textiles modified with a plant protein cationic auxiliaries includes the following steps: S1. Disperse 5g of zein in 100mL of water, add 2g of phosphorus oxychloride, adjust the pH to 9 with NaOH solution, stir and react at 25℃ for 1.5h to obtain a phosphorylated reaction solution, ultrafilter the phosphorylated reaction solution, freeze-dry the ultrafiltered product to obtain phosphorylated zein; dissolve the phosphorylated zein in 80% ethanol to obtain a 3g / L phosphorylated zein solution, and dissolve dimethyl diallyl ammonium chloride in water to obtain a 9g / L cationic precursor solution; S2. Mix 10 mL of phosphorylated zein solution with 10 mL of cationic precursor solution in equal volume, adjust the pH to 4.5, add 0.003 g of citric acid, and stir at 50℃ for 50 min to obtain a 6 g / L cationic auxiliary agent. S3. The viscose fabric is pretreated for 60 min by immersing it in cationic additives at 60°C with a bath ratio of 1:40, followed by cold water washing and drying to obtain cationic additive-modified viscose fabric. S4. Prepare a 2% (owf) Reactive Red 24 dye bath. Place the cationic auxiliary modified viscose fabric from S3 into the dye bath at a bath ratio of 1:50, and proceed according to the dyeing temperature process curve. Figure 2 The dyeing process involves immersion dyeing and drying to obtain salt-free dyed cellulose textiles.

[0048] K / S ratio and staining fastness were determined, and the results are shown in Table 7.

[0049] Table 7

[0050] Example 8

[0051] A method for salt-free dyeing of cellulose textiles modified with a plant protein cationic auxiliaries includes the following steps: S1. Disperse 5g of zein in 100mL of water, add 2.5g of sodium tripolyphosphate, adjust the pH to 9 with NaOH solution, stir and react at 25℃ for 1.5h to obtain a phosphorylated reaction solution, ultrafilter the phosphorylated reaction solution, freeze-dry the ultrafiltered product to obtain phosphorylated zein; dissolve the phosphorylated zein in water to obtain a 3g / L phosphorylated zein solution, dissolve dodecyltrimethylammonium chloride in 10% isopropanol solution to obtain an 8g / L cationic precursor solution; S2. Mix 10 mL of phosphorylated zein solution with 10 mL of cationic precursor solution in equal volume, adjust the pH to 4.5, add 0.003 g of ethylene glycol diglycidyl ether, stir at 50℃ for 50 min to obtain a 6 g / L cationic adjuvant. S3. The ramie fabric is pretreated by immersing it in a cationic additive at 60°C with a bath ratio of 1:40 for 60 minutes, then washed with cold water and dried to obtain the cationic additive modified ramie fabric. S4. Prepare a 2% (owf) Reactive Red 24 dye bath. Place the ramie fabric modified with the cationic auxiliary agent from S3 into the dye bath at a bath ratio of 1:50, and proceed according to the dyeing temperature process curve ( Figure 2 The dyeing process involves immersion dyeing and drying to obtain salt-free dyed cellulose textiles.

[0052] K / S ratio and staining fastness were determined, and the results are shown in Table 8.

[0053] Table 8

[0054] Example 9

[0055] A method for salt-free dyeing of cellulose textiles modified with a plant protein cationic auxiliaries includes the following steps: S1. Disperse 5g of zein in 100mL of water, add 4g of sodium trimetaphosphate, adjust the pH to 9 with NaOH solution, stir and react at 25℃ for 1.5h to obtain a phosphorylated reaction solution, ultrafilter the phosphorylated reaction solution, freeze-dry the ultrafiltered product to obtain phosphorylated zein; dissolve the phosphorylated zein in water to obtain a 3g / L phosphorylated zein solution, dissolve dimethyl diallyl ammonium chloride in water to obtain a 9g / L cationic precursor solution; S2. Mix 10 mL of phosphorylated zein solution with 10 mL of cationic precursor solution in equal volume, adjust the pH to 4.5, add 0.003 g of N-hydroxysuccinimide, stir at 50℃ for 50 min to obtain a 6 g / L cationic auxiliary agent. S3. The cotton / linen blended fabric is pretreated by immersing it in cationic auxiliaries at 40°C with a bath ratio of 1:20 for 50 minutes, then washed with cold water and dried to obtain the cationic auxiliaries modified cotton / linen blended fabric. S4. Prepare a 2% (owf) Reactive Red 24 dye bath. Place the cationic auxiliary modified cotton / linen blended fabric from S3 into the dye bath at a bath ratio of 1:50, and proceed according to the dyeing temperature process curve ( Figure 2 The dyeing process involves immersion dyeing and drying to obtain salt-free dyed cellulose textiles.

[0056] K / S ratio and staining fastness were determined, and the results are shown in Table 9.

[0057] Table 9

[0058] Example 10

[0059] A method for salt-free dyeing of cellulose textiles modified with a plant protein cationic auxiliaries includes the following steps: S1. Disperse 5g of zein in 100mL of water, add 2.5g of sodium tripolyphosphate, adjust the pH to 9 with NaOH solution, stir and react at 25℃ for 1.5h to obtain a phosphorylated reaction solution, ultrafilter the phosphorylated reaction solution, freeze-dry the ultrafiltered product to obtain phosphorylated zein; dissolve the phosphorylated zein in water to obtain a 3g / L phosphorylated zein solution, and dissolve 3-chloro-2-hydroxypropyltrimethylammonium chloride in water to obtain an 8g / L cationic precursor solution; S2. Mix 10 mL of phosphorylated zein solution with 10 mL of cationic precursor solution in equal volume, adjust the pH to 4.5, add 0.008 g of citric acid, and stir at 50℃ for 50 min to obtain 8 g / L cationic auxiliary agent; S3. The cotton fabric is immersed in cationic auxiliaries at 60℃ and treated for 15 minutes at a bath ratio of 1:30. Then, 5 g / L of NaOH is added and the fabric is kept at 60℃ for 25 minutes. Finally, the fabric is taken out and thoroughly washed with water until neutral to obtain cationic auxiliaries modified cotton textiles. S4. Prepare a 2% (owf) Reactive Red 24 dye bath. Place the cationic auxiliary modified cotton textiles from S3 into the dye bath at a bath ratio of 1:50, and proceed according to the dyeing temperature process curve ( Figure 2 The dyeing process involves immersion dyeing and drying to obtain salt-free dyed cellulose textiles.

[0060] K / S ratio and staining fastness were measured, and the results are shown in Table 10.

[0061] Table 10

[0062] Example 11

[0063] S1. Disperse 5g of wheat gliadin in 100mL of water, add 2.5g of sodium pyrophosphate, adjust the pH to 9 with NaOH solution, stir and react at 25℃ for 1.5h to obtain a phosphorylated reaction solution, ultrafilter the phosphorylated reaction solution, freeze-dry the ultrafiltered product to obtain phosphorylated wheat gliadin; dissolve the phosphorylated wheat gliadin in water to obtain a 1g / L phosphorylated wheat gliadin solution, and dissolve betaine in water to obtain a 9g / L cationic precursor solution; S2. Mix 10 mL of phosphorylated wheat gliadin solution with 10 mL of cationic precursor solution in equal volumes, adjust the pH to 4.5, add 0.003 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, stir at 50 °C for 50 min to obtain a 6 g / L cationic adjuvant. S3. The cotton fabric is pretreated for 60 minutes by immersing it in cationic auxiliaries at 60°C with a bath ratio of 1:40, followed by cold water washing and drying to obtain cationic auxiliaries modified cotton textiles. S4. Prepare a 2% (owf) Reactive Red 24 dye bath. Place the cationic auxiliary modified cotton textiles from S3 into the dye bath at a bath ratio of 1:50, and proceed according to the dyeing temperature process curve ( Figure 2 The dyeing process involves immersion dyeing and drying to obtain salt-free dyed cellulose textiles.

[0064] K / S ratio and staining fastness were determined, and the results are shown in Table 11.

[0065] Table 11

[0066] Example 12

[0067] A method for salt-free dyeing of cellulose textiles modified with a plant protein cationic auxiliaries includes the following steps: S1. Disperse 5g of zein in 100mL of water, add 2.5g of sodium tripolyphosphate, adjust the pH to 9 with NaOH solution, stir and react at 25℃ for 1.5h to obtain a phosphorylated reaction solution, ultrafilter the phosphorylated reaction solution, freeze-dry the ultrafiltered product to obtain phosphorylated zein; dissolve the phosphorylated zein in water to obtain a 3g / L phosphorylated zein solution, dissolve 4-chloromethylpyridine hydrochloride in water to obtain a 9g / L cationic precursor solution; S2. Mix 10 mL of phosphorylated zein solution with 10 mL of cationic precursor solution in equal volume, adjust the pH to 4.5, add 0.003 g of gallic acid, stir at 50℃ for 50 min to obtain a 6 g / L cationic auxiliary agent; S3. The cotton / viscose blended fabric is pretreated by immersing it in a cationic auxiliary agent at 40°C with a bath ratio of 1:30 for 40 min, then washed with cold water and dried to obtain the cationic auxiliary modified cotton / viscose blended fabric. S4. Prepare a 2% (owf) Reactive Red 24 dye bath. Place the cationic auxiliary modified cotton / viscose blended fabric from S3 into the dye bath at a bath ratio of 1:50, and proceed according to the dyeing temperature process curve ( Figure 2 The dyeing process involves immersion dyeing and drying to obtain salt-free dyed cellulose textiles.

[0068] K / S ratio and staining fastness were determined, and the results are shown in Table 12.

[0069] Table 12

[0070] Comparative Example 1 Conventional dyeing process: Prepare a 2% (owf) Reactive Red 24 dye bath. Place the unmodified cotton fabric in the dye bath at a bath ratio of 1:50, and follow the dyeing temperature process curve. Figure 3 The dyeing process involves immersion dyeing, followed by drying to obtain dyed cellulose textiles.

[0071] K / S ratio and staining fastness were measured, and the results are shown in Table 13.

[0072] Table 13

[0073] Comparative Example 2 Conventional dyeing process: Prepare a 2% (owf) reactive yellow dye bath. Place the unmodified cotton fabric in the dye bath at a bath ratio of 1:50, and follow the dyeing temperature process curve. Figure 3 The dyeing process involves immersion dyeing, followed by drying to obtain dyed cellulose textiles.

[0074] K / S ratio and staining fastness were determined, and the results are shown in Table 14.

[0075] Table 14

[0076] Comparative Example 3 Conventional dyeing process: Prepare a 2% (owf) reactive brilliant blue KN-G dye bath. Place the unmodified cotton fabric in the dye bath at a bath ratio of 1:50, and follow the dyeing temperature process curve. Figure 3 The dyeing process involves immersion dyeing, followed by drying to obtain dyed cellulose textiles.

[0077] K / S ratio and staining fastness were determined, and the results are shown in Table 15.

[0078] Table 15

[0079] In Comparative Examples 1-3, unmodified cotton fabrics were directly dyed with reactive dyes. Because the cellulose fiber surface carries a negative charge, there is electrostatic repulsion between the cellulose fiber and the similarly negatively charged reactive dye molecules, making it difficult for the dye to be effectively adsorbed onto the fiber surface. Furthermore, a large amount of unadsorbed dye remains in the dye bath and is discharged with the wastewater. In contrast, the embodiments of this invention pretreat the cellulose textiles with a plant protein cationic auxiliaries, constructing a cationic auxiliary layer with a porous three-dimensional network structure on the fiber surface. The hydroxyl and amino groups abundant in the plant protein molecular chains are firmly bonded to the cellulose fibers through hydrogen bonds and van der Waals forces. Simultaneously, the high-density positive charge provided by the quaternizing reagent and the amino-containing reagent transforms the original electrostatic repulsion into electrostatic attraction, allowing the negatively charged reactive dye molecules to be efficiently adsorbed onto the fiber surface and fully penetrate and diffuse. Then, under alkaline fixing conditions, they covalently bond with the hydroxyl groups on the fiber, achieving efficient dye fixation.

[0080] Comparative Example 4 The difference between Comparative Example 4 and Example 5 is that no plant protein components are added to the cationic adjuvant of Comparative Example 4; S1. Dissolve chitosan in a 1% acetic acid solution to obtain an 8 g / L cationic precursor solution; S2. Adjust the pH of the cationic precursor solution to 4.5, add 0.008 g of aldehyde-modified arabinoxylan, and stir at 50℃ for 120 min to obtain an 8 g / L cationic auxiliary agent; S3. The cotton fabric is pretreated for 30 minutes by immersing it in cationic auxiliaries at 30°C with a bath ratio of 1:20, followed by cold water washing and drying to obtain cationic auxiliaries modified cotton textiles. S4. Prepare a 2% (owf) Reactive Red 24 dye bath. Place the cationic auxiliary modified cotton textiles from S3 into the dye bath at a bath ratio of 1:50, and proceed according to the dyeing temperature process curve ( Figure 2 The dyeing process involves immersion dyeing and drying to obtain salt-free dyed cellulose textiles.

[0081] K / S ratio and staining fastness were determined, and the results are shown in Table 16.

[0082] Table 16

[0083] In Comparative Example 4, the cationic auxiliaries did not contain any plant protein components; the modifier was formed solely by cross-linking chitosan and aldehyde-modified arabinoxylan. Without plant protein as the macromolecular backbone, the chitosan cross-linked polymer still possessed certain cationic properties and film-forming ability. However, due to the lack of multiple anchoring effects provided by the abundant hydroxyl and amino groups on the plant protein molecular chains, the bonding between the cross-linked network and cellulose fibers was mainly based on hydrogen bonds and electrostatic interactions between the amino groups of chitosan and the fibers. The number of binding sites and the binding strength were both limited, making it difficult to form a uniform, dense, and stable three-dimensional network structure on the fiber surface. Under the same dyeing conditions, the modification effect of Comparative Example 4 was inferior to the examples with added plant protein, with lower dye uptake and fixation amounts.

[0084] Comparative Example 5 The difference between Comparative Example 5 and Example 11 is that animal protein was used instead of plant protein; S1. Dissolve chicken feather protein in water to obtain an 8 g / L chicken feather protein solution, and dissolve 3-chloro-2-hydroxypropyltrimethylammonium chloride in water to obtain an 8 g / L cationic precursor solution; S2. Mix 10 mL of chicken feather protein solution with 10 mL of cationic precursor solution in equal volume, adjust the pH to 4.5, add 0.008 g of genipin, stir and react at 50℃ for 50 min to obtain 8 g / L cationic auxiliaries. S3. The cotton fabric is pretreated by immersing it in cationic auxiliaries at 65°C with a bath ratio of 1:30 for 15 minutes. Then, 5 g / L of NaOH is added and the fabric is kept warm for 25 minutes. Finally, the fabric is taken out and thoroughly washed with water until neutral to obtain cationic auxiliaries modified cotton textiles. S4. Prepare a 2% (owf) Reactive Red 24 dye bath. Place the cationic auxiliary modified cotton textiles from S3 into the dye bath at a bath ratio of 1:50, and proceed according to the dyeing temperature process curve ( Figure 2 The dyeing process involves immersion dyeing and drying to obtain salt-free dyed cellulose textiles.

[0085] K / S ratio and staining fastness were determined, and the results are shown in Table 17.

[0086] Table 17

[0087] Comparative Example 6 S1. Chicken feather protein was dissolved in sodium hydroxide solution to obtain a 4 g / L chicken feather protein solution. Sodium hydroxide, triethanolamine, and epichlorohydrin were mixed in a mass ratio of 5:4:12 and stirred at 50°C for 4 h to prepare the crosslinking modifier WLS. WLS was mixed with the above chicken feather protein sodium hydroxide solution in a mass ratio of 2.5:3 and stirred at 50°C for 5 h to obtain a cationic additive. S2. The cotton fabric is pretreated by immersing it in cationic auxiliaries at 40°C with a bath ratio of 1:20 for 30 minutes, then washed with cold water and dried to obtain cationic auxiliaries modified cotton textiles. S3. Prepare a 2% (owf) Reactive Red 24 dye bath. Place the cationic auxiliary modified cotton textiles of S3 into the dye bath at a bath ratio of 1:50, and follow the dyeing temperature process curve. Figure 2 The dyeing process was carried out by immersion dyeing. The remaining cationic auxiliary liquid after modification in S2 was used to perform a second immersion and color-fixing treatment on the dyed cotton fabric at 30℃ for 10 min, followed by washing with cold water. Subsequently, the fabric was soaped in a soap solution containing 2 g / L soap powder and 2 g / L sodium carbonate at 80℃ for 10 min, and finally washed with water and dried.

[0088] K / S ratio and staining fastness were determined, and the results are shown in Table 18.

[0089] Table 18

[0090] Comparative Example 7 S1. Dissolve gelatin protein and 2,3-ethylene oxide trimethylammonium chloride in water at a mass ratio of 1:2, and dissolve completely to obtain a clear solution of 8 g / L. S2. Adjust the pH to 4.5, add 0.008 g of glutaraldehyde, and stir at 40℃ for 120 min to obtain 8 g / L of cationic additive; S3. The cotton fabric is pretreated for 40 minutes by immersing it in cationic auxiliaries at 40°C with a bath ratio of 1:20, followed by cold water washing and drying to obtain cationic auxiliaries modified cotton textiles. S4. Prepare a 2% (owf) Reactive Red 24 dye bath. Place the cationic auxiliary modified cotton textiles from S3 into the dye bath at a bath ratio of 1:50, and proceed according to the dyeing temperature process curve ( Figure 2 The dyeing process involves immersion dyeing and drying to obtain salt-free dyed cellulose textiles.

[0091] K / S ratio and staining fastness were determined, and the results are shown in Table 19.

[0092] Table 19

[0093] Comparative Examples 5-7, which used animal protein as the protein backbone for cationic auxiliaries, exhibited lower dyeing performance than the examples using plant protein in this invention. Both chicken feather protein and gelatin protein are animal-derived proteins. Chicken feather protein contains numerous disulfide bonds, has high crystallinity, a rigid molecular structure, and strong hydrophobicity, resulting in poor interfacial compatibility with hydrophilic cotton fibers. This makes it difficult to spread evenly during pretreatment, leading to uneven distribution of the cationic auxiliaries on the fabric surface. Furthermore, the modified layer formed by its hydrophobic rigid molecular chains on the fiber surface lacks flexibility, hindering the uniform adsorption and penetration of dye molecules. While gelatin protein has some water solubility, it readily undergoes uncontrollable over-crosslinking reactions under the action of crosslinking agents, rapidly forming a dense film layer on the fiber surface. Although this film is grafted with cationic groups, the significant steric hindrance and dense crosslinking structure impede the diffusion and penetration of reactive dye molecules into the fiber interior. Consequently, the dye is mainly fixed on the fiber surface, making it difficult to form sufficient covalent bonds with the hydroxyl groups inside the fiber.

[0094] Comparative Example 8 The difference between Comparative Example 8 and Example 6 is that Comparative Example 8 modifies the polyester fabric before dyeing; S1. Disperse 5g of zein in 100mL of water, add 2.5g of sodium tripolyphosphate, adjust the pH to 9 with NaOH solution, stir and react at 25℃ for 1.5h to obtain a phosphorylated reaction solution, ultrafilter the phosphorylated reaction solution, freeze-dry the ultrafiltered product to obtain phosphorylated zein; dissolve the phosphorylated zein in water to obtain an 8g / L phosphorylated zein solution, and dissolve polyethyleneimine in water to obtain an 8g / L cationic precursor solution; S2. Mix 10 mL of phosphorylated zein solution with 10 mL of cationic precursor solution in equal volume, adjust the pH to 4.5, add 0.008 g of aldehyde-modified arabinoxylan, and stir at 50 °C for 120 min to obtain 8 g / L cationic adjuvant. S3. The polyester fabric is pretreated for 30 minutes by immersing it in cationic additives at 30°C with a bath ratio of 1:20, followed by cold water washing and drying to obtain cationic additive-modified polyester textiles. S4. Prepare a 2% (owf) reactive brilliant blue KN-G dye bath. Place the cationic auxiliary modified polyester textile from S3 into the dye bath at a bath ratio of 1:50, and proceed according to the dyeing temperature process curve ( Figure 2 The polyester textiles are then immersed and dyed, dried, and salt-free dyed.

[0095] K / S ratio and staining fastness were measured, and the results are shown in Table 20.

[0096] Table 20

[0097] In Comparative Example 8, polyester fabric was used instead of cotton fabric for the same modification treatment and salt-free dyeing with reactive dyes. The K / S value was extremely low, making it almost impossible to achieve effective dyeing depth. This is because polyester fiber molecules lack active functional groups such as hydroxyl and amino groups. On the one hand, they cannot form hydrogen bonds or chemical bonds with the cationic plant protein auxiliaries, resulting in extremely limited adsorption of the cationic auxiliaries on the polyester fiber surface, making it difficult to construct an effective cationic layer. On the other hand, the fixation of reactive dyes requires a covalent bond reaction with the hydroxyl groups on the fiber, but polyester fibers lack the groups that react with reactive dyes. Even if a small amount of dye is adsorbed onto the fiber surface due to electrostatic attraction, it cannot form a strong covalent bond under alkaline fixing conditions, resulting in extremely poor dyeing effects. This indicates that the plant protein cationic auxiliaries modification method of the present invention is specific to cellulose fibers and is applicable to cellulose textiles rich in hydroxyl groups, such as cotton, linen, and viscose, verifying the applicability and relevance of the present invention.

[0098] Comparative Example 9 The difference between Comparative Example 9 and Example 13 is that Comparative Example 9 only uses unmodified plant protein to modify cotton / viscose blended fabrics; S1. Disperse zein in water to obtain a 3 g / L zein dispersion; S2. The cotton / viscose blended fabric is pretreated for 40 min by immersing it in a zein dispersion at a bath ratio of 1:30 at 40°C, followed by washing with cold water and drying to obtain the modified textile. S3. Prepare a 2% (owf) Reactive Red 24 dye bath. Place the modified textiles from S2 into the dye bath at a bath ratio of 1:50, and proceed according to the dyeing temperature process curve. Figure 2 The dyeing process involves immersion dyeing and drying to obtain salt-free dyed cellulose textiles.

[0099] K / S ratio and staining fastness were measured, and the results are shown in Table 21.

[0100] Table 21

[0101] Comparative Example 9 used only unmodified zein solution to modify cotton / viscose blended fabrics without adding quaternizing agents or crosslinking agents. Unmodified zein has extremely low solubility in water, making it difficult to form a uniform and continuous adsorption layer on the fiber surface. Due to the lack of high-density positive charge provided by quaternizing agents and the stable three-dimensional network structure constructed by crosslinking agents, single-protein modification can only rely on the limited amino groups on the protein molecule to protonate under acidic conditions to form a small amount of positive charge. The density and uniformity of cationic groups are far inferior to the three-component synergistic crosslinking system of this invention. Furthermore, the unmodified protein and fiber are only bound by physical adsorption and hydrogen bonding, resulting in limited binding strength. Therefore, the K / S value of Comparative Example 9 is significantly lower than that of Example 13, and the color fastness is also significantly worse than that of Example 13, fully demonstrating the necessity of phosphorylation modification and the introduction of quaternizing agents and crosslinking agents for improving dyeing effects.

[0102] Comparative Example 10 The difference between Comparative Example 10 and Example 11 is that Comparative Example 10 uses phosphorylated modified chicken feather protein instead of phosphorylated zein protein; S1. Disperse 5g of chicken feather protein in 100mL of water, add 2.5g of sodium tripolyphosphate, adjust the pH to 9 with NaOH solution, stir and react at 25℃ for 1.5h to obtain a phosphorylated reaction solution, ultrafilter the phosphorylated reaction solution, freeze-dry the ultrafiltered product to obtain phosphorylated chicken feather protein; dissolve the phosphorylated chicken feather protein in water to obtain a 3g / L phosphorylated chicken feather protein solution, dissolve 3-chloro-2-hydroxypropyltrimethylammonium chloride in water to obtain an 8g / L cationic precursor solution; S2. Mix 10 mL of phosphorylated chicken feather protein solution with 10 mL of cationic precursor solution in equal volume, adjust the pH to 4.5, add 0.008 g of citric acid, stir and react at 50 °C for 50 min to obtain 8 g / L cationic auxiliary agent; S3. The cotton fabric is immersed in cationic auxiliaries at 60℃ and treated for 15 minutes at a bath ratio of 1:30. Then, 5 g / L of NaOH is added and the fabric is kept at the temperature for 25 minutes. Finally, the fabric is taken out and thoroughly washed with water until neutral to obtain cationic auxiliaries modified cotton textiles. S4. Prepare a 2% (owf) Reactive Red 24 dye bath. Place the cationic auxiliary modified cotton textiles from S3 into the dye bath at a bath ratio of 1:50, and proceed according to the dyeing temperature process curve ( Figure 2 The cotton textiles are then immersed and dyed, dried, and thus obtained without salt dyeing.

[0103] K / S ratio and staining fastness were determined, and the results are shown in Table 22.

[0104] Table 22

[0105] Comparative Example 10 used phosphorylated chicken feather protein as the protein backbone of the cationic auxiliary agent. Even after phosphorylation modification, the rigidity and crystallinity conferred by the large number of disulfide bonds in the molecular structure of chicken feather protein still exist, and its interfacial compatibility with hydrophilic cotton fibers is still not as good as that of plant protein.

[0106] Reference Figure 4 , Figure 5 As shown, the cationic auxiliaries modified cotton fabrics prepared in this embodiment of the invention exhibit good antibacterial and wash-resistant properties against Escherichia coli and Staphylococcus aureus. This is mainly because the cationic groups provided by amino-containing reagents such as chitosan and quaternizing reagents in the cationic auxiliaries can electrostatically adsorb with the negatively charged lipopolysaccharides, teichoic acid, and membrane proteins in the bacterial cell wall, thereby disrupting the integrity of the cell wall, causing changes in cell membrane permeability, and leading to leakage of intracellular substances and metabolic disorders, ultimately inhibiting or killing bacteria. At the same time, the hydroxyl and amino polar groups on the plant protein molecular chain endow the auxiliaries with good hydrophilicity and biocompatibility, which is conducive to the uniform distribution and full exposure of cationic antibacterial groups on the fiber surface, thereby enhancing the effective contact between antibacterial active sites and bacteria. Through the covalent bond action of the crosslinking agent, chitosan and quaternizing reagents are stably anchored on the plant protein skeleton and fiber surface. The three-dimensional network structure formed firmly fixes the antibacterial components on the fabric, avoiding the defect of small molecule antibacterial agents being lost during washing due to physical ionization. The above results indicate that the cationic auxiliary modification method of the present invention can impart excellent salt-free dyeing properties to cotton fabrics while also giving them long-lasting and highly effective antibacterial functions.

[0107] Tests: The evenness test refers to the multi-point measurement method of the colorimeter and colorimeter. Ten different positions are randomly selected on the surface of the dyed fabric to measure the K / S value and calculate its coefficient of variation (CV value) (the smaller the value, the better the evenness). The softness test refers to the bending stiffness and stiffness of the fabric according to FZ / T01171-2023 "Textile Fabric Touch Test and Evaluation Method Three-point beam method" (the lower the value, the softer the hand feel).

[0108] Table 23 Comparison of fabric levelness and hand softness

[0109] The leveling CV values ​​of all embodiments of the present invention are lower than those of the comparative examples. This is because the plant protein molecular chains are rich in polar groups such as hydroxyl and amino groups, which can spread evenly on the fiber surface through hydrogen bonds and van der Waals forces, avoiding the local aggregation of cationic groups. At the same time, the porous three-dimensional network structure constructed by the crosslinking agent provides a moderate physical obstacle to the diffusion of dye molecules, exerting a slow dyeing effect, allowing the dye to be fully and evenly adsorbed on the fiber surface before diffusing and penetrating into the interior, thereby avoiding uneven dyeing caused by excessively rapid dyeing. The plant protein molecular chains themselves have flexibility, and the hydrophilic groups such as phosphate introduced by phosphorylation modification further reduce the coefficient of friction of the fiber surface, enhance the lubrication, and make the fabric feel soft and smooth. Comparative Example 4 lacks a plant protein backbone, and the chitosan crosslinks are unevenly distributed on the fiber surface and the film formation is discontinuous, resulting in significantly poor leveling. Comparative Examples 5-7 use animal proteins. Chicken feather protein is difficult to spread evenly due to the rigidity and hydrophobicity given by disulfide bonds, and gelatin protein is prone to uncontrollable excessive crosslinking under the action of crosslinking agents, forming a local dense film. The leveling of both is far inferior to that of the embodiments of the present invention. In terms of feel, the bending stiffness and rigidity of the embodiments of the present invention are lower than those of the comparative examples. This is because the plant protein molecular chains themselves are flexible, and the hydrophilic film formed on the fiber surface reduces the coefficient of friction between fibers. At the same time, the hydrophilic groups such as phosphate introduced by phosphorylation further enhance the lubrication of the fiber surface, making the fabric feel soft and smooth. In contrast, the animal proteins in comparative examples 5 to 7 have higher bending stiffness and rigidity due to the strong rigidity of the molecular chains or excessive cross-linking to form a hard film, resulting in a noticeably harder and rougher feel.

[0110] Note: (1) K / S The color depth K / S value of the fabric surface was measured using a computer colorimeter, with three measurements taken and the average value recorded. The readings were taken from a D65 light source at a 10° observation angle.

[0111] (2) Color fastness The color fastness to washing was tested in accordance with GB / T 3921.1-2008 "Textiles - Tests for color fastness - Color fastness to washing". The color fastness to rubbing was tested in accordance with GB / T 3920-2008 "Textiles - Tests for color fastness - Color fastness to rubbing". The color fastness to perspiration was tested in accordance with GB / T 3922-2013 "Textiles - Tests for color fastness to perspiration".

[0112] (3) Fabric antibacterial test The antibacterial properties of the samples were tested in accordance with GB / T 20944.3-2008 "Evaluation of antibacterial properties of textiles - Part 3: Vibration method".

[0113] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A method for salt-free dyeing of cellulose textiles modified with a plant protein cationic auxiliaries, characterized in that, The method includes the following steps: S1. The plant protein is phosphorylated to obtain phosphorylated plant protein. The phosphorylated plant protein is dissolved in a good solvent to obtain a phosphorylated plant protein solution. The quaternizing reagent and / or amino-containing reagent are dissolved in a good solvent to obtain a cationic precursor solution. S2. Mix the phosphorylated plant protein solution and the cationic precursor solution in equal volumes, adjust the pH to 4.5, add the cross-linking agent, and stir at 20~70℃ for 30~120 min to obtain the cationic auxiliary agent; S3. Pre-treat the cellulose textiles in a cationic auxiliaries: impregnate, wash with cold water, and dry to obtain cationic auxiliaries modified cellulose textiles; S4. Prepare a dye bath for reactive dyes, place the cellulose textile modified with cationic auxiliaries in the dye bath, immerse and dye it, and dry it to obtain salt-free dyed cellulose textiles.

2. The method according to claim 1, characterized in that: In step S1, the plant protein is an alcohol-soluble protein, which is selected from one or more of corn alcohol-soluble protein, wheat alcohol-soluble protein, and sorghum alcohol-soluble protein.

3. The method according to claim 2, characterized in that, The phosphorylation modification includes the following steps: S11. Disperse alcohol-soluble protein in water, add phosphorylation reagent, wherein the mass ratio of phosphorylation reagent to alcohol-soluble protein is 1:1 to 1:4, adjust pH to 8 to 10, stir and react at 20 to 50°C for 0.5 to 3 hours to obtain phosphorylation reaction solution; S12. Ultrafilter the phosphorylation reaction solution to remove unreacted phosphorylation reagent; S13. Freeze-dry the ultrafiltration product to obtain phosphorylated modified prolysin.

4. The method according to claim 3, characterized in that, In step S11, the phosphorylation reagent is any one of sodium tripolyphosphate, phosphorus oxychloride, sodium pyrophosphate, or sodium trimetaphosphate.

5. The method according to claim 1, characterized in that: The quaternizing agent in step S1 includes one or more of 2,3-epoxypropyltrimethylammonium chloride, 3-chloro-2-hydroxypropyltrimethylammonium chloride, dodecyltrimethylammonium chloride, dimethyldiallylammonium chloride, dodecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, triethylamine hydrochloride, and 4-chloromethylpyridine hydrochloride. The amino-containing agent includes one or more of ethylenediamine, diethylenetriamine, polyethyleneimine, cationic polyacrylamide, chitosan, and betaine.

6. The method according to claim 1, characterized in that: The good solvent in step S1 includes one or more of methanol, ethanol, water, isopropanol, and dilute acetic acid.

7. The method according to claim 1, characterized in that: The crosslinking agent in step S2 includes one or more of the following: 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide, ethylene glycol diglycidyl ether, glycerol triglycidyl ether, glutaraldehyde, genipin, citric acid, aldehyde-modified arabinoxylan, tea polyphenols, gallic acid, and sodium tripolyphosphate.

8. The method according to claim 1, characterized in that: In step S2, the mass ratio of phosphorylated plant protein to cationic precursor in the cationic adjuvant is 1:1 to 1:3, and the amount of crosslinking agent is 10% of the total amount of quaternizing agent and / or amino-containing agent.

9. The method according to claim 1, characterized in that: In step S3, the cellulose textile is cotton, hemp, ramie, jute, apocynum, viscose, Modal, Lyocell, cotton / linen blend, or cotton / viscose blend. The concentration of the cationic auxiliaries is 2–8 g / L, the pH of the pretreatment is 3–5, the bath ratio of the pretreatment is 1:10–1:40, the impregnation temperature is 20–60°C, and the impregnation time is 20–60 min.

10. The method according to claim 1, characterized in that: In step S4, the concentration of reactive dye in the dye bath is 1-5% (owf), the bath ratio is 1:10-1:50, the immersion time is 20-50 min, and the immersion temperature is 40-90℃.

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