Washable easily-colored wool fabric treatment process

Abstract

The invention discloses a washable easily-colored wool fabric treatment process, belongs to the technical field of wool fabric processing, and aims to solve the technical problem that the dyeing degree, the anti-felting performance and the color fastness of wool fabrics in the prior art need to be further improved. The method includes the following steps that disulfide bonds of wool fibers are opened through L-cysteine, the washable and easy-to-color wool fabric is obtained, the pretreated wool fibers prepared through the method are grafted with methoxy polyethylene glycol methacrylate under catalysis of hydrogen peroxide and horse radish peroxidase, modified wool fibers are obtained, and the washable and easy-to-color wool fabric is obtained. After the modified wool fibers are woven into the wool fabric, the wool fabric is respectively subjected to padding modification by using the modified dye solution and the finishing liquid, so that the degree of dyeing, the anti-felting performance and the color fastness of the wool fabric are improved.

Description

Technical Field

[0001] The invention relates to the technical field of wool fabric processing, and in particular to a process for processing washable and easily colorable wool fabric. Background Art

[0002] Wool is one of the important raw materials in the textile industry. It has excellent properties such as good warmth retention, soft and elastic feel, natural and soft luster, and processing plasticity. However, wool products also have disadvantages such as easy felting and deformation, difficult care, itching, poor dyeing performance, and easy mildew. Wool is mainly composed of four parts, namely the scale layer, cortex layer, medulla layer and cell membrane complex. The scale layer is coated on the outermost layer of the wool fiber. There is a peptide amine bond cross-linking, which is located between the glutamic acid residue of the peptide chain and the lysine residue of another peptide chain, which makes it have good chemical stability and protects the wool fiber. However, in the dyeing application process, due to the coating of the scale layer, it is difficult for the dye to enter the fiber under low temperature conditions. The higher the cysteine ​​content in the scale layer, the tighter the structure. Only when the disulfide bond is broken can the dye easily enter the fiber.

[0003] In the prior art, in order to improve the anti-felting performance and dyeing performance of wool fabrics when washed, the method for modifying wool is mainly to physically and chemically modify the scale layer of wool fibers, and the commonly used method is to enzymatically hydrolyze the scale layer with proteases; however, this method will first hydrolyze the cortical layer inside the scales by destroying the wool intercellular globulin, causing the wool strength to drop excessively, affecting the mechanical properties of the wool, and when dyeing the wool, the commonly used acid dyes are mainly bound to the fibers of the wool fabric by weak forces such as ionic bonds, hydrogen bonds, and van der Waals forces, resulting in poor color uptake and color fastness of the dyed fabric, and the dyeing process generally needs to be carried out under high temperature conditions, which not only requires high energy consumption, but may also damage the fibers, causing them to lose their luster or have a poor hand feel.

[0004] In view of the technical defects in this aspect, a solution is now proposed. Summary of the invention

[0005] The object of the present invention is to provide a washable and easy-to-color wool fabric processing process, which is used to solve the technical problem that the wool fabric in the prior art needs to be further improved in terms of anti-felting performance, color uptake rate and soap-washing and rubbing color fastness.

[0006] The purpose of the present invention can be achieved by the following technical scheme: A process for treating washable and easily colorable wool fabric, comprising the following steps:

[0007] S1, placing the pretreated wool fiber, hydrogen peroxide solution, phosphate buffer and horseradish peroxidase in a three-necked flask under a nitrogen atmosphere, cooling to 0-5°C, shaking for 30-60 minutes, and post-treating to obtain activated wool fiber;

[0008] S2. Under a nitrogen atmosphere, place the activated wool fiber, N,N-dimethylformamide and methoxy polyethylene glycol methacrylate in a three-necked flask at a temperature of 30-40° C., stir for 12-15 hours, wash with deionized water 1-2 times, and dry to obtain the modified wool fiber;

[0009] The reaction equation for preparing modified wool fiber is:

[0010]

[0011] Where: Indicates crude wool fiber.

[0012] The reaction principle for preparing modified wool fiber is as follows: horseradish peroxidase is an enzyme catalyst, and its active site can catalyze the decomposition of hydrogen peroxide to generate oxygen free radicals. Under the joint action of horseradish peroxidase and hydrogen peroxide, the sulfhydryl groups on the pretreated wool fiber can be oxidized to generate sulfhydryl free radicals, which react with the electrophilic olefin double bonds in methoxy polyethylene glycol methacrylate to form chemical bonds. Phosphate buffer is used as a buffer for the reaction system to maintain appropriate acidic and alkaline conditions, maintain the activity of horseradish peroxidase, and improve the reaction efficiency.

[0013] S3, converting the wool fiber into yarn by washing, carding, combing and stretching, spinning the yarn into long and thin wool yarn by a spinning machine, and then adding it to a loom for weaving to obtain a wool fabric;

[0014] S4. After the wool fabric is modified by padding, a washable and easy-to-color wool fabric is obtained.

[0015] Further, in step S1, the concentration of the hydrogen peroxide solution is 0.03-0.05 g / mL, the phosphate buffer is composed of disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium chloride and deionized water in a dosage ratio of 0.3-0.4 g: 0.03-0.05 g: 0.6-1 g: 80-100 mL, the concentration of the horseradish peroxidase is 250-300 U / mL, and the dosage ratio of the pretreated wool fiber, the hydrogen peroxide solution, the phosphate buffer and the horseradish peroxidase is 5-10 g :0.3-0.5mL:1-2L:1-2g, the post-treatment step comprises: after the reaction is completed, the temperature of the three-necked flask is lowered to room temperature, the filter is filtered, the filter cake is washed with purified water until it is neutral and then dried, the filter cake is transferred to a drying oven at a temperature of 70-80°C, and vacuum dried to constant weight to obtain activated wool fiber; in step S2, the amount ratio of the activated wool fiber, N,N-dimethylformamide and methoxy polyethylene glycol methacrylate is 5-10g:200-250mL:20-30g.

[0016] Furthermore, in step S1, the method for preparing the pretreated wool fiber comprises the following steps:

[0017] A1. Place wool fiber and acetone in a Soxhlet extractor and extract for 24-26 hours, remove the solvent, and dry to obtain a crude wool fiber product;

[0018] The reaction principle for preparing crude wool fiber is:

[0019] Acetone is a polar solvent that can dissolve grease, natural wax and dirt in wool. The Soxhlet extractor consists of a round-bottom flask, a long straight tube and a condenser. The wool fiber to be extracted is placed in the round-bottom flask of the extractor and acetone is added as a solvent. As the round-bottom flask is heated, the acetone vapor rises through the straight tube of the extractor, condenses into liquid and flows back to the extraction chamber. The evaporated acetone condenses and flows back to the extraction chamber and contacts the wool fiber again. Each acetone cycle dissolves more grease and dirt from the wool fiber into the acetone.

[0020] A2. Place the crude wool fiber and L-cysteine ​​solution in a three-necked flask at a temperature of 60-80°C and stir for 1-2 hours. After the reaction is completed, filter and wash the fiber with deionized water and anhydrous ethanol for 1-2 times, and dry to obtain pretreated wool fiber.

[0021] The reaction principle for preparing pretreated wool fibers is:

[0022] During the preparation process, L-cysteine ​​is used as a reducing agent to undergo a reduction reaction with sulfur atoms in disulfide bonds in wool fibers, so that the disulfide bonds are reduced to thiol groups, thereby preparing pretreated wool fibers.

[0023] Furthermore, in step A1, the wool fiber and acetone are used in a ratio of 1-5 g:50-100 mL; in step A2, the L-cysteine ​​solution is composed of deionized water and L-cysteine ​​solution in a ratio of 250-300 mL:1.5-2 g, and the wool fiber crude product and L-cysteine ​​solution are used in a ratio of 5-7 g:250-300 mL.

[0024] Furthermore, in step S4, the padding modification of the wool fabric comprises the following steps:

[0025] B1. Immerse the wool fabric in the modified dye solution, add dilute hydrochloric acid to adjust the pH to 3.5-4, raise the temperature to 50-60°C, keep the temperature for reaction for 3-4 hours, and post-treat to obtain the dyed wool fabric;

[0026] The reaction principle for preparing dyed wool fabric is:

[0027] During the reaction, the carbonyl group on the acetone molecule is protonated under acidic conditions, undergoes a nucleophilic addition reaction with the amino group of the modified dye, deprotonates, transfers electrons on nitrogen, and leaves water to form a Schiff base modified dye. Under acidic conditions, the Schiff base modified dye forms a modified dye carbon cation, which acts as an electrophilic reagent to attack compounds containing active hydrogen, and undergoes a substitution reaction with the carbon atom adjacent to the phenolic hydroxyl group in the tyrosine residue in the wool fabric to form a CCN covalent bond.

[0028] B2, immersing the dyed wool fabric in the finishing solution, adding sodium hydroxide solution to adjust the pH to 8±0.2, heating to 60-80°C, keeping the temperature for 1-2h, and post-treating to obtain a washable and easy-to-color wool fabric;

[0029] The reaction principle for preparing washable and easy-to-color wool fabric is:

[0030] Transglutaminase is a transferase. During the reaction, it uses the amino group of the lysine residues of the protein contained in the wool fabric as an acyl acceptor to catalyze the cross-linking reaction between glutamine residues and lysine residues to form peptide bonds and isopeptide bonds within and between protein molecules.

[0031] Furthermore, in step B1, the concentration of the dilute hydrochloric acid is 1-2 mol / L, the modified dye solution is composed of the modified dye, deionized water and methylglyoxal in a dosage ratio of 4-5 g:50-100 mL:1-2 g, the bath ratio of the wool fabric and the modified dye solution is 1:45-50, and the post-treatment step comprises: washing the reacted fabric with deionized water and ethanol for 1-2 times, drying, and obtaining a dyed wool fabric; in step B2, the concentration of the sodium hydroxide solution is 0.5-1 mol / L, the bath ratio of the dyed wool fabric and the finishing solution is 1:20-25, and the finishing solution is composed of transglutaminase, JFC-6 and deionized water in a dosage ratio of 1-5 g:0.5-0.8 g:20-80 mL, and the post-treatment step comprises: washing the reacted fabric with deionized water and ethanol for 1-2 times, drying, and obtaining a washable and easy-to-color wool fabric.

[0032] Furthermore, the preparation method of the modified dye comprises the following steps:

[0033] C1. Place p-phenylenediamine, concentrated hydrochloric acid, deionized water and sodium nitrite in a three-necked flask, cool to -5-5°C, stir for 30-40 minutes, add urea, and test the reaction solution with starch-potassium iodide test paper. If the test paper does not turn blue, the reaction is complete and a diazonium salt solution is obtained.

[0034] The reaction equation for preparing diazonium salt solution is:

[0035]

[0036] The reaction principle for preparing diazonium salt solution is:

[0037] During the reaction, under acidic conditions, sodium nitrate generates nitrous acid, which reacts with the nitrogen atom of p-phenylenediamine to generate an unstable intermediate product, which then rapidly decomposes to generate a diazonium salt;

[0038] The mass spectrometry analysis data of the diazonium salt solution were: 155.00 (100.0%), 156.99 (32.0%), 156.00 (6.6%), 158.00 (2.1%), 155.99 (1.1%).

[0039] C2, 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, deionized water and 4-acetamidobenzenesulfonyl chloride are placed in a three-necked flask, the temperature is raised to 50-60°C, acetic acid solution is added to adjust the pH to 3-5, the temperature is kept for reaction for 3-4 hours, and the intermediate I is obtained by post-treatment;

[0040] The reaction equation for preparing intermediate I is:

[0041]

[0042] The reaction principle for preparing intermediate I is:

[0043] During the reaction, the lone pair of electrons on the amino nitrogen atom in 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid attacks the chlorine atom in p-acetylaminobenzenesulfonyl chloride, resulting in nucleophilic substitution, and the chlorine atom leaves to generate intermediate Ⅰ;

[0044] The mass spectrometry analysis data of intermediate Ⅰ were: 516.03 (100.0%), 517.03 (22.4%), 518.02 (13.6%), 518.03 (4.6%), 519.03 (3.2%).

[0045] C3, place intermediate I in a three-necked flask, add sodium hydroxide solution to adjust the pH to 9-10, cool to 0-5°C, drop diazonium salt solution, keep warm for 2-3h, and post-treat to obtain intermediate II;

[0046] The reaction equation for preparing intermediate II is:

[0047]

[0048] The reaction principle for preparing intermediate II is:

[0049] Under alkaline conditions, the carbon atom between the sulfonic acid group and the phenolic hydroxyl group on the benzene ring structure of intermediate I is protonated and undergoes a substitution reaction with the diazo group in the diazonium salt to generate intermediate II.

[0050] The mass spectrometry analysis data of intermediate II are: 635.02 (100.0%), 636.02 (26.6%), 637.01 (13.6%), 637.02 (6.6%), 636.01 (4.2%), 638.01 (4.0%).

[0051] C4. Place intermediate II, sodium hydroxide and deionized water in a three-necked flask, heat to 100-110°C, and reflux for 5-6 hours to obtain a modified dye.

[0052] The reaction equation for preparing modified dyes is:

[0053]

[0054] The reaction principle for preparing modified dyes is:

[0055] Under alkaline conditions, OH in water - As a nucleophile, it attacks the carbonyl carbon atom of the carboxamide on the intermediate II, and the intermediate dissociates into the acid and the modified dye;

[0056] The mass spectrometry analysis data of the modified dye are: 593.06 (100.0%), 594.07 (24.4%), 595.06 (14.1%), 595.07 (5.3%), 594.06 (4.2%), 596.06 (3.8%), 597.06 (1.0%).

[0057] Further, in step C1, the amount ratio of p-phenylenediamine, concentrated hydrochloric acid, deionized water and sodium nitrite is 1-1.5g:10-15mL:20-30mL:0.7-0.9g; in step C2, the concentration of the acetic acid solution is 0.1-0.2mol / L, the amount ratio of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, deionized water and p-acetylaminobenzenesulfonyl chloride is 4-5g:30-50mL:5-6g, and the post-treatment step includes: removing the solvent from the reaction solution, washing the residue with ethyl acetate and deionized water 1-2 times, the organic phase is low-pressure rotary evaporation to obtain intermediate I; in step C3, the concentration of the sodium hydroxide is 0.1-0.2mol / L, the amount ratio of the intermediate I and the diazonium salt solution is 5-7g:30-45mL, and the post-treatment step comprises: adding 1-2mol / L hydrochloric acid solution to the reaction solution until a solid is precipitated, filtering, washing the solid with deionized water 1-2 times, and drying to obtain intermediate II; in step C4, the amount ratio of the intermediate II, sodium hydroxide and deionized water is 6-8g:0.1-0.2g:25-50mL.

[0058] The present invention has the following beneficial effects:

[0059] 1. The present invention prepares pretreated wool fibers, uses L-cysteine ​​to open the disulfide bonds in the wool fibers, and reduces them to sulfhydryl groups. Under the catalysis of horseradish peroxidase and hydrogen peroxide, the sulfhydryl groups are grafted with methoxy polyethylene glycol methacrylate, and the methoxy polyethylene glycol methacrylate, as a hydrophilic polymer compound, is cross-linked with the wool fibers to form a thin film on the surface of the wool fibers, thereby reducing the influence of the directional friction effect of the wool fibers, and making the wool fibers have better anti-felting performance. The density of the grafted and modified wool fiber felt balls is low, and the anti-felting performance of the modified wool fibers is further enhanced. After the disulfide bonds of the wool fibers are reduced to sulfhydryl groups, the chemical affinity between the sulfhydryl structure and the modified dye molecules is stronger than that of the disulfide bonds, and the modified dyes are further enhanced to penetrate into the wool fabric, thereby enhancing the coloring rate and color fastness of the wool fabric.

[0060] 2. The present invention also prepares multi-amino acid modified dyes, and through the bridging effect of methylglyoxal, a substitution reaction occurs with the carbon atom adjacent to the phenolic hydroxyl group in the amino acid residue in the wool fabric to form a CCN covalent bond, thereby increasing the bonding strength between the wool fabric and the modified dye, and improving the coloring rate and color fastness of the wool fabric. When preparing the pretreated wool fiber, L-cysteine ​​opens the disulfide bonds in the wool fabric, which is beneficial to the entry of the acid modified dye and increases the coloring rate of the wool fabric. When preparing the acid modified dye, a diamino acid modified dye is prepared, and the amino group can increase the steric hindrance and reaction site, further increasing the dyeing rate and dyeing concentration of the modified dye on wool dyeing. In addition, methylglyoxal is less polluting than traditional formaldehyde and is more environmentally friendly.

[0061] 3. The present invention also prepares a finishing liquid to repair the damage to the wool scales on the surface of the wool fabric during pretreatment. The main components of the finishing liquid are transglutaminase and a darkening agent JFC-6. The transglutaminase can catalyze the cross-linking reaction between glutamine residues and lysine residues, repair the damage to the wool fabric caused by grafting methoxy polyethylene glycol methacrylate and combining with acid modified dyes, and increase the anti-felting performance and elongation at break of the wool fabric. The darkening agent JFC-6 can cooperate with the transglutaminase to form a low eutectic, accelerate the diffusion of the modified dye into the fiber, and improve the coloring rate and color fastness of the wool fabric. DETAILED DESCRIPTION

[0062] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0063] Example 1

[0064] This embodiment provides a washable and easy-to-color wool fabric processing process, comprising the following steps:

[0065] S1. Preparation of modified dyes

[0066] Weigh: 100g p-phenylenediamine, 1L concentrated hydrochloric acid, 2L deionized water and 70g sodium nitrite in a three-necked flask, cool to -5°C, stir for 30 minutes, add urea, test the reaction solution with starch-potassium iodide test paper, if the test paper does not turn blue, the reaction is over, and a diazonium salt solution is obtained;

[0067] Weigh: 400 g of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 3 L of deionized water and 500 g of 4-acetylaminobenzenesulfonyl chloride are placed in a reaction kettle, the temperature is raised to 50° C., 0.1 mol / L acetic acid solution is added to adjust the pH to 3.5, the temperature is kept for 3 h, and intermediate I is obtained by post-treatment;

[0068] Weigh: Place 500 g of intermediate Ⅰ in a reaction kettle, add 0.1 mol / L sodium hydroxide solution to adjust pH=9.1, cool to 0°C, drop 3 L of diazonium salt solution, keep warm for 2 h, drop 1 mol / L hydrochloric acid solution into the reaction solution until solid precipitates, filter, wash the solid with deionized water twice, and dry to obtain intermediate Ⅱ;

[0069] Weigh: 600 g of intermediate II, 10 g of sodium hydroxide and 2.5 L of deionized water are placed in a reaction kettle, heated to 105° C., and refluxed for 5 h to obtain a modified dye.

[0070] S2. Preparation of modified wool fiber

[0071] Weigh: 100 g of wool fiber and 5 L of acetone, place in a Soxhlet extractor for extraction for 24 hours, remove the solvent, and dry to obtain a crude wool fiber;

[0072] Weigh: 25 L of deionized water and 150 g of L-cysteine, mix well to obtain an L-cysteine ​​solution for later use;

[0073] Weigh: 500 g of crude wool fiber and 25 L of L-cysteine ​​solution are placed in a reactor at 60° C. and stirred for 2 h. After the reaction is completed, the fibers are filtered and washed twice with deionized water and anhydrous ethanol, and dried to obtain pretreated wool fibers;

[0074] Weigh: 30 g of disodium hydrogen phosphate, 3 g of sodium dihydrogen phosphate, 60 g of sodium chloride and 8 L of deionized water, mix well to obtain phosphate buffer, and set aside;

[0075] Weigh: 500 g of pretreated wool fiber, 30 mL of 0.03 g / mL hydrogen peroxide solution, 100 L of phosphate buffer and 100 g of 250 U / mL horseradish peroxidase, place in a reactor in a nitrogen atmosphere, cool to 0°C, and shake for 30 minutes. After the reaction is completed, the temperature of the three-necked flask is lowered to room temperature, filtered, the filter cake is washed with purified water until neutral and then dried, the filter cake is transferred to a drying oven at a temperature of 70°C, and vacuum dried to constant weight to obtain activated wool fiber;

[0076] Weigh: 500 g of activated wool fiber, 20 L of N,N-dimethylformamide and 2 kg of methoxy polyethylene glycol methacrylate, place in a reactor at 30° C., stir for 12 h under a nitrogen atmosphere, wash once with deionized water, and dry to obtain modified wool fiber;

[0077] S3. Preparation of wool fabric

[0078] Weigh: Weigh: 100g transglutaminase, 50g JFC-6 and 2L deionized water, mix well to obtain finishing solution, set aside;

[0079] The modified wool fiber is converted into yarn through washing, carding, combing and stretching, and the yarn is spun into long and thin wool yarn by a spinning machine, and then added to a loom for weaving to obtain a wool fabric;

[0080] The wool fabric was immersed in the modified dye solution, 1 mol / L dilute hydrochloric acid was added to adjust the pH to 3.5, the temperature was raised to 50°C, and the reaction was kept for 3 hours. The fabric after the reaction was washed once with deionized water and ethanol, and dried to obtain the dyed wool fabric;

[0081] The dyed wool fabric is immersed in the finishing liquid, sodium hydroxide solution is added to adjust the pH to 8.1, the temperature is raised to 60°C, and the reaction is kept for 1 hour. The fabric after the reaction is washed once with deionized water and ethanol, and dried to obtain the wool fabric.

[0082] Example 2

[0083] S1. Preparation of modified dyes

[0084] Weigh: 125g of p-phenylenediamine, 1.25L of concentrated hydrochloric acid, 2.5mL of deionized water and 80g of sodium nitrite into a reaction kettle, cool to 0°C, stir for 35 minutes, add urea, and test the reaction solution with starch-potassium iodide test paper. If the test paper does not turn blue, the reaction is over and a diazonium salt solution is obtained;

[0085] Weigh: 450 g of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 4 L of deionized water and 550 g of 4-acetylaminobenzenesulfonyl chloride are placed in a reaction kettle, the temperature is raised to 55° C., 0.15 mol / L acetic acid solution is added to adjust the pH to 4, the reaction is kept warm for 3.5 h, and intermediate I is obtained by post-treatment;

[0086] Weigh: 600 g of intermediate Ⅰ is placed in a reaction kettle, 0.15 mol / L sodium hydroxide solution is added to adjust the pH to 9.5, the temperature is lowered to 2°C, 4 L of diazonium salt solution is added dropwise, the temperature is kept for 2 h, 1.5 mol / L hydrochloric acid solution is added dropwise to the reaction solution until solids are precipitated, the solids are filtered, washed twice with deionized water, and dried to obtain intermediate Ⅱ;

[0087] Weigh: 700 g of intermediate II, 15 g of sodium hydroxide and 4 L of deionized water are placed in a reaction kettle, heated to 105° C., and refluxed for 5.5 h to obtain a modified dye.

[0088] S2. Preparation of modified wool fiber

[0089] Weigh: 250 g wool fiber and 7.5 L acetone, place in a Soxhlet extractor and extract for 25 h, remove the solvent, and dry to obtain a crude wool fiber;

[0090] Weigh: 27 mL of deionized water and 175 g of L-cysteine, mix well to obtain an L-cysteine ​​solution for later use;

[0091] Weigh: 600 g of crude wool fiber and 27 L of L-cysteine ​​solution are placed in a reactor at 70° C. and stirred for 2 h. After the reaction is completed, the fibers are filtered and washed twice with deionized water and anhydrous ethanol, and dried to obtain pretreated wool fibers;

[0092] Weigh: 35 g disodium hydrogen phosphate, 4 g sodium dihydrogen phosphate, 80 g sodium chloride and 9 L deionized water, mix well to obtain phosphate buffer, set aside;

[0093] Weigh: 750 g of pretreated wool fiber, 40 mL of 0.04 g / mL hydrogen peroxide solution, 150 L of phosphate buffer and 150 g of 275 U / mL horseradish peroxidase, place in a reactor in a nitrogen atmosphere, cool to 3°C, and shake for 45 minutes. After the reaction is completed, the temperature of the three-necked flask is lowered to room temperature, filtered, the filter cake is washed with purified water until neutral and then dried, the filter cake is transferred to a drying oven at a temperature of 75°C, and vacuum dried to constant weight to obtain activated wool fiber;

[0094] Weigh: 750 g of activated wool fiber, 22 L of N,N-dimethylformamide and 2.5 kg of methoxy polyethylene glycol methacrylate, place in a reactor at 35° C., stir for 13 h under a nitrogen atmosphere, wash twice with deionized water, and dry to obtain modified wool fiber;

[0095] S3. Preparation of wool fabric

[0096] Weigh: Weigh: 250g transglutaminase, 70g JFC-6 and 5L deionized water, mix well to obtain finishing solution, set aside;

[0097] The modified wool fiber is converted into yarn through washing, carding, combing and stretching, and the yarn is spun into long and thin wool yarn by a spinning machine, and then added to a loom for weaving to obtain a wool fabric;

[0098] The wool fabric was immersed in the modified dye solution, 1.5 mol / L dilute hydrochloric acid was added to adjust the pH to 3.5, the temperature was raised to 55°C, and the reaction was kept for 3.5 hours. The fabric after the reaction was washed twice with deionized water and ethanol, and dried to obtain a dyed wool fabric;

[0099] The dyed wool fabric was immersed in the finishing liquid, sodium hydroxide solution was added to adjust the pH to 8.15, the temperature was raised to 70°C, and the reaction was kept warm for 1.5 hours. The fabric after the reaction was washed twice with deionized water and ethanol, and dried to obtain the wool fabric.

[0100] Example 3

[0101] S1. Preparation of modified dyes

[0102] Weigh: 150g p-phenylenediamine, 1.5L concentrated hydrochloric acid, 3L deionized water and 90g sodium nitrite into a reaction kettle, cool to 5°C, stir for 40min, add urea, test the reaction solution with starch-potassium iodide test paper, if the test paper does not turn blue, the reaction is over, and a diazonium salt solution is obtained;

[0103] Weigh: 500 g of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 5 L of deionized water and 600 g of 4-acetylaminobenzenesulfonyl chloride are placed in a reaction kettle, the temperature is raised to 60° C., 0.2 mol / L acetic acid solution is added to adjust the pH to 5, the reaction is kept warm for 4 h, and intermediate I is obtained by post-treatment;

[0104] Weigh: 700 g of intermediate I was placed in a reaction kettle, 0.2 mol / L sodium hydroxide solution was added to adjust the pH to 10, the temperature was lowered to 5°C, 4.5 L of diazonium salt solution was added dropwise, and the reaction was kept warm for 3 h. 2 mol / L hydrochloric acid solution was added dropwise to the reaction solution until solids precipitated, and the solids were filtered, washed twice with deionized water, and dried to obtain intermediate II;

[0105] Weigh: 800 g of intermediate II, 20 g of sodium hydroxide and 5 L of deionized water are placed in a reaction kettle, heated to 110° C., and refluxed for 6 h to obtain a modified dye.

[0106] S2. Preparation of modified wool fiber

[0107] Weigh: 500 g of wool fiber and 10 L of acetone, place in a Soxhlet extractor and extract for 26 hours, remove the solvent, and dry to obtain a crude wool fiber;

[0108] Weigh: 30L of deionized water and 200g of L-cysteine, mix them evenly to obtain an L-cysteine ​​solution for later use;

[0109] Weigh: 700 g of crude wool fiber and 30 L of L-cysteine ​​solution, place in a reactor at 80°C, stir for 2 hours, after the reaction is completed, filter, wash the fiber with deionized water and anhydrous ethanol twice, and dry to obtain pretreated wool fiber;

[0110] Weigh: 40 g of disodium hydrogen phosphate, 5 g of sodium dihydrogen phosphate, 100 g of sodium chloride and 10 L of deionized water, mix well to obtain phosphate buffer, and set aside;

[0111] Weigh: 1 kg of pretreated wool fiber, 50 mL of 0.05 g / mL hydrogen peroxide solution, 200 L of phosphate buffer and 200 g of 300 U / mL horseradish peroxidase, place in a reactor in a nitrogen atmosphere, cool to 5°C, and shake for 60 minutes. After the reaction is completed, the temperature of the three-necked flask is lowered to room temperature, filtered, the filter cake is washed with purified water until neutral and then dried, and the filter cake is transferred to a drying oven at a temperature of 80°C and vacuum dried to constant weight to obtain activated wool fiber;

[0112] Weigh: 1 kg of activated wool fiber, 25 L of N,N-dimethylformamide and 3 kg of methoxy polyethylene glycol methacrylate, place in a reactor at 40°C, stir for 15 hours under a nitrogen atmosphere, wash twice with deionized water, and dry to obtain modified wool fiber;

[0113] S3. Preparation of wool fabric

[0114] Weigh: Weigh: 500g transglutaminase, 80g JFC-6 and 8L deionized water, mix evenly to obtain finishing solution, set aside;

[0115] The modified wool fiber is converted into yarn through washing, carding, combing and stretching, and the yarn is spun into long and thin wool yarn by a spinning machine, and then added to a loom for weaving to obtain a wool fabric;

[0116] The wool fabric was immersed in the modified dye solution, 2 mol / L dilute hydrochloric acid was added to adjust the pH to 4, the temperature was raised to 60°C, and the reaction was kept for 4 hours. The fabric after the reaction was washed twice with deionized water and ethanol, and dried to obtain the dyed wool fabric;

[0117] The dyed wool fabric was immersed in the finishing liquid, sodium hydroxide solution was added to adjust the pH to 8.2, the temperature was raised to 80°C, and the reaction was kept warm for 2 hours. The fabric after the reaction was washed twice with deionized water and ethanol, and dried to obtain the wool fabric.

[0118] Comparative Example 1

[0119] The difference between this comparative example and Example 3 is that step S1 is eliminated, and an equal amount of acid green 25 is used in step S3 to replace the modified dye.

[0120] Comparative Example 2

[0121] The difference between this comparative example and Example 3 is that the step of using L-cysteine ​​solution to prepare pretreated wool fibers in step S2 is eliminated, and an equal amount of crude wool fibers is used to replace pretreated wool fibers in step S2.

[0122] Comparative Example 3

[0123] The difference between this comparative example and Example 3 is that the step of preparing the finishing liquid is omitted in step S3, and the step of preparing the wool fabric in step S3 does not use the finishing liquid.

[0124] Performance Test:

[0125] The color uptake of the washable and easily colored wool fabrics prepared in Examples 1-3 and Comparative Examples 1-3 was tested with reference to the standard GB / T 9337-2009 "Determination of the color uptake of disperse modified dyes at high temperature".

[0126] The visual felt shrinkage grades of the washable and easily colored wool fabrics prepared in Examples 1-3 and Comparative Examples 1-3 were tested with reference to Standard FZ / T 20024-2012 “Wool Strip Felting Test Washing Method”;

[0127] The elongation at break of the washable and easily colorable wool fabrics prepared in Examples 1-3 and Comparative Examples 1-3 was tested with reference to the standard GB / T 3923.1-2013 "Tensile properties of textile fabrics - Part 1: Determination of breaking strength and elongation at break (strip method)";

[0128] The color fastness to washing of the washable and easily colored wool fabrics prepared in Examples 1-3 and Comparative Examples 1-3 was tested with reference to the standard GB / T 3921-2008 "Textiles - Tests for Color Fastness - Color Fastness to Washing with Soap";

[0129] The color fastness to rubbing of the washable and easily colored wool fabrics prepared in Examples 1-3 and Comparative Examples 1-3 was tested with reference to the standard GB / T 3920-2008 "Textiles - Tests for Color Fastness - Color Fastness to Rubbing". For specific data, see Table 1 - Performance test data table of each sample.

[0130] Table 1-Performance test data of each sample

[0131]

[0132] Data Analysis:

[0133] Comparative analysis of the data in Table 1 above shows that the washable and easily colored wool fabric prepared by the present invention has a coloring rate of 99.5%, a visual felting grade of 3, an elongation at break of 51.0%, a color fastness to soaping of 4-5, and a color fastness to wet rubbing of 4;

[0134] By comparing the data of Example 3 and Comparative Example 1, it can be found that the coloring rate and color fastness of the wool fabric are both reduced, indicating that the modified dye prepared by the present invention can undergo a substitution reaction with the carbon atom adjacent to the phenolic hydroxyl group in the amino acid residue in the wool fabric through the bridging effect of methylglyoxal to form a CCN covalent bond, thereby improving the coloring rate and color fastness of the washable and easy-to-color wool fabric;

[0135] By comparing the data of Example 3 and Comparative Example 2, it can be found that the dyeing rate, visual felting grade and color fastness of the wool fabric are all reduced, indicating that the present invention uses L-cysteine ​​as a reducing agent before preparing the modified wool fiber to open the disulfide bonds in the wool fiber, which is beneficial to the subsequent grafting reaction of methoxy polyethylene glycol methacrylate, and can further improve the water-resistant and anti-felting ability of the wool fabric, and is beneficial to the subsequent padding modification, so that the dye can penetrate into the interior of the wool fabric for dyeing, thereby improving the dyeing rate, visual felting grade and color fastness of the washable and easy-to-color wool fabric;

[0136] By comparing the data of Example 3 and Comparative Example 3, it can be found that the visual felt shrinkage grade and elongation at break of the wool fabric are both reduced, indicating that when preparing the impregnated and modified wool fabric, the finishing liquid composed of transglutaminase, JFC-6 and deionized water used in the present invention can catalyze the cross-linking reaction between the glutamine residues and the lysine residues in the wool fabric, forming peptide bonds and isopeptide bonds within and between protein molecules, thereby improving the visual felt shrinkage grade and elongation at break of the wool fabric.

[0137] The above are only examples and explanations of the structure of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the structure of the invention or exceed the scope defined by the claims, they should all fall within the protection scope of the present invention.

Claims

1. A process for treating washable and easily colorable wool fabric, characterized in that: The following steps are involved: S1, placing the pretreated wool fiber, hydrogen peroxide solution, phosphate buffer and horseradish peroxidase in a three-necked flask under a nitrogen atmosphere, cooling to 0-5°C, shaking for 30-60 minutes, and post-treating to obtain activated wool fiber; S2. Under a nitrogen atmosphere, place the activated wool fiber, N,N-dimethylformamide and methoxy polyethylene glycol methacrylate in a three-necked flask at a temperature of 30-40° C., stir for 12-15 hours, wash with deionized water 1-2 times, and dry to obtain the modified wool fiber; S3, converting the modified wool fiber into yarn by washing, carding, combing and stretching, spinning the yarn into long and thin wool yarn by a spinning machine, and then adding it to a loom for weaving to obtain a wool fabric; S4. After the wool fabric is modified by padding, a washable and easy-to-color wool fabric is obtained.

2. A washable and easily colorable wool fabric treatment process according to claim 1, characterized in that: In step S1, the concentration of the hydrogen peroxide solution is 0.03-0.05 g / mL, the phosphate buffer is composed of disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium chloride and deionized water in a dosage ratio of 0.3-0.4 g:0.03-0.05 g:0.6-1 g:80-100 mL, the concentration of the horseradish peroxidase is 250-300 U / mL, and the dosage ratio of the pretreated wool fiber, the hydrogen peroxide solution, the phosphate buffer and the horseradish peroxidase is 5-10 g:0.3-0.5 mL:1-2 L:1-2 g; in step S2, the dosage ratio of the activated wool fiber, N,N-dimethylformamide and methoxy polyethylene glycol methacrylate is 5-10 g:200-250 mL:20-30 g.

3. A washable and easily colorable wool fabric treatment process according to claim 1, characterized in that: The preparation method of the pretreated wool fiber comprises the following steps: A1. Place wool fiber and acetone in a Soxhlet extractor and extract for 24-26 hours, remove the solvent, and dry to obtain a crude wool fiber product; A2. Place the crude wool fiber and L-cysteine ​​solution in a three-necked flask at a temperature of 60-80°C and stir for 1-2 hours. After the reaction is completed, filter and wash the fiber with deionized water and anhydrous ethanol for 1-2 times, and dry to obtain pretreated wool fiber.

4. A washable and easily colorable wool fabric treatment process according to claim 3, characterized in that: In step A1, the wool fiber and acetone are used in a ratio of 1-5 g:50-100 mL; in step A2, the L-cysteine ​​solution is composed of deionized water and L-cysteine ​​in a ratio of 250-300 mL:1.5-2 g, and the wool fiber crude product and L-cysteine ​​solution are used in a ratio of 5-7 g:250-300 mL.

5. A washable and easily colorable wool fabric treatment process according to claim 1, characterized in that: The padding modification operation of the wool fabric comprises the following steps: B1. Immerse the wool fabric in the modified dye solution, add dilute hydrochloric acid to adjust the pH to 3.5-4, raise the temperature to 50-60°C, keep the temperature for reaction for 3-4 hours, and post-treat to obtain the dyed wool fabric; B2. Immerse the dyed wool fabric in the finishing solution, add sodium hydroxide solution to adjust the pH to 8±0.2, raise the temperature to 60-80°C, keep the temperature for 1-2 hours, and post-treat to obtain washable and easy-to-color wool fabric.

6. A process for treating washable and easily colorable wool fabric according to claim 5, characterized in that: In step B1, the concentration of the dilute hydrochloric acid is 1-2 mol / L, the modified dye solution is composed of the modified dye, deionized water and methylglyoxal in a dosage ratio of 4-5 g:50-100 mL:1-2 g, and the bath ratio of the wool fabric and the modified dye solution is 1:45-50; in step B2, the bath ratio of the dyed wool fabric and the finishing liquid is 1:20-25, and the finishing liquid is composed of transglutaminase, JFC-6 and deionized water in a dosage ratio of 1-5 g:0.5-0.8 g:20-80 mL.

7. A washable and easily colorable wool fabric treatment process according to claim 6, characterized in that: The preparation method of the modified dye comprises the following steps: C1. Place p-phenylenediamine, concentrated hydrochloric acid, deionized water and sodium nitrite in a three-necked flask, cool to -5-5°C, stir for 30-40 minutes, add urea, and test the reaction solution with starch-potassium iodide test paper. If the test paper does not turn blue, the reaction is complete and a diazonium salt solution is obtained. C2, 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, deionized water and 4-acetamidobenzenesulfonyl chloride are placed in a three-necked flask, the temperature is raised to 50-60°C, acetic acid solution is added to adjust the pH to 3-5, the temperature is kept for reaction for 3-4 hours, and intermediate I is obtained by post-treatment; C3, place intermediate I in a three-necked flask, add sodium hydroxide solution to adjust the pH to 9-10, cool to 0-5°C, drop diazonium salt solution, keep warm for 2-3h, and post-treat to obtain intermediate II; C4. Place intermediate II, sodium hydroxide and deionized water in a three-necked flask, heat to 100-110°C, and reflux for 5-6 hours to obtain a modified dye.

8. A process for treating washable and easily colorable wool fabric according to claim 7, characterized in that: In step C1, the dosage ratio of p-phenylenediamine, concentrated hydrochloric acid, deionized water and sodium nitrite is 1-1.5g:10-15mL:20-30mL:0.7-0.9g; in step C2, the concentration of the acetic acid solution is 0.1-0.2mol / L, and the dosage ratio of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, deionized water and p-acetylaminobenzenesulfonyl chloride is 4-5g:30-50mL:5-6g; in step C3, the concentration of sodium hydroxide is 0.1-0.2mol / L, and the dosage ratio of the intermediate I and the diazonium salt solution is 5-7g:30-45mL; the dosage ratio of the intermediate II, sodium hydroxide and deionized water is 6-8g:0.1-0.2g:25-50mL.

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