A processing technology for washable and easily colorable wool fabrics

Abstract

The present invention discloses a processing technology for washable and easily colorable wool fabrics, belonging to the technical field of wool fabric processing, and is used to solve the technical problems that the coloring rate, felting resistance performance and color fastness of existing wool fabrics need to be further improved; the present invention includes the following steps: using L-cysteine to open the disulfide bonds of wool fibers to obtain washable and easily colorable wool fabrics. The pretreated wool fibers prepared by the present invention are grafted with methoxypolyethylene glycol methacrylate under the catalysis of hydrogen peroxide and horseradish peroxidase to obtain modified wool fibers. After the modified wool fibers are woven into wool fabrics, they are respectively impregnated and rolled with modified dye solutions and finishing solutions to improve the coloring rate, felting resistance performance and color fastness of the wool fabrics.

Description

Technical Field

[0001] The present invention relates to the technical field of wool fabric processing, and particularly relates to a processing technology for washable and easily colorable wool fabrics. Background Art

[0002] Wool is one of the important raw materials in the textile industry, and has excellent properties such as good warmth retention, soft and elastic feel, natural and gentle luster, and good processing plasticity. However, wool products also have disadvantages such as easy felting and deformation, difficult care, itchy feeling, poor dyeing performance, and easy mildew. Wool mainly consists of four parts, namely the scale layer, the cortical layer, the medullary layer, and the cell membrane complex. The scale layer covers the outermost layer of the wool fiber, and there is a peptide amide bond crosslinking, which is located between the glutamic acid residue of the peptide chain and the lysine residue of another peptide chain, making it have good chemical stability and playing a protective role for the wool fiber. However, during the dyeing application process, due to the coverage of the scale layer, it is very difficult for dyes to enter the fiber interior under low-temperature conditions. The higher the cystine content in the scale layer, the tighter the structure. Only when the disulfide bond is broken can the dye easily enter the fiber interior.

[0003] In the prior art, in order to improve the felting resistance and dyeing performance of wool fabrics during washing, the method of modifying wool is mainly to carry out physical and chemical modification on the scale layer of wool fibers, and the commonly used method is to enzymatically hydrolyze the scale layer with protease. However, this method will damage the globular protein in the wool cell matrix and first hydrolyze the cortical layer inside the scale, resulting in an excessive decrease in the strength of wool and affecting the mechanical properties of wool. Moreover, when dyeing wool, the commonly used acid dyes and the fibers of wool fabrics are mainly combined by weak forces such as ionic bonds, hydrogen bonds, and van der Waals forces. After dyeing, the color yield and color fastness of the fabric are not good, and the dyeing process generally needs to be carried out under high-temperature conditions, which not only requires high energy consumption but also may cause damage to the fibers, resulting in loss of luster or poor feel.

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

[0005] The purpose of the present invention is to provide a processing technology for washable and easily colorable wool fabrics, which is used to solve the technical problems that the felting resistance, color yield, and soaping fastness to rubbing of wool fabrics in the prior art need to be further improved.

[0006] The purpose of the present invention can be achieved by the following technical solutions: A processing technology for washable and easily colorable wool fabrics includes the following steps:

[0007] S1. Place the pretreated wool fibers, hydrogen peroxide solution, phosphate buffer, and horseradish peroxidase in a three-necked flask under a nitrogen atmosphere, cool to 0 - 5 °C, shake for 30 - 60 min, and then post-treat to obtain activated wool fibers;

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

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

[0010]

[0011] In the formula: represents the crude wool fibers.

[0012] The reaction principle for preparing the modified wool fibers 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 combined action of horseradish peroxidase and hydrogen peroxide, the thiol groups on the pretreated wool fibers can be oxidized to generate thiyl free radicals, which undergo an electrophilic addition reaction with the electrophilic olefin double bond in methoxypolyethylene glycol methacrylate to form a chemical bond. The phosphate buffer acts as a buffer in the reaction system to maintain appropriate acid-base conditions, maintain the activity of horseradish peroxidase, and improve the reaction efficiency.

[0013] S3. Wash, card, comb, and stretch the wool fibers to convert them into yarns. After the yarns are spun into slender wool yarns by a spinning machine, they are added to a loom for weaving to obtain a wool fabric;

[0014] S4. After impregnating and padding the wool fabric, a washable and easily colorable 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 solution 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 horseradish peroxidase is 250 - 300 U / mL, and the dosage ratio of the pretreated wool fiber, hydrogen peroxide solution, phosphate buffer solution and horseradish peroxidase is 5 - 10 g: 0.3 - 0.5 mL: 1 - 2 L: 1 - 2 g. The post-treatment steps include: after the reaction is completed, the temperature of the three-necked flask is reduced to room temperature, suction filtration is carried out, the filter cake is washed with purified water until neutral and then dried by suction, the filter cake is transferred to an oven at 70 - 80 °C, and vacuum dried to constant weight to obtain activated wool fiber; in step S2, the dosage ratio of the activated wool fiber, N,N-dimethylformamide and methoxypolyethylene glycol methacrylate is 5 - 10 g: 200 - 250 mL: 20 - 30 g.

[0016] Further, in step S1, the preparation method of the pretreated wool fiber includes the following steps:

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

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

[0019] Acetone is a polar solvent that can dissolve the grease, natural wax and dirt in wool. The Soxhlet extractor consists of a round-bottom flask, a long straight tube and a condenser. Place the wool fiber to be extracted in the round-bottom flask of the extractor, add acetone as the solvent. As the round-bottom flask is heated, the acetone vapor rises through the straight tube of the extractor, condenses into a liquid and flows back to the extraction chamber. The evaporated acetone condenses and flows back to the extraction chamber, contacting the wool fiber again. Each acetone cycle will dissolve 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 60 - 80 °C, stir for 1 - 2 h. After the reaction is completed, carry out suction filtration, wash the fiber with deionized water and absolute ethanol for 1 - 2 times, and dry to obtain the pretreated wool fiber.

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

[0022] During the preparation process, L-cysteine is used as a reducing agent to react with the sulfur atoms in the disulfide bonds of the wool fiber, reducing the disulfide bonds to mercapto groups, and the pretreated wool fiber is prepared.

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

[0024] Further, in step S4, the operation of padding modification of the wool fabric includes 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, heat up to 50-60 °C, keep warm and react for 3-4 h, and perform post-treatment to obtain the dyed wool fabric;

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

[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, the electrons on the nitrogen transfer, water leaves, forming a Schiff base modified dye. Under acidic conditions, the Schiff base modified dye forms a modified dye carbocation, which, as an electrophilic reagent, attacks the compound containing active hydrogen and undergoes a substitution reaction with the ortho-carbon atom of the phenolic hydroxyl group in the tyrosine residue in the wool fabric, forming a C-C-N covalent bond.

[0028] B2. Immerse the dyed wool fabric in the finishing solution, add sodium hydroxide solution to adjust the pH to 8 ± 0.2, heat up to 60-80 °C, keep warm and react for 1-2 h, and perform post-treatment to obtain a washable and easily colorable wool fabric;

[0029] The reaction principle for preparing the washable and easily colorable wool fabric is as follows:

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

[0031] Further, in step B1, the concentration of the dilute hydrochloric acid is 1 - 2 mol / L, the modified dye solution is composed of a 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 to the modified dye solution is 1:45 - 50, and the post-treatment steps include: washing the reacted fabric with deionized water and ethanol 1 - 2 times, and drying to obtain 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 to the finishing solution is 1:20 - 25, 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 steps include: washing the reacted fabric with deionized water and ethanol 1 - 2 times, and drying to obtain a washable and easily colorable wool fabric.

[0032] Further, the preparation method of the modified dye includes the following steps:

[0033] C1. Place p-phenylenediamine, concentrated hydrochloric acid, deionized water, and sodium nitrite in a three-necked flask, cool down to -5 - 5 °C, stir for 30 - 40 min, then add urea, test the reaction solution with starch-iodide test paper, and when the test paper does not turn blue, the reaction ends to obtain a diazonium salt solution;

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

[0035]

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

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

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

[0039] C2. Place 1-amino-8-hydroxy-3,6-naphthalenedisulfonic acid, deionized water, and p-acetamidobenzenesulfonyl chloride in a three-necked flask, heat up to 50 - 60 °C, add acetic acid solution to adjust the pH to 3 - 5, keep the temperature for reaction for 3 - 4 h, and perform post-treatment to obtain intermediate I;

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

[0041]

[0042] The reaction principle for preparing Intermediate Ⅰ is as follows:

[0043] During the reaction process, the lone pair electrons on the amino nitrogen atom in 1-amino-8-hydroxy naphthalene-3,6-disulfonic acid attack the chlorine atom in p-acetamidobenzenesulfonyl chloride, resulting in nucleophilic substitution. The chlorine atom leaves, generating Intermediate Ⅰ.

[0044] The mass spectrometry analysis data of Intermediate Ⅰ are as follows: 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 down to 0 - 5 °C, dropwise add the diazonium salt solution, keep the temperature for reaction for 2 - 3 h, and perform post-treatment to obtain Intermediate II.

[0046] The reaction equation for preparing Intermediate II is as follows:

[0047]

[0048] The reaction principle for preparing Intermediate Ⅱ is as follows:

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

[0050] The mass spectrometry analysis data of Intermediate Ⅱ are as follows: 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 up to 100 - 110 °C, and reflux for 5 - 6 h to obtain the modified dye.

[0052] The reaction equation for preparing the modified dye is as follows:

[0053]

[0054] The reaction principle for preparing the modified dye is as follows:

[0055] Under alkaline conditions, OH - in water attacks the carbonyl carbon atom of the formamide on Intermediate Ⅱ as a nucleophile, and Intermediate Ⅱ dissociates into an acid and the modified dye.

[0056] The mass spectrometry analysis data of the modified dye are as follows: 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 dosage ratio of p-phenylenediamine, concentrated hydrochloric acid, deionized water and sodium nitrite is 1 - 1.5 g: 10 - 15 mL: 20 - 30 mL: 0.7 - 0.9 g; in step C2, the concentration of the acetic acid solution is 0.1 - 0.2 mol / L, and the dosage ratio of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, deionized water and p-acetamidobenzenesulfonyl chloride is 4 - 5 g: 30 - 50 mL: 5 - 6 g. The post-treatment steps include: removing the solvent from the reaction solution, washing and extracting the residue with ethyl acetate and deionized water for 1 - 2 times, and performing low-pressure rotary evaporation on the organic phase to obtain intermediate I; in step C3, the concentration of sodium hydroxide is 0.1 - 0.2 mol / L, and the dosage ratio of intermediate I and the diazonium salt solution is 5 - 7 g: 30 - 45 mL. The post-treatment steps include: dropping a 1 - 2 mol / L hydrochloric acid solution into the reaction solution until a solid precipitates, performing suction filtration, washing the solid with deionized water for 1 - 2 times, and drying to obtain intermediate II; in step C4, the dosage ratio of intermediate II, sodium hydroxide and deionized water is 6 - 8 g: 0.1 - 0.2 g: 25 - 50 mL.

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

[0059] 1. In the present invention, pretreated wool fibers are prepared. L-cysteine is used to open the disulfide bonds in the wool fibers and reduce them to mercapto groups. Under the catalysis of horseradish peroxidase and hydrogen peroxide, the mercapto groups are grafted with methoxypolyethylene glycol methacrylate. As a hydrophilic polymer compound, methoxypolyethylene glycol methacrylate crosslinks with the wool fibers and forms a film on the surface of the wool fibers, reducing the influence of the directional friction effect of the wool fibers, enabling the wool fibers to have better felting resistance performance, and the density of the felted balls of the graft-modified wool fibers is lower, further enhancing the felting resistance performance of the modified wool fibers. After reducing the disulfide bonds of the wool fibers to mercapto groups, the chemical affinity between the mercapto group structure and the modified dye molecules is stronger than that of the disulfide bonds, further enhancing the penetration of the modified dye into the interior of the wool fabric and enhancing the coloring rate and color fastness of the wool fabric.

[0060] 2. The present invention also prepares a multi-amino acid modified dye. Through the bridging effect of methylglyoxal, a substitution reaction occurs with the carbon atom adjacent to the phenolic hydroxyl group in the amino acid residues in the wool fabric, forming a C-C-N covalent bond, increasing the binding 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, facilitating the entry of the acidic modified dye and increasing the coloring rate of the wool fabric. When preparing the acidic modified dye, a double-amino acid modified dye is prepared. The amino group can increase the steric hindrance and reaction sites, further increasing the dyeing rate and dyeing concentration of the modified dye on wool. Moreover, methylglyoxal has lower pollution than traditional formaldehyde and is more environmentally friendly.

[0061] 3. The present invention also prepares a finishing solution to repair the damage of the surface wool scales during the pretreatment of the wool fabric. The main components of the finishing solution are transglutaminase and the deepening agent JFC-6. Transglutaminase can catalyze the cross-linking reaction between glutamine residues and lysine residues, repair the damage caused by grafting methoxypolyethylene glycol methacrylate and binding with the acidic modified dye in the wool fabric, and increase the felting resistance and elongation at break of the wool fabric. The deepening agent JFC-6 can cooperate with transglutaminase synergistically to form a eutectic mixture, accelerate the diffusion of the modified dye into the fiber interior, and improve the coloring rate and color fastness of the wool fabric. Detailed implementation mode

[0062] Next, the technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the protection scope of the present invention.

[0063] Example 1

[0064] This example provides a processing technology for washable and easily colorable wool fabric, including the following steps:

[0065] S1. Prepare the modified dye

[0066] Weigh: 100 g of p-phenylenediamine, 1 L of concentrated hydrochloric acid, 2 L of deionized water, and 70 g of sodium nitrite and place them in a three-necked flask. Cool down to -5 °C, stir for 30 min, then add urea. Test the reaction solution with a starch-potassium iodide test paper. When the test paper does not turn blue, the reaction ends, and a diazonium salt solution is obtained;

[0067] Weighing: Place 400 g of 1-amino-8-hydroxy-3,6-naphthalenedisulfonic acid, 3 L of deionized water, and 500 g of p-acetamidobenzenesulfonyl chloride into a reaction kettle. Heat up to 50 °C, add 0.1 mol / L acetic acid solution to adjust the pH to 3.5, keep the temperature for reaction for 3 h, and perform post-treatment to obtain Intermediate Ⅰ;

[0068] Weighing: Place 500 g of Intermediate Ⅰ into a reaction kettle, add 0.1 mol / L sodium hydroxide solution to adjust the pH to 9.1, cool down to 0 °C, dropwise add 3 L of diazonium salt solution, keep the temperature for reaction for 2 h, dropwise add 1 mol / L hydrochloric acid solution to the reaction solution until a solid precipitates, perform suction filtration, wash the solid with deionized water twice, and dry to obtain Intermediate Ⅱ;

[0069] Weighing: Place 600 g of Intermediate Ⅱ, 10 g of sodium hydroxide, and 2.5 L of deionized water into a reaction kettle, heat up to 105 °C, and reflux for 5 h to obtain the modified dye.

[0070] S2. Preparation of modified wool fiber

[0071] Weighing: Place 100 g of wool fiber and 5 L of acetone into a Soxhlet extractor for extraction for 24 h, remove the solvent, and dry to obtain the crude wool fiber;

[0072] Weighing: Mix 25 L of deionized water and 150 g of L-cysteine evenly to obtain an L-cysteine solution for standby;

[0073] Weighing: Place 500 g of the crude wool fiber and 25 L of the L-cysteine solution into a reaction kettle at 60 °C, stir for 2 h. After the reaction is completed, perform suction filtration, wash the fiber with deionized water and absolute ethanol twice, and dry to obtain the pretreated wool fiber;

[0074] Weighing: Mix 30 g of disodium hydrogen phosphate, 3 g of sodium dihydrogen phosphate, 60 g of sodium chloride, and 8 L of deionized water evenly to obtain a phosphate buffer solution for standby;

[0075] Weighing: Place 500 g of the pretreated wool fiber, 30 mL of 0.03 g / mL hydrogen peroxide solution, 100 L of the phosphate buffer solution, and 100 g of 250 U / mL horseradish peroxidase into a reaction kettle under a nitrogen atmosphere, cool down to 0 °C, shake for 30 min. After the reaction is completed, lower the temperature of the three-necked flask to room temperature, perform suction filtration, wash the filter cake with purified water until neutral and then drain, transfer the filter cake to a drying oven at 70 °C, and vacuum dry to constant weight to obtain the activated wool fiber;

[0076] Weighing: Place 500 g of the activated wool fiber, 20 L of N,N-dimethylformamide, and 2 kg of methoxypolyethylene glycol methacrylate into a reaction kettle at 30 °C under a nitrogen atmosphere, stir for 12 h, wash once with deionized water, and dry to obtain the modified wool fiber;

[0077] S3. Preparation of Wool Fabric

[0078] Weigh: Weigh 100 g of transglutaminase, 50 g of JFC-6 and 2 L of deionized water, mix them evenly to obtain a finishing solution for standby;

[0079] Wash, card, comb and stretch the modified wool fibers to convert them into yarns. After the yarns are spun into slender wool yarns by a spinning machine, they are added to a loom for weaving to obtain a wool fabric;

[0080] Immerse the wool fabric in the modified dye solution, add 1 mol / L dilute hydrochloric acid to adjust the pH to 3.5, heat up to 50 °C, keep warm and react for 3 h. Wash the reacted fabric once with deionized water and ethanol, and dry it to obtain a dyed wool fabric;

[0081] Immerse the dyed wool fabric in the finishing solution, add sodium hydroxide solution to adjust the pH to 8.1, heat up to 60 °C, keep warm and react for 1 h. Wash the reacted fabric once with deionized water and ethanol, and dry it to obtain a wool fabric.

[0082] Example 2

[0083] S1. Preparation of Modified Dye

[0084] Weigh: Place 125 g of p-phenylenediamine, 1.25 L of concentrated hydrochloric acid, 2.5 mL of deionized water and 80 g of sodium nitrite in a reaction kettle, cool down to 0 °C, stir for 35 min, then add urea, test the reaction solution with starch-potassium iodide test paper. When the test paper does not turn blue, the reaction ends to obtain a diazonium salt solution;

[0085] Weigh: Place 450 g of 1-amino-8-hydroxy-3,6-naphthalenedisulfonic acid, 4 L of deionized water and 550 g of p-acetamidobenzenesulfonyl chloride in a reaction kettle, heat up to 55 °C, add 0.15 mol / L acetic acid solution to adjust the pH to 4, keep warm and react for 3.5 h, and perform post-treatment to obtain Intermediate Ⅰ;

[0086] Weigh: Place 600 g of Intermediate Ⅰ in a reaction kettle, add 0.15 mol / L sodium hydroxide solution to adjust the pH to 9.5, cool down to 2 °C, dropwise add 4 L of the diazonium salt solution, keep warm and react for 2 h. Dropwise add 1.5 mol / L hydrochloric acid solution to the reaction solution until a solid precipitates, filter by suction, wash the solid twice with deionized water, and dry to obtain Intermediate Ⅱ;

[0087] Weigh: Place 700 g of Intermediate Ⅱ, 15 g of sodium hydroxide and 4 L of deionized water in a reaction kettle, heat up to 105 °C, reflux for 5.5 h to obtain a modified dye.

[0088] S2. Preparation of Modified Wool Fibers

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

[0090] Weigh: Mix 27 mL of deionized water and 175 g of L-cysteine evenly to obtain an L-cysteine solution for standby;

[0091] Weigh: Place 600 g of crude wool fibers and 27 L of the L-cysteine solution in a reaction kettle at 70 °C, stir for 2 h. After the reaction, perform suction filtration, wash the fibers twice with deionized water and absolute ethanol, and dry to obtain pretreated wool fibers;

[0092] Weigh: Mix 35 g of disodium hydrogen phosphate, 4 g of sodium dihydrogen phosphate, 80 g of sodium chloride and 9 L of deionized water evenly to obtain a phosphate buffer solution for standby;

[0093] Weigh: Place 750 g of pretreated wool fibers, 40 mL of 0.04 g / mL hydrogen peroxide solution, 150 L of the phosphate buffer solution and 150 g of 275 U / mL horseradish peroxidase in a reaction kettle under a nitrogen atmosphere, cool down to 3 °C, oscillate for 45 min. After the reaction is completed, lower the temperature of the three-necked flask to room temperature, perform suction filtration, wash the filter cake with purified water until neutral and then drain it, transfer the filter cake to a drying oven at 75 °C, and vacuum dry to constant weight to obtain activated wool fibers;

[0094] Weigh: Place 750 g of activated wool fibers, 22 L of N,N-dimethylformamide and 2.5 kg of methoxypolyethylene glycol methacrylate in a reaction kettle at 35 °C. Under a nitrogen atmosphere, stir for 13 h, wash twice with deionized water, and dry to obtain modified wool fibers;

[0095] S3. Prepare wool fabric

[0096] Weigh: Mix 250 g of transglutaminase, 70 g of JFC-6 and 5 L of deionized water evenly to obtain a finishing solution for standby;

[0097] Wash, card, comb and stretch the modified wool fibers to convert them into yarns. After the yarns are spun into slender wool yarns by a spinning machine, add them to a loom for weaving to obtain a wool fabric;

[0098] Immerse the wool fabric in a modified dye solution, add 1.5 mol / L dilute hydrochloric acid to adjust the pH to 3.5, heat up to 55 °C, keep warm and react for 3.5 h. Wash the reacted fabric twice with deionized water and ethanol, and dry to obtain a dyed wool fabric;

[0099] The dyed wool fabric was immersed in the finishing solution, and sodium hydroxide solution was added to adjust the pH to 8.15. Then the temperature was raised to 70 °C and the reaction was carried out for 1.5 h while maintaining the temperature. After the reaction, the fabric was washed twice with deionized water and ethanol, and then dried to obtain the wool fabric.

[0100] Example 3

[0101] S1. Preparation of modified dye

[0102] Weigh: 150 g of p-phenylenediamine, 1.5 L of concentrated hydrochloric acid, 3 L of deionized water and 90 g of sodium nitrite were placed in a reaction kettle. The temperature was lowered to 5 °C, and after stirring for 40 min, urea was added. The reaction solution was tested with starch-potassium iodide test paper, and when the test paper did not turn blue, the reaction ended to obtain a diazonium salt solution;

[0103] Weigh: 500 g of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 5 L of deionized water and 600 g of p-acetamidobenzenesulfonyl chloride were placed in a reaction kettle. The temperature was raised to 60 °C, and 0.2 mol / L acetic acid solution was added to adjust the pH to 5. The reaction was carried out for 4 h while maintaining the temperature, and then post-treatment was carried out to obtain Intermediate Ⅰ;

[0104] Weigh: 700 g of Intermediate Ⅰ was placed in a reaction kettle, and 0.2 mol / L sodium hydroxide solution was added to adjust the pH to 10. The temperature was lowered to 5 °C, and 4.5 L of the diazonium salt solution was added dropwise. The reaction was carried out for 3 h while maintaining the temperature. 2 mol / L hydrochloric acid solution was added dropwise to the reaction solution until a solid was precipitated. The solid was filtered by suction, 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 were placed in a reaction kettle. The temperature was raised to 110 °C and refluxed for 6 h to obtain the modified dye.

[0106] S2. Preparation of modified wool fiber

[0107] Weigh: 500 g of wool fiber and 10 L of acetone were placed in a Soxhlet extractor and extracted for 26 h. After removing the solvent, it was dried to obtain the crude wool fiber;

[0108] Weigh: 30 L of deionized water and 200 g of L-cysteine were mixed evenly to obtain an L-cysteine solution for standby;

[0109] Weigh: 700 g of the crude wool fiber and 30 L of the L-cysteine solution were placed in a reaction kettle at 80 °C and stirred for 2 h. After the reaction ended, it was filtered by suction, and the fiber was washed twice with deionized water and absolute ethanol, and then dried to obtain the 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 were mixed evenly to obtain a phosphate buffer solution for standby;

[0111] Weigh: 1 Kg of pretreated wool fibers, 50 mL of 0.05 g / mL hydrogen peroxide solution, 200 L of phosphate buffer, and 200 g of 300 U / mL horseradish peroxidase and place them in a reaction kettle under a nitrogen atmosphere. Cool down to 5 °C and shake for 60 min. After the reaction is completed, lower the temperature of the three-necked flask to room temperature, perform suction filtration. Wash the filter cake with purified water until it is neutral and then drain it. Transfer the filter cake to a drying oven at 80 °C and vacuum dry it to constant weight to obtain activated wool fibers;

[0112] Weigh: 1 Kg of activated wool fibers, 25 L of N,N-dimethylformamide, and 3 Kg of methoxypolyethylene glycol methacrylate and place them in a reaction kettle at 40 °C. Under a nitrogen atmosphere, stir for 15 h, wash twice with deionized water, and dry to obtain modified wool fibers;

[0113] S3. Prepare wool fabric

[0114] Weigh: Weigh 500 g of transglutaminase, 80 g of JFC-6, and 8 L of deionized water, mix them evenly to obtain a finishing solution for standby;

[0115] Wash, card, comb, and stretch the modified wool fibers to convert them into yarns. After the yarns are spun into slender wool yarns by a spinning machine, add them to a loom for weaving to obtain a wool fabric;

[0116] Immerse the wool fabric in a modified dye solution, add 2 mol / L dilute hydrochloric acid to adjust the pH to 4, heat up to 60 °C, and keep the temperature for reaction for 4 h. Wash the reacted fabric twice with deionized water and ethanol, and dry it to obtain a dyed wool fabric;

[0117] Immerse the dyed wool fabric in the finishing solution, add sodium hydroxide solution to adjust the pH to 8.2, heat up to 80 °C, and keep the temperature for reaction for 2 h. Wash the reacted fabric twice with deionized water and ethanol, and dry it to obtain a wool fabric.

[0118] Comparative Example 1

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

[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 cancelled, and the crude wool fibers are used in step S2 to replace the pretreated wool fibers in equal amount.

[0122] Comparative Example 3

[0123] The difference between this comparative example and Example 3 is that in step S3, the step of preparing the finishing liquid is cancelled, and in the step of preparing the wool fabric in step S3, the use of the finishing liquid is cancelled.

[0124] Performance test:

[0125] Referring to the standard GB / T 9337-2009 "Determination of the dyeing uptake of disperse modified dyes at high temperature", the dyeing uptake of the washable and easily colorable wool fabrics prepared in Examples 1-3 and Comparative Examples 1-3 was tested;

[0126] Referring to the standard FZ / T 20024-2012 "Testing method for felting shrinkage of wool top - Washing method", the visual felting shrinkage grade of the washable and easily colorable wool fabrics prepared in Examples 1-3 and Comparative Examples 1-3 was tested;

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

[0128] Referring to the standard GB / T 3921-2008 "Textiles - Tests for colour fastness - Colour fastness to soaping", the colour fastness to soaping of the washable and easily colorable wool fabrics prepared in Examples 1-3 and Comparative Examples 1-3 was tested;

[0129] Referring to the standard GB / T 3920-2008 "Textiles - Tests for colour fastness - Colour fastness to rubbing", the colour fastness to rubbing of the washable and easily colorable wool fabrics prepared in Examples 1-3 and Comparative Examples 1-3 was tested. The specific data are shown in Table 1 - Performance test data table of each sample.

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

[0131]

[0132] Data analysis:

[0133] By comparing and analyzing the data in Table 1 above, the dyeing uptake of the washable and easily colorable wool fabric prepared by the present invention is 99.5%, the visual felting shrinkage grade is 3, the elongation at break is 51.0%, the colour fastness to soaping is 4-5, and the wet colour fastness to rubbing is 4;

[0134] By comparing the data of Example 3 and Comparative Example 1, it can be found that both the coloring rate and color fastness of the wool fabric have decreased, indicating that the modified dye prepared by the present invention can undergo a substitution reaction with the ortho-carbon atom of the phenolic hydroxyl group in the amino acid residues in the wool fabric through the bridging action of methylglyoxal, forming a C-C-N covalent bond, and improving the coloring rate and color fastness of the washable and easily colorable wool fabric;

[0135] By comparing the data of Example 3 and Comparative Example 2, it can be found that the coloring rate, visual felting shrinkage grade, and color fastness of the wool fabric have all decreased, indicating that before preparing the modified wool fiber in the present invention, using L-cysteine as a reducing agent to break the disulfide bonds in the wool fiber is beneficial to the subsequent grafting reaction of methoxypolyethylene glycol methacrylate, which can further improve the washable and felting shrinkage resistance ability of the wool fabric, and is beneficial to the dye penetrating into the interior of the wool fabric for dyeing during subsequent padding modification, thereby improving the coloring rate, visual felting shrinkage grade, and color fastness of the washable and easily colorable wool fabric;

[0136] By comparing the data of Example 3 and Comparative Example 3, it can be found that the visual felting shrinkage grade and elongation at break of the wool fabric have both decreased, indicating that when preparing the padded and modified wool fabric in the present invention, using a finishing solution composed of transglutaminase, JFC-6, and deionized water can catalyze the cross-linking reaction between glutamine residues and lysine residues in the wool fabric, forming peptide bonds and isopeptide bonds within and between protein molecules, and improving the visual felting 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. Those skilled in the art of this technology can make various modifications, supplements, or use similar methods to replace the specific embodiments described, as long as they do not deviate from the structure of the invention or exceed the scope defined by this claim book, they should all fall within the protection scope of the present invention.

Claims

1. A processing technology for washable and easily colorable wool fabrics, characterized in that, It includes the following steps: S1. Place the pretreated wool fibers, hydrogen peroxide solution, phosphate buffer solution, and horseradish peroxidase in a three-necked flask under a nitrogen atmosphere, cool down to 0 - 5 °C, oscillate for 30 - 60 min, and perform post-treatment to obtain activated wool fibers; S2. Under a nitrogen atmosphere, place the activated wool fibers, N,N-dimethylformamide, and methoxypolyethylene glycol methacrylate in a three-necked flask at a temperature of 30 - 40 °C, stir for 12 - 15 h, wash 1 - 2 times with deionized water, and dry to obtain modified wool fibers; S3. Wash, card, comb, and stretch the modified wool fibers to convert them into yarns. After the yarns are spun into slender wool yarns by a spinning machine, add them to a loom for weaving to obtain a wool fabric; S4. After impregnating and padding the wool fabric, a washable and easily colorable wool fabric is obtained; The preparation method of the pretreated wool fibers includes the following steps: A1. Place the wool fibers and acetone in a Soxhlet extractor for extraction for 24 - 26 h, remove the solvent, and dry to obtain crude wool fibers; A2. Place the crude wool fibers and L-cysteine solution in a three-necked flask at a temperature of 60 - 80 °C, stir for 1 - 2 h. After the reaction ends, perform suction filtration, wash the fibers 1 - 2 times with deionized water and absolute ethanol, and dry to obtain pretreated wool fibers.

2. The processing technology of a washable and easily colorable wool fabric 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 solution is composed of disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium chloride, and deionized water according to the 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 fibers, hydrogen peroxide solution, phosphate buffer solution, and 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 fibers, N,N-dimethylformamide, and methoxypolyethylene glycol methacrylate is 5 - 10 g:200 - 250 mL:20 - 30 g.

3. A processing technology for washable and easily colorable wool fabrics according to claim 1, characterized in that, In step A1, the dosage ratio of the wool fibers and acetone is 1 - 5 g:50 - 100 mL; in step A2, the L-cysteine solution is composed of deionized water and L-cysteine according to the dosage ratio of 250 - 300 mL:1.5 - 2 g, and the dosage ratio of the crude wool fibers and the L-cysteine solution is 5 - 7 g:250 - 300 mL.

4. A processing technology for washable and easily colorable wool fabrics according to claim 1, characterized in that, The operation of impregnating and padding the wool fabric includes 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 warm and react for 3 - 4 h, and perform post-treatment to obtain a 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 warm and react for 1 - 2 h, and perform post-treatment to obtain a washable and easily colorable wool fabric.

5. A processing technology for a washable and easily colorable wool fabric according to claim 4, 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 a 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 to the modified dye solution is 1:45 - 50. In step B2, the bath ratio of the dyed wool fabric to the finishing solution is 1:20 - 25. 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.

6. A process for treating a washable and easily colorable wool fabric according to claim 4, 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 down to -5 - 5 °C, stir for 30 - 40 min, then add urea, test the reaction solution with starch-iodide paper. When the paper does not turn blue, the reaction ends to obtain a diazonium salt solution; C2. Place 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, deionized water, and p-acetamidobenzenesulfonyl chloride in a three-necked flask, heat up to 50 - 60 °C, add an acetic acid solution to adjust the pH to 3 - 5, keep the temperature for reaction for 3 - 4 h, and perform post-treatment to obtain intermediate I; C3. Place intermediate I in a three-necked flask, add a sodium hydroxide solution to adjust the pH to 9 - 10, cool down to 0 - 5 °C, dropwise add the diazonium salt solution, keep the temperature for reaction for 2 - 3 h, and perform post-treatment to obtain intermediate II; C4. Place intermediate II, sodium hydroxide, and deionized water in a three-necked flask, heat up to 100 - 110 °C, reflux for 5 - 6 h to obtain the modified dye.

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

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