阅读说明：本技术 一种用于羊绒制品的扎染方法 (Tie-dyeing method for cashmere products ) 是由 单珊珊 薛惊理 秦保新 徐媛媛 候会 于 2021-09-22 设计创作，主要内容包括：本发明公开了一种用于羊绒制品的扎染方法,涉及纺纱技术领域,具体包括：剥鳞、丝光前处理→扎花→纤维表面改性→染色→拆扎→柔软整理；其中纤维表面改性工序中,所用改性剂包括：甲基4-咖啡酰奎尼酸酯和阳离子化试剂。本发明提供的用于羊绒制品的扎染方法,可使扎染的羊绒织物具有传统的扎染风格的同时,具有更加优异的色牢度、竭染率和固色率,产品花色自然、稳定性高；且有效改善了产品的染色效果。(The invention discloses a tie-dyeing method for cashmere products, which relates to the technical field of spinning and specifically comprises the following steps: scale stripping, mercerizing pretreatment → flower binding → fiber surface modification → dyeing → bundling → soft finishing; wherein in the fiber surface modification procedure, the used modifying agent comprises: methyl 4-caffeoylquinic acid ester and cationizing agent. The tie-dyeing method for the cashmere products, provided by the invention, can enable tie-dyed cashmere fabrics to have traditional tie-dyeing style, and meanwhile, the tie-dyed cashmere fabrics have more excellent color fastness, exhaustion degree and fixation rate, and the products have natural color and high stability; and effectively improves the dyeing effect of the product.)

1. A tie-dyeing method for cashmere products comprises the following process flows:

scale stripping, mercerizing pretreatment → flower binding → fiber surface modification → dyeing → bundling → soft finishing;

in the fiber surface modification step, the modifier comprises: methyl 4-caffeoylquinic acid ester and a cationizing agent;

the softening finishing process adopts a dipping finishing process.

2. The tie-dyeing method for cashmere products according to claim 1, characterized in that: the flower binding method comprises the following steps: the fabric is locally bound, pricked, stitched with needles and threads, twisted or clipped.

3. The tie-dyeing method for cashmere products according to claim 1, characterized in that: in the dyeing process, neutral dye and/or weakly acidic dye are/is adopted as dyeing raw materials;

the dyeing prescription comprises: 2.2-5.6% (owf) of dye, 2.4-5.8% (owf) of anhydrous sodium sulphate and 1.2-2.4% (owf) of glacial acetic acid, and 0.6-1.2 g/L of leveling agent Albizzia B.

4. The tie-dyeing method for cashmere products according to claim 1, characterized in that: and in the disassembling and binding procedure, the dyeing fabric is subjected to anti-staining treatment.

5. The tie-dyeing method for cashmere products according to claim 1, characterized in that: in the softening finishing procedure, the used softening agent is a cashmere and wool softening agent; meanwhile, a color fixing agent is also added.

6. The tie-dyeing method for cashmere products according to claim 5, characterized in that: the color fixing agent comprises 6-fluoro-7-piperazine-1-methyl-4-oxo- [1,3] thiazacyclo [3,2-a ] quinoline-3-carboxylic acid ethyl ester and/or D-pantothenic acid modified waterborne polyurethane color fixing agent.

7. A method of modifying the surface of a fiber as set forth in claim 1, comprising:

carrying out reduction treatment on the surface of the cashmere fabric to generate sulfydryl;

using HRP/H₂O₂Enzymatic catalysis of sulfydryl-alkene click reaction, and grafting methyl 4-caffeoyl quinic acid ester on the surface of cashmere fabric;

and finally, performing functional treatment on the grafted cashmere fabric by adopting a cationization reagent.

8. The method of fiber surface modification of claim 7, wherein: the cationizing agent comprises 2,3 epoxypropyltrimethylammonium chloride.

9. A tie-dyed product obtained by the tie-dyeing method according to claim 1, wherein the fixation rate of dyeing of the product is more than 95%.

Technical Field

The invention belongs to the technical field of spinning, and particularly relates to a tie-dyeing method for cashmere products.

Background

The tie-dyed decorative patterns show that the patterns are naturally running and have larger randomness, and the obtained patterns are unique and are abstract styles. Each piece is a single piece with individuality, since the pattern does not produce a complete mechanical repetition at the base of its large style. Compared with space dyeing, the tie-dyed pattern is more free, flexible and non-reproducible. Because the dyeing is needed after the tying, the working hours are longer, the effect of the finished product is different, and the product caters to the new trend and fashion of the young generation, especially the pursuit psychology of the young generation. And the tie-dyeing dye can use chemical dye and also can use plant dye, has less harm to the environment and accords with a sustainable development mode.

The tie-dyeing method is mainly used on the fabrics of real silk, cotton, hemp, etc. or clothes, according to the design intention, the producer adopts the means of cotton thread winding, tying, sewing, twisting, clamping, etc. or selects various manual folding methods to form the physical dye-resisting area of the fabric, and the fabric is soaked in clean water and then placed in the dyeing liquor for repeated dip-dyeing to obtain the invented product. In the dyeing process, due to different dye-proofing properties generated at the bound parts of the fabric or ready-made clothes, the difference of dye liquor to the permeation of the fabric is formed, and after the dyeing, the fabric is subjected to the procedures of washing, dewatering, drying, stitch removing and the like, so that the fabric presents tie-dyeing patterns with rich layers and unique style. The fabric or dress for tie-dyeing generally adopts light and thin real silk, cotton, hemp and other fabrics, and has the characteristics of rapid penetration, good color fastness, dye prevention and clear dyeing area during dyeing, so that the dyed fabric can achieve the conception effect of a designer. Because the cashmere fabric is thick and heavy, the cashmere fabric has a barrier effect on the permeation and diffusion of dyes and other chemical reagents, and when the tie-dyeing is carried out, the dye has slow permeation to cashmere fibers, poor color fixation fastness, fuzzy levels of dye-resistant and dyed areas and poor visual effect, so that the expected conception effect cannot be achieved.

Disclosure of Invention

The invention aims to provide a tie-dyeing method for cashmere products, which can lead tie-dyed cashmere fabrics to have more excellent color fastness, exhaustion rate and fixation rate while having the traditional tie-dyeing style, and the products have natural color and high stability; and effectively improves the dyeing effect of the product.

The technical scheme adopted by the invention for realizing the purpose is as follows:

a tie-dyeing method for cashmere products comprises the following process flows:

scale stripping, mercerizing pretreatment → flower binding → fiber surface modification → dyeing → bundling → soft finishing;

in the fiber surface modification step, the modifier used comprises: methyl 4-caffeoylquinic acid ester and a cationizing agent;

the softening finishing process adopts a dipping finishing process. In the process of tie-dyeing the cashmere fabric, methyl 4-caffeoylquinic acid ester is connected on the surface of the fiber through a chemical bond to modify the fiber, and then a cationization reagent is added to perform secondary functionalization treatment on the fiber, so that the dye is subjected to composite crosslinking or adsorption on a microstructure with the cashmere fiber, the adhesive force of the dye on the fiber is obviously improved, the movement of dye molecules to the interior of the fiber is promoted, the most total retention amount of the dye in a fiber unit space is effectively improved, the utilization rate of the dye is fully improved, the dyeing efficiency of the cashmere fabric is improved, the dyeing depth of the dye on the cashmere fabric is improved, the exhaustion rate of the cashmere fabric is obviously enhanced, the diffusion of the dye to the interior of the fiber is accelerated, and the time required by boiling dyeing can be effectively shortened; in addition, the color fastness of the dyed cashmere fabric is improved to a certain extent, and the color fastness to acid perspiration and the color fastness to rubbing are improved. And the fiber grafted and modified by the methyl 4-caffeoylquinic acid ester has more excellent anti-felting performance.

Further, the tie-dyeing method for the cashmere products comprises the following specific process flows:

(1) pretreatment, namely performing pretreatment such as scale stripping, mercerizing and the like on the cashmere fabric;

(2) binding, namely binding the fabric by using a cotton rope or stitching or screwing or clamping by using a manual needle thread according to a pattern to be bound and dyed, and forming an artistic effect of different dyed depths and different lines by utilizing the difference of width, looseness, tightness, looseness, density and the like during binding and the dye-repellent effect of a binding part;

(3) modifying the surface of the fiber, namely treating the fiber by adopting a modifier;

(4) dyeing, namely performing regional dyeing on the modified fiber, performing dip dyeing at the water temperature of 85-100 ℃, treating for 10-20 min, and taking out;

(5) removing the bundle, after dyeing is finished, washing the dyed cashmere fabric with water at room temperature for 10-15 min, then dehydrating, performing anti-staining treatment, and finally removing the bundle objects such as cords and the like;

(6) and (3) softening finishing, namely softening finishing the disassembled and bound cashmere fabric by adopting an impregnation process for 10-15 min.

In addition, the method for modifying the surface of the fiber in the step (3) includes:

carrying out reduction treatment on the surface of the cashmere fabric to generate sulfydryl;

using HRP/H₂O₂Enzymatic catalysis of sulfydryl-alkene click reaction, and grafting methyl 4-caffeoyl quinic acid ester on the surface of cashmere fabric;

and finally, performing functional treatment on the grafted cashmere fabric by adopting a cationization reagent.

Further, the fiber surface modification is specifically:

and (3) immersing the pretreated cashmere fabric into 0.015-0.024 mol/L cationization reagent solution, treating for 1-2 h at 30-35 ℃, taking out, washing with water, and drying at 30-35 ℃ to obtain the surface modified cashmere fabric.

Or the like, or, alternatively,

a. performing reduction treatment on the cashmere fabric, namely extracting the cashmere fabric for 22-25 hours in a Soxhlet extractor by using acetone; then soaking the substrate into a solution of L L-cysteine with the concentration of 4.8-7 g/8 at the temperature of 60-65 ℃ for treatment for 1-2 h; taking out the mixture after the reaction is finished, washing the mixture with water, and ultrasonically oscillating the mixture for 20-30 min by using absolute ethyl alcohol;

b. fiber surface modification, namely immersing the pretreated cashmere fabric into a phosphate buffer solution (0.18-0.25 mol/L, pH 7-7.5) containing methyl 4-caffeoylquinic acid ester (9-11 mg/mL) and HRP (0.8-1.4 mg/mL, 0.8-0.9 mL, 250U), and oscillating for 25-40 min at 0-2 ℃ under the condition of introducing nitrogen; then injecting hydrogen peroxide (2.5-4%, w/v), heating to 35-40 ℃, and reacting for 12-16 h; washing the finished fabric with deionized water after the reaction is finished, and drying at 28-32 ℃; and then soaking the cashmere fabric into 0.015-0.024 mol/L cationization reagent solution, treating for 1-2 h at 30-35 ℃, taking out, washing with water, and drying at 30-35 ℃ to obtain the surface modified cashmere fabric.

In the step a, the solid-to-liquid ratio of the cashmere fabric to the L-cysteine solution is 1 g: 45-60 mL.

In step b, the solid-to-liquid ratio of the cashmere fabric to the phosphate buffer solution is 1 g: 180-220 mL; the volume ratio of the hydrogen peroxide to the phosphate buffer solution is 0.08-0.2: 100, respectively; the solid-to-liquid ratio of the cashmere fabric to the cationization reagent solution is 1 g: 200-240 mL.

It is noted that the cationizing agent includes 2,3 epoxypropyltrimethylammonium chloride.

In the dyeing step of the step (4), a neutral dye and/or a weakly acidic dye is/are used as a dyeing raw material; the dyeing prescription comprises: 2.2-5.6% of dye (owf, abbreviation of weight ratio), 2.4-5.8% of anhydrous sodium sulphate and 1.2-2.4% of glacial acetic acid, and 0.6-1.2 g/L of leveling agent Albizzia B.

In the step (5), the staining prevention treatment specifically includes: dipping and treating for 10-15 min by using 6-8 wt% of antifouling agent at the temperature of 50-55 ℃, wherein the bath ratio is 1: 18 to 22.

It should be noted that, in the step (6), the soft finishing process specifically includes: dipping 6-8 wt% of softening agent for cashmere and wool for 10-15 min at 45-50 ℃, wherein the bath ratio is 1: 15 to 30.

More preferably, a color fixing agent F-322 or a modified waterborne polyurethane color fixing agent is added in the soft finishing process of the step (6), and the concentration of the color fixing agent F-322 or the modified waterborne polyurethane color fixing agent is 4.8-7.6 wt%; namely, the color fixing agent and the softening agent are used for finishing the cashmere fabric in one bath.

The preparation method of the modified waterborne polyurethane color fixing agent specifically comprises the following steps:

s1: pre-polymerizing, mixing PPG and HDI, and stirring and reacting for 1.5-2.5 h at 70-80 ℃ under the protection of nitrogen;

s2: chain extension, namely adding dihydroxybutyric acid and D-pantothenic acid into the system, continuing to react for 0.5-1.5 h, and then cooling to 38-45 ℃ for reaction for 1-2 h; then adding a neutralizing agent for neutralization, and fully stirring for 10-15 min;

s3: carrying out end-capping crosslinking modification, adding ECH and 6-fluoro-7-piperazine-1-methyl-4-oxo- [1,3] thiazacyclo [3,2-a ] quinoline-3-carboxylic acid ethyl ester into the system at 38-45 ℃, and reacting for 0.5-1 h;

s4: and (3) emulsifying, namely cooling the system to room temperature, adding deionized water, stirring at a high speed, and emulsifying for 0.5-1 h to obtain the modified waterborne polyurethane color fixing agent. According to the invention, 6-fluoro-7-piperazine-1-methyl-4-oxo- [1,3] thiazacyclo [3,2-a ] quinoline-3-carboxylic acid ethyl ester and/or D-pantothenic acid modified waterborne polyurethane are adopted to prepare the color fixing auxiliary agent, the dyed fabric is subjected to dip finishing, and the dye can be effectively improved in retention effect on the fabric through mutual combination or winding with the dye, so that the color fastness of the dye on the fabric is obviously improved, and the perspiration stain fastness, the friction fastness and the washing fastness of the dye are obviously enhanced; and the color fixing rate of the fabric is improved, the utilization rate of the dye is improved, and the dyeing effect of the fabric is further improved. Wherein, under the condition that 6-fluoro-7-piperazine-1-methyl-4-oxo- [1,3] thiazacyclo [3,2-a ] quinoline-3-carboxylic acid ethyl ester and D-pantothenic acid exist simultaneously, the enhancing effect on the fabric color fastness and the color fixing rate is better.

In step S1, the molar ratio of PPG to HDI is 1: 1-2;

in step S2, the molar ratio of dihydroxybutyric acid to D-pantothenic acid is 1: 0.4 to 0.7; the total adding amount of the dihydroxybutyric acid and the D-pantothenic acid is 4.2-6% of the total mass of the monomers; the neutralizing agent is triethylamine, and the neutralization degree is 90-100%.

In step S3, the molar ratio of ECH to ethyl 6-fluoro-7-piperazine-1-methyl-4-oxo- [1,3] thiazacyclo [3,2-a ] quinoline-3-carboxylate is 1: 0.8-1.2, and the total addition amount is 75.5-88.5% of the total mass of the monomers.

The invention also aims to provide the application of the methyl 4-caffeoylquinic acid ester in improving the degree of exhaustion of the dye on cashmere fabric.

The invention also aims to provide a tie-dyeing product prepared by the tie-dyeing method, wherein the color fixing rate of the dyeing of the product is more than 95%.

Compared with the prior art, the invention has the following beneficial effects:

in the process of tie-dyeing the cashmere fabric, methyl 4-caffeoylquinic acid ester is connected to the surface of the fiber through a chemical bond, and a cationization reagent is added to carry out secondary functionalization treatment on the fiber, so that the obtained modified cashmere fiber has more excellent anti-felting performance; the adhesive force of the dye on the fiber is obviously improved, the most total remaining amount of the dye in the space of a fiber unit is effectively improved, the dyeing efficiency of the cashmere fabric is further improved, the dyeing depth of the dye on the cashmere fabric is improved, the exhaustion rate of the cashmere fabric is obviously enhanced, and the time required by boiling dyeing can be effectively shortened; meanwhile, the color fastness of the dyed cashmere fabric is improved to a certain extent, and the color fastness to acid perspiration and the color fastness to friction are improved. In addition, 6-fluoro-7-piperazine-1-methyl-4-oxo- [1,3] thiazacyclo [3,2-a ] quinoline-3-carboxylic acid ethyl ester and/or D-pantothenic acid modified waterborne polyurethane are adopted to prepare a color fixing auxiliary agent, and the color fastness of the dye on the fabric is remarkably improved by performing dip finishing on the dyed fabric, so that the color fastness of the dye on the fabric is remarkably improved, and the color fastness to perspiration, the color fastness to rubbing and the color fastness to washing are remarkably enhanced; and the color fixing rate of the fabric is improved, and the dyeing effect of the fabric is further improved. The tie-dyeing method for the cashmere products provided by the invention can enable tie-dyed cashmere fabrics to have traditional tie-dyeing style, and meanwhile, the tie-dyed cashmere fabrics have more excellent color fastness, exhaustion rate and fixation rate, the product has natural color and high stability, and abundant and variable texture patterns are presented, so that more beautiful visual enjoyment is brought to consumers.

Therefore, the tie-dyeing method for the cashmere products provided by the invention can enable tie-dyed cashmere fabrics to have traditional tie-dyeing style, and meanwhile, the tie-dyed cashmere fabrics have more excellent color fastness, exhaustion degree and color fixation rate, and the products have natural color and high stability; and effectively improves the dyeing effect of the product.

Drawings

Fig. 1 is SEM test results of unmodified cashmere fibers of the present invention;

FIG. 2 is a SEM test result of the surface modified fiber of the present invention;

FIG. 3 shows the results of mid-IR spectroscopy in test example 1 of the present invention;

fig. 4 is a schematic diagram of the cashmere scarf after tie-dyeing and coloring.

Detailed Description

The technical solution of the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings:

the embodiment of the invention takes tie dyeing of cashmere scarves as an example, the used dye is a weak acid dye, and the formula comprises: dye (prasugrel red B: prasugrel yellow GN ═ 0.42: 1) 4.1% (owf), anhydrous sodium sulphate 3.6% (owf) and glacial acetic acid 1.7% (owf) were added, and further 0.9g/L leveling agent albuge B was added.

The cationizing agent used in the embodiment of the invention is 2,3 epoxypropyltrimethylammonium chloride.

Example 1:

the tie-dyeing method for the cashmere products comprises the following specific process flows:

(1) performing pretreatment, namely performing scale stripping and mercerizing pretreatment on the cashmere fabric;

(2) binding flowers, namely binding the fabric by using a cotton rope according to a flower type to be bound and dyed to cause the artistic effects of different dyeing depths and different lines;

(3) modifying the surface of the fiber, namely treating the fiber by adopting a modifier;

(4) dyeing, namely performing regional dyeing on the modified fiber, performing dip dyeing at the water temperature of 90 ℃, treating for 15min, and taking out;

(5) removing the bundle, washing the dyed cashmere fabric with water at room temperature for 15min after dyeing, dewatering, performing anti-staining treatment, and performing immersion treatment with 7.2 wt% of antifouling agent QP-W for 10min at 50 ℃ in a bath ratio of 1: 19; finally removing the tying objects such as the ropes and the like;

(6) softening finishing, namely performing softening finishing on the disassembled and bound cashmere fabric by adopting an impregnation process, and performing impregnation treatment for 15min by using mixed finishing liquid containing 6.8 wt% of softening agent QP-IA and 5.5 wt% of color fixing agent F-322 at the temperature of 46 ℃, wherein the bath ratio is 1: 22; and finally drying to obtain a finished product.

The fiber surface modification in the step (3) is specifically as follows:

immersing the figured cashmere fabric into 0.019mol/L cationization reagent solution (the solid-to-liquid ratio of the cashmere fabric to the cationization reagent solution is 1 g: 220mL), treating for 1.5h at 32 ℃, taking out, washing with water, and drying at 35 ℃ to obtain the surface modified cashmere fabric.

Example 2:

the tie-dyeing method for cashmere products differs from example 1 in that:

the fiber surface modification in the step (3) is specifically,

a. performing reduction treatment on the cashmere fabric, namely extracting the cashmere fabric for 24 hours in a Soxhlet extractor by using acetone; then soaking the mixture into a cysteine solution with the concentration of 5.6g/L L-at the temperature of 62 ℃ for treatment for 1.5 h; taking out after the reaction is finished, washing with water, and ultrasonically oscillating with absolute ethyl alcohol for 25 min; wherein the solid-to-liquid ratio of the cashmere fabric to the L-cysteine solution is 1 g: 52.5 mL.

b. Fiber surface modification, namely immersing the pretreated cashmere fabric into a phosphate buffer (0.21mol/L, pH 7.5) containing methyl 4-caffeoylquinic acid ester (10.2mg/mL) and HRP (1.1mg/mL, 0.85mL, 250U), wherein the solid-to-liquid ratio of the cashmere fabric to the phosphate buffer is 1 g: 195 mL; oscillating for 30min at 0 ℃ under the condition of introducing nitrogen; then injecting hydrogen peroxide (3.2%, w/v) (the volume ratio of the hydrogen peroxide to the phosphate buffer solution is 0.13: 100), heating to 32 ℃, and reacting for 14 h; washing the finished fabric with deionized water after the reaction is finished, and drying at 30 ℃; then immersing the cashmere fabric into 0.019mol/L cationization reagent solution (the solid-to-liquid ratio of the cashmere fabric to the cationization reagent solution is 1 g: 220mL), treating for 1.5h at 32 ℃, taking out, washing with water, and drying at 35 ℃ to obtain the surface modified cashmere fabric.

Example 3:

the tie-dyeing method for cashmere products differs from example 2 in that:

in the fiber surface modification in the step (3), the solid-to-liquid ratio of the cashmere fabric to the L-cysteine solution in the step a is 1 g: 47 mL; in the step b, the solid-to-liquid ratio of the cashmere fabric to the phosphate buffer solution is 1 g: 205 mL; the volume ratio of hydrogen peroxide to phosphate buffer was 0.09: 100, respectively; the solid-to-liquid ratio of the cashmere fabric to the cationization reagent solution is 1 g: 210 mL.

Example 4:

the tie-dyeing method for cashmere products differs from example 2 in that:

in the fiber surface modification in the step (3), the solid-to-liquid ratio of the cashmere fabric to the L-cysteine solution in the step a is 1 g: 57 mL; in the step b, the solid-to-liquid ratio of the cashmere fabric to the phosphate buffer solution is 1 g: 212 mL; the volume ratio of hydrogen peroxide to phosphate buffer is 0.17: 100, respectively; the solid-to-liquid ratio of the cashmere fabric to the cationization reagent solution is 1 g: 230 mL.

Example 5:

the tie-dyeing method for cashmere products differs from example 2 in that:

the color fixing agent is added in the softening finishing process in the step (6) and is a modified waterborne polyurethane color fixing agent, and the preparation method specifically comprises the following steps:

s1: prepolymerization, taking a mixture of the components according to a molar ratio of 1: 1.4, mixing PPG and HDI according to the proportion, and stirring and reacting for 2 hours at 75 ℃ under the protection of nitrogen;

s2: chain extension, namely adding dihydroxybutyric acid and D-pantothenic acid (the molar ratio of the dihydroxybutyric acid to the D-pantothenic acid is 1: 0.56) into the system, continuing to react for 1.5h, and then cooling to 42 ℃ for reacting for 1.5 h; then adding neutralizing agent triethylamine for neutralization, fully stirring for 15min, wherein the neutralization degree is 95%; wherein the total adding amount of the dihydroxybutyric acid and the D-pantothenic acid is 5.1 percent of the total mass of the monomers;

s3: end-capping, crosslinking and modifying, namely adding ECH and 6-fluoro-7-piperazine-1-methyl-4-oxo- [1,3] thiazacyclo [3,2-a ] quinoline-3-carboxylic acid ethyl ester (the molar ratio of the two is 1: 1, and the total addition amount is 80.55% of the total mass of the monomers) into the system at 42 ℃ and reacting for 1 h;

s4: and (3) emulsifying, cooling the system to room temperature, adding deionized water, stirring at a high speed, and emulsifying for 1h to obtain the modified waterborne polyurethane color fixing agent.

Example 6:

the tie-dyeing method for cashmere products differs from example 1 in that:

the color fixing agent added in the softening finishing process of the step (6) is a modified waterborne polyurethane color fixing agent, and the preparation method is the same as that of the embodiment 5.

Example 7:

the tie-dyeing method for cashmere products differs from example 6 in that:

the color fixing agent is added in the softening finishing process of the step (6) and is a modified waterborne polyurethane color fixing agent, and the difference of the preparation method and the embodiment 5 is as follows: ECH and ethyl 6-fluoro-7-piperazine-1-methyl-4-oxo- [1,3] thiazepin [3,2-a ] quinoline-3-carboxylate were not added.

Example 8:

the tie-dyeing method for cashmere products differs from example 6 in that:

the color fixing agent is added in the softening finishing process of the step (6) and is a modified waterborne polyurethane color fixing agent, and the difference of the preparation method and the embodiment 5 is as follows: d-pantothenic acid was not added.

Comparative example 1:

the tie-dyeing method for cashmere products differs from example 6 in that:

the color fixing agent is added in the softening finishing process of the step (6) and is a modified waterborne polyurethane color fixing agent, and the difference of the preparation method and the embodiment 5 is as follows: ECH and ethyl 6-fluoro-7-piperazine-1-methyl-4-oxo- [1,3] thiazepin [3,2-a ] quinoline-3-carboxylate and D-pantothenic acid were not added.

Test example 1:

1. scanning Electron Microscope (SEM) testing

The surface morphology of the cashmere fabric samples was observed using a QUANTA-200 scanning electron microscope at an accelerating voltage of 5 kV.

The results of the above tests on the pretreated cashmere fabric and the surface-modified cashmere fabric of example 1 are shown in fig. 1 and 2. From the analysis in the figure, the scale on the surface of the reduction pretreated cashmere fabric has a broken feel because part of disulfide bonds in keratin are broken during the reduction treatment, so that stratum corneum particles are generated on the surface of the fiber; after the surface grafting modification treatment, a scanning electron microscope image shows that the surface of the cashmere fabric is provided with a layer of wrinkled film, which indicates that the cashmere fabric surface modification is successful.

2. Infrared Spectroscopy (FTIR) characterization

Testing by an 8400s Fourier transform infrared spectrometer, performing potassium bromide tabletting and coating on a sample, and then performing infrared spectrum testing to analyze each structural group on the spectrum. Wherein the test wave number range is 4000-500 cm^-1Resolution of 2cm^-1。

The results of the above tests on the modified aqueous polyurethane fixing agents prepared in comparative example 1 and example 5 are shown in fig. 3. From the analysis in the figure, the infrared spectra of the two substances are 2278cm^-1The absorption peaks with-NCO characteristics appear nearby, which shows that the-NCO in the raw materials are completely reacted. Compared with the infrared spectrum of the modified waterborne polyurethane prepared in the comparative example 1, the infrared spectrum of the substance prepared in the example 5 is 3000-2800 cm^-1The characteristic absorption peak intensity of methyl and methylene appeared in the range is increased; at 1714cm^-1The characteristic absorption peak intensity of nearby C ═ O bonds is obviously enhanced and ranges from 1500 cm to 1400cm^-1A benzene ring skeleton vibration characteristic absorption peak appears in the range; at 1270cm^-1A characteristic absorption peak of C-N bond appears nearby; at 1199cm^-1A characteristic absorption peak of C-F bond appears nearby; at 1048cm^-1A characteristic absorption peak of C-S bond appears nearby; the results show that the modified waterborne polyurethane color fixing agent in example 5 is successfully prepared.

3. Modified fiber felting property test

Determined according to the IWTO-20-69(E) method using YH-A cup spin quick test Infrared dyeing machine. The sample is pretreated before testing, and is placed in a standard atmosphere with the temperature of (22 +/-1) DEG C and the relative humidity of (65 +/-3)% for balancing for 24h, then 1g of the sample is put into a steel cup filled with 50mL of distilled water and is put into a dyeing machine, the temperature is set to be 42 ℃, the steel cup is rotated for 30min, and the sample is taken out and dried at the temperature of 50 ℃. The average density δ of the felted balls was calculated according to the following formula:

δ＝6/(πd_m ³)

wherein δ is the average density of the felted balls, g/cm³；d_mIs the average diameter of the felted balls, in cm.

The results of the above tests on the surface-modified fibers obtained in comparative example 1 and examples 1 to 4 are shown in Table 1:

TABLE 1 felting Performance test results

Sample (I)	δ(g/cm3)
		Comparative example 1	0.076
Example 1	0.078
		Example 2	0.041
Example 3	0.043
		Example 4	0.039

From the analysis in table 1, the average density of the felting balls of the surface modified fiber prepared in example 2 is significantly lower than that of the fibers prepared in comparative example 1 and example 1, which shows that the anti-felting performance of the fiber can be effectively enhanced by grafting the modified fiber with methyl 4-caffeoylquinic acid ester.

Test example 2:

cashmere fabric dyeing performance test

The color fastness to perspiration is tested according to GB/T3922-.

The results of the above tests on the cashmere products prepared in comparative example 1 and examples 1 to 8 are shown in table 2:

TABLE 2 dyeing Property test results

As can be seen from the analysis in Table 2, the acid perspiration fastness and the rubbing fastness of the cashmere product prepared in example 2 are higher than those of the cashmere product prepared in comparative example 1 and example 1, and the color fastness of the cashmere product can be improved to a certain extent by grafting and modifying the fiber surface with methyl 4-caffeoylquinic acid ester in the tie-dyeing process of the cashmere product, so that the grade of the acid perspiration fastness and the rubbing fastness of the cashmere product is improved. The color fastness to perspiration, the color fastness to rubbing and the color fastness to washing of the cashmere product prepared in example 5 are all obviously better than those of example 2, and the effect of example 6 is better than that of comparative example 1, and example 7 and example 8, which shows that the color fastness of the cashmere product is obviously enhanced by using the D-pantothenic acid and/or 6-fluoro-7-piperazine-1-methyl-4-oxo- [1,3] thiazacyclo [3,2-a ] quinoline-3-carboxylic acid ethyl ester modified waterborne polyurethane color fixing agent in the process of tie-dyeing the cashmere product, and under the condition that the D-pantothenic acid and the 6-fluoro-7-piperazine-1-methyl-4-oxo- [1,3] thiazacyclo [3,2-a ] quinoline-3-carboxylic acid ethyl ester are simultaneously added, the cashmere product has better effects of enhancing the color fastness to perspiration, the color fastness to rubbing and the color fastness to washing.

The Color-Eye computer Color measuring and matching system is used for determining the dyeing depth of the cashmere fabric, and the value is expressed by K/S value. Calculating the exhaustion degree of the cashmere fabric according to the following formula by the change of the absorbance of the dye solution at the maximum absorption wavelength:

degree of exhaustion%₀－A₁)/A₀

In the formula, A₀Is the absorbance of the dye solution before dyeing, L/(g cm); a. the₁The absorbance L/(g · cm) of the dyed dye solution is shown.

The results of the above tests on the cashmere products prepared in comparative example 1 and examples 1 to 8 are shown in table 3:

TABLE 3K/S values and results of the degree of exhaustion tests

From the analysis in table 3, the K/S value of the cashmere product prepared in example 2 is higher than that of the cashmere product prepared in comparative example 1 and example 1, which shows that the surface of the fiber is grafted and modified by methyl 4-caffeoylquinic acid ester in the process of tie-dyeing the cashmere product, and the dyeing depth of the dye on the cashmere fabric can be effectively enhanced. The exhaustion rate of the cashmere product prepared in the example 2 is obviously higher than that of the cashmere product prepared in the comparative example 1 and the example 1, which shows that the existence of the methyl 4-caffeoylquinic acid ester graft modified fiber can obviously enhance the exhaustion rate of cashmere fabric and accelerate the dye to diffuse into the fiber, thereby effectively shortening the time required by boiling dyeing.

Determination of fixation Rate

The test method refers to GB/T2319-.

The results of the above tests on the cashmere products prepared in comparative example 1 and examples 1 to 8 are shown in table 4:

table 4 fixation test results

Sample (I)	Degree of fixation/%)
		Comparative example 1	93.1
Example 1	92.3
		Example 2	95.9
Example 3	95.4
		Example 4	95.7
Example 5	99.4
		Example 6	98.0
Example 7	96.2
		Example 8	96.7

From the analysis in table 4, it can be seen that the fixation rate of the cashmere product prepared in example 2 is higher than that of comparative example 1 and example 1, which indicates that the surface of the fiber is modified by grafting methyl 4-caffeoylquinic acid ester in the process of tie-dyeing the cashmere product, and the dyeing effect of the dye on the cashmere fabric can be improved to a certain extent. The fixation rate of the cashmere product prepared in example 5 is obviously better than that of example 2, and the effect of example 6 is better than that of comparative example 1, and example 7 and example 8, which shows that the dyeing effect of the dye on the cashmere product is remarkably enhanced by using the D-pantothenic acid and/or 6-fluoro-7-piperazine-1-methyl-4-oxo- [1,3] thiazacyclo [3,2-a ] quinoline-3-carboxylic acid ethyl ester modified aqueous polyurethane fixing agent in the process of tie dyeing the cashmere product, and under the condition that the D-pantothenic acid and the 6-fluoro-7-piperazine-1-methyl-4-oxo- [1,3] thiazacyclo [3,2-a ] quinoline-3-carboxylic acid ethyl ester are simultaneously added, the dyeing effect of the cashmere product is better.

Conventional techniques in the above embodiments are known to those skilled in the art, and therefore, will not be described in detail herein.

The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.