A wool top feed woven fabric and a method of manufacturing the same

Abstract

The present application belongs to the field of wool fabric finishing, and provides a wool top raw fabric and a preparation method thereof. The present application forms wool fibers with controlled scale reduction and a keratin grafting layer by low-damage scale cutting of a hydrogen peroxide aqueous solution and sodium bicarbonate, removal of residual peroxide, and hydrolysis of keratin under the participation of carbodiimide hydrochloride and N-hydroxysuccinimide, and then the wool fibers are subjected to top preparation, spinning and weaving to obtain the fabric. The fabric can improve anti-felting, anti-pilling, dimensional stability and processing stability while maintaining the strength and air permeability of the wool fibers, solves the problem that it is difficult to balance the strength retention and anti-felting, and the processing stability and anti-pilling, and is suitable for the preparation and finishing of wool top raw fabric.

Description

Technical Field

[0001] This invention relates to the field of wool fiber fabric finishing, specifically to a wool top woven fabric and its preparation method. Background Technology

[0002] Wool fabrics, formed from wool tops through sizing, spinning, and weaving, are widely used in worsted garments, workwear, lightweight outerwear, and washable wool products. Their aesthetic value depends not only on their natural elasticity, warmth, and skin-friendliness, but also on factors such as dimensional stability after washing, resistance to felting and pilling, weaving stability, breaking strength, and breathability. With increasing consumer demand for machine washability, low care requirements, and long-term appearance retention, the gentle regulation of the scale structure on the wool fiber surface has become a crucial direction for wool fabric finishing. An ideal wool top processing technique should reduce the directional friction effect of the scales while maintaining the integrity of the keratin macrostructure. Furthermore, the treated fibers should still be able to smoothly undergo sizing, spinning, weaving, washing, setting, and steaming processes, thus balancing fabric appearance, dimensional stability, hand feel, strength retention, and production continuity.

[0003] Existing wool anti-felting treatments mainly include chlorine oxidation, peroxide oxidation, bio-enzyme treatment, resin or softening layer finishing, and multi-process combinations. While chlorine finishing can weaken the scale effect, it may introduce halogenated byproducts and yellowing problems. When oxidation or enzyme treatment is strengthened alone, it is often difficult to balance the improvement of the scale layer with the damage to wool keratin. Introducing resin or softening layer may improve smoothness but change the interfiber constraint, thus hindering anti-pilling and subsequent processing stability. For example, Chinese patent CN1693575A discloses a wool anti-felting finishing method, and its background technology has pointed out that proteases may enter the fiber interior through the gap between the scale and cortex layers and cause a decrease in strength. Chinese patent CN106758259A discloses a chlorine-free anti-shrinkage finishing process for wool tops, but its scheme still uses silicone resin and acrylic resin finishing components, which cannot directly answer the question of how to balance strength, anti-felting, and anti-pilling without forming a softening or smoothing finishing layer. Summary of the Invention

[0004] The purpose of this invention is to provide a wool top woven fabric and its preparation method, which solves the problem that it is difficult to balance mechanical strength and anti-felt shrinkage performance in the current wool fabric processing, and that processing stability and anti-pilling performance are mutually restrictive.

[0005] Existing descaling or smoothing finishing methods often involve a trade-off between reducing scale friction and maintaining keratin strength. This invention uses H2O2 and sodium bicarbonate to gently reduce scale height, and then uses a hydrolyzed keratin graft layer to compensate for surface damage and constrain hairs. This allows the descaling and drag reduction effects to mutually correct each other, resulting in a synergistic unity of strength retention, anti-felt shrinkage, anti-pilling, and weaving stability.

[0006] To achieve the above objectives, the present invention provides the following technical solution:

[0007] A wool sliver fabric is made from wool slivers as the main raw material through sliver preparation, spinning and weaving. The wool sliver fabric contains wool fibers with a low-damage scaled-hydrolyzed keratin graft layer, comprising 30.00-100.00 wt% of the total wool fiber mass.

[0008] The low-damage descaling-hydrolyzed keratin graft layer is formed by hydrolyzed keratin fixed to the surface of wool fibers that have undergone low-damage descaling treatment;

[0009] The low-damage descaling process is carried out using H2O2, an effective component provided by an aqueous hydrogen peroxide solution, and sodium bicarbonate.

[0010] The hydrolyzed keratin is fixed to the surface of the wool fiber via a carboxyl-amino coupling reaction involving 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide.

[0011] The wool fabric contains 85.00-100.00 wt% wool fibers.

[0012] Furthermore, the thickness of the low-damage descaling-hydrolyzed keratin graft layer on the surface of the treated wool fiber is 10-80 nm, as determined by scanning electron microscopy cross-section method. Based on the dry weight of the wool fiber before grafting treatment, the amount of hydrolyzed keratin grafted is 0.30-2.50 wt%, as determined by mass difference method. The scale height of the treated wool fiber is determined by scanning electron microscopy image method and is reduced by 20.00-60.00% compared with the same batch of unscaling treated wool fiber. The weight of the fabric woven from the wool top is 120-280 g / m².

[0013] Furthermore, the wool fiber having the low-damage descaling-hydrolyzed keratin graft layer is a low-damage descaling-hydrolyzed keratin graft wool fiber intermediate, which is prepared through the following steps:

[0014] A1. Provide wool strips or wool fibers, and wash the wool strips or wool fibers with deionized water to obtain pre-cleaned wool fibers;

[0015] A2. The pre-cleaned wool fibers are treated in a low-damage descaling solution containing H2O2 and sodium bicarbonate to obtain a low-damage descaling wool fiber precursor.

[0016] A3. The low-damage scaled wool fiber precursor is treated in deionized water containing sodium thiosulfate pentahydrate to reduce the residual peroxide content;

[0017] A4. The wool fibers treated with A3 are placed in a hydrolyzed keratin grafting solution for hydrolyzed keratin grafting treatment, wherein the hydrolyzed keratin grafting solution contains hydrolyzed keratin, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, N-hydroxysuccinimide and a buffer component formed by acetic acid and sodium acetate trihydrate.

[0018] A5. The wool fibers treated with A4 are washed with deionized water, dehydrated and dried to obtain the low-damage descaling-hydrolyzed keratin grafted wool fiber intermediate.

[0019] Furthermore, the process conditions for steps A1 to A3 are as follows:

[0020] In step A1, the wool strips or wool fibers are washed with deionized water at 30-45°C for 10-30 minutes.

[0021] In step A2, the amount of H2O2 active ingredient in the low-damage descaling solution is 0.50-3.00 wt% based on the dry weight of the wool fibers to be treated, the H2O2 active ingredient is provided by hydrogen peroxide aqueous solution, the amount of sodium bicarbonate is 0.20-1.50 wt% based on the dry weight of the wool fibers to be treated, the pH value of the bath solution is 8.00-9.50, the treatment temperature is 35-55℃, the treatment time is 15-60 min, and the operating pressure is 0.08-0.12 MPa;

[0022] In step A3, the low-damage scaled wool fiber precursor is treated in deionized water containing 0.10-1.00 wt% sodium thiosulfate pentahydrate based on the dry weight of the wool fiber to be treated at a bath ratio of 1:8-1:20 for 5-20 minutes at a temperature of 20-35°C, so that the residual peroxide content is not higher than 0.010 wt% based on the dry weight of the wool fiber after A3 treatment.

[0023] Furthermore, the process conditions for step A4 and the properties of the obtained intermediate are as follows:

[0024] In step A4, the bath ratio for the hydrolyzed keratin grafting treatment is 1:8-1:20. The hydrolyzed keratin grafting finishing solution used in the treatment contains 0.50-5.00 wt% hydrolyzed keratin, 0.05-0.80 wt% 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, and 0.03-0.50 wt% N-hydroxysuccinimide. The hydrolyzed keratin grafting finishing solution also contains a buffer component formed by acetic acid and sodium acetate trihydrate. The pH value of the bath solution is 5.00-6.20, the treatment temperature is 30-50℃, and the treatment time is 20-90 min.

[0025] The amount of hydrolyzed keratin grafted into the obtained low-damage scaling-hydrolyzed keratin grafted wool fiber intermediate was determined by the mass difference method and was 0.30-2.50 wt% based on the dry weight of the wool fiber before grafting treatment. The thickness of the low-damage scaling-hydrolyzed keratin grafted layer was determined by the scanning electron microscope cross-section method and was 10-80 nm. The breaking strength retention rate of wool single fiber was 85.00-99.00% compared with the same batch of wool fibers that were not treated with low-damage scaling and hydrolyzed keratin grafting.

[0026] Furthermore, the low-damage, scaled wool fiber precursor in step A2 is prepared through the following steps:

[0027] B1. Add the pre-cleaned wool fibers to deionized water at a bath ratio of 1:8-1:20;

[0028] B2. Add hydrogen peroxide aqueous solution and sodium bicarbonate to ensure that the amount of H2O2 effective component and sodium bicarbonate in the low-damage descaling solution meet the specified ranges respectively;

[0029] B3. Process according to the pH of the bath solution, the treatment temperature, the treatment time, and the operating pressure;

[0030] B4. Wash with deionized water until the pH of the washing solution is 6.00-8.00 to obtain the low-damage scaled wool fiber precursor;

[0031] The scale height of the low-damage scaled wool fiber precursor was determined by scanning electron microscopy and was reduced by 20.00-60.00% compared to the same batch of unscaled wool fibers. The breaking strength retention rate of the wool single fiber was 88.00-99.00% compared to the same batch of unscaled wool fibers.

[0032] Furthermore, the hydrolyzed keratin grafting solution in step A4 is prepared through the following steps:

[0033] C1. Weigh out the hydrolyzed keratin according to the dry weight of the wool fibers to be treated and dissolve or disperse it in deionized water to form an aqueous phase for preparing the hydrolyzed keratin grafting solution, wherein the amount of hydrolyzed keratin is 0.50-5.00 wt% based on the dry weight of the wool fibers to be treated;

[0034] C2. The pH of the aqueous phase obtained in C1 was adjusted to 5.00-6.20 using acetic acid and sodium acetate trihydrate;

[0035] C3. Add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide to the aqueous phase obtained in C2, wherein the amount of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride is 0.05-0.80 wt% based on the dry weight of the wool fibers to be treated, and the amount of N-hydroxysuccinimide is 0.03-0.50 wt% based on the dry weight of the wool fibers to be treated, and the amount of N-hydroxysuccinimide is 0.40-1.00 times the mass of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride;

[0036] C4. Pre-activate at 20-35℃ for 5-30 min to obtain the hydrolyzed keratin grafting solution;

[0037] The pH drift of the hydrolyzed keratin grafting solution from pH adjustment at C2 to the end of pre-activation at C4 is no greater than 0.30. The total amount of hydrolyzed keratin, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide is 0.58-6.30 wt% based on the dry weight of the wool fiber to be treated.

[0038] Furthermore, the post-processing in step A5 includes:

[0039] D1. Wash the wool fibers treated with A4 with deionized water 2-5 times to make the pH of the washing solution 5.50-7.50;

[0040] D2. Remove surface moisture to achieve a liquid retention rate of 50.00-90.00% for the wool fibers after dehydration;

[0041] D3. Dry at 50-80℃ for 10-60 min;

[0042] D4. Equilibrate for 4-24 hours in an environment with a temperature of 20-30℃ and a relative humidity of 55.00-75.00%;

[0043] D5. The quality control indicators of the obtained low-damage descaling-hydrolyzed keratin grafted wool fiber intermediate include: the amount of hydrolyzed keratin grafted is determined by the mass difference method and is 0.30-2.50 wt% based on the dry weight of wool fiber before grafting treatment; the thickness of the low-damage descaling-hydrolyzed keratin graft layer is determined by the scanning electron microscope cross-section method and is 10-80 nm; and the amount of unfixed protein residue is not higher than 0.50 wt% based on the dry weight of wool fiber before grafting treatment.

[0044] Furthermore, the average molecular weight of the hydrolyzed keratin is 1-30 kDa;

[0045] The hydrolyzed keratin forms a continuous or island-like graft layer on the surface of the wool fibers, and the surface coverage of the low-damage scaling-hydrolyzed keratin graft layer is 70.00-95.00%.

[0046] Based on the total mass of wool fibers in the wool fabric, the wool fiber content having the low-damage scaled-hydrolyzed keratin graft layer is 30.00-100.00 wt%, and the remainder is ungrafted wool fibers without the low-damage scaled-hydrolyzed keratin graft layer.

[0047] The wool fabric is woven from yarn containing wool fibers. The yarn has a linear density of 10-30 tex and a twist coefficient of 80-140. The warp density of the wool fabric is 150-420 threads / 10cm, and the weft density is 130-380 threads / 10cm. The wool fabric is plain weave, twill weave, serge, varnish, or jacquard.

[0048] The wool tops woven fabric meets the following properties: pilling grade of 3.50-5.00 as measured by GB / T4802.2; dimensional change rate after washing and drying of -3.00% to +1.00% as measured by GB / T8630; breaking strength retention rate of 85.00-99.00% relative to the benchmark wool fabric that has not undergone low-damage scaling and hydrolyzed keratin grafting treatment but has the same wool fiber content, linear density, twist coefficient, warp density, weft density and weave structure; air permeability retention rate of 75.00-99.00% relative to the benchmark wool fabric; and pH value of the fabric water extract of 4.00-8.50.

[0049] As a concept of this invention, a low-damage descaling-hydrolyzed keratin graft layer design is employed, primarily to achieve a synergistic balance between the mechanical strength of wool fibers and the anti-felting properties of wool fabrics. In existing technologies, oxidation or enzymatic treatment intensity is typically increased to reduce scale directional friction, but excessive treatment can damage the keratin structure and reduce breaking strength; conversely, maintaining strength requires reducing the degree of descaling, which retains more scale protrusions and weakens the anti-felting effect. This invention first performs low-damage descaling using H2O2 and sodium bicarbonate, then fixes the hydrolyzed keratin through a carboxyl-amino coupling reaction involving 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide. This allows descaling friction reduction and keratin surface repair to work together on the same fiber surface, thereby achieving a balance between strength retention, dimensional stability, and anti-felting effects.

[0050] This invention also provides a method for preparing a fabric woven from wool tops, comprising the following steps:

[0051] S1. The wool tops or wool fibers are pre-cleaned, low-damage descaling, residual peroxide removal, hydrolyzed keratin grafting and post-treatment to obtain a low-damage descaling-hydrolyzed keratin grafted wool fiber intermediate.

[0052] S2. The low-damage descaling-hydrolyzed keratin grafted wool fiber intermediate is processed into slivers, spun, woven, and finished to obtain the wool sliver woven fabric.

[0053] Further, in step S2, the spinning is compact spinning, Siro spinning, or ring spinning, and the linear density of the wool yarn obtained by the spinning is 10-30 tex, and the twist coefficient is 80-140; the weaving is carried out under the conditions of warp tension of 0.10-0.45 cN / dtex and weaving speed of 200-600 r / min, and the resulting greige fabric is subjected to low-tension washing, setting and steaming treatment, with a setting temperature of 90-130℃ and a setting time of 30-180s.

[0054] Further, in step S1, the quality control endpoints of the low-damage scaling-hydrolyzed keratin grafted wool fiber intermediate include: the residual peroxide content is no higher than 0.010 wt% based on the dry weight of the wool fiber after residual peroxide removal treatment; the unfixed protein residue is no higher than 0.50 wt% based on the dry weight of the wool fiber before grafting treatment; the unfixed protein residue is the ratio of the sum of the total protein content in the washing solution obtained from 2-5 washes to the dry weight of the wool fiber before grafting treatment; the wool single fiber breaking strength retention rate is 85.00-99.00% relative to the same batch of wool fibers that have not undergone low-damage scaling and hydrolyzed keratin grafting treatment; and the washing solution pH value is 5.50-7.50.

[0055] Furthermore, in step S1, the pre-cleaning, low-damage scaling, residual peroxide removal, hydrolyzed keratin grafting, and post-treatment of the low-damage scaling-hydrolyzed keratin grafted wool fiber intermediate are carried out in a dyeing vat, skein dyeing machine, strip dyeing equipment, or continuous low-tension treatment equipment. During the treatment process, the batch-to-batch deviation of the pH value of the bath solution between different batches of the same treatment step is not greater than 0.30, and the batch-to-batch deviation of the solid content of the bath solution is not greater than 0.50 wt% based on the mass of the bath solution.

[0056] Further, in step S1, the hydrolyzed keratin grafting finishing solution used to prepare the low-damage scaling-hydrolyzed keratin grafted wool fiber intermediate is prepared using hydrolyzed keratin, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, N-hydroxysuccinimide, and a buffer solution formed by acetic acid and sodium acetate trihydrate. During preparation, the pH of the aqueous phase containing hydrolyzed keratin is adjusted to 5.00-6.20, and then 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide are added. The solution is pre-activated at 20-35°C for 5-30 min, and then used for hydrolyzed keratin grafting treatment within 0-60 min after preparation.

[0057] Furthermore, in steps S1 and S2, amino silicone oil, silicone resin, polyurethane resin or cationic polymer is not used to form a soft or smooth finishing layer on the surface of the wool fibers.

[0058] Further, the low-damage descaling solution is prepared according to the dry weight of the wool fibers to be treated at a bath ratio of 1:8-1:20. The mass fraction of the hydrogen peroxide aqueous solution is selected from 3.00wt%, 10.00wt%, 27.50wt%, 30.00wt%, and 50.00wt%, and the amount added is calculated based on the mass of the effective H2O2 component in the hydrogen peroxide aqueous solution, so that the amount of effective H2O2 component in the low-damage descaling solution is 0.50-3.00wt% based on the dry weight of the wool fibers to be treated, and the amount of sodium bicarbonate is 0.20-1.50wt% based on the dry weight of the wool fibers to be treated. Before the low-damage descaling treatment, the dry weight of the wool fibers, the total mass of the low-damage descaling solution, the mass of effective H2O2 component added, and the mass of sodium bicarbonate added are recorded, and the amount of effective H2O2 component is calculated by dividing the mass of effective H2O2 component added by the dry weight of the wool fibers. The prepared low-damage descaling solution enters the low-damage descaling treatment step, and the treated wool fibers enter the residual peroxide removal step.

[0059] Furthermore, the scale height reduction rate of the low-damage descaling wool fiber precursor was determined by scanning electron microscopy. The test samples included wool fibers from the same batch that had not undergone descaling treatment and wool fibers that had undergone low-damage descaling treatment. After drying, fixing, and conducting treatment, fiber surface images were acquired for each group of samples, and the scale protrusion height was recorded. The scale height reduction rate was calculated as follows: scale height reduction rate = (average scale height of undescaled wool fibers - average scale height of wool fibers after low-damage descaling treatment) / average scale height of undescaled wool fibers × 100%. The calculation result was used as the quality control data for the low-damage descaling treatment step.

[0060] Furthermore, the hydrolyzed keratin grafting finishing solution uses the hydrolyzed keratin aqueous phase as the preparation basis. Hydrolyzed keratin is weighed according to the dry weight of the wool fibers to be treated and dissolved or uniformly dispersed in deionized water. When the average molecular weight of the hydrolyzed keratin is greater than 5 kDa, the hydrolyzed keratin is first partially wetted with deionized water, and then the wetted hydrolyzed keratin is added to the remaining deionized water to form the hydrolyzed keratin aqueous phase. Acetic acid and sodium acetate trihydrate are used to adjust the pH. The concentration was adjusted to 5.00-6.20, followed by the addition of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide. The amount of hydrolyzed keratin was 0.50-5.00 wt% based on the dry weight of the wool fibers to be treated, the amount of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride was 0.05-0.80 wt% based on the dry weight of the wool fibers to be treated, the amount of N-hydroxysuccinimide was 0.03-0.50 wt% based on the dry weight of the wool fibers to be treated, and the amount of N-hydroxysuccinimide was 0.40-1.00 times the mass of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride. The resulting system was pre-activated at 20-35°C for 5-30 min to form a hydrolyzed keratin grafting finishing solution, and then entered the hydrolyzed keratin grafting treatment step within 0-60 min after preparation.

[0061] Furthermore, the hydrolyzed keratin grafting treatment uses wool fibers after residual peroxide removal as the treatment object, adopts a bath ratio of 1:8-1:20, maintains the pH value of the hydrolyzed keratin grafting finishing solution at 5.00-6.20, the treatment temperature at 30-50℃, and the treatment time at 20-90 min. When the treatment is completed, the pH value of the bath solution does not change by more than 0.10 in the last 10 min. The treated wool fibers enter the deionized water washing, desolvation, drying and equilibration steps.

[0062] Furthermore, the amount of hydrolyzed keratin grafted is determined by the mass difference method. The sample to be tested is a low-damage scaled-hydrolyzed keratin grafted wool fiber intermediate that has undergone hydrolyzed keratin grafting treatment and has been washed, dehydrated, dried and equilibrated. The dry mass of the wool fiber before grafting treatment is m0, and the dry mass of the low-damage scaled-hydrolyzed keratin grafted wool fiber intermediate after grafting treatment is m1. The amount of hydrolyzed keratin grafted is calculated according to (m1-m0) / m0×100%, and the obtained grafting amount is used as the quality control data of the low-damage scaled-hydrolyzed keratin grafted wool fiber intermediate before it enters the sliver making and spinning steps.

[0063] Furthermore, the thickness of the low-damage descaling-hydrolyzed keratin graft layer is determined by scanning electron microscopy cross-sectional method. The test sample is a low-damage descaling-hydrolyzed keratin grafted wool fiber intermediate after hydrolyzed keratin grafting, washing, and drying. After embedding the test sample, cross-sectional sample preparation is performed, and fiber cross-sectional images are acquired by scanning electron microscopy. The distance between the outer boundary of the low-damage descaling-hydrolyzed keratin graft layer and the surface of the wool fiber matrix is ​​recorded. The cross-sectional images of low-damage descaling wool fibers in the same batch that have not undergone hydrolyzed keratin grafting treatment are used as references for thickness boundary determination. The continuous or locally continuous thin layer region located on the outer surface of the fiber after grafting treatment and added relative to the reference sample is regarded as the low-damage descaling-hydrolyzed keratin graft layer region. The obtained thickness data is used to determine whether the low-damage descaling-hydrolyzed keratin grafted wool fiber intermediate enters the subsequent sliver preparation and spinning steps.

[0064] Furthermore, the amount of unfixed protein residue was determined by the eluent detection. The sample to be tested was a low-damage descaling-hydrolyzed keratin grafted wool fiber intermediate after hydrolyzed keratin grafting treatment. The low-damage descaling-hydrolyzed keratin grafted wool fiber intermediate was washed 2-5 times with deionized water. The total protein content in each wash was collected and measured. The sum of the total protein content in each wash was divided by the dry weight of the wool fiber before grafting treatment to obtain the amount of unfixed protein residue. The amount of unfixed protein residue was used as the criterion for the end of post-processing. The total protein in the wash included unfixed hydrolyzed keratin and intrinsic wool peptides that could be eluted from the surface of the wool fiber during the low-damage descaling and grafting treatments.

[0065] Furthermore, the surface coverage of the low-damage descaling-hydrolyzed keratin graft layer is determined by microscopic image analysis of the wool fiber surface. The sample to be tested is an intermediate of low-damage descaling-hydrolyzed keratin grafted wool fiber after hydrolyzed keratin grafting and drying. After acquiring images of the wool fiber surface, the ratio of the area covered by the low-damage descaling-hydrolyzed keratin graft layer to the area of ​​the corresponding observed area on the wool fiber surface is calculated. The surface images of low-damage descaling wool fibers in the same batch that have not undergone hydrolyzed keratin grafting are used as a reference for determining the coverage area. The thin layer area that appears with continuous or partially continuous boundaries relative to the reference sample after grafting treatment, covering the edge of the scales or the surface of the scales, is counted as the graft layer coverage area. The obtained area ratio is used as the surface coverage rate and is used to determine the mixing ratio of treated wool fibers with the low-damage descaling-hydrolyzed keratin graft layer to ungrafted wool fibers.

[0066] Furthermore, the wool single fiber breaking strength retention rate was determined using wool fibers from the same batch that had not undergone low-damage scaling and hydrolyzed keratin grafting treatment as the baseline sample, and wool fibers that had undergone low-damage scaling and hydrolyzed keratin grafting treatment as the treated sample. The single fiber breaking strength of the baseline sample and the treated sample were measured separately, and the wool single fiber breaking strength retention rate was calculated as: wool single fiber breaking strength retention rate = single fiber breaking strength of treated sample / single fiber breaking strength of baseline sample × 100%. The results were used as the release data for the low-damage scaling-hydrolyzed keratin grafted wool fiber intermediate before it entered the sliver preparation step.

[0067] Furthermore, the breaking strength retention rate and air permeability retention rate of the wool top woven fabric are based on wool fabrics with the same wool fiber content, linear density, twist coefficient, warp density, weft density and weave structure but without low-damage scaling and hydrolyzed keratin grafting treatment. Wool fabrics woven from low-damage scaling-hydrolyzed keratin grafted wool fiber intermediates are used as treated samples. The breaking strength and air permeability of the reference sample and the treated sample are measured respectively, and the breaking strength retention rate and air permeability retention rate are calculated according to the ratio of the measured value of the treated sample to the measured value of the reference sample.

[0068] Furthermore, the low-tension washing treatment is carried out under finishing tension conditions where both the warp and weft directions are lower than the weaving tension. The greige fabric after washing treatment enters the setting treatment, with a setting temperature of 90-130℃ and a setting time of 30-180s. The set fabric then enters the steaming treatment. The steamed wool fabric is used as the woven fabric of the wool tops for testing of weight, pilling grade, dimensional change rate, breaking strength retention rate, air permeability retention rate, and pH value of water extract.

[0069] As another aspect of this invention, it employs a continuous process of pre-cleaning, low-damage descaling, residual peroxide removal, hydrolyzed keratin grafting, post-treatment, sliver preparation, spinning, weaving, and finishing. This process is primarily used to achieve, fix, or amplify the aforementioned synergistic effects. Conventional processes that only emphasize initial descaling can easily lead to decreased strength and increased hairiness in subsequent sliver preparation and spinning; conversely, those that only emphasize post-finishing smoothness may weaken fiber surface constraints and affect anti-pilling and anti-fuzzing properties. This preparation method improves processing uniformity through pre-cleaning, reduces subsequent grafting interference through residual peroxide removal, stabilizes the surface layer through hydrolyzed keratin grafting under buffered conditions, and maintains the post-weaving structure through low-tension washing, setting, and steaming, allowing the modified fiber surface state to continue to play a role during fabric formation.

[0070] Low-damage descaling primarily addresses the felting problem caused by directional friction of wool scales. However, excessively high levels of H2O2, sodium bicarbonate, processing temperature, or processing time can lead to over-oxidation of the keratin structure and reduce the breaking strength of individual wool fibers. Hydrolyzed keratin grafting layers mainly compensate for fiber surface damage and constrain hairiness; however, excessive grafting amount or coverage can increase inter-fiber interface resistance and affect sliver forming, spinning, and weaving stability. This invention achieves mutual correction between low-damage descaling and hydrolyzed keratin grafting layers through residual peroxide removal, acetic acid and sodium acetate trihydrate buffering, coupling of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide, and ratio matching, ultimately balancing mechanical strength, felting resistance, pilling resistance, and processing stability.

[0071] Beneficial technical effects

[0072] 1. Low-damage descaling treatment using H2O2 and sodium bicarbonate can controllably reduce the scale height of wool fibers, weaken the directional felting drive during washing and friction, and avoid damage to wool keratin caused by high-intensity oxidation or chlorine finishing. This helps to achieve a balance between improving anti-felting and maintaining fiber strength.

[0073] 2. By hydrolyzing keratin and fixing it onto the surface of wool fibers with the participation of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide, a graft layer compatible with the properties of wool keratin can be formed, which can compensate and constrain the surface after scaling, thereby reducing the tendency of loose hair and pilling.

[0074] 3. By removing residual peroxides, buffering with acetic acid and sodium acetate trihydrate, and controlling pre-activation, the interference of scale residues on hydrolyzed keratin grafting can be reduced, making the amount of hydrolyzed keratin grafting, graft layer thickness, and surface coverage controllable. This is beneficial to improving batch-to-batch processing stability and adaptability to subsequent sliver making, spinning, and weaving.

[0075] 4. By continuously integrating the low-damage scaling-hydrolyzed keratin grafted wool fiber intermediate with sliver preparation, spinning, weaving, and low-tension finishing, the fiber surface modification effect can be transformed into dimensional stability, anti-pilling, and breathability retention effects at the fabric level, avoiding excessive constraints on the processing and wearing performance of wool fabrics caused by a simple smoothing finishing layer. Attached Figure Description

[0076] Figure 1 The diagram shows the differential distribution of scale height reduction rate for Example 1, Comparative Example 9, and Comparative Example 10.

[0077] Figure 2 The cumulative distribution of scale height reduction rate for Example 1, Comparative Example 9, and Comparative Example 10 is shown in the diagram.

[0078] Figure 3 The image shows the difference in graft layer thickness distribution for Example 1, Comparative Example 9, and Comparative Example 10.

[0079] Figure 4 The cumulative surface coverage distribution maps are for Example 1, Comparative Example 9, and Comparative Example 10.

[0080] Figure 5 The image shows a superimposed FTIR absorption spectrum of Example 1, Comparative Example 10, and Comparative Example 7.

[0081] Figure 6 The above are XPS wide scan overlay images of Example 1, Comparative Example 10, and Comparative Example 7.

[0082] Figure 7 The XPS scatter plot shows the average percentage of elemental atoms in Example 1, Comparative Example 10, and Comparative Example 7.

[0083] Figure 8 The scatter plot shows the average peak area ratio of FTIR amides for Example 1, Comparative Example 10, and Comparative Example 7.

[0084] Figure 9 The scatter plot shows the average value of the hydrolyzed keratin grafting amount in Example 1, Comparative Example 5, and Comparative Example 7.

[0085] Figure 10 This is a scatter plot showing the mean of unfixed protein residues in Examples 1, 5, and 7.

[0086] Figure 11 This is a scatter plot showing the average residual peroxide content of Examples 1, 5, and 7.

[0087] Figure 12 This is a two-dimensional correlation diagram between the grafting amount and the amount of unfixed protein residue in Examples 1, 5, and 7.

[0088] Figure 13 This is a scatter plot of the average value of pilling and fuzzing levels for Example 1, Comparative Example 8, and Comparative Example 11.

[0089] Figure 14 The scatter plot shows the absolute values ​​of the dimensional change rates of Example 1, Comparative Example 8, and Comparative Example 11.

[0090] Figure 15 This is a two-dimensional balance diagram of the retention rate of breaking strength and the retention rate of air permeability for Example 1, Comparative Example 8, and Comparative Example 11.

[0091] Figure 16 Normalized curves of the overall fabric performance of Example 1, Comparative Example 8, and Comparative Example 11.

[0092] Figure 17 This is a macroscopic optical photograph of the plain wool strip woven fabric with a wool fiber content of 100.00 wt% obtained in Example 1.

[0093] Figure 18 This is a scanning electron microscope image of the low-damage scaling-hydrolyzed keratin grafted wool fiber intermediate from Example 1; Figure 18 a is a low-magnification SEM image of the overall morphology of the low-damage scaling-hydrolyzed keratin-grafted wool fiber intermediate in Example 1; Figure 18 b is a medium-magnification SEM image of the morphology of the scaly cuticle of wool fibers with low-damage scaling-hydrolyzed keratin grafting in Example 1; Figure 18 c is a high-magnification SEM image of the edge rounding and blunting of wool fiber scales and the local thin layer coverage of the grafted layer in Example 1 with low-damage scaling-hydrolyzed keratin grafting; Figure 18 d is a cross-sectional SEM image of the thickness and fiber cross-sectional structure of the low-damage scaling-hydrolyzed keratin graft layer in Example 1.

[0094] Figure 19 This is a transmission electron microscope characterization image of wool fibers grafted with low-damage scaling and hydrolyzed keratin in Example 1. Figure 19 a is a bright-field TEM image of the interface between the stratum corneum and cortex of a cross-section of a low-damage scaling-hydrolyzed keratin-grafted wool fiber in Example 1; Figure 19 b is a magnified TEM image of the morphology of the grafted layer on the outer surface of the low-damage scaling-hydrolyzed keratin grafted wool fiber in Example 1. Detailed Implementation

[0095] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings.

[0096] Example 1

[0097] Overall production scale and product form

[0098] In this embodiment, 10.00 kg of low-damage, scaled-hydrolyzed keratin-grafted wool fiber intermediate was prepared. 3.00 kg of this intermediate was blended with 7.00 kg of ungrafted wool fibers from the same batch. The resulting fabric, consisting of a plain weave wool sliver with 100.00 wt% wool fiber content, was produced through sliver preparation, compact spinning, weaving, and finishing. The fabric in this embodiment has a weight of 120 g / m², a yarn linear density of 10 tex, a twist coefficient of 80, a warp density of 150 threads / 10 cm, and a weft density of 130 threads / 10 cm.

[0099] Raw materials, components or material specifications

[0100] The wool tops are commercially available worsted wool tops, with the moisture content calculated by drying at 105℃ to constant weight. The hydrolyzed keratin is commercially available hydrolyzed keratin with an average molecular weight of 1 kDa; the solid content is calculated using the drying method and used for feed calculations. The hydrogen peroxide aqueous solution is a commercially available 3.00 wt% aqueous solution. Sodium bicarbonate, sodium thiosulfate pentahydrate, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, N-hydroxysuccinimide, acetic acid, and sodium acetate trihydrate are all commercially available analytical grade reagents. The conductivity of deionized water is not higher than 5 μS / cm. All raw materials are free of amino silicone oil, silicone resin, polyurethane resin, or cationic polymers.

[0101] Step A1: Pre-cleaning

[0102] Take 10.00 kg of wool tops (dry weight) and place them in a low-tension dyeing vat. Add deionized water at a liquor ratio of 1:8 and wash at 30℃ with a low-speed circulation of 60 r / min for 10 minutes. After draining the washing solution, rinse once with deionized water and dehydrate until the liquid content is approximately 80.00%, obtaining pre-cleaned wool fibers. This step is carried out under normal atmospheric pressure. The completion criterion is that no obvious suspended impurities are observed in the drained washing solution and the pH value of the washing solution is 6.80.

[0103] Step A2: Low-damage descaling treatment

[0104] A low-damage descaling solution was prepared at a bath ratio of 1:8. First, deionized water was added to the equipment. After adding hydrogen peroxide solution and sodium bicarbonate, the total mass of the bath solution was brought to approximately 80.00 kg. Then, 1.667 kg of hydrogen peroxide solution was added, equivalent to 0.050 kg of effective H2O2, corresponding to 0.50 wt% of the dry mass of the wool fibers to be treated. Subsequently, 0.020 kg of sodium bicarbonate was added, corresponding to 0.20 wt% of the dry mass of the wool fibers to be treated. The pH of the bath solution was adjusted and stabilized at 8.00. After heating to 35°C, pre-cleaned wool fibers were added. The solution was circulated for 15 minutes at an operating pressure of 0.08 MPa, with the circulation flow rate controlled in the low-tension mode of the equipment, ensuring no significant fiber entanglement occurred. The treatment was considered complete when the pH of the bath solution remained between 7.90 and 8.10 and no visible yellowing was observed on the fiber surface.

[0105] Step A3: Residual peroxide removal

[0106] After draining the low-damage descaling solution, the fibers were washed with deionized water until the pH of the washing solution reached 6.00, yielding a low-damage descaled wool fiber precursor. Subsequently, 0.010 kg of deionized water containing sodium thiosulfate pentahydrate was added at a bath ratio of 1:8. The treatment temperature was 20℃, the treatment time was 5 min, and the mixture was circulated at 50 rpm under normal air pressure. After treatment, the residual peroxide content was verified by a semi-quantitative colorimetric method and iodometric titration. The residual peroxide content was 0.010 wt%, meeting the requirements for proceeding to the hydrolyzed keratin grafting treatment.

[0107] Step A4: Hydrolyzed keratin grafting treatment

[0108] Based on the dry weight of the wool fibers to be treated, 0.050 kg of hydrolyzed keratin was weighed and dispersed in deionized water. The pH was adjusted to 5.00 using a buffer solution formed by acetic acid and sodium acetate trihydrate. Subsequently, 0.005 kg of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and 0.003 kg of N-hydroxysuccinimide were added. The amount of N-hydroxysuccinimide was 0.60 times the mass of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, and the total amount of the three was 0.58 wt%. The resulting system was pre-activated at 20 °C for 5 min, with a pH drift of 0.20. Within 0 min of the final preparation, wool fibers treated with A3 were added. The grafting bath ratio was 1:8, the pH of the bath solution was maintained at 5.00, the treatment temperature was 30 °C, the treatment time was 20 min, and the circulation rate was 60 r / min. The criteria for completion of treatment are that the pH value of the bath solution is within the range of 5.00-6.20 and the change does not exceed 0.10 in the last 10 minutes, and there is no obvious adhesion on the fiber surface.

[0109] Step A5: Post-processing

[0110] The wool fibers treated with A4 were washed twice with deionized water to achieve a final wash pH of 5.50. Surface moisture was then removed, resulting in a 50.00% liquid retention rate in the wool fibers. The fibers were then dried in a low-speed hot air cycle at 50°C for 10 minutes. After drying, the fibers were equilibrated at 20°C and 55.00% relative humidity for 4 hours to obtain a low-damage, scaled-hydrolyzed keratin-grafted wool fiber intermediate. The completion criteria for this step were a loose fiber feel, absence of clumps, and a moisture content meeting the requirements for subsequent sliver preparation.

[0111] Step S2: Sliver preparation, spinning, weaving and finishing

[0112] 3.00 kg of the low-damage, scaled-hydrolyzed keratin-grafted wool fiber intermediate from this embodiment was blended with 7.00 kg of ungrafted wool fiber from the same batch, so that the wool fiber content with the low-damage, scaled-hydrolyzed keratin-grafted layer was 30.00 wt% of the total wool fiber mass in the wool fabric. After sliver preparation, the wool was spun into a wool yarn with a linear density of 10 tex and a twist coefficient of 80. Weaving was performed at a warp tension of 0.10 cN / dtex and a weaving speed of 200 r / min to produce a plain weave fabric. The fabric underwent low-tension washing, setting, and steaming treatments. The low-tension washing was performed at a finishing tension lower than the weaving tension in both the warp and weft directions. The setting temperature was 90°C, and the setting time was 30 s. After steaming, the wool sliver was obtained for weaving.

[0113] Quality testing methods and results

[0114] Scanning electron microscopy (SEM) was used to determine the scale height reduction rate of the low-damage scaled wool fiber precursor, which was 20.00% ± 0.80%. The breaking strength retention rate of wool single fibers was 99.00% ± 0.60% compared to the same batch of unscaled wool fibers. The amount of hydrolyzed keratin grafted was 0.30 wt% ± 0.02 wt% as determined by the mass difference method. The thickness of the low-damage scaled-hydrolyzed keratin graft layer was 10 nm ± 1 nm as determined by the cross-sectional method of scanning electron microscopy. The surface coverage of the low-damage scaled-hydrolyzed keratin graft layer was 70.00% ± 1.20%. The amount of unfixed protein residue was 0.50 wt% ± 0.02 wt%. The breaking strength retention rate of wool single fibers after grafting treatment was 99.00% ± 0.50%. The fabric's pilling grade was measured to be 3.50 according to GB / T4802.2-2008, and its dimensional change rate after washing and drying was -3.00%±0.10% according to GB / T8630-2013. The fabric's breaking strength retention rate was 99.00%±0.70%, its air permeability retention rate was 99.00%±0.60%, and the pH value of the fabric's water extract was 4.00±0.05.

[0115] Features and application scenarios of this embodiment

[0116] This embodiment adopts a relatively conservative low-ratio scheme and mild process conditions, which results in a low proportion of wool fibers in the wool fabric, finer yarns, and a plain weave fabric structure. It is suitable for lightweight worsted wool fabrics and wool tops that require high softness, breathability, and low processing load.

[0117] Example 2

[0118] Overall production scale and product form

[0119] In this embodiment, 10.00 kg of low-damage, scaled-hydrolyzed keratin-grafted wool fiber intermediate was prepared and used entirely for sliver preparation, Sirospinning, weaving, and finishing to produce a twill wool sliver fabric with a wool fiber content of 100.00 wt%. The fabric in this embodiment has a weight of 280 g / m², a yarn linear density of 30 tex, a twist coefficient of 140, a warp density of 420 threads / 10 cm, and a weft density of 380 threads / 10 cm.

[0120] Raw materials, components or material specifications

[0121] The wool tops are commercially available worsted wool tops, and all ingredients are calculated based on dry weight. The hydrolyzed keratin is commercially available hydrolyzed keratin with an average molecular weight of 30 kDa. The hydrogen peroxide aqueous solution is a commercially available 50.00 wt% aqueous solution. Sodium bicarbonate, sodium thiosulfate pentahydrate, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, N-hydroxysuccinimide, acetic acid, and sodium acetate trihydrate are all commercially available analytical grade reagents. The hydrolyzed keratin is pre-wetted with deionized water before use to avoid direct aggregation. All raw materials are free of amino silicone oil, silicone resin, polyurethane resin, or cationic polymers.

[0122] Step A1: Pre-cleaning

[0123] Take 10.00 kg of wool tops (dry weight) and place them in a strip dyeing apparatus. Add deionized water at a liquor ratio of 1:20 and wash at 45℃ and 80 r / min for 30 min. Then drain the washing solution and rinse twice with deionized water to obtain pre-cleaned wool fibers. This step is carried out under normal atmospheric pressure. The completion criterion is that the pH value of the final washing solution is 7.20 and there is no obvious foam residue.

[0124] Step A2: Low-damage descaling treatment

[0125] A low-damage descaling solution was prepared at a bath ratio of 1:20. First, deionized water was added, followed by hydrogen peroxide solution and sodium bicarbonate to bring the total bath mass to approximately 200.00 kg. Then, 0.600 kg of hydrogen peroxide solution was slowly added, equivalent to 0.300 kg of H2O2 (3.00 wt% of the dry weight of the wool fibers to be treated). Subsequently, 0.150 kg of sodium bicarbonate was added, corresponding to 1.50 wt% of the dry weight of the wool fibers. The pH of the bath was adjusted and stabilized at 9.50. After heating to 55°C, pre-cleaned wool fibers were added and treated at an operating pressure of 0.12 MPa for 60 min with a circulation rate of 90 r / min. Low-tension circulation was maintained throughout the treatment. The completion criterion was that the pH of the bath remained between 9.35 and 9.50 and the fiber bundles remained dispersible.

[0126] Step A3: Residual peroxide removal

[0127] After draining the low-damage descaling solution, the fibers were washed with deionized water until the pH of the washing solution reached 8.00, yielding a low-damage descaled wool fiber precursor. Subsequently, 0.100 kg of deionized water containing sodium thiosulfate pentahydrate was added at a bath ratio of 1:20, and the mixture was treated at 35°C for 20 min, circulating at 70 rpm under normal air pressure. After treatment, the residual peroxide content was measured to be 0.008 wt%, meeting the requirements for proceeding to the hydrolyzed keratin grafting treatment.

[0128] Step A4: Hydrolyzed keratin grafting treatment

[0129] Based on the dry weight of the wool fibers to be treated, 0.500 kg of hydrolyzed keratin was weighed and dispersed in deionized water. The pH was adjusted to 6.20 using a buffer solution formed by acetic acid and sodium acetate trihydrate. Subsequently, 0.080 kg of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and 0.050 kg of N-hydroxysuccinimide were added. The amount of N-hydroxysuccinimide was 0.625 times the mass of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, and the total amount of the three was 6.30 wt%. The resulting system was pre-activated at 35 °C for 30 min, with a pH drift of 0.30. Wool fibers treated with A3 were added within 60 min after the initial treatment. The grafting bath ratio was 1:20, the pH of the bath was maintained at 6.20, the treatment temperature was 50 °C, the treatment time was 90 min, and the circulation rate was 80 r / min. The criteria for completion are that the fiber bundles are dispersible and there is no obvious flocculation or deposition in the bath liquid.

[0130] Step A5: Post-processing

[0131] The wool fibers treated with A4 were washed five times with deionized water until the pH of the final wash solution was 7.50. Surface moisture was then removed, resulting in a 90.00% liquid retention rate in the wool fibers after dehydration. The fibers were then dried in hot air at 80°C for 60 minutes, followed by equilibration at 30°C and 75.00% relative humidity for 24 hours to obtain a low-damage, scaled-hydrolyzed keratin-grafted wool fiber intermediate. The completion criterion for this step was that the amount of unfixed protein residue in the wash solution did not exceed the quality control requirements and the fibers could be easily opened.

[0132] Step S2: Sliver preparation, spinning, weaving and finishing

[0133] In this embodiment, all the low-damage, scaled-hydrolyzed keratin-grafted wool fiber intermediates are used for sliver preparation, ensuring that the wool fiber content with the low-damage, scaled-hydrolyzed keratin-grafted layer is 100.00 wt% of the total wool fiber mass in the wool fabric. After sliver preparation, the wool yarn is spun using Sirospinning to achieve a linear density of 30 tex and a twist coefficient of 140. Weaving is performed at a warp tension of 0.45 cN / dtex and a weaving speed of 600 r / min to produce a twill fabric. The fabric undergoes low-tension washing, setting, and steaming treatments. The setting temperature is 130°C, and the setting time is 180 s. After steaming, the wool sliver fabric is obtained for weaving.

[0134] Quality testing methods and results

[0135] Scanning electron microscopy (SEM) was used to determine the scale height reduction rate of the low-damage scaled wool fiber precursor, which was 60.00% ± 1.50%. The breaking strength retention rate of wool single fibers was 88.00% ± 0.90% compared to the same batch of unscaled wool fibers. The amount of hydrolyzed keratin grafted was 2.50 wt% ± 0.05 wt% as determined by the mass difference method. The thickness of the low-damage scaled-hydrolyzed keratin graft layer was 80 nm ± 3 nm as determined by the cross-sectional method of scanning electron microscopy. The surface coverage of the low-damage scaled-hydrolyzed keratin graft layer was 95.00% ± 1.00%. The amount of unfixed protein residue was 0.32 wt% ± 0.03 wt%. The breaking strength retention rate of wool single fibers after grafting treatment was 85.00% ± 0.80%. The fabric's pilling grade was measured to be 5.00 according to GB / T4802.2**-2008**, and its dimensional change rate after washing and drying was +1.00%±0.08% according to GB / T8630-2013; the fabric's breaking strength retention rate was 85.00%±0.90%, its air permeability retention rate was 75.00%±0.80%, and the pH value of the fabric's water extract was 8.50±0.06.

[0136] Features and application scenarios of this embodiment

[0137] This embodiment adopts an optimized scheme with a higher load, which processes wool fibers with a higher proportion, thicker yarns, and higher fabric density. It is suitable for thicker twill wool fabrics and wool tops with high requirements for resisting felting shrinkage, pilling, and dimensional stability.

[0138] Example 3

[0139] Overall production scale and product form

[0140] In this embodiment, 8.50 kg of wool fiber was prepared, of which 5.10 kg was a low-damage, scaled-hydrolyzed keratin-grafted wool fiber intermediate, and 3.40 kg was ungrafted wool fiber from the same batch. This was blended with 1.50 kg of commercially available textile-grade polyester staple fiber to produce a serge fabric in the form of wool tops woven from supplied materials, with a wool fiber content of 85.00 wt%. The fabric in this embodiment has a weight of 190 g / m², a yarn linear density of 20 tex, a twist coefficient of 110, a warp density of 280 threads / 10 cm, and a weft density of 260 threads / 10 cm.

[0141] Raw materials, components or material specifications

[0142] The wool tops are commercially available worsted wool tops, and the polyester staple fibers are commercially available textile-grade staple fibers, with length and fineness suitable for wool top manufacturing processes. The hydrolyzed keratin is commercially available hydrolyzed keratin with an average molecular weight of 15 kDa. The hydrogen peroxide aqueous solution is a commercially available 27.50 wt% aqueous solution. Sodium bicarbonate, sodium thiosulfate pentahydrate, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, N-hydroxysuccinimide, acetic acid, and sodium acetate trihydrate are all commercially available analytical grade reagents. All raw materials are free of amino silicone oil, silicone resin, polyurethane resin, or cationic polymers.

[0143] Step A1: Pre-cleaning

[0144] Take 5.10 kg of wool tops (dry weight) and place them in a continuous low-tension treatment device. Add deionized water at a liquor ratio of 1:14 and wash at 37°C for 20 minutes with a circulation speed of 70 r / min. After draining, rinse once with deionized water to obtain pre-cleaned wool fibers. This step is carried out under normal atmospheric pressure. The completion criterion is that the washing solution is clear and the pH value of the washing solution is 7.00.

[0145] Step A2: Low-damage descaling treatment

[0146] A low-damage descaling solution was prepared at a bath ratio of 1:14. First, deionized water was added, followed by hydrogen peroxide solution and sodium bicarbonate to bring the total bath mass to approximately 71.40 kg. Then, 0.278 kg of hydrogen peroxide solution was added, equivalent to 0.0765 kg of effective H2O2, corresponding to 1.50 wt% of the dry weight of the wool fibers to be treated. Subsequently, 0.0408 kg of sodium bicarbonate was added, corresponding to 0.80 wt% of the dry weight of the wool fibers. The pH of the bath was adjusted and stabilized at 8.75. After heating to 45°C, pre-cleaned wool fibers were added and treated at an operating pressure of 0.10 MPa for 35 minutes with a circulation rate of 80 r / min. The completion criterion was that the bath pH was between 8.60 and 8.90 and the fiber bundles remained well-opened.

[0147] Step A3: Residual peroxide removal

[0148] After draining the low-damage descaling solution, the fibers were washed with deionized water until the pH of the washing solution reached 7.00, yielding a low-damage descaled wool fiber precursor. Subsequently, 0.0255 kg of deionized water containing sodium thiosulfate pentahydrate was added at a bath ratio of 1:14, and the mixture was treated at 25°C for 12 min, circulated at 60 rpm under normal air pressure. After treatment, the residual peroxide content was measured to be 0.006 wt%, meeting the requirements for proceeding to the hydrolyzed keratin grafting treatment.

[0149] Step A4: Hydrolyzed keratin grafting treatment

[0150] Based on the dry weight of the wool fibers to be treated, 0.1275 kg of hydrolyzed keratin was weighed and dispersed in deionized water. The pH was adjusted to 5.60 using a buffer solution formed by acetic acid and sodium acetate trihydrate. Subsequently, 0.0204 kg of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and 0.00816 kg of N-hydroxysuccinimide were added. The amount of N-hydroxysuccinimide was 0.40 times the mass of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, and the total amount of the three was 3.06 wt%. The resulting system was pre-activated at 28 °C for 15 min, with a pH drift of 0.12. Within 20 min after preparation, wool fibers treated with A3 were added. The grafting bath ratio was 1:14, the pH of the bath was maintained at 5.60, the treatment temperature was 40 °C, the treatment time was 55 min, and the circulation rate was 70 r / min. The completion criterion is that the treated fibers are slightly loosened and do not stick together or clump.

[0151] Step A5: Post-processing

[0152] The wool fibers treated with A4 were washed three times with deionized water, with the final wash solution having a pH of 6.50. Surface moisture was then removed, resulting in a 70.00% liquid retention rate in the wool fibers after dehydration. The fibers were then dried in hot air at 65°C for 35 minutes, followed by equilibration at 25°C and 65.00% relative humidity for 12 hours to obtain a low-damage, scaled-hydrolyzed keratin-grafted wool fiber intermediate. The completion criterion for this step was that the fibers could successfully pass a small-sample carding test without exhibiting significant entanglement or fly waste.

[0153] Step S2: Sliver preparation, spinning, weaving and finishing

[0154] 5.10 kg of the low-damage, scaled-hydrolyzed keratin-grafted wool fiber intermediate of this embodiment was blended with 3.40 kg of ungrafted wool fiber from the same batch and 1.50 kg of commercially available textile-grade polyester staple fiber, so that the wool fiber content in the wool fabric was 85.00 wt%, and the wool fiber content with the low-damage, scaled-hydrolyzed keratin-grafted layer was 60.00 wt% of the total wool fiber mass in the wool fabric. After sliver preparation, the wool fiber yarn containing wool fibers with a linear density of 20 tex and a twist coefficient of 110 was spun by ring spinning. Weaving was carried out with a warp tension of 0.25 cN / dtex and a weaving speed of 400 r / min to produce serge fabric. The serge fabric underwent low-tension washing, setting, and steaming treatment. The setting temperature was 110℃ and the setting time was 100 s. After steaming, the wool sliver woven fabric was obtained.

[0155] Quality testing methods and results

[0156] Scanning electron microscopy (SEM) was used to determine the scale height reduction rate of the low-damage scaled wool fiber precursor, which was 40.00% ± 1.10%. The breaking strength retention rate of wool single fibers was 94.00% ± 0.70% compared to the same batch of unscaled wool fibers. The amount of hydrolyzed keratin grafted was 1.20 wt% ± 0.04 wt% as determined by the mass difference method. The thickness of the low-damage scaled-hydrolyzed keratin graft layer was 45 nm ± 2 nm as determined by the cross-sectional method of scanning electron microscopy. The surface coverage of the low-damage scaled-hydrolyzed keratin graft layer was 80.00% ± 1.10%. The amount of unfixed protein residue was 0.28 wt% ± 0.03 wt%. The breaking strength retention rate of wool single fibers after grafting treatment was 92.00% ± 0.70%. The fabric's pilling grade was measured to be 4.20 according to GB / T4802.2**-2008**, and its dimensional change rate after washing and drying was -1.00%±0.09% according to GB / T8630-2013; the fabric's breaking strength retention rate was 92.00%±0.80%, its air permeability retention rate was 88.00%±0.70%, and the pH value of the fabric's water extract was 6.20±0.05.

[0157] Features and application scenarios of this embodiment

[0158] This embodiment adopts a medium ratio and blended weaving scheme, with a moderate proportion of wool fiber and a serge fabric structure, which takes into account strength retention, dimensional stability and weaving adaptability. It is suitable for wool blended fabric processing scenarios that require both shape stability and durability for daily wear.

[0159] Example 4

[0160] Overall production scale and product form

[0161] In this embodiment, 10.00 kg of low-damage, scaled-hydrolyzed keratin-grafted wool fiber intermediate was prepared. 7.50 kg of this intermediate was blended with 2.50 kg of ungrafted wool fiber from the same batch. The resulting fabric, consisting of a 100.00 wt% wool fiber content jacquard woven fabric, was produced from the wool sliver. The fabric in this embodiment has a weight of 230 g / m², a yarn linear density of 26 tex, a twist coefficient of 125, a warp density of 360 threads / 10 cm, and a weft density of 320 threads / 10 cm.

[0162] Raw materials, components or material specifications

[0163] The wool tops used were commercially available worsted wool tops; the hydrolyzed keratin was commercially available hydrolyzed keratin with an average molecular weight of 25 kDa; the hydrogen peroxide aqueous solution was a commercially available 30.00 wt% aqueous solution; sodium bicarbonate, sodium thiosulfate pentahydrate, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, N-hydroxysuccinimide, acetic acid, and sodium acetate trihydrate were all commercially available analytical grade reagents. Amino silicone oil, silicone resin, polyurethane resin, or cationic polymers were not used in the entire process of low-damage descaling, hydrolyzed keratin grafting, and finishing.

[0164] Step A1: Pre-cleaning

[0165] Take 10.00 kg of wool tops (dry weight) and place them in a skein dyeing machine. Add deionized water at a liquor ratio of 1:16 and wash at 42℃ for 25 minutes with a circulation speed of 75 r / min. Then drain the liquid and rinse twice with deionized water to obtain pre-cleaned wool fibers. This step is carried out under normal atmospheric pressure. The completion criterion is that the pH value of the final wash solution is 6.90 and the fibers have no obvious oily odor.

[0166] Step A2: Low-damage descaling treatment

[0167] A low-damage descaling solution was prepared at a bath ratio of 1:16. First, deionized water was added, followed by hydrogen peroxide solution and sodium bicarbonate to bring the total bath mass to approximately 160.00 kg. Then, 0.667 kg of hydrogen peroxide solution was added, equivalent to 0.200 kg of H2O2 (2.00 wt% of the dry weight of the wool fibers to be treated). Subsequently, 0.100 kg of sodium bicarbonate was added, corresponding to 1.00 wt% of the dry weight of the wool fibers. The pH of the bath was adjusted and stabilized at 9.10. After heating to 50°C, pre-cleaned wool fibers were added. Treatment was carried out at an operating pressure of 0.11 MPa for 45 minutes with a circulation rate of 85 r / min. During the treatment process, the batch-to-batch pH deviation of the bath solution was 0.30, and the batch-to-batch deviation of the bath solution solids content (based on bath mass) was 0.50 wt%. The completion criterion was that the batch-to-batch pH and bath solution solids content met the set requirements.

[0168] Step A3: Residual peroxide removal

[0169] After draining the low-damage descaling solution, the fibers were washed with deionized water until the pH of the washing solution reached 7.40, yielding a low-damage descaled wool fiber precursor. Subsequently, 0.060 kg of deionized water containing sodium thiosulfate pentahydrate was added at a bath ratio of 1:16, and the mixture was treated at 30°C for 15 min, circulated at 65 rpm under normal air pressure. After treatment, the residual peroxide content was measured to be 0.005 wt%, meeting the requirements for proceeding to the hydrolyzed keratin grafting treatment.

[0170] Step A4: Hydrolyzed keratin grafting treatment

[0171] Based on the dry weight of the wool fibers to be treated, 0.350 kg of hydrolyzed keratin was weighed and dispersed in deionized water. The pH was adjusted to 5.90 using a buffer solution formed by acetic acid and sodium acetate trihydrate. Subsequently, 0.050 kg of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and 0.050 kg of N-hydroxysuccinimide were added. The amount of N-hydroxysuccinimide was 1.00 times the mass of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, and the total amount of the three was 4.50 wt%. The resulting system was pre-activated at 35 °C for 30 min, with a pH drift of 0.08. Wool fibers treated with A3 were added within 60 min after the preparation. The grafting bath ratio was 1:16, the pH of the bath was maintained at 5.90, the treatment temperature was 45 °C, the treatment time was 75 min, and the circulation rate was 75 r / min. The criteria for completion were that the bath liquid showed no obvious sedimentation or agglomeration, and the surface of the fiber felt uniform after sampling and drying.

[0172] Step A5: Post-processing

[0173] The wool fibers treated with A4 were washed four times with deionized water until the pH of the final wash was 7.20. Surface moisture was then removed, resulting in a liquid-holding rate of 80.00% in the wool fibers. The fibers were then dried in hot air at 70°C for 45 minutes, followed by equilibration at 28°C and 70.00% relative humidity for 18 hours to obtain a low-damage, scaled-hydrolyzed keratin-grafted wool fiber intermediate. The completion criterion for this step was that the amount of unfixed protein residue met quality control requirements, and the fibers showed no hard lumps after opening.

[0174] Step S2: Sliver preparation, spinning, weaving and finishing

[0175] 7.50 kg of the low-damage, scaled-hydrolyzed keratin-grafted wool fiber intermediate from this embodiment was blended with 2.50 kg of ungrafted wool fiber from the same batch, so that the wool fiber content with the low-damage, scaled-hydrolyzed keratin-grafted layer was 75.00 wt% of the total wool fiber mass in the wool fabric. After sliver preparation, the yarn was compactly spun into wool yarn with a linear density of 26 tex and a twist coefficient of 125. Weaving was performed with a warp tension of 0.35 cN / dtex and a weaving speed of 520 r / min to produce a small jacquard fabric. The fabric underwent low-tension washing, setting, and steaming treatments. The setting temperature was 120°C, and the setting time was 150 s. After steaming, the wool sliver woven fabric was obtained.

[0176] Quality testing methods and results

[0177] Scanning electron microscopy (SEM) was used to determine the scale height reduction rate of the low-damage scaled wool fiber precursor, which was 52.00% ± 1.00%. The breaking strength retention rate of wool single fibers was 90.00% ± 0.80% compared to the same batch of unscaled wool fibers. The amount of hydrolyzed keratin grafted was 1.85 wt% ± 0.04 wt% as determined by the mass difference method. The thickness of the low-damage scaled-hydrolyzed keratin graft layer was 65 nm ± 2 nm as determined by the cross-sectional method of scanning electron microscopy. The surface coverage of the low-damage scaled-hydrolyzed keratin graft layer was 88.00% ± 1.00%. The amount of unfixed protein residue was 0.20 wt% ± 0.02 wt%. The breaking strength retention rate of wool single fibers after grafting treatment was 90.00% ± 0.80%. The fabric's pilling grade was measured to be 4.70 according to GB / T4802.2**-2008**, and the dimensional change rate after washing and drying was measured to be 0.20%±0.08% according to GB / T8630-2013; the fabric's breaking strength retention rate was 90.00%±0.70%, the air permeability retention rate was 82.00%±0.70%, and the pH value of the fabric's water extract was 7.10±0.05.

[0178] Features and application scenarios of this embodiment

[0179] This embodiment uses a combination of high grafting coverage and medium-high weaving density, with a small jacquard fabric structure. The process parameters are within a wide process window, making it suitable for processing medium-thick wool fabrics where requirements for fabric texture, appearance retention, dimensional stability, and anti-pilling are all necessary.

[0180] Comparative Example 1: Basically the same as Example 1, except that hydrogen peroxide aqueous solution is not added in step A2, and the mass of H2O2 active ingredient added is 0.000 kg, corresponding to 0.00 wt% of the dry mass of the wool fiber to be treated, while other conditions remain unchanged.

[0181] Comparative Example 2: It is basically the same as Example 1, except that in step A2, the mass of sodium bicarbonate added is 0.010 kg, which corresponds to 0.10 wt% of the dry mass of the wool fiber to be treated, and other conditions remain unchanged.

[0182] Comparative Example 3: It is basically the same as Example 1, except that the low-damage scaling treatment temperature in step A2 is 25°C, while other conditions remain unchanged.

[0183] Comparative Example 4: Basically the same as Example 1, except that the low-damage scaling treatment time in step A2 is 5 minutes, and other conditions remain unchanged.

[0184] Comparative Example 5: It is basically the same as Example 1, except that sodium thiosulfate pentahydrate is not added in step A3, and deionized water is used to treat the sample at 20°C for 5 min and circulated at 50 r / min, while other conditions remain unchanged.

[0185] Comparative Example 6: It is basically the same as Example 1, except that the mass of hydrolyzed keratin added in step A4 is 0.025 kg, which corresponds to 0.25 wt% of the dry mass of the wool fiber to be treated, and other conditions remain unchanged.

[0186] Comparative Example 7: It is basically the same as Example 1, except that in step A4, the mass of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride added is 0.001 kg, which corresponds to 0.01 wt% of the dry mass of the wool fiber to be treated, and other conditions remain unchanged.

[0187] Comparative Example 8: It is basically the same as Example 1, except that in step S2, 1.00 kg of low-damage descaling-hydrolyzed keratin grafted wool fiber intermediate is mixed with 9.00 kg of ungrafted wool fiber from the same batch, so that the wool fiber content with the low-damage descaling-hydrolyzed keratin grafted layer is 10.00 wt% of the total mass of wool fiber in the wool fabric, and other conditions remain unchanged.

[0188] Comparative Example 9: Essentially the same as Example 1, except that step A2 is omitted, and the pre-cleaned wool fibers obtained in step A1 are directly fed into step A3, where the hydrolyzed keratin grafting treatment continues as in step A4 of Example 1, with all other conditions remaining unchanged. This comparative example is used to verify the synergistic effect of low-damage descaling treatment and hydrolyzed keratin grafting treatment.

[0189] Comparative Example 10: Essentially the same as Example 1, except that hydrolyzed keratin, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, and N-hydroxysuccinimide were not added in step A4. Instead, a buffer bath solution with a pH of 5.00, formed from acetic acid and sodium acetate trihydrate, was used, and the treatment was carried out at 30°C for 20 min, with other conditions remaining unchanged. This comparative example was used to verify the synergistic effect of low-damage scaling treatment and hydrolyzed keratin grafting treatment.

[0190] Comparative Example 11: Essentially the same as Example 1, except that the hydrolyzed keratin grafting treatment in step A4 was performed after step A1 and before step A2. After the hydrolyzed keratin grafting treatment, steps A2, A3, and A5 were performed sequentially, with other conditions remaining unchanged. This comparative example was used to verify the synergistic effect of the order of low-damage scaling treatment, hydrolyzed keratin grafting treatment, and residual peroxide removal.

[0191] Characterization and performance testing:

[0192] The scale height reduction rate, graft layer thickness, and surface coverage of low-damage scaled-hydrolyzed keratin-grafted wool fiber intermediates were tested to evaluate the structural integrity of the scaled-graft interface. The principle involves extracting quantifiable geometric parameters from surface and cross-sectional images obtained using scanning electron microscopy (SEM). After drying, fixing, and sputtering with gold or carbon, surface and cross-sectional images of at least 30 fibers were acquired. Image analysis software was used to record the scale protrusion height, the distance from the outer boundary of the graft layer to the fiber matrix surface, and the coverage area. The graft layer thickness was measured using a cross-sectional image of low-damage scaled wool fibers from the same batch that had not undergone hydrolyzed keratin grafting as a boundary reference. The surface coverage was measured using the newly added continuous or locally continuous thin layer of coverage relative to the reference sample after grafting treatment. Test results are expressed as mean ± standard deviation. The scale height reduction rate was calculated as the ratio of the difference in average scale height before and after treatment to the average value before treatment. SEM can be used for two-dimensional image acquisition and regional morphology analysis of the fiber surface.

[0193] The grafting amount of hydrolyzed keratin, residual unfixed protein, and residual peroxide content of the low-damage descaling-hydrolyzed keratin-grafted wool fiber intermediate were tested to evaluate the degree of graft fixation and the cleanliness of post-treatment. The grafting amount was calculated using the mass difference method, with the dry weight of the wool fiber before grafting treatment as m0 and the dry weight of the intermediate after drying equilibrium as m1; the grafting amount was (m1-m0) / m0×100%. The residual unfixed protein was obtained by summing the total protein content in 2-5 washes and dividing by m0. This total protein content included unfixed hydrolyzed keratin and the mass of intrinsic wool peptides that could be eluted from the wool fiber surface. Residual peroxides were screened using a semi-quantitative colorimetric method and verified by iodine titration. Each group had n≥3, and results were recorded as mean ± standard deviation.

[0194] The wool monofiber breaking strength retention rate test for low-damage scaling-hydrolyzed keratin-grafted wool fiber intermediates is used to evaluate the impact of the treatment process on the mechanical integrity of wool fibers. The principle is to subject a monofiber to tension until it breaks under constant clamping length and stretching rate, and record the maximum breaking force. Using wool fibers from the same batch that have not undergone low-damage scaling and hydrolyzed keratin grafting treatment as the baseline sample, and the treated wool fibers as the treated sample, at least 30 monofibers are tested in each batch. The retention rate is calculated as (average breaking strength of the treated sample / average breaking strength of the baseline sample) × 100%, referring to the equivalent monofiber tensile method in GB / T13835.5 or ISO5079.

[0195] The pilling grade test for wool top-woven fabrics is used to evaluate the effects of surface scale reduction and graft layer constraint on pilling performance. The principle is that the sample produces surface pilling under a specified friction trajectory, load, and number of cycles, and the grade is then determined according to standard photographs or a rating system. After the fabric is equilibrated in the standard atmosphere specified in GB / T 6529 for textile conditioning and testing, samples are taken and tested using the modified Martindale method, referring to GB / T 4802.2-2008. At least three samples are used for each test, and the individual sample ratings are recorded and the average grade is calculated. GB / T 4802.2-2008 corresponds to the modified Martindale pilling method.

[0196] The dimensional change rate test for wool top-woven fabrics after washing and drying is used to evaluate resistance to felting shrinkage and dimensional stability. The principle is to compare the changes in warp and weft gauge lengths of the fabric before and after a specified washing and drying procedure. After conditioning, the initial length and width of the sample are marked. The sample is then treated according to the household washing and drying procedure for textiles, and the dimensional change rate is calculated according to GB / T8630-2013. The washing procedure can be selected and fixed with reference to GB / T8629-2017. For each group (n≥3), the warp, weft, and average dimensional change rates are recorded separately, expressed as percentages and standard deviations.

[0197] The breaking strength retention rate test for wool top woven fabrics is used to evaluate the strength retention of fabrics after low-damage scaling-hydrolyzed keratin grafting treatment. The principle is that the strip breaks under tensile load, and the maximum force reflects the fabric's load-bearing capacity. A reference wool fabric with the same wool fiber content, linear density, twist coefficient, warp density, weft density, and weave structure as the reference sample is used. The treated sample is used as the test sample. The warp and weft breaking strengths are tested according to the strip method in GB / T3923.1-2013. The retention rate is calculated as: (treated sample measured value / reference sample measured value) × 100%.

[0198] The air permeability retention test for wool top-woven fabrics is used to evaluate the influence of grafted layers and blending ratios on the fabric's air passageways. The principle is to measure the volume of air passing through a unit area of ​​fabric per unit time under a specified pressure difference. After conditioning the samples according to GB / T6529, the air permeability is measured under fixed test area and pressure difference conditions, referring to GB / T5453**-1997**. A reference wool fabric with the same structure is used as a control, and the retention rate is calculated as: (Air permeability of the treated sample / Air permeability of the reference sample) × 100%, where n≥3.

[0199] The weight per unit area, wool fiber content, and pH value of the water extract for fabrics woven from wool tops are tested to confirm the basic quality and safety indicators of the fabric. Weight per unit area is determined according to GB / T4669-2008, referring to sample cutting, conditioning, and weighing. Wool fiber content is determined according to the quantitative chemical analysis approach for textiles; when protein and non-protein fibers are mixed, GB / T2910.4-2022 can be referenced. The pH value of the water extract is determined according to GB / T7573**-2009**. For each item, n≥3, the mean ± standard deviation is recorded and compared with the target weight per unit area, wool fiber content, and pH control range.

[0200] Figure 1 This is a differential distribution diagram of the scale height reduction rate for Example 1, Comparative Example 9, and Comparative Example 10. Figure 2 This is a cumulative distribution chart of the scale height reduction rate for Example 1, Comparative Example 9, and Comparative Example 10. Figure 1 and Figure 2 It can be seen that after low-damage descaling treatment, the scale height reduction rate in Example 1 was mainly distributed at about 20%, and the cumulative distribution curve was relatively concentrated, indicating that the degree of descaling was well consistent among different measuring points. Comparative Example 9 did not achieve an effective descaling effect, with a scale height reduction rate close to 0%, indicating that the scale protrusions on the wool surface remained basically in their original state when the corresponding treatment was lacking. Although Comparative Example 10 still had a scale height reduction rate of about 20%, it lacked the subsequent construction of the hydrolyzed keratin graft layer. The above results show that the low-damage descaling step can stably reduce the scale protrusions on the wool fiber surface, providing a suitable surface morphology basis for the uniform adhesion and interface modification of the subsequent graft layer.

[0201] Figure 3 This is a differential thickness distribution diagram of the grafted layer in Example 1, Comparative Example 9, and Comparative Example 10. Figure 4 The images show the cumulative surface coverage distribution of Examples 1, 9, and 10. Figure 3 and Figure 4 It can be seen that the graft layer thickness in Example 1 is mainly concentrated at about 10 nm, with a surface coverage of about 70%, indicating that a relatively continuous and moderately thick hydrolyzed keratin graft layer is formed on the surface of the wool fibers after scaling. The graft layer thickness in Comparative Example 9 is reduced to about 6 nm, with a coverage of about 45%, indicating that when scaling is not sufficient, the scale protrusions on the fiber surface and the interface inhomogeneity will affect the spreading and fixation of the graft layer. Comparative Example 10 has almost no obvious graft layer, with a surface coverage of close to 0%, indicating that scaling alone is not enough to form an effective surface functional layer. It can be seen that there is a clear process connection between scaling treatment and hydrolyzed keratin grafting treatment. The former improves the fiber surface morphology, while the latter constructs a stable covering layer. The combination of the two can improve the quality of graft layer formation.

[0202] Figure 5 This is a superimposed diagram of the FTIR absorption spectra of Example 1, Comparative Example 10, and Comparative Example 7. Figure 6 These are XPS wide scan overlay images of Example 1, Comparative Example 10, and Comparative Example 7. Figure 7 This is a scatter plot of the average XPS elemental atom percentages for Example 1, Comparative Example 10, and Comparative Example 7. Figure 8 This is a scatter plot of the FTIR amide peak area ratios for Examples 1, 10, and 7. Figures 5 to 8 It can be seen that in Example 1, the signals in the amide I, amide II, and N–H / O–H related absorption regions are relatively enhanced, and the N-related signal in the XPS broad scan spectrum is also more obvious, with a surface N content of approximately 16%. In Comparative Example 10, the surface N content is approximately 12%, and the related amide absorption signal is weaker, indicating that the increase in nitrogen-containing components on the fiber surface is limited when hydrolyzed keratin grafting is not performed. In Comparative Example 7, the surface N content is approximately 13%, and the FTIR amide peak area ratio and XPS signal are both between those of Example 1 and Comparative Example 10, indicating that the degree of fixation of hydrolyzed keratin on the fiber surface is limited when the coupling activation conditions are insufficient. The above chemical characterization results are consistent with... Figure 3 , Figure 4 The morphological results are consistent, indicating that Example 1 formed an observable surface graft layer, and that the chemical composition and amide structure signal of the fiber surface changed in accordance with the hydrolyzed keratin grafting treatment.

[0203] Figure 9 This is a scatter plot showing the mean of the hydrolyzed keratin grafting amount in Example 1, Comparative Example 5, and Comparative Example 7. Figure 10This is a scatter plot showing the mean of the unfixed protein residue in Examples 1, 5, and 7. Figure 11 This is a scatter plot showing the average residual peroxide content of Examples 1, 5, and 7. Figure 12 This is a two-dimensional correlation graph showing the grafting amount versus the amount of unfixed protein residue in Examples 1, 5, and 7. Figures 9 to 12 It can be seen that in Example 1, the hydrolyzed keratin grafting amount was approximately 0.30 wt%, the unfixed protein residue was approximately 0.50 wt%, and the residual peroxide content was approximately 0.010 wt%, exhibiting a high grafting amount, low unfixed protein residue, and low oxidation residue level. In Comparative Example 5, the grafting amount was approximately 0.24 wt%, the unfixed protein residue was approximately 0.62 wt%, and the residual peroxide content increased to approximately 0.035 wt%, indicating that insufficient control of residual peroxides affects the subsequent coupling fixation efficiency and increases unstable residues. In Comparative Example 7, the grafting amount was approximately 0.12 wt%, and the unfixed protein residue was approximately 0.82 wt%, indicating that insufficient EDC / NHS coupling activation reduces the fixation degree of hydrolyzed keratin on the wool surface. Two-dimensional correlation results further show that Example 1 is in the optimal region of high grafting amount and low unfixed protein residue, indicating that the combined effect of residual peroxide removal and appropriate coupling activation can improve the effective fixation ratio of hydrolyzed keratin and improve the stability of the finishing layer. Figure 10 and Figure 12 The amount of unfixed protein residue in the washing solution is measured using the total protein content of the washing solution. The protein measured includes unfixed hydrolyzed keratin as well as intrinsic wool peptides that can be washed off the surface of wool fibers during low-damage scaling and grafting processes.

[0204] Figure 13 This is a scatter plot showing the average values ​​of pilling and fuzzing levels for Examples 1, 8, and 11. Figure 14 This is a scatter plot of the absolute values ​​of the dimensional change rates of Example 1, Comparative Example 8, and Comparative Example 11. Figure 15 This is a two-dimensional balance diagram showing the retention rates of breaking strength and air permeability for Examples 1, 8, and 11. Figure 16 Normalized curves of the overall fabric performance of Example 1, Comparative Example 8, and Comparative Example 11 are shown. Figures 13 to 16It can be seen that the pilling grade of Example 1 is approximately 3.5, the absolute value of the dimensional change rate is approximately 3.0%, and the retention rates of breaking strength and air permeability are both approximately 99%, indicating that it has good performance in terms of anti-pilling, dimensional stability, mechanical properties, and air permeability. The pilling grade of Comparative Example 8 is approximately 3.0, and the absolute value of the dimensional change rate is approximately 3.8%, indicating that an inappropriate blending ratio of treated wool fibers will weaken the overall improvement effect at the fabric level. The pilling grade of Comparative Example 11 is approximately 2.7, the absolute value of the dimensional change rate is approximately 4.0%, and the breaking strength retention rate drops to approximately 97%, indicating that abnormal process sequence or interface layer construction will simultaneously affect the fabric's appearance stability and mechanical properties. The normalized curve of comprehensive performance shows that the distribution of various indicators in Example 1 is more balanced, proving that there is a synergistic effect between low-damage modification of the fiber surface, stable construction of the graft layer, and subsequent low-tension weaving finishing, which can effectively transfer the modification effect at the fiber scale to the fabric scale.

[0205] Figure 17 This is a macroscopic optical photograph of the plain weave wool top woven fabric with a wool fiber content of 100.00 wt% obtained in Example 1. Figure 17 The fabric is opaque, ranging from off-white to light beige, and has a lightweight, finely spun plain weave. It weighs 120 g / m², has a yarn linear density of 10 tex, a warp density of 150 threads / 10 cm, and a weft density of 130 threads / 10 cm. The fabric surface exhibits a clear warp and weft interweaving structure, with no obvious yellowing, hard spots, macroscopic cracks, warping, or blocky adhesions. This result indicates that the low-damage, scaled-hydrolyzed keratin-grafted wool fiber intermediate, when blended with ungrafted wool fibers from the same batch, still meets the requirements for fiber dispersion, yarn continuity, and fabric smoothness in conventional weaving processes, demonstrating that this treatment method does not significantly adversely affect fabric formation.

[0206] Figure 18 This is a scanning electron microscope image of the low-damage scaling-hydrolyzed keratin-grafted wool fiber intermediate from Example 1, in which... Figure 18 a is a low-magnification SEM image. Figure 18 b is a medium-magnification SEM image. Figure 18 c is a high-magnification SEM image. Figure 18 d represents the cross-sectional SEM image. (From...) Figure 18 As can be seen from a, the treated wool fibers are continuous and loosely overlapped, without obvious clumps adhering together; Figure 18 b indicates that the scaly cuticle of the wool fiber is still preserved, and the scale height reduction rate of the low-damage descaling wool fiber precursor is 20.00% ± 0.80%, indicating that the descaling treatment does not completely remove the cuticle, but reduces scale protrusion while preserving the basic outer structure of the fiber; Figure 18c indicates that the scale edges are rounded and blunted, and a thin layer of hydrolyzed keratin grafted layer is visible in local areas, with a surface coverage rate of 70.00% ± 1.20%; Figure 18 As shown in d, the thickness of the low-damage scaling-hydrolyzed keratin graft layer is 10 nm ± 1 nm, and the outer fiber layer and inner cortical layer are completely bonded together, with no obvious interlayer delamination or through cracks observed. These results further demonstrate that this treatment method can maintain the integrity of the main wool fiber structure while reducing scale height and constructing the surface graft layer, thus meeting the objectives of low-damage surface modification.

[0207] Figure 19 Transmission electron microscopy characterization of low-damage scaling-hydrolyzed keratin-grafted wool fibers in Example 1, wherein... Figure 19 a is a cross-sectional image of a bright-field TEM. Figure 19 b is a magnified TEM image of a portion of the image. (From...) Figure 19 As can be seen from a, wool fibers retain the solid keratin fiber structure, and the interface between the outer keratin layer and the inner cortex is clear and continuous, indicating that no significant structural damage occurred to the fiber cross-section after treatment; Figure 19 As shown in b, a hydrolyzed keratin graft layer with a thickness of approximately 10 nm ± 1 nm is formed on the outer surface of the fiber, and the graft layer exhibits a localized continuous coverage characteristic. This TEM result is consistent with the SEM cross-sectional observation results, further characterizing the existence and thickness range of the surface graft layer in Example 1 from the ultrastructural level, indicating that this scheme can achieve controllable outer layer modification without causing significant damage to the internal main structure of the wool fiber.

[0208] Table 1. Characterization results of fiber surface structure and single fiber properties

[0209]

[0210] Table 2. Results of Comprehensive Performance and Safety Characterization of Fabrics

[0211] As can be seen from the performance of the examples and comparative examples in Table 1, examples 1-4 show a relatively continuous structure-performance correspondence between scale height reduction rate, hydrolyzed keratin grafting amount, graft layer thickness, surface coverage, pilling grade, and dimensional stability after washing. Example 1 uses a mild, low-ratio treatment, resulting in high strength and breathability retention; Example 2 has the highest graft layer thickness and coverage, with more outstanding pilling grade and dimensional stability, but strength and breathability retention are somewhat reduced; Examples 3 and 4 are in the medium-high ratio range, demonstrating balanced performance. Comparative examples 1-4 have insufficient scaling, leaving more surface scales, resulting in a decrease in dimensional change rate and pilling grade; Comparative example 5 has insufficient removal of residual peroxides, resulting in a reduced strength retention rate; Comparative examples 6 and 7 have insufficient graft fixation, resulting in a decrease in coverage and surface constraint; Comparative example 8 has a low wool fiber content, resulting in insufficient anti-pilling and dimensional stability at the fabric level; Comparative examples 9-11 show that low-damage scaling, residual removal, grafting treatment, and sequential control jointly affect the formation of the interface layer and overall performance.

[0212] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that any equivalent structural transformations made under the concept of the present invention and using the contents of the specification and drawings of the present invention should be covered within the scope of protection of the claims of the present invention.

Claims

1. A fabric woven from wool strips, characterized in that, The wool sliver fabric is made of wool fabric formed by sliver preparation, spinning and weaving, with wool sliver as the main raw material. 30.00-100.00 wt% of the wool fibers in the wool fabric are wool fibers treated with a low-damage scaled-hydrolyzed keratin graft layer. The low-damage descaling-hydrolyzed keratin graft layer is formed by hydrolyzed keratin fixed to the surface of wool fibers that have undergone low-damage descaling treatment; The low-damage descaling process is carried out using H2O2, an effective component provided by an aqueous hydrogen peroxide solution, and sodium bicarbonate. The hydrolyzed keratin is fixed to the surface of the wool fiber via a carboxyl-amino coupling reaction involving 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide. The wool fabric contains 85.00-100.00 wt% wool fibers.

2. The wool top-woven fabric according to claim 1, characterized in that, The thickness of the low-damage descaling-hydrolyzed keratin graft layer on the surface of the treated wool fiber is 10-80 nm, as determined by scanning electron microscopy cross-section method. Based on the dry weight of the wool fiber before grafting treatment, the amount of hydrolyzed keratin grafted is 0.30-2.50 wt%, as determined by mass difference method. The scale height of the treated wool fiber is determined by scanning electron microscopy image method and is reduced by 20.00-60.00% compared with the same batch of un-scaling treated wool fiber. The weight of the fabric woven from the wool top is 120-280 g / m².

3. The wool top-woven fabric according to claim 1, characterized in that, Wool fibers with the aforementioned low-damage descaling-hydrolyzed keratin grafted layer are intermediates of low-damage descaling-hydrolyzed keratin grafted wool fibers. These intermediates are prepared through the following steps: A1. Provide wool strips or wool fibers, and wash the wool strips or wool fibers with deionized water to obtain pre-cleaned wool fibers; A2. The pre-cleaned wool fibers are treated in a low-damage descaling solution containing H2O2 and sodium bicarbonate to obtain a low-damage descaling wool fiber precursor. A3. The low-damage scaled wool fiber precursor is treated in deionized water containing sodium thiosulfate pentahydrate to reduce the residual peroxide content; A4. The wool fibers treated with A3 are placed in a hydrolyzed keratin grafting solution for hydrolyzed keratin grafting treatment, wherein the hydrolyzed keratin grafting solution contains hydrolyzed keratin, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, N-hydroxysuccinimide and a buffer component formed by acetic acid and sodium acetate trihydrate. A5. The wool fibers treated with A4 are washed with deionized water, dehydrated and dried to obtain the low-damage descaling-hydrolyzed keratin grafted wool fiber intermediate.

4. The wool top-woven fabric according to claim 3, characterized in that, The process conditions for steps A1 to A3 are as follows: In step A1, the wool strips or wool fibers are washed with deionized water at 30-45°C for 10-30 minutes. In step A2, the amount of H2O2 active ingredient in the low-damage descaling solution is 0.50-3.00 wt% based on the dry weight of the wool fibers to be treated, the H2O2 active ingredient is provided by hydrogen peroxide aqueous solution, the amount of sodium bicarbonate is 0.20-1.50 wt% based on the dry weight of the wool fibers to be treated, the pH value of the bath solution is 8.00-9.50, the treatment temperature is 35-55℃, the treatment time is 15-60 min, and the operating pressure is 0.08-0.12 MPa; In step A3, the low-damage scaled wool fiber precursor is treated in deionized water containing 0.10-1.00 wt% sodium thiosulfate pentahydrate based on the dry weight of the wool fiber to be treated at a bath ratio of 1:8-1:20 for 5-20 minutes at a temperature of 20-35°C, so that the residual peroxide content is not higher than 0.010 wt% based on the dry weight of the wool fiber after A3 treatment.

5. The wool top-woven fabric according to claim 3, characterized in that, The low-damage descaled wool fiber precursor in step A2 is prepared through the following steps: B1. Add the pre-cleaned wool fibers to deionized water at a bath ratio of 1:8-1:20; B2. Add hydrogen peroxide aqueous solution and sodium bicarbonate to ensure that the amount of H2O2 effective component and sodium bicarbonate in the low-damage descaling solution meet the specified ranges respectively; B3. Process according to the pH of the bath solution, the treatment temperature, the treatment time, and the operating pressure; B4. Wash with deionized water until the pH of the washing solution is 6.00-8.00 to obtain the low-damage scaled wool fiber precursor; The scale height of the low-damage scaled wool fiber precursor was determined by scanning electron microscopy and was reduced by 20.00-60.00% compared to the same batch of unscaled wool fibers. The breaking strength retention rate of the wool single fiber was 88.00-99.00% compared to the same batch of unscaled wool fibers.

6. The wool top-woven fabric according to claim 3, characterized in that, The hydrolyzed keratin grafting solution in step A4 is prepared through the following steps: C1. Weigh out the hydrolyzed keratin according to the dry weight of the wool fibers to be treated and dissolve or disperse it in deionized water to form an aqueous phase for preparing the hydrolyzed keratin grafting solution, wherein the amount of hydrolyzed keratin is 0.50-5.00 wt% based on the dry weight of the wool fibers to be treated; C2. The pH of the aqueous phase obtained in C1 was adjusted to 5.00-6.20 using acetic acid and sodium acetate trihydrate; C3. Add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide to the aqueous phase obtained in C2, wherein the amount of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride is 0.05-0.80 wt% based on the dry weight of the wool fibers to be treated, and the amount of N-hydroxysuccinimide is 0.03-0.50 wt% based on the dry weight of the wool fibers to be treated, and the amount of N-hydroxysuccinimide is 0.40-1.00 times the mass of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride; C4. Pre-activate at 20-35℃ for 5-30 min to obtain the hydrolyzed keratin grafting solution; The pH drift of the hydrolyzed keratin grafting solution from pH adjustment at C2 to the end of pre-activation at C4 is no greater than 0.

30. The total amount of hydrolyzed keratin, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide is 0.58-6.30 wt% based on the dry weight of the wool fiber to be treated.

7. The wool top-woven fabric according to claim 1, characterized in that, The average molecular weight of the hydrolyzed keratin is 1-30 kDa; The hydrolyzed keratin forms a continuous or island-like graft layer on the surface of the wool fibers, and the surface coverage of the low-damage scaling-hydrolyzed keratin graft layer is 70.00-95.00%. Based on the total mass of wool fibers in the wool fabric, the wool fiber content having the low-damage scaled-hydrolyzed keratin graft layer is 30.00-100.00 wt%, and the remainder is ungrafted wool fibers without the low-damage scaled-hydrolyzed keratin graft layer. The wool fabric is woven from yarn containing wool fibers. The yarn has a linear density of 10-30 tex and a twist coefficient of 80-140. The warp density of the wool fabric is 150-420 threads / 10cm, and the weft density is 130-380 threads / 10cm. The wool fabric is plain weave, twill weave, serge, varnish, or jacquard. The wool tops woven fabric meets the following properties: pilling grade of 3.50-5.00 as measured by GB / T4802.2; dimensional change rate after washing and drying of -3.00% to +1.00% as measured by GB / T8630; breaking strength retention rate of 85.00-99.00% relative to the benchmark wool fabric that has not undergone low-damage scaling and hydrolyzed keratin grafting treatment but has the same wool fiber content, linear density, twist coefficient, warp density, weft density and weave structure; air permeability retention rate of 75.00-99.00% relative to the benchmark wool fabric; and pH value of the fabric water extract of 4.00-8.

50.

8. A method for preparing a fabric woven from wool tops as described in any one of claims 1-7, characterized in that, Includes the following steps: S1. The wool tops or wool fibers are pre-cleaned, low-damage descaling, residual peroxide removal, hydrolyzed keratin grafting and post-treatment to obtain a low-damage descaling-hydrolyzed keratin grafted wool fiber intermediate. S2. The low-damage descaling-hydrolyzed keratin grafted wool fiber intermediate is processed into slivers, spun, woven, and finished to obtain the wool sliver woven fabric.

9. The preparation method according to claim 8, characterized in that, In step S2, the spinning is compact spinning, Siro spinning, or ring spinning, and the linear density of the wool yarn obtained by the spinning is 10-30 tex, and the twist coefficient is 80-140; the weaving is carried out under the conditions of warp tension of 0.10-0.45 cN / dtex and weaving speed of 200-600 r / min, and the resulting greige fabric is subjected to low-tension washing, setting and steaming treatment, with a setting temperature of 90-130℃ and a setting time of 30-180s.

10. The preparation method according to claim 8, characterized in that, In step S1, the quality control endpoints of the low-damage scaling-hydrolyzed keratin grafted wool fiber intermediate include: the residual peroxide content is no higher than 0.010 wt% based on the dry weight of the wool fiber after residual peroxide removal treatment; the unfixed protein residue is no higher than 0.50 wt% based on the dry weight of the wool fiber before grafting treatment; the unfixed protein residue is the ratio of the sum of the total protein content in the washing solution obtained from 2-5 washes to the dry weight of the wool fiber before grafting treatment; the wool single fiber breaking strength retention rate is 85.00-99.00% relative to the same batch of wool fibers that have not undergone low-damage scaling and hydrolyzed keratin grafting treatment; and the washing solution pH value is 5.50-7.50.

Images