Method for finishing wool fabric through synergistic effect of composite carrier and pH response

Abstract

The invention discloses a method for finishing a wool fabric through a synergistic effect of a composite carrier and pH response, and belongs to the technical field of functional finishing of textile materials. The invention solves the problems of high energy consumption, unstable enzyme activity, serious chemical reagent pollution, wool fiber damage, poor fuzzing and pilling resistance and the like in the existing wool fabric finishing technology. Elastic microspheres and amino-modified mesoporous silica nanoparticles form a composite carrier, the carrier is used for loading plant protease, and meanwhile, a pH response layer is constructed outside the carrier, so that the compound is obtained. When the wool fabric is oscillated in the pH-adjusted compound working solution, the compound rubs with the wool scale layer to generate local slight heat, so that the swelling of the pH response layer and the release of plant protease are accelerated, the enzyme activity is activated, and the efficient enzymolysis of the wool scale layer at normal temperature is realized. The finishing process disclosed by the invention has the advantages of low temperature, high efficiency, excellent anti-pilling effect, green and environment-friendly raw materials and easiness in industrial large-scale application.

Description

Technical Field

[0001] This invention belongs to the field of functional finishing technology of textile materials, specifically relating to a method for finishing wool fabrics through the synergistic effect of a composite carrier and pH response. Background Technology

[0002] Wool fabrics, with their superior properties such as softness, warmth, breathability, and moisture absorption, hold an important position in high-end apparel and home textiles, and are highly favored by consumers. However, the unique scaly structure of wool fibers makes them prone to fiber slippage, entanglement, and breakage during daily wear, washing, and friction, leading to pilling. This problem not only severely damages the appearance and comfort of wool fabrics but also shortens their lifespan, greatly restricting their market competitiveness and application expansion. To solve the pilling problem of wool fabrics, the industry has developed various anti-pilling finishing technologies, but current mainstream technologies still have many insurmountable technical defects, as follows: (1) High temperature dependence, high energy consumption and damage to wool fibers: Traditional enzymatic finishing technology requires reaction at a high temperature of about 60℃ to ensure the activity of protease. On the one hand, the high temperature environment leads to a sharp increase in energy consumption during the production process, which does not meet the development needs of green production; on the other hand, high temperature easily causes changes in the internal structure of wool fibers, resulting in fiber felting and a decrease in strength. The strength loss rate is usually as high as 15-20%, which seriously damages the original wearing performance and durability of wool fabrics.

[0003] (2) Poor enzyme activity stability and low repeatability of finishing process: Free proteases used in wool finishing are extremely sensitive to environmental conditions. Temperature fluctuations, pH changes, and impurity interference can all easily lead to the destruction of enzyme molecular structure and loss of activity. This makes the enzymatic hydrolysis efficiency unstable in actual production, and the finishing effect is not uniform. Enzyme preparations need to be added frequently to maintain the finishing effect, which not only increases the production cost, but also makes it difficult to accurately control the process parameters, and makes it difficult to guarantee production stability and repeatability.

[0004] (3) Chemical finishing agents cause serious pollution and have poor ecological compatibility: Currently, industrial processes commonly use resin-based chemical finishing agents (such as polyurethane and epoxy resins) to treat wool fabrics to prevent pilling. Although these agents can improve the anti-pilling performance of fabrics in the short term, they pose a significant risk of skin sensitization. Long-term exposure may cause skin discomfort or even allergic reactions. Resin finishing also leads to a decrease in the wearability of fabrics. In addition, resin-based finishing agents have extremely low biodegradability and are prone to accumulate in the environment after large-scale use, causing soil and water pollution, which is seriously inconsistent with the current industry development trend of ecological textiles and green consumption.

[0005] To address the aforementioned technical challenges, the textile industry urgently needs to develop a low-temperature, high-efficiency, enzyme-active, eco-friendly, and cost-controllable anti-pilling finishing technology for wool. Summary of the Invention

[0006] To address the problems of high energy consumption, unstable enzyme activity, serious chemical reagent pollution, wool fiber damage, and poor anti-pilling performance in existing anti-pilling finishing technologies for wool fabrics, this invention provides a method for finishing wool fabrics through the synergistic effect of a composite carrier and pH response.

[0007] To achieve the above objectives, the technical solution of the present invention is as follows: One objective of this invention is to provide a method for treating wool fabrics using a composite carrier and pH response synergistic effect, the method comprising the following steps: (1) Preparation of composite carrier: Amino-modified mesoporous silica nanoparticles (AMSNs) and elastic microspheres were added to deionized water, followed by the addition of silane coupling agent. The reaction was carried out under water bath conditions, so that AMSNs and elastic microspheres were covalently bonded to obtain composite carrier. (2) Preparation of enzyme-composite carrier complex (ECCs) with pH responsive layer: Carboxymethyl chitosan (CMCS) was dissolved in water to form a carboxymethyl chitosan aqueous solution. The composite carrier was added to the carboxymethyl chitosan aqueous solution and stirred at room temperature to modify the surface of the composite carrier with CMCS. Then, plant protease was added and the mixture was shaken to adsorb. Glutaraldehyde solution was then added and the mixture was cross-linked at low temperature to successfully load the plant protease onto the composite carrier, thus obtaining enzyme-composite carrier complex (ECCs) with pH responsive layer. (3) Tribothermation-enzymatic hydrolysis synergistic treatment: The enzyme-complex carrier complex with pH response layer is dispersed in deionized water to form an enzyme-complex carrier complex working solution. The pH of the working solution is adjusted to 5-6 with citrate-sodium citrate buffer. Then, wool fabric is mixed with the enzyme-complex carrier complex working solution with pH 5-6 and treated with shaking at room temperature. (4) Post-treatment: The wool fabric after vibration treatment is washed and dried to obtain wool fabric with anti-pilling properties.

[0008] Further specifying, the preparation method of the elastic microspheres in step (1) is as follows: using biodegradable polyester copolymers as raw materials, the elastic microspheres are prepared by emulsification-solvent evaporation method.

[0009] Furthermore, the specific preparation method of the elastic microspheres is as follows: dissolve a biodegradable polyester copolymer in an organic solvent to form an organic phase solution, drop the organic phase solution into an aqueous solution of polyvinyl alcohol, and emulsify it under ultrasonic conditions to obtain elastic microspheres with a particle size of 50~100nm.

[0010] Furthermore, the concentration of the organic phase solution is 80~120g / L, and the concentration of the polyvinyl alcohol aqueous solution is 0.8~1.2wt%.

[0011] Further specifying, the preparation method of amino-modified mesoporous silica nanoparticles in step (1) includes the following steps: S1. Preparation of mesoporous silica nanoparticles (MSNs): A template solution was prepared, and ammonia was added to the template solution to adjust the pH of the system to 10-11. Then, tetraethyl silicate was added as a silicon source, and the reaction was carried out under water bath conditions. After the reaction was completed, the mesoporous silica nanoparticles with a pore size of 5-10 nm were obtained by centrifugation and washing. S2. Preparation of amino-modified mesoporous silica nanoparticles (AMSNs): Mesoporous silica nanoparticles were dispersed in anhydrous ethanol to form an MSNs-ethanol dispersion. Silane with amino-modifying effect was added to the MSNs-ethanol dispersion to carry out the reaction, so that amino groups were grafted onto the surface of the MSNs. After the reaction was completed, the nanoparticles were obtained by centrifugation and washing with ethanol.

[0012] Further specifying, in step S1, the concentration of the template agent solution is 0.2~0.4wt%, the concentration of tetraethyl silicate is 0.7~1.2vol%, the water bath temperature is 30~35℃, and the reaction time is 4~6h; in step S2, the concentration of MSNs-ethanol dispersion is 10~20g / L, the silane with amino modification is 3-aminopropyltriethoxysilane (APTES), 3-aminopropylmethyldimethoxysilane or 3-aminopropyltrimethoxysilane, the mass ratio of MSNs to the silane with amino modification is (1~3):1, the reaction temperature is 70~80℃, and the time is 6~8h.

[0013] Further specifying, in step (1), the mass ratio of amino-modified mesoporous silica nanoparticles to elastic microspheres is (8~12):1.

[0014] Further, in step (1), the amount of silane coupling agent used is 0.5 to 1 wt% of the sum of the mass of the amino-modified mesoporous silica nanoparticles and the elastic microspheres.

[0015] Further, in step (2), the degree of substitution of carboxymethyl chitosan is ≥0.8, and the concentration of the carboxymethyl chitosan aqueous solution is 0.1~0.5wt%.

[0016] Further specifying, the stirring time in step (2) is 10~16h.

[0017] Further, in step (2), the plant protease activity unit is ≥200U / mg, and the mass ratio of plant protease to complex carrier is 1:(4~8).

[0018] Further, the oscillation adsorption temperature in step (2) is 30~35℃ and the time is 2~3h.

[0019] Further specified, the concentration of glutaraldehyde solution in step (2) is 0.8~1.2wt%.

[0020] Further specifying, the cross-linking reaction temperature in step (2) is 3~6℃ and the time is 1~4h.

[0021] Further, the concentration of the enzyme-complex carrier working solution in step (3) is 1~3g / L.

[0022] Further specifying, in step (3), the bath ratio of wool fabric to enzyme-complex carrier complex working solution with pH 5-6 is 1:(20-30).

[0023] The second objective of this invention is to provide a wool fabric with anti-pilling properties obtained by the above method.

[0024] Further restrictions are imposed: the directional friction effect (DFE) value of wool fabrics is ≤0.15, and the pilling grade is ≥4.

[0025] The beneficial effects of this invention are as follows: (1) This invention first constructs a core-shell structured nanocomposite carrier, with elastic microspheres as the core and amino-modified mesoporous silica as the shell. Plant proteases are loaded onto this composite carrier. The enzymes are not only loaded on the surface of the composite carrier, but also exist in the mesopores and inside the composite carrier. At the same time, this invention utilizes carboxymethyl chitosan to form a pH-responsive layer on the outside of the composite carrier, thus obtaining an enzyme-composite carrier complex (ECCs) with a pH-responsive layer. When wool fabric is shaken in a pH-adjusted ECCs working solution, the ECCs and the wool cuticle layer undergo mechanical friction, which can generate local micro-heat of 40-50°C. This micro-heat can accelerate the swelling of the pH-responsive layer and the release of plant proteases, while activating the activity of plant proteases, thereby achieving efficient enzymatic hydrolysis of the wool cuticle layer at room temperature. (2) The nanocomposite carrier in this invention has a protective function: the mesoporous structure of AMSNs can provide a stable loading space for plant proteases. The elastic microspheres, as part of the composite carrier, can absorb and disperse mechanical impact during the frictional heat generation process, avoiding direct mechanical shearing and inactivation of enzyme molecules. In addition, after the elastic microspheres are combined with amino-modified mesoporous silica, local micro-heat is generated on the surface of wool scales through mechanical friction, which accelerates the enzymatic reaction and avoids overheating and damage to the main structure of wool fibers. Furthermore, the composite carrier formed by the elastic microspheres and amino-modified mesoporous silica allows the enzyme to be effectively adsorbed in the mesopores of the composite carrier. The pH response layer is wrapped on the surface of the composite carrier. Under weakly acidic conditions, the response layer releases the enzyme step by step. Moreover, the composite carrier can reduce the direct contact between the enzyme and impurities on the surface of wool fabrics and reduce the non-specific adsorption loss of plant proteases.

[0026] (3) Enzyme release effect of pH-responsive layer in this invention: The pH-responsive layer formed by CMCS modification has a compact structure under neutral or alkaline conditions, which can inhibit enzyme release. However, in the weakly acidic ECCs working solution at pH 5-6, CMCS swells and gradually releases the loaded plant protease, achieving precise and controllable enzyme release and avoiding enzyme activity loss in the non-reaction stage. Frictional heat generation acceleration effect: During the oscillation process, the mechanical friction between ECCs and the wool scale layer generates local micro-heat of 40-50℃. This micro-heat only acts on the scale layer on the surface of wool fibers and will not affect the main structure of the fiber. The micro-heat can significantly improve the catalytic activity of plant protease, accelerate the hydrolysis reaction of scale layer proteins, and promote the diffusion of enzyme molecules on the scale layer surface, thereby improving the enzymatic hydrolysis efficiency. This invention constructs the above-mentioned synergistic system of nanocomposite carrier protection - pH-responsive layer enzyme release - frictional heat generation to accelerate enzymatic hydrolysis. By utilizing the local micro-heat generated by mechanical friction, efficient and precise enzymatic hydrolysis of wool scale layer can be achieved under normal temperature conditions, while effectively solving the problems of enzyme inactivation, wool fiber damage, and high cost of anti-pilling treatment equipment for wool fabrics.

[0027] (4) In the preparation of elastic microspheres in this invention, the concentration of the organic phase solution is controlled at 80~120 g / L. If the concentration is too low, the elastic microspheres will be too small and have poor dispersibility; if the concentration is too high, the microspheres will easily agglomerate, affecting the subsequent composite effect with AMSNs. The concentration of polyvinyl alcohol aqueous solution is 0.7~1.2 wt%. This concentration range can ensure stable emulsification effect and avoid uneven dispersion of organic phase. In the preparation of MSNs, the concentration of the template machine solution is 0.2~0.4 wt%. This concentration can effectively control the pore size and pore volume of the mesoporous structure. Adding ammonia water to adjust the pH value of the system to 10~11 provides a suitable alkaline environment for the hydrolysis and condensation of tetraethyl silicate. The reaction temperature is 30~35℃ and the reaction time is 4~6h, which can ensure that the mesoporous structure of MSNs is intact and the pore size is uniform.

[0028] (5) In the preparation of the composite carrier of the present invention, the mass ratio of AMSNs to elastic microspheres is (8~12):1. This ratio can make the mesoporous structure of AMSNs and the mechanical properties of elastic microspheres work synergistically, ensuring both the enzyme loading and good tribothermic effect. The amount of silane coupling agent is 0.5~1wt% of the sum of the masses of AMSNs and elastic microspheres, which can achieve stable covalent binding between AMSNs and elastic microspheres and avoid dissociation of the composite carrier during the processing.

[0029] (6) In the preparation of ECCs, the concentration of CMCS aqueous solution is 0.1~0.5wt%. This concentration can form a complete pH-responsive layer on the surface of the composite carrier without causing the composite carrier to agglomerate due to excessive CMCS concentration. The mass ratio of plant protease to composite carrier is 1:(4~8), which can ensure enzyme activity while avoiding cost waste caused by excessive enzyme. The concentration of glutaraldehyde solution is 0.8~1.2wt%, and the cross-linking temperature is 3~6℃, which can achieve stable enzyme fixation and reduce enzyme activity loss. The concentration of ECCs working solution is 1~3g / L, and the pH value is 5~6, which can ensure that the enzyme concentration in the working solution is appropriate and the pH value matches the response characteristics of CMCS (CMCS swells and releases enzyme under acidic conditions).

[0030] (7) The role of amino-modified mesoporous silica in this invention is to introduce amino groups on mesoporous silica, which significantly enhances the interaction between silica and plant proteases, making plant proteases more effectively adsorbed on the surface of mesoporous silica; in addition, amino modification can also improve the dispersibility and stability of mesoporous silica, preventing it from agglomerating or precipitating in the enzyme-complex carrier complex working solution.

[0031] (8) The wool fabric treated by the method of the present invention exhibits the following degradation effect on the scale layer: the thickness of the wool scale layer is reduced by 30-32%, indicating that the wool scale layer structure is effectively destroyed, which can significantly reduce the directional friction effect between fibers. The directional friction effect value (DFE) ≤ 0.15 indicates that the slip resistance between wool fibers is greatly reduced, effectively suppressing the occurrence of pilling.

[0032] The pilling and fuzzing grade of wool fabrics reaches 4-5, fully meeting the appearance quality requirements of high-end wool products. Enzyme stability: The half-life of plant protease is extended to 70-72 hours, which is 5-6 times higher than that of traditional free enzymes (half-life approximately 12 hours). Wool fiber damage: The main strength loss rate of wool fibers is <5%, far lower than that of traditional high-temperature enzymatic hydrolysis processes, effectively preserving the wearing performance and durability of wool fabrics.

[0033] (9) The finishing method of the present invention is applicable to the optimization of anti-pilling function of various wool products such as wool woven fabrics, knitted fabrics, and wool blended fabrics. It is especially suitable for industrial continuous production scenarios with high requirements for energy consumption control, ecological environmental protection and production efficiency. It can be widely used in the finishing processing of high-end wool clothing, home textile fabrics and other products.

[0034] (10) The finishing process of the present invention has the advantages of low temperature and high efficiency, and low energy consumption: no high temperature heating is required, and efficient enzymatic hydrolysis can be achieved under normal temperature conditions, achieving excellent anti-pilling effect, and the energy consumption is reduced compared with the traditional high temperature process. Stable enzyme activity and controllable process: through the synergistic effect of composite carrier protection and pH-responsive enzyme release, the enzyme half-life is greatly extended, the enzymatic hydrolysis efficiency is stable, the process repeatability is high, and there is no need to frequently add enzyme preparations, which reduces production costs while ensuring the uniformity of wool fabric finishing effect. Eco-friendly and safe: all raw materials used have good biodegradability and no toxic or harmful chemical residues. Strong equipment compatibility and easy industrialization: no special equipment is required, and traditional impregnation-vibration equipment can be directly used. The process adjustment is simple, adaptable to the production lines of existing textile enterprises, and easy to realize large-scale industrial application. Attached Figure Description

[0035] Figure 1 Here is a photograph of the wool fabric obtained in Example 1 after a pilling test. Figure 2 This is a photograph of the wool fabric obtained in Example 2 after a pilling test. Figure 3 This is a photograph of the wool fabric obtained in Example 3 after a pilling test. Figure 4 Here is a photograph of the wool fabric obtained in Example 4 after a pilling test. Figure 5 This is a photograph of the wool fabric obtained in Example 5 after a pilling test. Figure 6 A photograph of the wool fabric obtained in Comparative Example 1 after a pilling test. Figure 7 A photograph of the wool fabric obtained in Comparative Example 2 after a pilling test. Figure 8 This is a photograph of the wool fabric obtained in Comparative Example 3 after a pilling test. Detailed Implementation

[0036] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the present invention will be described in detail below with reference to specific embodiments in the specification.

[0037] Many specific details are set forth in the following description in order to provide a full understanding of the invention. However, the invention may also be practiced in other ways different from those described herein, and those skilled in the art can make similar extensions without departing from the spirit of the invention. Therefore, the invention is not limited to the specific embodiments disclosed below.

[0038] Unless otherwise specified, the experimental methods used in the following specific embodiments are conventional methods. Unless otherwise specified, the materials, reagents, methods, and instruments used are all conventional materials, reagents, methods, and instruments in the art, and can be obtained commercially by those skilled in the art.

[0039] In the following examples, the polycaprolactone-polyethylene glycol block copolymer was obtained from Xiamen Sainobange Biotechnology Co., Ltd., and the carboxymethyl chitosan (CMCS, degree of substitution ≥0.8), hexadecyltrimethylammonium bromide (CTAB, 99%), tetraethyl silicate (TEOS, 98%), 3-aminopropyltriethoxysilane (APTES, 99%), bromelain (activity unit 300U / mg), papain (activity unit 200U / mg), waterborne polyurethane, and glycidyl etheroxypropyltrimethoxysilane were all purchased from Shanghai Maclean Biochemical Technology Co., Ltd.; the wool knitted fabric was purchased from Wujiang Xianfeng Knitting Co., Ltd.

[0040] Example 1 1. Preparation of composite carriers (1) Synthesis of elastic microspheres: elastic microspheres were prepared by emulsification-solvent evaporation method using polycaprolactone-polyethylene glycol block copolymer as raw material. The specific process is as follows: polycaprolactone-polyethylene glycol block copolymer is dissolved in dichloromethane to form an organic phase solution with a concentration of 100 g / L. The organic phase solution is added dropwise to a polyvinyl alcohol aqueous solution with a mass fraction of 1.0 wt% (polyvinyl alcohol is added to water to obtain the solution). The volume ratio of the organic phase solution to the polyvinyl alcohol aqueous solution is 1:5. Then, the solution is emulsified under ultrasonic conditions until the dichloromethane solvent is completely evaporated. The precipitate is collected by centrifugation and the residual polyvinyl alcohol is removed by washing with deionized water to obtain elastic microspheres with a particle size of 70-80 nm and good dispersibility. The microspheres are then dried in a vacuum drying oven for later use. (2) Preparation of AMSNs S1, MSNs preparation: Hexadecyltrimethylammonium bromide (CTAB) was used as a template agent and added to deionized water. The mixture was stirred until completely dissolved to prepare a 0.2 wt% CTAB aqueous solution. Ammonia was added to the CTAB aqueous solution to adjust the pH of the system to 10.5. Then, a 0.8 wt% tetraethyl silicate solution (tetraethyl silicate dissolved in anhydrous ethanol) was added as a silicon source. The molar ratio of CTAB to tetraethyl silicate was 1:2. The reaction was carried out under constant temperature water bath conditions of 32℃ for 5 h. After the reaction was completed, the reaction mixture was centrifuged and the precipitate was collected. The precipitate was washed three times alternately with deionized water and anhydrous ethanol to remove residual CTAB template agent, thus obtaining MSNs with a pore size of 7-8 nm. S2, AMSNs preparation: MSNs were dispersed in anhydrous ethanol and ultrasonically dispersed for 30 min to prepare an MSNs-ethanol dispersion with a concentration of 10 g / L. 0.88 g of 3-aminopropyltriethoxysilane (APTES) was added to the MSNs-ethanol dispersion. The mass ratio of APTES to MSNs was 2:1. The mixture was then stirred at 75 °C for 7 h to graft amino groups onto the surface of MSNs. After the reaction was completed, the precipitate was collected by centrifugation and washed with anhydrous ethanol to remove unreacted APTES, thus obtaining AMSNs. The AMSNs were then vacuum dried for later use. (3) AMSNs and elastic microspheres were added to deionized water (AMSNs to elastic microspheres mass ratio 10:1), ultrasonically dispersed and mixed evenly, and then silane coupling agent KH-550 was added at a dosage of 0.5wt% of the total mass of AMSNs and elastic microspheres. The reaction was carried out under constant temperature water bath at 50℃ for 6 hours with stirring, so that AMSNs and elastic microspheres were covalently bonded. After the reaction was completed, the precipitate was collected by centrifugation, and unreacted silane coupling agent was removed by washing with deionized water to obtain the composite carrier, which was then vacuum dried for later use. 2. Preparation of ECCs: 0.2 g of CMCS with a degree of substitution ≥0.8 was dissolved in 100 mL of deionized water and stirred until completely dissolved to prepare a CMCS aqueous solution with a concentration of 0.2 wt%. 0.44 g of the composite carrier was added to the above CMCS aqueous solution and stirred at room temperature for 13 h to allow CMCS to be modified on the outside of the composite carrier to form a pH-appropriate layer. Then, 0.088 g of bromelain (300 U / mg activity unit, enzyme to composite carrier mass ratio 1:5) was added and the mixture was shaken and adsorbed at 32 °C for 2.5 h. Finally, 5 mL of 1.0 wt% glutaraldehyde solution (glutaraldehyde dissolved in water) was added and the mixture was subjected to a low-temperature cross-linking reaction at 4 °C for 2.5 h to successfully load the composite carrier with bromelain. After the reaction was completed, the solid material was collected by centrifugation and washed with deionized water to remove unfixed enzyme and glutaraldehyde, thus obtaining ECCs for later use. 3. Tribothermia-enzymatic hydrolysis synergistic treatment: ECCs are dispersed in deionized water and stirred evenly to form an ECCs working solution with a concentration of 2 g / L. The pH of the working solution is adjusted to 5.5 with 0.1 mol / L citrate-sodium citrate buffer. The wool fabric to be treated is taken and mixed with the ECCs working solution at a bath ratio of 1:25. The mixture is then added to a shaking reactor and shaken for 60 min at room temperature. 4. Post-treatment: Take the wool fabric after shaking treatment out of the working solution, wash it with deionized water at room temperature to remove the residual ECCs and enzymatic hydrolysis products on the surface of the fabric, and then put the washed wool fabric into the oven to dry it to obtain anti-pilling wool fabric. To determine the anti-pilling performance of the finishing method in this embodiment for wool fabrics, steps 1 to 4 of the process were repeated multiple times to finish the wool fabrics, resulting in a total of 5 wool fabrics for pilling tests.

[0041] Performance tests were conducted on the wool fabric treated in this embodiment: the physical thickness of the wool scale layer before and after treatment was measured using SEM and compared. The method for calculating the reduction in wool scale layer thickness was as follows:

[0042] Where m1 is the thickness of the wool scale layer before finishing, and m2 is the thickness of the wool scale layer after finishing.

[0043] In this embodiment, the wool scale layer thickness was reduced by 31.2%. The directional friction effect (DFE) value of the treated wool fabric was tested using the winch method, and the result was 0.13. Pilling tests were performed on the wool fabric obtained in this embodiment, referring to GB / T 4802.1-2008 "Textiles - Determination of Pilling Properties - Part 1: Circular Trajectory Method". The results showed that the pilling grade of the wool fabric obtained in this embodiment was level 5 (with 94% of the products at level 5). The absorbance of the enzymatic reaction product was measured using a phosphate buffer and the reaction substrate casein with a UV spectrophotometer. The test results showed that the half-life of bromelain in this embodiment was 72 hours. The breaking strength of the untreated and treated wool fibers was tested using a single fiber strength tester to calculate the strength loss rate. The strength loss rate of the wool fibers in this embodiment was 4.2%.

[0044] The actual photograph of the wool fabric obtained in this embodiment after undergoing a pilling test is shown below. Figure 1 As shown, the fabric surface is smooth and flat, with virtually no pilling or fuzzing. This indicates that the wool fabric treated by the method in this embodiment has a high pilling resistance level of 5, demonstrating good anti-pilling performance.

[0045] Example 2 The difference between this embodiment and embodiment 1 is that: (1) the concentration of the organic phase solution in the elastic microsphere synthesis stage is 80 g / L, the mass fraction of the polyvinyl alcohol aqueous solution is 0.8 wt%, and the particle size of the elastic microspheres is 50~60 nm; (3) The mass ratio of AMSNs to elastic microspheres is 8:1, the amount of silane coupling agent is 0.8wt% of the total mass of AMSNs and elastic microspheres, the stirring reaction temperature is 40℃, and the reaction time is 8h; During the preparation of ECCs, the concentration of CMCS aqueous solution was 0.1 wt%, the stirring time after adding the composite carrier to the CMCS aqueous solution was 10 h, the enzyme used was papain, the mass ratio of papain to the composite carrier was 1:4, the concentration of glutaraldehyde solution was 0.8 wt%, the cross-linking reaction temperature was 3℃, and the reaction time was 4 h.

[0046] In the tribothermic heat generation-enzymatic hydrolysis synergistic treatment stage, the concentration of the ECCs working solution was 1 g / L, the pH was adjusted to 5.0, the bath ratio was 1:20, and the shaking reaction time was 50 min. The remaining process steps and parameters are the same as in Example 1.

[0047] The wool fabric treated in this embodiment was subjected to performance tests, and the test methods were the same as in Example 1. The results are as follows: the wool scale layer thickness decreased by 30.1%, and the directional friction effect (DFE) value was 0.14. The pilling grade of the wool fabric obtained in this embodiment was grade 5 (of which grade 5 accounted for 91%). In this embodiment, the papain half-life was 70.2 h, and the wool fiber strength loss rate was 4.8%.

[0048] The actual photograph of the wool fabric obtained in this embodiment after undergoing a pilling test is shown below. Figure 2 As shown, the fabric surface is smooth and flat, with virtually no pilling or fuzzing. This indicates that the wool fabric treated by the method in this embodiment has a high pilling resistance level of 5, demonstrating good anti-pilling performance.

[0049] Example 3 The difference between this embodiment and embodiment 1 is that: in step S1 of process (2), the concentration of CTAB aqueous solution is 0.4 wt%, the pH value of the system is adjusted to 11, the concentration of tetraethyl silicate is 1.0 vol%, the reaction temperature is 35°C, the time is 4 h, and the pore size of MSNs is 9-10 nm. In step S2, the concentration of MSNs-ethanol dispersion is 20 g / L, the amount of APTES added is 1.5 g, the reaction temperature is 80℃, and the time is 6 h. During the preparation of ECCs, the concentration of CMCS aqueous solution was 0.5wt%, the stirring time after adding the composite carrier to the CMCS aqueous solution was 16h, the mass ratio of bromelain to composite carrier was 1:8, the cross-linking reaction temperature was 6℃, and the time was 1h. In the tribothermic heat generation-enzymatic hydrolysis synergistic treatment stage, the concentration of the ECCs working solution was 3 g / L, the pH was adjusted to 6.0, the bath ratio was 1:30, and the shaking reaction time was 55 min. The remaining process steps and parameters are the same as in Example 1.

[0050] The wool fabric treated in this embodiment was subjected to performance tests, and the test methods were the same as in Example 1. The results are as follows: the wool scale layer thickness decreased by 31.8%, and the directional friction effect (DFE) value was 0.12. The pilling grade of the wool fabric obtained in this embodiment was grade 5 (of which grade 5 accounted for 95%). In this embodiment, the half-life of bromelain was 72 hours, and the wool fiber strength loss rate was 3.9%.

[0051] The actual photograph of the wool fabric obtained in this embodiment after undergoing a pilling test is shown below. Figure 3 As shown, the fabric surface is smooth and flat, with virtually no pilling or fuzzing. This indicates that the wool fabric treated by the method in this embodiment has a high pilling resistance level of 5, demonstrating good anti-pilling performance.

[0052] Example 4 The difference between this embodiment and Example 1 is that: (1) the concentration of the organic phase solution in the elastic microsphere synthesis stage is 120 g / L, the mass fraction of the polyvinyl alcohol aqueous solution is 1.2 wt%, and the particle size of the elastic microspheres is 90-100 nm; (3) The mass ratio of AMSNs to elastic microspheres is 12:1, the amount of silane coupling agent is 1.0 wt% of the total mass of AMSNs and elastic microspheres, the stirring reaction temperature is 60℃, and the reaction time is 5h. The enzyme used in the preparation of ECCs is papain. The oscillating reaction time for the frictional heat generation-enzymatic hydrolysis synergistic treatment stage was 40 min. The remaining process steps and parameters are the same as in Example 1.

[0053] The wool fabric treated in this embodiment was subjected to performance tests, and the test methods were the same as in Example 1. The results are as follows: the wool scale layer thickness decreased by 30.9%, and the directional friction effect (DFE) value was 0.14. The pilling grade of the wool fabric obtained in this embodiment was 4-5 (of which 92% were grade 5). In this embodiment, the papain half-life was 71 hours, and the wool fiber strength loss rate was 4.5%.

[0054] The actual photograph of the wool fabric obtained in this embodiment after undergoing a pilling test is shown below. Figure 4 As shown, the fabric surface is smooth and flat, with virtually no pilling or fuzzing. This indicates that the wool fabric treated by the method in this embodiment has a high pilling resistance level of 4-5, demonstrating good anti-pilling performance.

[0055] Example 5 The difference between this embodiment and embodiment 1 is that in step S1 of process (2), the pH value of the system is adjusted to 10, the concentration of tetraethyl silicate is 0.7%, the reaction temperature is 30°C, the time is 6h, and the pore size of MSNs is 5-6nm. In step S2, the reaction temperature is 70℃ and the time is 8 hours. During the tribothermic heat generation-enzymatic hydrolysis synergistic treatment stage, the pH of the ECCs working solution was adjusted to 5.2, the bath ratio was 1:22, and the shaking reaction time was 50 min. The remaining process steps and parameters are the same as in Example 1.

[0056] The wool fabric treated in this embodiment was subjected to performance tests, and the test methods were the same as in Example 1. The results are as follows: the wool scale layer thickness decreased by 30.5%, and the directional friction effect (DFE) value was 0.15. The pilling grade of the wool fabric obtained in this embodiment was 4-5 (with 90% of the products being grade 5). In this embodiment, the half-life of bromelain was 70.5 h, and the wool fiber strength loss rate was 4.7%.

[0057] The actual photograph of the wool fabric obtained in this embodiment after undergoing a pilling test is shown below. Figure 1 As shown, the fabric surface is smooth and flat, with virtually no pilling or fuzzing. This indicates that the wool fabric treated by the method in this embodiment has a high pilling resistance level of 4-5, demonstrating good anti-pilling performance.

[0058] Comparative Example 1 (Traditional High-Temperature Enzymatic Hydrolysis) (1) Preparation of plant protease working solution: Dissolve 0.088g of bromelain in 0.1mol / L citrate-sodium citrate buffer (pH5.5) to prepare an enzyme working solution with a concentration of 0.4g / L; (2) Enzymatic hydrolysis: Take wool fabric of the same specifications as in Example 1, mix it with enzyme working solution at a bath ratio of 1:25, put it into a constant temperature water bath shaker, set the temperature to 60℃ (the temperature of traditional high temperature process), and shake for 60 min. (3) Post-treatment: The wool fabric after the oscillation treatment is washed and dried according to the post-treatment steps in Example 1.

[0059] The performance of the wool fabric treated in this comparative example was tested using the same methods as in Example 1. The results are as follows: the wool scale layer thickness decreased by 28.3%, and the directional friction effect (DFE) value was 0.18. The pilling grade of the wool fabric obtained in this comparative example was grade 3 (with 0% of the products being grade 5). The half-life of bromelain in this comparative example was 70.5 h, and the wool fiber strength loss rate was 16.5%.

[0060] The photograph of the wool fabric obtained in this comparative example after undergoing pilling and fuzzing tests is shown below. Figure 6 As shown, there is obvious pilling on the fabric surface, with a large number of pills, indicating that the wool fabric treated by traditional high-temperature enzymatic hydrolysis has a low pilling grade of only 3, and poor anti-pilling performance.

[0061] Comparative Example 2 (Frictionless heat generation, room temperature enzymatic hydrolysis and preparation) 1. Preparation of composite carrier: The preparation method is the same as that of the composite carrier in Example 1; 2. Preparation of enzyme-complex carrier complex: 0.44 g of complex carrier and 0.088 g of bromelain (activity unit 300 U / mg, enzyme to complex carrier mass ratio 1:5) were dissolved in 100 mL of deionized water and the mixture was shaken and adsorbed at 32 °C for 2.5 h. Finally, 5 mL of 1.0 wt% glutaraldehyde solution was added, and the mixture was subjected to a low-temperature cross-linking reaction at 4 °C for 2.5 h to successfully load bromelain onto the complex carrier. After the reaction was completed, the solid material was collected by centrifugation and washed with deionized water to remove unfixed enzyme and glutaraldehyde, thus obtaining the enzyme-complex carrier complex for later use. 3. Enzymatic hydrolysis: The difference between this step and the frictional heat generation-enzymatic hydrolysis synergistic treatment process in Example 1 is that the oscillation temperature is 30°C, and the rest of the operation is the same as in Example 1; 4. Post-processing: This step is the same as the post-processing process in Example 1.

[0062] The performance of the wool fabric treated in this comparative example was tested using the same methods as in Example 1. The results are as follows: the wool scale layer thickness decreased by 15.2%, and the directional friction effect (DFE) value was 0.32. The pilling grade of the wool fabric obtained in this comparative example was 2-3 (with 0% of the products being grade 5). The half-life of bromelain in this comparative example was 71.2 h, and the wool fiber strength loss rate was 2.1%.

[0063] The photograph of the wool fabric obtained in this comparative example after undergoing pilling and fuzzing tests is shown below. Figure 7 As shown, there is obvious pilling on the fabric surface, with a large number of pills. This indicates that the pilling grade of the wool fabric treated with frictionless heat generation and room temperature enzymatic hydrolysis is low, only grade 3. This is because the enzymatic hydrolysis efficiency is extremely low under room temperature conditions, making it impossible to carry out effective anti-pilling treatment.

[0064] Comparative Example 3 (Chemical Resin Finishing) (1) Preparation of resin finishing solution: Dissolve waterborne polyurethane in deionized water, add crosslinking agent glycidyl etheroxypropyltrimethoxysilane, stir evenly, and prepare a resin finishing solution with a polyurethane concentration of 100 g / L. The amount of crosslinking agent is 0.5 wt% of the finishing solution; (2) Padding treatment: Take wool fabric of the same specifications as in Example 1, immerse it in resin finishing solution for 10 minutes according to the bath ratio of wool fabric to resin finishing solution of 1:20, and then perform padding treatment by padding machine (80% padding rate). (3) Baking and curing: Place the rolled wool fabric in an oven and bake at 120°C for 15 minutes to complete the curing.

[0065] The performance of the wool fabric treated in this comparative example was tested using the same methods as in Example 1. The results are as follows: there was no significant degradation of the wool scale layer (thickness decreased by 2.1%), and the directional friction effect (DFE) was 0.21. The pilling grade of the wool fabric obtained in this example was 3-4 (of which 15% were at grade 5). Although a small portion of the wool fabric reached grade 5 after treatment, most of the wool fabric was at grade 3 or 4, indicating that the traditional chemical resin finishing method has limited effect on improving the pilling resistance of wool fabrics, and its effect is worse than that of this invention. The wool fiber strength loss rate in this comparative example was 8.7%.

[0066] The photograph of the wool fabric obtained in this comparative example after undergoing pilling and fuzzing tests is shown below. Figure 8 As shown, it can be seen that there is obvious pilling on the fabric surface, with a large number of pills, indicating that the pilling level of the wool fabric treated with chemical resin is low.

[0067] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A method for treating wool fabrics using a composite carrier and pH-responsive synergistic effect, characterized in that, The method includes the following steps: (1) Preparation of composite carrier: Amino-modified mesoporous silica nanoparticles and elastic microspheres were added to deionized water, followed by the addition of silane coupling agent, and reacted under water bath conditions to obtain composite carrier; (2) Preparation of enzyme-composite carrier complex with pH response layer: carboxymethyl chitosan was dissolved in water to form carboxymethyl chitosan aqueous solution, the composite carrier was added to the carboxymethyl chitosan aqueous solution, stirred at room temperature, then plant protease was added, oscillated and adsorbed, then glutaraldehyde solution was added, and cross-linking reaction was carried out at low temperature to obtain enzyme-composite carrier complex with pH response layer. (3) Tribothermation-enzymatic hydrolysis synergistic treatment: The enzyme-complex carrier complex with pH response layer is dispersed in deionized water to form an enzyme-complex carrier complex working solution. The pH of the working solution is adjusted to 5-6 with citrate-sodium citrate buffer. Then, wool fabric is mixed with the enzyme-complex carrier complex working solution with pH 5-6 and treated with shaking at room temperature. (4) Post-treatment: The wool fabric after vibration treatment is washed and dried to obtain wool fabric with anti-pilling properties.

2. The method according to claim 1, characterized in that, The preparation method of elastic microspheres in step (1) is as follows: biodegradable polyester copolymer is dissolved in an organic solvent to form an organic phase solution, the organic phase solution is dropped into a polyvinyl alcohol aqueous solution, and emulsified under ultrasonic conditions to obtain elastic microspheres with a particle size of 50~100nm.

3. The method according to claim 2, characterized in that, The concentration of the organic phase solution is 80~120 g / L, and the concentration of the polyvinyl alcohol aqueous solution is 0.8~1.2 wt%.

4. The method according to claim 1, characterized in that, The preparation method of amino-modified mesoporous silica nanoparticles in step (1) includes the following steps: S1. Preparation of mesoporous silica nanoparticles: Prepare a template solution, add ammonia to the template solution to adjust the pH of the system to 10-11, then add tetraethyl silicate, and react under water bath conditions to obtain mesoporous silica nanoparticles with a pore size of 5-10 nm. S2. Preparation of amino-modified mesoporous silica nanoparticles: Mesoporous silica nanoparticles are dispersed in anhydrous ethanol to form a mesoporous silica nanoparticle-ethanol dispersion. Silane with amino-modifying effect is added to the mesoporous silica nanoparticle-ethanol dispersion, and the reaction is carried out to obtain amino-modified mesoporous silica nanoparticles.

5. The method according to claim 4, characterized in that, In step S1, the concentration of the template agent solution is 0.2~0.4wt%, the concentration of the tetraethyl silicate solution is 0.7~1.2vol%, the water bath temperature is 30~35℃, and the reaction time is 4~6h. In step S2, the concentration of the mesoporous silica nanoparticle-ethanol dispersion is 10~20g / L, the silane with amino modification is 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane or 3-aminopropyltrimethoxysilane, the mass ratio of mesoporous silica nanoparticles to amino-modified silane is (1~3):1, the reaction temperature is 70~80℃, and the time is 6~8h.

6. The method according to claim 1, characterized in that, In step (1), the mass ratio of amino-modified mesoporous silica nanoparticles to elastic microspheres is (8~12):1, and the amount of silane coupling agent is 0.5~1wt% of the sum of the masses of amino-modified mesoporous silica nanoparticles and elastic microspheres.

7. The method according to claim 1, characterized in that, In step (2), the concentration of the carboxymethyl chitosan aqueous solution is 0.1~0.5wt%, the mass ratio of plant protease to composite carrier is 1:(4~8), the oscillation adsorption temperature is 30~35℃, the time is 2~3h, the cross-linking reaction temperature is 3~6℃, and the time is 1~4h.

8. The method according to claim 1, characterized in that, In step (3), the concentration of the enzyme-complex carrier working solution is 1~3g / L, and the bath ratio of the wool fabric to the enzyme-complex carrier working solution with pH 5~6 is 1:(20~30).

9. A wool fabric with anti-pilling properties, characterized in that, The wool fabric is obtained by processing the method according to any one of claims 1 to 8.

10. The wool fabric according to claim 9, characterized in that, The directional friction effect value of this wool fabric is ≤0.15, and the pilling grade is ≥4.

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