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

Abstract

The application discloses a method for finishing wool fabric by using a composite carrier and pH response synergy, and belongs to the technical field of functional finishing of textile materials. The method solves the problems of high energy consumption, unstable enzyme activity, serious chemical reagent pollution, damage to wool fibers and poor anti-pilling performance in the existing finishing technology of wool fabric. The composite carrier is formed by elastic microspheres and amino-modified mesoporous silica nanoparticles, plant protease is loaded on the carrier, a pH response layer is constructed on the outside of the carrier, and a composite is obtained. When the wool fabric is oscillated in the working solution of the composite with adjusted pH, local micro-heat is generated by the friction between the composite and the scale layer of the wool, so that the swelling of the pH response layer and the release of the plant protease are accelerated, the enzyme activity is activated, and efficient enzymolysis of the scale layer of the wool at normal temperature is realized. The finishing process has the advantages of low temperature and high efficiency, excellent anti-pilling effect, green and environment-friendly raw materials, and easy industrialization and large-scale application.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of functional finishing technology of textile materials, and particularly relates to a method for finishing wool fabric by using a composite carrier and pH response synergistic effect. BACKGROUND

[0002] Wool fabric occupies an important position in the field of high-end clothing and home textiles due to its excellent wearing performance such as softness, warmth, air permeability and moisture absorption, and is deeply favored by consumers. However, the unique scale layer structure on the surface of wool fibers makes them prone to fiber slippage, entanglement and breakage during daily wear, washing and friction, which in turn causes pilling. This problem not only seriously damages the appearance and comfort of wool fabric, but also shortens the service life of the fabric, greatly restricting the market competitiveness and application expansion of wool fabric. To solve the problem of pilling of wool fabric, various anti-pilling finishing technologies have been developed in the industry, but the current mainstream technologies still have many technical defects that are difficult to overcome, as follows:

[0003] (1) Strong dependence on high temperature, high energy consumption and damage to wool fibers: Traditional enzymatic finishing technology requires a reaction at a high temperature of about 60℃ to ensure the activity of protease. On the one hand, high temperature leads to a sharp increase in energy consumption during production, 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 strength loss, usually with a strength loss rate of 15-20%, which seriously damages the original wearing performance and durability of wool fabric.

[0004] (2) Poor stability of enzyme activity and low repeatability of finishing process: Free protease used for wool finishing is extremely sensitive to environmental conditions, and factors such as temperature fluctuations, pH changes and impurities interference can easily cause damage to the enzyme molecular structure and loss of activity. This makes the enzymatic efficiency unstable in actual production, and the uniformity of finishing effect is poor, which requires frequent addition of enzyme preparations to maintain the finishing effect, increasing the production cost and making it difficult to accurately control the process parameters, thus affecting the production stability and repeatability.

[0005] (3) Serious pollution by chemical finishing agents and poor ecological compatibility: Currently, resin-based chemical finishing agents such as polyurethane and epoxy resin are commonly used in industry to treat wool fabric for anti-pilling. Although these agents can improve the anti-pilling performance of the fabric in the short term, they have a significant skin sensitization risk, and long-term contact may cause skin discomfort or even allergic reactions in humans. Resin finishing also leads to poor wearing performance of the fabric. In addition, resin-based finishing agents have very low biodegradability and can easily accumulate in the environment, causing soil and water pollution, which is inconsistent with the current trend of ecological textiles and green consumption.

[0006] In view of the above technical problems, the textile industry urgently needs to develop a low-temperature high-efficiency, enzyme activity stable, eco-friendly and cost-controllable wool anti-pilling finishing technology. SUMMARY

[0007] In order to solve the problems of high energy consumption, unstable enzyme activity, serious chemical reagent pollution, wool fiber damage and poor anti-pilling performance caused by high temperature conditions in the existing wool fabric anti-pilling finishing technology, a method for finishing wool fabric by composite carrier and pH response synergistic action is provided.

[0008] To achieve the above purpose, the technical scheme of the present application is as follows:

[0009] One of the purposes of the present application is to provide a method for finishing wool fabric by composite carrier and pH response synergistic action, which comprises the following steps:

[0010] (1) Composite carrier preparation: amino-modified mesoporous silica nanoparticles (AMSNs) and elastic microspheres are added to deionized water, then silane coupling agent is added, and the reaction is carried out under water bath conditions to make AMSN and elastic microspheres combine through covalent bond to obtain a composite carrier;

[0011] (2) Enzyme-composite carrier complex (ECCs) with pH response layer preparation: carboxymethyl chitosan (CMCS) is dissolved in water to form a carboxymethyl chitosan aqueous solution, the composite carrier is added to the carboxymethyl chitosan aqueous solution, and stirring is carried out at room temperature to modify CMCS on the surface of the composite carrier, then plant protease is added and adsorbed by oscillation, and then glutaraldehyde solution is added and cross-linking reaction is carried out at low temperature to successfully load plant protease on the composite carrier to obtain enzyme-composite carrier complex (ECCs) with pH response layer;

[0012] (3) Friction heat-enzymolysis synergistic treatment: the enzyme-composite carrier complex with pH response layer is dispersed in deionized water to form enzyme-composite carrier complex working solution, the pH value of the working solution is adjusted to 5-6 with citric acid-sodium citrate buffer solution, then the wool fabric is mixed with the enzyme-composite carrier complex working solution with pH value of 5-6, and oscillation treatment is carried out at room temperature;

[0013] (4) Post-treatment: the wool fabric after oscillation treatment is washed and dried to obtain wool fabric with anti-pilling performance.

[0014] Further limited, the preparation method of the elastic microspheres in step (1) is: using biodegradable polyester copolymer as raw material, and using emulsification-solvent evaporation method to prepare elastic microspheres.

[0015] Further, the elastic microspheres are prepared by dissolving a biodegradable polyester copolymer in an organic solvent to form an organic phase solution, dropping the organic phase solution into a polyvinyl alcohol aqueous solution, and emulsifying under ultrasonic conditions to obtain elastic microspheres with a particle size of 50-100 nm.

[0016] Further, 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%.

[0017] Further, the preparation method of the amino-modified mesoporous silica nanoparticles in step (1) comprises the following steps:

[0018] S1, mesoporous silica nanoparticle (MSN) preparation: preparing a template solution, adding ammonia water to the template solution to adjust the pH value of the system to 10-11, then adding tetraethyl orthosilicate as a silicon source, and reacting under water bath conditions; after the reaction is completed, centrifugation and washing are performed to obtain mesoporous silica nanoparticles with a pore size of 5-10 nm;

[0019] S2, amino-modified mesoporous silica nanoparticle preparation (AMSNs): dispersing the mesoporous silica nanoparticles in anhydrous ethanol to form an MSNs-ethanol dispersion, adding a silane with an amino-modifying effect to the MSNs-ethanol dispersion, and reacting to graft amino groups to the surface of the MSNs; after the reaction is completed, centrifugation and ethanol washing are performed to obtain amino-modified mesoporous silica nanoparticles.

[0020] Further, in step S1, the concentration of the template solution is 0.2-0.4 wt%, the concentration of the tetraethyl orthosilicate is 0.7-1.2 vol%, the water bath temperature is 30-35°C, and the reaction time is 4-6 h; in step S2, the concentration of the MSNs-ethanol dispersion is 10-20 g / L, the silane with an amino-modifying effect is 3-aminopropyl triethoxysilane (APTES), 3-aminopropyl methyldimethoxysilane, or 3-aminopropyl trimethoxysilane, the mass ratio of the MSNs to the silane with an amino-modifying effect is (1-3):1, the reaction temperature is 70-80°C, and the reaction time is 6-8 h.

[0021] Further, the mass ratio of the amino-modified mesoporous silica nanoparticles to the elastic microspheres in step (1) is (8-12):1.

[0022] Further, the amount of the silane coupling agent used in step (1) is 0.5-1 wt% of the sum of the mass of the amino-modified mesoporous silica nanoparticles and the mass of the elastic microspheres.

[0023] Further, the degree of substitution of the carboxymethyl chitosan is ≥0.8, and the concentration of the carboxymethyl chitosan aqueous solution is 0.1-0.5 wt%.

[0024] Further limit, the stirring time in step (2) is 10-16h.

[0025] Further limit, the plant protease activity unit in step (2) is ≥200U / mg, and the mass ratio of plant protease to complex carrier is 1: (4-8).

[0026] Further limit, the oscillation adsorption temperature in step (2) is 30-35℃, and the time is 2-3h.

[0027] Further limit, the glutaraldehyde solution concentration in step (2) is 0.8-1.2wt%.

[0028] Further limit, the crosslinking reaction temperature in step (2) is 3-6℃, and the time is 1-4h.

[0029] Further limit, the enzyme-complex carrier complex working solution concentration in step (3) is 1-3g / L.

[0030] Further limit, the bath ratio of wool fabric to enzyme-complex carrier complex working solution with pH 5-6 in step (3) is 1: (20-30).

[0031] The second purpose of the application is to provide a wool fabric with anti-pilling performance treated by the above method.

[0032] Further limit, the directional friction effect value (D.F.E.) of the wool fabric is ≤0.15, and the pilling grade is ≥4.

[0033] The beneficial effects of the application are:

[0034] (1) The application firstly constructs a nano-composite carrier with core-shell structure, taking elastic microspheres as the core and amino-modified mesoporous silica as the shell, and uses the composite carrier to load plant protease, so that the enzyme is not only loaded on the surface of the composite carrier, but also exists in the mesoporous and inside the composite carrier, and the application uses carboxymethyl chitosan to form a pH-responsive layer outside the composite carrier, to obtain enzyme-composite carrier complex (ECCs) with pH-responsive layer. When the wool fabric is treated by oscillation in the ECCs working solution with adjusted pH, mechanical friction occurs between the ECCs and the wool scale layer, which can produce local micro-heat of 40-50℃, the micro-heat can accelerate the swelling of the pH-responsive layer and the release of plant protease, and activate the activity of plant protease, to realize efficient enzymolysis of the wool scale layer at room temperature.

[0035] (2) The nano-composite carrier in the application has a protective effect: the mesoporous structure of AMSN can provide a stable loading space for plant protease, and the elastic microspheres, as part of the composite carrier, can absorb and disperse mechanical impact force in the friction heat production process, avoiding the direct mechanical shearing of enzyme molecules and inactivation; in addition, after the elastic microspheres are combined with the amino-modified mesoporous silica, local micro-heat is generated on the surface of the wool scale through mechanical friction, accelerating the enzymatic reaction, while avoiding damage to the main structure of the wool fiber due to overheating; in addition, the composite carrier formed by the elastic microspheres and the amino-modified mesoporous silica can enable the enzyme to be effectively adsorbed in the mesopores of the composite carrier, and the pH-responsive layer is wrapped on the surface of the composite carrier, which releases the enzyme in stages under weak acidic conditions; and the composite carrier can reduce the direct contact of the enzyme with impurities on the surface of the wool fabric, and reduce the non-specific adsorption loss of the plant protease.

[0036] (3) The pH-responsive layer releases the enzyme in the application: the pH-responsive layer formed by CMCS modification is compact in structure under neutral or alkaline conditions, which can inhibit the release of the enzyme, while in the weakly acidic ECCs working solution with pH 5-6, CMCS swells and gradually releases the loaded plant protease, realizing precise and controllable release of the enzyme and avoiding the activity loss of the enzyme in the non-reaction stage. Friction heat production accelerates the reaction: the mechanical friction between ECCs and the scale layer of wool during oscillation generates local micro-heat of 40-50℃, which only acts on the scale layer on the surface of the wool fiber and does not affect the main structure of the fiber; the micro-heat can significantly improve the catalytic activity of the plant protease, accelerate the hydrolysis reaction of the protein in the scale layer, and promote the diffusion of the enzyme molecules on the surface of the scale layer, thereby improving the enzymatic hydrolysis efficiency. The application constructs the above-mentioned nano-composite carrier protection-pH-responsive layer enzyme release-friction heat production to accelerate the enzymatic hydrolysis of the synergistic system, and utilizes the local micro-heat generated by mechanical friction to realize efficient and precise enzymatic hydrolysis of the scale layer of wool at room temperature, while effectively solving the problems of enzyme inactivation, wool fiber damage and high cost of anti-pilling treatment equipment for wool fabrics.

[0037] (4) In the preparation of the elastic microspheres, the concentration of the organic phase solution is controlled to be 80-120 g / L; if the concentration is too low, the elastic microspheres are prone to be too small in size and poor in dispersibility; if the concentration is too high, the microspheres are prone to agglomeration, affecting the subsequent compounding effect with AMSN. The concentration of the polyvinyl alcohol aqueous solution is 0.7-1.2 wt%, which can ensure stable emulsification effect and avoid uneven dispersion of the organic phase. In the preparation of MSNs, the concentration of the template machine solution is 0.2-0.4 wt%, which can effectively control the pore size and pore volume of the mesoporous structure; the addition of ammonia adjusts the pH value of the system to 10-11, providing a suitable alkaline environment for the hydrolysis and condensation of tetraethyl orthosilicate; the reaction temperature is 30-35℃, and the reaction time is 4-6h, which can ensure that the mesoporous structure of MSNs is complete and the pore size is uniform.

[0038] (5) The mass ratio of AMSN and elastic microspheres in the preparation process of the composite carrier is (8-12):1, which can make the mesoporous structure of AMSN and the mechanical properties of elastic microspheres form a synergistic effect, ensure the enzyme loading capacity, and ensure good friction heat production effect; the amount of silane coupling agent is 0.5-1 wt% of the sum of the mass of AMSN and elastic microspheres, which can realize the stable covalent combination of AMSN and elastic microspheres, and avoid the dissociation of the composite carrier during the treatment process.

[0039] (6) The concentration of CMCS aqueous solution in the preparation process of ECCs is 0.1-0.5 wt%, which can form an integrated pH response layer on the surface of the composite carrier, and will not cause the agglomeration of the composite carrier due to the too high concentration of CMCS; the mass ratio of plant protease and composite carrier is 1:(4-8), which can ensure the enzyme activity while avoiding the cost waste caused by excessive enzyme; the concentration of glutaraldehyde solution is 0.8-1.2 wt%, and the crosslinking temperature is 3-6℃, which can realize the stable fixation of the enzyme and reduce the loss of enzyme activity. The concentration of ECCs working solution is 1-3 g / L, and the pH value is 5-6, which can ensure the appropriate enzyme concentration in the working solution and match the response characteristics of CMCS (CMCS swells and releases enzymes under acidic conditions).

[0040] (7) The role of the amino-modified mesoporous silica is to introduce amino groups on the mesoporous silica, which significantly enhances the interaction between the silica and the plant protease, so that the plant protease is more effectively adsorbed on the surface of the mesoporous silica; in addition, amino modification can also improve the dispersibility and stability of the mesoporous silica, preventing it from aggregating or precipitating in the enzyme-composite carrier composite working solution.

[0041] (8) The scale layer degradation effect of the wool fabric treated by the method is that the thickness of the scale layer of the wool is reduced by 30-32%, which indicates that the scale layer structure of the wool is effectively destroyed, and the directional friction effect between the fibers can be significantly reduced. The directional friction effect value (D.F.E.) is ≤0.15, which indicates that the sliding resistance between the wool fibers is greatly reduced, effectively inhibiting the occurrence of pilling.

[0042] The pilling grade of the wool fabric reaches 4-5 levels, which fully meets the appearance quality requirements of high-end wool products. The enzyme stability: the half-life of the plant protease is extended to 70-72h, which is 5-6 times higher than that of the traditional free enzyme (half-life of about 12h). The damage degree of wool fiber: the loss rate of the main strength of wool fiber is less than 5%, which is much lower than that of the traditional high-temperature enzymatic process, and the wearability and durability of the wool fabric are effectively preserved.

[0043] (9) The finishing method of the present application is suitable for optimizing the anti-pilling function of various wool products such as wool woven fabrics, knitted fabrics, and wool blended fabrics, and is particularly suitable for industrialized continuous production scenarios with high requirements for energy consumption control, ecological environmental protection, and production efficiency, and can be widely applied to the finishing processing of high-end wool garments, home textile fabrics, and the like.

[0044] (10) The finishing process of the present application has low temperature and high efficiency, and low energy consumption: without high temperature heating, efficient enzymatic hydrolysis can be achieved at room temperature, achieving excellent anti-pilling effect, and the energy consumption is lower than that of traditional high temperature process. Stable enzyme activity, controllable process: through the synergistic effect of composite carrier protection and pH response 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 supplement enzyme preparations, which reduces the production cost while ensuring the uniformity of the finishing effect of wool fabrics. Ecologically friendly and high safety: the raw materials used have good biodegradability, and there is no toxic and harmful chemical residue. Strong equipment compatibility, easy industrialization: without special equipment, the traditional impregnation-oscillation equipment can be directly used, the process adjustment is simple, and it is suitable for the production line of existing textile enterprises, and easy to realize industrialized large-scale application. BRIEF DESCRIPTION OF DRAWINGS

[0045] Figure 1 The actual photo of the wool fabric obtained from Example 1 after pilling test;

[0046] Figure 2 The actual photo of the wool fabric obtained from Example 2 after pilling test;

[0047] Figure 3 The actual photo of the wool fabric obtained from Example 3 after pilling test;

[0048] Figure 4 The actual photo of the wool fabric obtained from Example 4 after pilling test;

[0049] Figure 5 The actual photo of the wool fabric obtained from Example 5 after pilling test;

[0050] Figure 6 The actual photo of the wool fabric obtained from Comparative Example 1 after pilling test;

[0051] Figure 7 The actual photo of the wool fabric obtained from Comparative Example 2 after pilling test;

[0052] Figure 8 The actual photo of the wool fabric obtained from Comparative Example 3 after pilling test. DETAILED DESCRIPTION

[0053] In order to make the above objectives, characteristics and advantages of the present application more obvious and easy to understand, the present application will be described in detail below with the description of specific embodiments.

[0054] In the following description, a large number of specific details are set forth in order to provide a thorough understanding of the present application, but the present application can also be implemented in other ways different from those described herein, and those skilled in the art can make similar extensions without departing from the concept of the present application, therefore the present application is not limited by the specific embodiments disclosed below.

[0055] The experimental methods used in the following specific embodiments are all conventional methods unless otherwise specified. The materials, reagents, methods and instruments used are all conventional materials, reagents, methods and instruments in the art unless otherwise specified, and can be obtained by commercial channels by those skilled in the art.

[0056] The polycaprolactone-polyethylene glycol block copolymer in the following examples is from Xiamen Senobangge Biotechnology Co., Ltd., carboxymethyl chitosan (CMCS, degree of substitution ≥0.8), cetyltrimethylammonium bromide (CTAB, 99%), tetraethyl silicate (TEOS, 98%), 3-aminopropyl triethoxysilane (APTES, 99%), bromelain (active units 300 U / mg), papain (active units 200 U / mg), aqueous polyurethane, glycidyl ether oxypropyl trimethoxysilane are all purchased from Shanghai Maikelin Biochemical Technology Co., Ltd.; wool knitted fabric is purchased from Wujing Xianfeng Knitting Co., Ltd.

[0057] Example 1

[0058] 1. Preparation of composite carrier

[0059] (1) Synthesis of elastic microspheres: polycaprolactone-polyethylene glycol block copolymer as raw material, emulsification-solvent evaporation method was used to prepare elastic microspheres, the specific process was as follows: polycaprolactone-polyethylene glycol block copolymer was dissolved in dichloromethane to form an organic phase solution with a concentration of 100 g / L, the organic phase solution was dropped into a 1.0wt% polyvinyl alcohol aqueous solution (polyvinyl alcohol was added to water to obtain), the volume ratio of organic phase solution to polyvinyl alcohol aqueous solution was 1:5, then emulsification treatment was carried out under ultrasonic condition until the dichloromethane solvent was completely volatilized, the precipitate was collected by centrifugation, and the residual polyvinyl alcohol was removed by washing with deionized water to prepare elastic microspheres with a particle size of 70-80 nm and good dispersibility, which were placed in a vacuum drying oven for drying;

[0060] (2) Preparation of AMSN

[0061] S1, MSNs preparation: cetyltrimethylammonium bromide (CTAB) was used as a template agent, which was added to deionized water and stirred until completely dissolved to prepare a 0.2w% CTAB aqueous solution. Ammonia water was added to the CTAB aqueous solution to adjust the pH value of the system to 10.5. Then, a 0.8vol% tetraethyl orthosilicate solution (tetraethyl orthosilicate was dissolved in anhydrous ethanol to obtain) was added as a silicon source, and the molar ratio of CTAB to tetraethyl orthosilicate was 1:2. The reaction was stirred in a constant temperature water bath at 32°C for 5h. After the reaction was completed, the reaction mixture was centrifuged, and the precipitate was collected. The precipitate was washed with deionized water and anhydrous ethanol alternately for three times to remove residual CTAB template agent, and MSNs with a pore size of 7-8nm were prepared.

[0062] S2, AMSN preparation: MSNs were dispersed in anhydrous ethanol and ultrasonically dispersed for 30min to prepare a 10g / L MSNs-ethanol dispersion. Then, 0.88g of 3-aminopropyltriethoxysilane (APTES) was added to the MSNs-ethanol dispersion, and the mass ratio of APTES to MSNs was 2:1. Subsequently, the reaction was stirred at 75°C for 7h to graft amino groups onto the surface of MSNs. After the reaction was completed, the precipitate was collected by centrifugation, and the unreacted APTES was removed by washing with anhydrous ethanol to prepare AMSN. The AMSN was vacuum dried for later use.

[0063] (3) The AMSN and the elastic microspheres were added to deionized water (the mass ratio of AMSN to elastic microspheres was 10:1), and ultrasonically dispersed to mix uniformly. Then, 0.5wt% of silane coupling agent KH-550 was added, and the reaction was stirred in a constant temperature water bath at 50°C for 6h to covalently bond the AMSN and the elastic microspheres. After the reaction was completed, the precipitate was collected by centrifugation, and the unreacted silane coupling agent was removed by washing with deionized water to obtain a composite carrier, which was vacuum dried for later use.

[0064] 2, ECCs preparation: 0.2g of CMCS with a degree of substitution of ≥0.8 was dissolved in 100mL of deionized water to prepare a 0.2wt% CMCS aqueous solution. Then, 0.44g of the composite carrier was added to the CMCS aqueous solution, and stirred at room temperature for 13h to modify the CMCS on the outside of the composite carrier to form a pH corresponding layer. Subsequently, 0.088g of bromelain (active units 300U / mg, and the mass ratio of enzyme to composite carrier was 1:5) was added, and adsorbed by oscillation at 32°C for 2.5h. Finally, 5mL of 1.0w% glutaraldehyde solution (glutaraldehyde was dissolved in water to obtain) was added, and crosslinked at a low temperature of 4°C for 2.5h to successfully load the bromelain on the composite carrier. After the reaction was completed, the solid material was collected by centrifugation, and washed with deionized water to remove the un-fixed enzyme and glutaraldehyde to prepare the ECCs for later use.

[0065] 3. Synergistic treatment of friction heat and enzymatic hydrolysis: ECCs were dispersed in deionized water, stirred uniformly to form a working solution of ECCs with a concentration of 2 g / L, and the pH value of the working solution was adjusted to 5.5 with 0.1 mol / L citric acid-sodium citrate buffer. The wool fabric to be arranged was mixed with the working solution of ECCs at a bath ratio of 1:25, and then put into a shaking reactor for shaking reaction at room temperature for 60 min.

[0066] 4. Post-treatment: The wool fabric after shaking treatment was taken out of the working solution, washed with deionized water at room temperature to remove the residual ECCs and enzymatic hydrolysis products on the surface of the fabric, and then the washed wool fabric was placed in an oven for drying to obtain the anti-pilling wool fabric.

[0067] To determine the anti-pilling performance of the arranged wool fabric by the arrangement method of the present embodiment, steps 1-4 were repeated several times to arrange the wool fabric, and 5 pieces of wool fabric were obtained for pilling test.

[0068] Performance test was conducted on the wool fabric arranged in the present embodiment: the physical thickness of the wool scale layer before and after arrangement was measured by SEM, and the calculation method of the thickness reduction of the wool scale layer was as follows:

[0069]

[0070] Wherein, m1 is the thickness of the wool scale layer before arrangement, and m2 is the thickness of the wool scale layer after arrangement.

[0071] The thickness reduction of the wool scale layer in the present embodiment was 31.2%, the directional friction effect value (D.F.E.) of the arranged wool fabric was tested by the capstan method, and the test result was 0.13. The wool fabric obtained in the present embodiment was subjected to pilling test, and the test standard referred to GB / T 4802.1-2008 “Textiles-Determination of the Pilling Behavior of Textile - Part 1: Circular Track Method”. The result showed that the pilling grade of the wool fabric obtained in the present embodiment was 5 (94% of which was grade 5). The absorbance of the enzymatic reaction product was measured by ultraviolet spectrophotometer with phosphate buffer and reaction substrate casein, and the test result showed that the half-life of bromelain in the present embodiment was 72 h. The breaking strength of the unarranged and arranged wool fibers was tested by a single fiber strength tester to calculate the strength loss rate, and the strength loss rate of the wool fiber in the present embodiment was 4.2%.

[0072] The actual photograph of the wool fabric obtained in the present embodiment after pilling test is shown in Figure 1 As can be seen from the photograph, the surface of the fabric is smooth and flat, and there is basically no pilling phenomenon, which indicates that the pilling grade of the wool fabric arranged by the method of the present embodiment is high, i.e. grade 5, and the anti-pilling performance is good.

[0073] Example 2

[0074] The difference between this example and Example 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;

[0075] (3) the mass ratio of AMSN to elastic microspheres is 8:1, the amount of silane coupling agent is 0.8 wt% of the total mass of AMSN and elastic microspheres, the stirring reaction temperature is 40℃, and the reaction time is 8h;

[0076] The concentration of the CMCS aqueous solution in the ECC preparation process is 0.1 wt%, the stirring time after adding the composite carrier into the CMCS aqueous solution is 10h, the enzyme used is papain, the mass ratio of papain to the composite carrier is 1:4, the concentration of glutaraldehyde solution is 0.8w%, the crosslinking reaction temperature is 3℃, and the reaction time is 4h.

[0077] The concentration of the ECCs working solution in the friction heat-enzymatic hydrolysis synergistic treatment stage is 1 g / L, the pH value is adjusted to 5.0, the bath ratio is 1:20, and the oscillation reaction time is 50 min;

[0078] The remaining process steps and parameters are the same as those of Example 1.

[0079] The wool fabric arranged in this example is tested for performance, and each test method is the same as that of Example 1, and the results are as follows: the thickness of the wool scale layer is reduced by 30.1%, and the directional friction effect value (D.F.E.) is 0.14. The wool fabric obtained in this example has a pilling level of 5 (of which 5 accounts for 91%). The half-life of papain in this example is 70.2h, and the loss rate of wool fiber strength is 4.8%.

[0080] The actual photograph of the wool fabric obtained in this example after pilling test is shown in Figure 2 It can be seen that the surface of the fabric is smooth and flat, and there is basically no pilling phenomenon, which indicates that the wool fabric arranged by the method of this example has a high pilling level of 5 and good anti-pilling performance.

[0081] Example 3

[0082] The difference between this example and Example 1 is that: in the S1 step of process (2), the concentration of the CTAB aqueous solution is 0.4w%, the pH value of the system is adjusted to 11, the concentration of tetraethyl silicate is 1.0vol%, the reaction temperature is 35℃, the time is 4h, and the pore size of the MSNs is 9-10nm;

[0083] The concentration of the MSNs-ethanol dispersion in the S2 step is 20 g / L, the amount of APTES added is 1.5 g, the reaction temperature is 80°C, and the reaction time is 6 h;

[0084] In the preparation of the ECCs, the concentration of the CMCS aqueous solution is 0.5 wt%, the stirring time after the composite carrier is added to the CMCS aqueous solution is 16 h, the mass ratio of bromelain to the composite carrier is 1:8, the cross-linking reaction temperature is 6°C, and the reaction time is 1 h;

[0085] In the friction heat-enzymatic hydrolysis synergistic treatment stage, the concentration of the ECCs working solution is 3 g / L, the pH value is adjusted to 6.0, the bath ratio is 1:30, and the oscillation reaction time is 55 min;

[0086] The remaining process steps and parameters are the same as in Example 1.

[0087] The wool fabric treated in this example is subjected to performance testing, and the test methods are the same as in Example 1. The results are as follows: the thickness of the wool scale is reduced by 31.8%, and the directional friction effect value (D.F.E.) is 0.12. The wool fabric obtained in this example has a pilling level of 5 (95% of which is level 5). The half-life of the bromelain in this example is 72 h, and the loss rate of the strength of the wool fiber is 3.9%.

[0088] The actual photograph of the wool fabric obtained in this example after pilling testing is shown in Figure 3 As can be seen, the surface of the fabric is smooth and flat, and there is basically no pilling phenomenon, indicating that the wool fabric treated by the method of this example has a high pilling level of 5 and good anti-pilling performance.

[0089] Example 4

[0090] The difference between this example and Example 1 is that: (1) in the elastic microsphere synthesis stage, the concentration of the organic phase solution 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;

[0091] (3) the mass ratio of the AMSN to the elastic microspheres is 12:1, the amount of the silane coupling agent is 1.0 wt% of the total mass of the AMSN and the elastic microspheres, the stirring reaction temperature is 60°C, and the reaction time is 5 h;

[0092] In the preparation of the ECCs, the enzyme used is papain,

[0093] In the friction heat-enzymatic hydrolysis synergistic treatment stage, the oscillation reaction time is 40 min;

[0094] The remaining process steps and parameters are the same as in Example 1.

[0095] The wool fabric treated in this example was tested for performance, and each test method was the same as in Example 1. The results were as follows: the wool scale layer thickness was reduced by 30.9%, and the directional friction effect value (D.F.E.) was 0.14. The wool fabric obtained in this example had a pilling grade of 4-5 (with 92% being grade 5). The papain half-life in this example was 71 h, and the wool fiber strength loss rate was 4.5%.

[0096] The actual photograph of the wool fabric obtained in this example after pilling testing is shown in Figure 4 As can be seen, the fabric surface was smooth and flat, and there was basically no pilling phenomenon, indicating that the wool fabric treated by the method in this example had a high pilling grade of 4-5 and good anti-pilling performance.

[0097] Example 5

[0098] The difference between this example and Example 1 was that in step S1 of process (2), the system pH was adjusted to 10, the concentration of tetraethyl silicate was 0.7%, the reaction temperature was 30°C, the time was 6 h, and the MSNs pore size was 5-6 nm.

[0099] In step S2, the reaction temperature was 70°C, and the time was 8 h.

[0100] In the friction heat-enzyme synergistic treatment stage ECCs, the working solution pH was adjusted to 5.2, the bath ratio was 1:22, and the oscillation reaction time was 50 min.

[0101] The remaining process steps and parameters were the same as in Example 1.

[0102] The wool fabric treated in this example was tested for performance, and each test method was the same as in Example 1. The results were as follows: the wool scale layer thickness was reduced by 30.5%, and the directional friction effect value (D.F.E.) was 0.15. The wool fabric obtained in this example had a pilling grade of 4-5 (with 90% being grade 5). The papain half-life in this example was 70.5 h, and the wool fiber strength loss rate was 4.7%.

[0103] The actual photograph of the wool fabric obtained in this example after pilling testing is shown in Figure 1 As can be seen, the fabric surface was smooth and flat, and there was basically no pilling phenomenon, indicating that the wool fabric treated by the method in this example had a high pilling grade of 4-5 and good anti-pilling performance.

[0104] Comparative Example 1 (traditional high-temperature enzyme treatment)

[0105] (1) Preparation of plant protease working solution: 0.088 g of bromelain was dissolved in 0.1 mol / L citric acid-sodium citrate buffer (pH 5.5) to prepare an enzyme working solution with a concentration of 0.4 g / L;

[0106] (2) Enzymatic treatment: the same size of wool fabric as in Example 1 was mixed with the enzyme working solution at a bath ratio of 1:25, and was put into a constant-temperature water bath shaker, with the temperature set at 60°C (traditional high-temperature process temperature), and was treated by oscillation for 60 min;

[0107] (3) Post-treatment: the wool fabric after oscillation treatment was washed and dried according to the post-treatment steps in Example 1.

[0108] The wool fabric after finishing in the present comparative example was subjected to performance testing, and the test methods were the same as in Example 1, and the results were as follows: the wool scale layer thickness was reduced by 28.3%, and the directional friction effect value (D.F.E.) was 0.18. The wool fabric obtained in the present comparative example had a pilling level of 3 (with 5% of 5-level). The half-life of bromelain in the present comparative example was 70.5 h, and the wool fiber strength loss rate was 16.5%.

[0109] The actual photograph of the wool fabric after pilling test obtained in the present comparative example is shown in Figure 6 It can be seen that there is obvious pilling phenomenon on the surface of the fabric, and there are many pills, which indicates that the wool fabric finished by traditional high-temperature enzymatic finishing has a low pilling level of 3, and has poor anti-pilling performance.

[0110] Comparative Example 2 (no friction heat production normal temperature enzymatic finishing)

[0111] 1. Preparation of composite carrier: the same as the preparation method of the composite carrier in Example 1;

[0112] 2. Preparation of enzyme-composite carrier complex: 0.44 g of composite carrier and 0.088 g of bromelain (activity unit 300 U / mg, mass ratio of enzyme to composite carrier 1:5) were dissolved in 100 mL of deionized water, and were oscillated for 2.5 h at 32°C for adsorption. Finally, 5 mL of glutaraldehyde solution with a concentration of 1.0 wt% was added, and a low-temperature crosslinking reaction was carried out at 4°C for 2.5 h, so that the composite carrier successfully loaded the bromelain. After the reaction was completed, the solid material was collected by centrifugation, and was washed with deionized water to remove the un-fixed enzyme and glutaraldehyde, so as to prepare the enzyme-composite carrier complex for use;

[0113] 3. Enzymatic treatment: the difference between this step and the friction heat production-enzymatic finishing synergistic treatment process in Example 1 is that the oscillation temperature is 30°C, and the rest of the operations are the same as in Example 1;

[0114] 4. Post-treatment: this step is the same as the post-treatment process in Example 1.

[0115] The wool fabric after the finishing of the present comparative example was subjected to performance testing, and each testing method was the same as that of Example 1, and the results were as follows: the thickness of the wool scale layer was reduced by 15.2%, and the directional friction effect value (D.F.E.) was 0.32. The wool fabric obtained in the present comparative example had a pilling level of 2-3 (of which 5 accounted for 0%). The half-life of the bromelain in the present comparative example was 71.2 h, and the loss rate of the strength of the wool fiber was 2.1%.

[0116] The actual fabric photograph of the wool fabric obtained in the present comparative example after the pilling test is shown in FIG. 2. Figure 7 As can be seen from FIG. 2, the surface of the fabric had obvious pilling phenomenon, and there were many pills, which indicated that the pilling level of the wool fabric subjected to the non-friction heat-producing enzyme finishing at room temperature was low, and was only 3. This was because the enzyme efficiency was extremely low at room temperature, and effective anti-pilling treatment could not be performed.

[0117] Comparative Example 3 (chemical resin finishing)

[0118] (1) Preparation of resin finishing liquid: waterborne polyurethane was dissolved in deionized water, glycidol ether oxypropyl trimethoxysilane was added, and stirring was performed until uniform, to prepare a resin finishing liquid with a polyurethane concentration of 100 g / L, and the amount of the crosslinking agent was 0.5 wt% of the finishing liquid;

[0119] (2) padding treatment: wool fabric of the same specification as that of Example 1 was immersed in the resin finishing liquid according to a bath ratio of 1:20 between the wool fabric and the resin finishing liquid for 10 min, and then pad-pressing treatment was performed by using a mangle (padding rate: 80%);

[0120] (3) baking and curing: the pad-pressed wool fabric was placed in an oven, and baking and curing were performed at 120°C for 15 min.

[0121] The wool fabric after the finishing of the present comparative example was subjected to performance testing, and each testing method was the same as that of Example 1, and the results were as follows: the thickness of the wool scale layer was reduced by 15.2%, and the directional friction effect value (D.F.E.) was 0.32. The wool fabric obtained in the present comparative example had a pilling level of 2-3 (of which 5 accounted for 0%). The half-life of the bromelain in the present comparative example was 71.2 h, and the loss rate of the strength of the wool fiber was 2.1%.

[0122] The actual fabric photograph of the wool fabric obtained in the present comparative example after the pilling test is shown in FIG. 2. Figure 8 As can be seen from FIG. 2, the surface of the fabric had obvious pilling phenomenon, and there were many pills, which indicated that the pilling level of the wool fabric subjected to the non-friction heat-producing enzyme finishing at room temperature was low, and was only 3. This was because the enzyme efficiency was extremely low at room temperature, and effective anti-pilling treatment could not be performed.

[0123] The above description is only the preferred embodiment of the present application, but the protection scope of the present application is not limited to this. Any person skilled in the art can make equivalent substitutions or changes according to the technical solution and the inventive concept of the present application within the technical range disclosed by the present application, which should be covered in the protection scope of the present application.

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 a wool fabric with anti-pilling properties; 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. 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.

2. The method according to claim 1, 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%.

3. The method according to claim 1, 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.

4. 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.

5. 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.

6. 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).

7. 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 6.

8. The wool fabric according to claim 7, 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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