Wool bio-enzyme anti-felting finishing method based on subtraction-addition

Abstract

The invention provides a wool bio-enzyme anti-felting finishing method based on subtraction-addition, and belongs to the technical field of textile dyeing and finishing processing, the method comprises the following steps: dissolving keratinase and 2-cyclohexylamine sodium ethanesulfonate in water, immersing a wool fiber product, and carrying out anti-felting treatment to obtain a subtraction anti-felting wool fiber product; the preparation method comprises the following steps: dissolving disulfide bond-containing phenol micromolecules and horse radish peroxidase in water, and dipping a subtraction anti-felting wool fiber product to prepare a polyphenol macromolecular grafted wool fiber product; the polyphenol macromolecule grafted wool fiber product is soaked in hot water, washed and dried, and the subtraction-addition anti-felting wool fiber product is prepared. The finishing method is ecological, safe, low-carbon and green, the felting shrinkage rate of the wool fiber product is remarkably reduced, the strength loss of wool fibers is low, the strength of the wool fibers is improved, and the influence on the hand feeling is small; the prepared subtraction-addition anti-felting wool fiber product is low in felting rate, low in strength loss and inferior in hand feeling.

Description

Technical Field

[0001] The invention relates to a wool bioenzyme anti-felting finishing method based on subtraction-addition method, and belongs to the technical field of textile dyeing and finishing. Background Art

[0002] At present, the anti-felting finishing of wool fiber products in the textile industry mostly adopts the chlorination method, among which the chlorination-Hercosett process is the most widely used in the commercial field. This finishing process has a good anti-felting finishing effect, but a large amount of adsorbable organic halides will be produced during the treatment process. Its inherent toxicity, non-microbial degradability and carcinogenicity have great harm to the human body and the environment. Therefore, seeking an environmentally friendly wool bio-anti-felting finishing process with low energy consumption, less pollution and good effect has gradually become a research hotspot in the wool textile dyeing and finishing industry in recent years.

[0003] Compared with the traditional chemical wool anti-felting finishing method, the use of biological enzymes for wool anti-felting has many advantages, including mild treatment conditions, less environmental pollution, and soft fabric after finishing. In the wool enzymatic anti-shrinkage finishing, the most commonly used enzyme preparation is protease. Its basic principle is to use protease to hydrolyze and destroy the keratin in the scale layer of wool fibers to achieve the purpose of subtractive anti-felting finishing. Although there are many research reports on the use of protease for wool anti-felting, the effect of protease alone in actual production is not ideal. The main reason is that protease is easy to diffuse into the fiber to hydrolyze the intercellular matrix and cortex between the scale layers, which can easily cause greater damage to the wool fibers. In order to compensate for the fiber damage caused by the subtractive anti-felting finishing of wool by biological enzymes, some researchers have used resin deposition method for additive anti-felting. The basic idea is to deposit a layer of resin film on the surface of wool fibers. On the one hand, it can cover the wool fiber scale layer to reduce the felting between fibers under hot and humid conditions; on the other hand, the resin film also has a certain degree of fiber strength repair effect. Existing production practice shows that the resin deposition method based on addition can significantly reduce the felt shrinkage of wool fiber products. However, its disadvantage is that it will affect the feel of wool fiber products to varying degrees. In addition, some resin films have poor bonding strength with the wool fiber surface, which also has an adverse effect on the durability of the anti-felting finishing effect. Therefore, how to construct an eco-friendly wool anti-felting method that not only meets the requirements of low felt shrinkage and low strength loss, but also has little effect on the feel of wool fiber products is a technical problem that needs to be solved in the current wool textile dyeing and finishing production. Summary of the invention

[0004]

Technical issues

[0005] In the anti-felting finishing process of wool fiber products, the chlorination method of anti-felting is prone to adverse environmental pollution, the single protease subtractive method of anti-felting is prone to damage the wool fibers, and the additive anti-felting based on resin deposition will affect the feel of the fiber products. The above-mentioned problems affect the anti-felting finishing process of wool fiber products.

[0006]

Technical solution

[0007] In order to solve the above problems, the present invention firstly adopts keratinase which is specific to the wool scale layer, hydrolyzes the wool fiber scale layer, and performs subtractive anti-felting finishing on the wool fiber products; on this basis, with the help of horseradish peroxidase, catalyzes the oxidation of disulfide bond-containing phenolic small molecules and reacts with tyrosine in wool fiber macromolecules, and forms polyphenol macromolecules on the wool surface through graft polymerization; finally, heating is used to induce the opening of disulfide bonds in the side groups of polyphenol macromolecules, promote the reconstruction of disulfide bonds between polyphenol macromolecules, form a network cross-linked structure on the wool fiber surface, realize additive anti-felting, and give wool fiber products an additive anti-felting finishing effect.

[0008] The first object of the present invention is to provide a wool bioenzyme anti-felting finishing method based on subtraction-addition method, comprising the steps of:

[0009] (1) Subtractive anti-felting: dissolving keratinase and sodium 2-cyclohexylaminoethanesulfonate in water, adjusting the pH value, obtaining an anti-felting treatment solution, immersing the wool fiber product in the anti-felting treatment solution, performing an anti-felting treatment, and obtaining a subtractive anti-felting wool fiber product;

[0010] (2) Enzymatic grafting polymerization of phenolic small molecules: dissolving disulfide bond-containing phenolic small molecules and horseradish peroxidase in water to prepare a grafting reaction solution, and immersing the subtractive anti-felting wool fiber product in the grafting reaction solution to prepare a polyphenolic macromolecule grafted wool fiber product;

[0011] (3) Additive anti-felting: The wool fiber product grafted with polyphenol macromolecules is immersed in hot water, washed and dried to obtain the subtractive-additive anti-felting wool fiber product.

[0012] In one embodiment of the present invention, in step (1), the wool fiber product is one or more of yarn, woven fabric, knitted fabric and non-woven fabric processed from wool fiber as raw material.

[0013] In one embodiment of the present invention, in step (1), the keratinase is produced by animals, plants or microorganisms.

[0014] In one embodiment of the present invention, in step (1), the enzymatic activity of keratinase is 18000-22000 U / mL.

[0015] In one embodiment of the present invention, in step (1), the mass concentration of keratinase in the anti-felting treatment liquid is 1-2.5 g / L, and the mass concentration of sodium 2-cyclohexylaminoethanesulfonate is 10-15 g / L.

[0016] In one embodiment of the present invention, in step (1), the pH value is adjusted to 8-9; the temperature of the anti-felting treatment is 50-60° C., the time of the anti-felting treatment is 45-60 min, and the bath ratio is 1-8:1-12.

[0017] In one embodiment of the present invention, in step (1), the pH value is adjusted with an aqueous solution of pure alkali.

[0018] In one embodiment of the present invention, in step (2), the disulfide bond-containing phenolic small molecule has the following structural formula:

[0019]

[0020] Among them, -R1 is

[0021] In one embodiment of the present invention, in step (2), the disulfide bond-containing phenolic small molecule is preferably:

[0022]

[0023] In one embodiment of the present invention, the preparation method of disulfide bond-containing phenolic small molecules includes the steps of: taking one of tyramine hydrochloride and m-hydroxyphenylethylamine hydrochloride, dissolving it with thioctic acid, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide in an ethanol aqueous solution, adjusting the pH value, obtaining a reaction solution for reaction, removing ethanol after the reaction, separating and removing unreacted thioctic acid, and freeze-drying to obtain disulfide bond-containing phenolic small molecules.

[0024] In one embodiment of the present invention, in the method for preparing disulfide bond-containing phenolic small molecules, the mass fraction of ethanol in the ethanol aqueous solution is 45-55%.

[0025] In one embodiment of the present invention, in the method for preparing disulfide bond-containing phenolic small molecules, the mass concentration of tyramine hydrochloride or m-hydroxyphenylethylamine hydrochloride in the reaction solution is 8 to 12 g / L; the mass concentration of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride is 8 to 12 g / L; and the mass concentration of N-hydroxysuccinimide is 2.5 to 4 g / L.

[0026] In one embodiment of the present invention, in the method for preparing disulfide bond-containing phenolic small molecules, the mass concentration of tyramine hydrochloride or m-hydroxyphenylethylamine hydrochloride in the reaction solution is preferably 10 g / L.

[0027] In one embodiment of the present invention, in the method for preparing disulfide bond-containing phenolic small molecules, the molar ratio of lipoic acid to tyramine hydrochloride or m-hydroxyphenylethylamine hydrochloride is 2:1 or 3:1.

[0028] In one embodiment of the present invention, in the method for preparing disulfide bond-containing phenolic small molecules, the pH value is adjusted to 5-7; the reaction temperature is 20-30° C., and the reaction time is 8-12 hours.

[0029] In one embodiment of the present invention, in the method for preparing disulfide bond-containing phenolic small molecules, an acetic acid aqueous solution is used to adjust the pH.

[0030] In one embodiment of the present invention, in the method for preparing disulfide bond-containing phenolic small molecules, removing ethanol is removing ethanol from the reaction solution by rotary evaporation.

[0031] In one embodiment of the present invention, in the method for preparing disulfide bond-containing phenolic small molecules, unreacted lipoic acid is removed by centrifugation.

[0032] In one embodiment of the present invention, in step (2), the horseradish peroxidase is produced by animals, plants or microorganisms.

[0033] In one embodiment of the present invention, in step (2), the enzyme activity of horseradish peroxidase is 250-350 U / mg.

[0034] In one embodiment of the present invention, in step (2), the pH of the grafting reaction solution is 6.5-7.0; the mass concentration of horseradish peroxidase in the grafting reaction solution is 1.5-5 g / L, and the mass concentration of disulfide bond-containing phenolic small molecules is 7.5-10 g / L.

[0035] In one embodiment of the present invention, in step (2), the immersion temperature is 30-40° C., the immersion treatment time is 1-2 hours, and the bath ratio is 1-8:1-12.

[0036] In one embodiment of the present invention, in step (3), the temperature of the hot water is 80-90° C., the pH value of the hot water is 6.5-7.0, and the immersion time is 20-30 minutes.

[0037] The second object of the present invention is to provide a subtractive-additive anti-felting wool fiber product prepared by the above wool biological enzyme anti-felting finishing method.

[0038] The third object of the present invention is to provide the application of the above subtractive-additive anti-felting wool fiber product in the field of textiles.

[0039] Beneficial effects:

[0040] The present invention combines keratinase, horseradish peroxidase and disulfide bond-containing phenolic small molecules to perform wool bioenzyme anti-felting finishing based on subtraction-addition. Compared with the subtraction anti-felting finishing of traditional chemical method or protease and the addition anti-felting finishing of resin deposition, the present invention has the following advantages:

[0041] (1) Ecological safety of finishing process. Biological enzymes are protein macromolecular biological agents with good ecological safety. No chlorine-containing oxidants or chemical reducing agents are used in the finishing process of the method, achieving zero AOX emissions in the anti-felting finishing process of wool fiber products, which meets the requirements of low-carbon green dyeing and finishing.

[0042] (2) Low felting shrinkage and low strength loss. Keratinase can hydrolyze the keratin in the wool scale layer during subtractive anti-felting. After adding sodium 2-cyclohexylaminoethanesulfonic acid and combining with keratinase, it can inhibit the enzyme molecules from over-hydrolyzing the wool cortical layer and scale cell matrix, thereby reducing the fiber strength loss during subtractive anti-felting of wool. On this basis, horseradish peroxidase is used to catalyze the reaction between tyrosine on the wool surface and disulfide-bonded phenolic small molecules, and polyphenol macromolecules containing disulfide side groups are formed on the fiber through grafting polymerization. High-temperature heating is combined to promote the opening of disulfide bonds on the side groups of polyphenol macromolecules and intermolecular reconstruction, forming a network cross-linking on the fiber surface, further reducing the felting shrinkage of the fiber products and improving their strength.

[0043] (3) The fiber products have a better feel: Compared with the traditional resin deposition method, the method of the present invention uses disulfide bond-containing phenolic small molecules as raw materials, and forms covalently bonded polyphenolic small molecules on the fiber surface through enzyme-catalyzed graft polymerization. The disulfide bonds are opened and reconstructed during the heating process, thereby improving the anti-felting finishing effect. The finishing method has little effect on the feel of the fiber products. DETAILED DESCRIPTION

[0044] The keratinase used in the examples and comparative examples was purchased from Jinan Baisijie Bioengineering Co., Ltd. with an enzyme activity of 20,000 U / g; horseradish peroxidase was purchased from Shanghai Aladdin Reagent Co., Ltd. with an enzyme activity of 300 U / mg; and protease was purchased from Xiasheng Enzyme Biotechnology Co., Ltd. with an enzyme activity of 200,000 U / g.

[0045] Test Method

[0046] Felting rate: refer to GB / T 8628-2013 to determine the area felting rate (%) of wool fabric.

[0047] Strength loss rate: The strength of wool woven fabrics before and after finishing is determined by referring to GB / T 3923.1-1997 to determine its warp breaking strength; the strength of wool knitted fabrics before and after finishing is determined by referring to GB / T19976-2005 to determine its bursting strength; the strength loss rate is calculated according to the following formula:

[0048] Strength loss rate (%) = (strength before finishing - strength after finishing) / strength before finishing × 100%

[0049] Drape coefficient: refer to GB / T 23329-2009 to measure the drape coefficient (%) of wool fabric.

[0050] Example 1

[0051] A wool bioenzyme anti-felting finishing method based on subtraction-addition method comprises the following steps:

[0052] (1) Preparation of disulfide bond-containing phenolic small molecules: dissolving lipoic acid, tyramine hydrochloride, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide in an ethanol aqueous solution, adjusting the pH value, obtaining a reaction solution for reaction, removing ethanol by rotary evaporation after the reaction, and then removing unreacted lipoic acid by centrifugation to obtain disulfide bond-containing phenolic small molecules, which are freeze-dried for later use;

[0053] The mass fraction of ethanol in the ethanol aqueous solution is 50%; the mass concentration of tyramine hydrochloride in the reaction solution is 10 g / L, the mass concentration of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride is 8 g / L, and the mass concentration of N-hydroxysuccinimide is 2.5 g / L; the molar ratio of lipoic acid to tyramine hydrochloride is 2:1; the pH value is adjusted to 5 using acetic acid aqueous solution; the reaction temperature is 25°C, and the reaction time is 8 hours;

[0054] The structural formula of the prepared disulfide bond-containing phenolic small molecule is as follows:

[0055]

[0056] (2) Subtractive anti-felting: dissolving keratinase and sodium 2-cyclohexylaminoethanesulfonate in water, adjusting the pH value, obtaining an anti-felting treatment solution, immersing the wool woven fabric in the anti-felting treatment solution, performing an anti-felting treatment, and obtaining a subtractive anti-felting wool woven fabric;

[0057] The mass concentration of keratinase in the anti-felting treatment solution is 1 g / L, and the mass concentration of sodium 2-cyclohexylaminoethanesulfonate is 10 g / L; the pH value is adjusted to 8 with a soda ash aqueous solution; the anti-felting treatment temperature is 50°C, the anti-felting treatment time is 45 minutes, and the bath ratio is 1:8;

[0058] (3) Enzymatic grafting polymerization of phenolic small molecules: dissolving disulfide bond-containing phenolic small molecules and horseradish peroxidase in water to prepare a grafting reaction solution, and immersing subtractive anti-felting wool woven fabric in the grafting reaction solution to prepare polyphenolic macromolecule grafted wool woven fabric;

[0059] The mass concentration of horseradish peroxidase in the grafting reaction solution is 1.5 g / L, and the mass concentration of disulfide bond-containing phenolic small molecules is 7.5 g / L; the pH of the grafting reaction solution is 6.5; the immersion temperature is 30°C, the immersion time is 1 hour, and the bath ratio is 1:8;

[0060] (4) Additive anti-felting: The polyphenol macromolecule grafted wool woven fabric is immersed in hot water, washed and dried to obtain a subtractive-additive anti-felting wool woven fabric;

[0061] The temperature of the hot water is 80°C, the pH value is 6.5, and the immersion time is 20 minutes.

[0062] Example 2

[0063] A wool bioenzyme anti-felting finishing method based on subtraction-addition method comprises the following steps:

[0064] (1) Preparation of disulfide bond-containing phenolic small molecules: dissolving lipoic acid, tyramine hydrochloride, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide in an ethanol aqueous solution, adjusting the pH value, obtaining a reaction solution for reaction, removing ethanol by rotary evaporation after the reaction, and then removing unreacted lipoic acid by centrifugation to obtain disulfide bond-containing phenolic small molecules, which are freeze-dried for later use;

[0065] The mass fraction of ethanol in the ethanol aqueous solution is 50%; the mass concentration of tyramine hydrochloride in the reaction solution is 12 g / L, the mass concentration of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride is 12 g / L, and the mass concentration of N-hydroxysuccinimide is 4 g / L; the molar ratio of lipoic acid to tyramine hydrochloride is 3:1; the pH value is adjusted to 5 using acetic acid aqueous solution; the reaction temperature is 25°C, and the reaction time is 12 hours;

[0066] The structural formula of the prepared disulfide bond-containing phenolic small molecule is as follows:

[0067]

[0068] (2) Subtractive anti-felting: dissolving keratinase and sodium 2-cyclohexylaminoethanesulfonate in water, adjusting the pH value, obtaining an anti-felting treatment solution, immersing the wool knitted fabric in the anti-felting treatment solution, performing an anti-felting treatment, and obtaining a subtractive anti-felting wool knitted fabric;

[0069] The mass concentration of keratinase in the anti-felting treatment solution is 2.5 g / L, and the mass concentration of sodium 2-cyclohexylaminoethanesulfonate is 15 g / L; the pH value is adjusted to 9 using a soda ash aqueous solution; the temperature of the anti-felting treatment is 60°C, the anti-felting treatment time is 60 min, and the bath ratio is 1:12;

[0070] (3) Enzymatic grafting polymerization of phenolic small molecules: dissolving disulfide bond-containing phenolic small molecules and horseradish peroxidase in water to prepare a grafting reaction solution, and immersing subtractive anti-felting wool knitted fabric in the grafting reaction solution to prepare polyphenolic macromolecule grafted wool knitted fabric;

[0071] The mass concentration of horseradish peroxidase in the grafting reaction solution is 5 g / L, and the mass concentration of disulfide bond-containing phenolic small molecules is 10 g / L; the pH of the grafting reaction solution is 7.0; the immersion temperature is 40°C, the immersion time is 2 hours, and the bath ratio is 1:12;

[0072] (4) Additive anti-felting: The wool knitted fabric grafted with polyphenol macromolecules is immersed in hot water, washed and dried to obtain a subtractive-additive anti-felting wool knitted fabric;

[0073] The temperature of the hot water is 90°C, the pH value is 7.0, and the immersion time is 30 minutes.

[0074] Comparative Example 1

[0075] Untreated wool woven fabric.

[0076] Comparative Example 2

[0077] The wool woven fabric was treated by step (2) of Example 1, but sodium 2-cyclohexylaminoethanesulfonate was not added to the anti-felting treatment solution.

[0078] Comparative Example 3

[0079] The wool woven fabric was treated by step (2) of Example 1.

[0080] Comparative Example 4

[0081] The wool woven fabric was treated by step (2) of Example 1, except that keratinase was replaced by protease, and the mass concentration of protease in the anti-felting treatment solution was 0.1 g / L.

[0082] Comparative Example 5

[0083] The difference from Example 1 is that step (2) is not performed.

[0084] Comparative Example 6

[0085] The difference from Example 1 is that step (4) is not performed.

[0086] Comparative Example 7

[0087] Untreated wool knit.

[0088] Comparative Example 8

[0089] The wool knitted fabric was treated by step (2) of Example 2, but sodium 2-cyclohexylaminoethanesulfonate was not added to the anti-felting treatment solution.

[0090] Comparative Example 9

[0091] The wool knitted fabric is treated by step (2) of Example 2.

[0092] Comparative Example 10

[0093] The wool knitted fabric was treated by step (2) of Example 2, except that keratinase was replaced by protease, and the mass concentration of protease in the anti-felting treatment solution was 0.25 g / L.

[0094] Comparative Example 11

[0095] The difference from Example 2 is that step (2) is not performed.

[0096] Comparative Example 12

[0097] The difference from Example 2 is that step (4) is not performed.

[0098] The wool fabrics prepared in Examples 1 and 2 and Comparative Examples 1 to 12 were tested, and the results are shown in Table 1.

[0099] Table 1

[0100]

[0101] The area felting rate of the subtractive-additive anti-felting wool fabric (Example 1, Example 2) prepared by the present invention is ≤6%, which meets the requirements of the anti-shrinkage wool fabric; the strength loss rate of the subtractive-additive anti-felting wool fabric is less than 10%, indicating that the fiber is less damaged during the treatment; the drape coefficient of the prepared subtractive-additive anti-felting wool fabric is similar to that of the wool fabric of Comparative Example 1 or 7, and the hand feel is good.

[0102] The wool fabrics without any treatment (Comparative Example 1, Comparative Example 7) have a higher area felting rate (>15%), indicating that the anti-felting effect is poor.

[0103] The wool fabrics treated only by step (2) without adding sodium 2-cyclohexylaminoethanesulfonate (Comparative Example 2 and Comparative Example 8) have a certain degree of reduced area felting rate compared with the untreated wool fabrics, but are still far higher than 6%, and still fail to meet the standard of shrink-proof wool products; at the same time, the strength loss rate of the wool fabrics made by Comparative Example 2 and Comparative Example 8 is greater than 15%, indicating that the wool scale cell matrix components and cortical layer are hydrolyzed to a certain extent by only keratinase treatment, causing wool fiber damage. This result shows that it is difficult to meet the requirements for wool anti-felting finishing by only keratinase.

[0104] Compared with the wool fabrics without adding sodium 2-cyclohexylaminoethanesulfonate (Comparative Example 2, Comparative Example 8), the wool fabrics treated only by step (2) (Comparative Example 3, Comparative Example 9) have a slightly lower area felt shrinkage rate and a slightly lower strength loss rate. The reason is that sodium 2-cyclohexylaminoethanesulfonate binds to the keratinase enzyme protein, preventing the keratinase enzyme protein from diffusing into the wool fiber. This shows that the addition of sodium 2-cyclohexylaminoethanesulfonate can reduce the fiber damage in the anti-felting finishing of wool protease to a certain extent.

[0105] For wool fabrics treated only by step (2) but using protease instead of keratinase in the treatment (Comparative Examples 4 and 10), under the same total enzyme activity conditions, the felting rate of the fabrics is similar to that of the samples in Comparative Examples 3 and 9, but the strength loss rate is higher, indicating that in the presence of sodium 2-cyclohexylaminoethanesulfonate, keratinase can more effectively hydrolyze keratin with a high disulfide bond content than protease, thereby reducing damage to the inside of the wool fiber.

[0106] The wool fabrics not treated with step (2) (Comparative Example 5 and Comparative Example 11) have a lower area felting rate than the wool fabrics not treated with any treatment (Comparative Example 1 and Comparative Example 7). The reason is that the wool fabrics are grafted and polymerized on the wool fiber surface by horseradish peroxidase, so that the wool fabrics have an additive anti-felting finishing effect. On the other hand, since the wool fabrics have not been treated with keratinase, there are more hydrophobic lipid structures on the fiber scale surface (that is, there are fewer exposed tyrosine acids), which makes the number of polyphenol macromolecules bound to the wool fiber surface by horseradish peroxidase less, so the felting rate of the wool fabric cannot meet the requirement of less than 6%. In addition, the strength of the prepared wool fabric is slightly increased because it has not been hydrolyzed by keratinase and thus no fiber damage is caused.

[0107] The wool fabrics (Comparative Example 6 and Comparative Example 12) that were not treated in step (4) had a lower felting rate, but were still higher than the subtractive-additive anti-felting wool fabrics (Example 1 and Example 2) prepared by the present invention, because they were not treated with hot water in step (4). The effect of hot water treatment is to break the disulfide bonds on the side groups of the polyphenol macromolecules on the wool surface at high temperature to generate sulfhydryl groups, and further form disulfide bonds between the polyphenol macromolecules through the combination of sulfhydryl groups, so that a cross-linked network is formed on the surface of the wool fibers, which has an additive anti-felting effect and improves the strength of the wool fibers. The wool fabrics prepared in Comparative Examples 6 and 12 were not treated with hot water, and a mesh structure was not formed on the fiber surface, so the finishing effect was inferior to that of Examples 1 and 2.

[0108] The embodiments provided above are not intended to limit the scope of the present invention, and the steps described are not intended to limit the execution order thereof. Those skilled in the art may make obvious improvements to the present invention in combination with existing common knowledge, which also fall within the scope of protection defined by the claims of the present invention.

Claims

1. A wool bioenzyme anti-felting finishing method based on subtraction-addition method, characterized in that: Includes steps: (1) Subtractive anti-felting: dissolving keratinase and sodium 2-cyclohexylaminoethanesulfonate in water, adjusting the pH value, obtaining an anti-felting treatment solution, immersing the wool fiber product in the anti-felting treatment solution, performing an anti-felting treatment, and obtaining a subtractive anti-felting wool fiber product; (2) Enzymatic grafting polymerization of phenolic small molecules: dissolving disulfide bond-containing phenolic small molecules and horseradish peroxidase in water to prepare a grafting reaction solution, and immersing the subtractive anti-felting wool fiber product in the grafting reaction solution to prepare a polyphenolic macromolecule grafted wool fiber product; (3) Additive anti-felting: The wool fiber product grafted with polyphenol macromolecules is immersed in hot water, washed and dried to obtain the subtractive-additive anti-felting wool fiber product.

2. The method for anti-felting wool with biological enzymes according to claim 1, characterized in that: In step (1), the enzyme activity of keratinase is 18000-22000 U / mL; the mass concentration of keratinase in the anti-felting treatment solution is 1-2.5 g / L, and the mass concentration of sodium 2-cyclohexylaminoethanesulfonate is 10-15 g / L.

3. The method for anti-felting wool with biological enzymes according to claim 1, characterized in that: In step (1), the pH value is adjusted to 8-9; the pH value is adjusted using a pure alkali aqueous solution.

4. The method for anti-felting wool with biological enzymes according to claim 1, characterized in that: In step (1), the temperature of the anti-felting treatment is 50-60° C., the time of the anti-felting treatment is 45-60 min, and the bath ratio is 1-8:1-12.

5. The method for anti-felting wool with biological enzyme according to claim 1, characterized in that: In step (2), the structural formula of the disulfide bond-containing phenolic small molecule is as follows: Among them, -R1 is 6. The method for anti-felting wool with biological enzymes according to claim 1, characterized in that: In step (2), the enzyme activity of horseradish peroxidase is 250-350 U / mg; the pH of the grafting reaction solution is 6.5-7.5; the mass concentration of horseradish peroxidase in the grafting reaction solution is 1.5-5 g / L, and the mass concentration of disulfide bond-containing phenolic small molecules is 7.5-10 g / L.

7. The method for anti-felting wool with biological enzymes according to claim 1, characterized in that: In step (2), the immersion temperature is 30-40° C., the immersion treatment time is 1-2 hours, and the bath ratio is 1-8:1-12.

8. The method for anti-felting wool with biological enzymes according to claim 1, characterized in that: In step (3), the temperature of the hot water is 80 to 90° C., the pH value of the hot water is 6.5 to 7.5, and the immersion is performed for 20 to 30 minutes.

9. The subtractive-additive anti-felting wool fiber product prepared by the wool bio-enzyme anti-felting finishing method according to claim 1.

10. Use of the subtractive-additive anti-felting wool fiber product according to claim 9 in the field of textiles.

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