A subtraction-addition-based method for wool bioenzyme anti-felting finishing

Abstract

The present invention provides a subtractive-additive bioenzyme anti-felting finishing method for wool, which belongs to the technical field of textile dyeing and finishing. The method comprises the following steps: dissolving keratinase and sodium 2-cyclohexylaminoethanesulfonate in water, immersing the wool fiber product in the anti-felting treatment, and obtaining a subtractive anti-felting wool fiber product; dissolving a disulfide bond-containing phenolic small molecule and horseradish peroxidase in water, immersing the subtractive anti-felting wool fiber product in the anti-felting treatment, and obtaining a polyphenol macromolecule grafted wool fiber product; immersing the polyphenol macromolecule grafted wool fiber product in hot water, washing it with water, and drying it to obtain a subtractive-additive anti-felting wool fiber product. The finishing method of the present invention is ecologically safe, low-carbon, and green, significantly reduces the felting rate of the wool fiber product, has low strength loss on the wool fiber, improves the strength of the wool fiber, and has little effect on the hand feel; the subtractive-additive anti-felting wool fiber product obtained has low felting rate, low strength loss, and no deterioration in the hand feel.

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] Currently, the anti-felting treatment of wool fiber products in the textile industry primarily relies on chlorination, with the chlorination-Hercosett process being the most widely used commercially. While this process offers excellent anti-felting results, it also produces significant amounts of adsorbable organic halides, which pose significant risks to both humans and the environment due to their inherent toxicity, lack of microbial degradation, and carcinogenicity. Therefore, the search for environmentally friendly, energy-efficient, and effective bio-based anti-felting treatments for wool has become a research hotspot within the wool textile dyeing and finishing industry in recent years.

[0003] Compared to traditional chemical wool anti-felting methods, enzymatic methods offer several advantages, including mild treatment conditions, reduced environmental pollution, and a softer feel after finishing. Protease is the most commonly used enzyme in enzymatic wool shrinkage-proofing. The basic principle is to hydrolyze and destroy the keratin in the scale layer of wool fibers, achieving a subtractive anti-felting effect. Although numerous studies have reported on the use of proteases for wool anti-felting, the effectiveness of protease-based shrinkage-proofing alone in actual production is suboptimal. This is primarily due to the protease's tendency to diffuse into the fiber and hydrolyze the intercellular matrix and cortex between the scale layers, causing significant fiber damage. To compensate for the fiber damage caused by subtractive enzymatic anti-felting, some researchers have employed a resin deposition method for additive anti-felting. The basic idea is to deposit a thin resin film on the surface of the wool fibers. This film, by covering the scale layer, reduces the risk of felting between fibers under humid and hot conditions. Furthermore, the resin film also has a certain degree of fiber-strengthening properties. Existing production practices have shown that additive resin deposition methods can significantly reduce the felt shrinkage of wool fiber products. However, their drawback is that they can affect the handle of wool fiber products to varying degrees. Furthermore, some resin films exhibit poor bonding strength to the wool fiber surface, adversely affecting the durability of the anti-felting effect. Therefore, developing an eco-friendly anti-felting method for wool that not only meets the requirements of low felting and strength loss, but also minimizes the impact on the handle of wool fiber products, is a technical challenge that urgently needs to be addressed in wool textile dyeing and finishing. 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 cause adverse environmental pollution, the single protease subtractive method of anti-felting is prone to cause wool fiber damage, and the additive method based on resin deposition will affect the feel of the fiber products. The above problems affect the anti-felting finishing process of wool fiber products.

[0006]

Technical solution

[0007] To solve the above problems, the present invention first uses keratinase, which is specific to the wool scale layer, to hydrolyze the wool fiber scale layer to perform subtractive anti-felting finishing on wool fiber products; on this basis, with the help of horseradish peroxidase, catalyzes the oxidation of disulfide-bond phenolic small molecules to react 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 the polyphenol macromolecules, promote the reconstruction of disulfide bonds between the polyphenol macromolecules, and form a network cross-linked structure on the wool fiber surface, thereby achieving additive anti-felting and giving 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 to obtain an anti-felting treatment solution, immersing the wool fiber product in the anti-felting treatment solution, and performing an anti-felting treatment to obtain 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 products grafted with polyphenol macromolecules are immersed in hot water, washed and dried to obtain subtractive-additive anti-felting wool fiber products.

[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 18,000 to 22,000 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, preparing a reaction solution for reaction, removing ethanol after the reaction, separating and removing unreacted thioctic acid, and freeze-drying to obtain a disulfide bond-containing phenolic small molecule.

[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 preparation method of 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 preparation method of 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 h.

[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-mentioned wool bio-enzyme anti-felting finishing method.

[0038] The third object of the present invention is to provide the application of the above-mentioned 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-bonded phenolic small molecules to perform a subtractive-additive enzymatic anti-felting treatment for wool. Compared with conventional chemical or protease-based subtractive anti-felting treatments and resin deposition-based additive anti-felting treatments, the present invention has the following advantages:

[0041] (1) Ecological safety of the 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, meeting 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 to combine with keratinase, it can inhibit the excessive hydrolysis of the wool cortex and scale cell matrix by enzyme molecules, thereby reducing the fiber strength loss in the subtractive anti-felting of wool. On this basis, horseradish peroxidase catalyzes the reaction between tyrosine on the wool surface and disulfide-bonded phenolic small molecules, and grafting polymerization is performed on the fiber to form polyphenol macromolecules containing disulfide side groups. Combined with high-temperature heating, the disulfide bond ring opening and intermolecular reconstruction on the side groups of the polyphenol macromolecule are promoted, forming a network cross-linking on the fiber surface, further reducing the felting shrinkage of the fiber product and improving the 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 shrinkage: refer to GB / T 8628-2013 to determine the area felting shrinkage (%) of wool fabric.

[0047] Strength loss rate: The strength of wool woven fabrics before and after finishing is determined by measuring the warp breaking strength in accordance with GB / T 3923.1-1997. The strength of wool knitted fabrics before and after finishing is determined by measuring the bursting strength in accordance with GB / T 19976-2005. 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 determine the drape coefficient (%) of wool fabric.

[0050] Example 1

[0051] A wool bioenzyme anti-felting finishing method based on subtraction-addition method, comprising the steps of:

[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, and reacting the obtained reaction solution. After the reaction, ethanol is removed by rotary evaporation, and unreacted lipoic acid is removed by centrifugation to obtain disulfide bond-containing phenolic small molecules, which are freeze-dried for later use.

[0053] The ethanol mass fraction of 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 to obtain an anti-felting treatment solution, immersing the wool woven fabric in the anti-felting treatment solution, and performing an anti-felting treatment to obtain a subtractive anti-felting wool woven fabric;

[0057] The anti-felting treatment solution contained 1 g / L keratinase and 10 g / L sodium 2-cyclohexylaminoethanesulfonate. The pH value was adjusted to 8 using a soda ash aqueous solution. The anti-felting treatment temperature was 50° C., the treatment time was 45 min, and the bath ratio was 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 polyphenol macromolecule grafted wool woven fabric;

[0059] The grafting reaction solution had a horseradish peroxidase concentration of 1.5 g / L and a disulfide-bonded phenolic small molecule concentration of 7.5 g / L. The grafting reaction solution had a pH of 6.5. The immersion temperature was 30° C., the immersion time was 1 h, and the bath ratio was 1:8.

[0060] (4) Additive anti-felting: The polyphenol macromolecule grafted wool woven fabric is immersed in hot water, washed and dried to obtain the 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, comprising the steps of:

[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, and reacting the obtained reaction solution. After the reaction, ethanol is removed by rotary evaporation, and unreacted lipoic acid is removed by centrifugation to obtain disulfide bond-containing phenolic small molecules, which are freeze-dried for later use.

[0065] The ethanol mass fraction of 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 to obtain an anti-felting treatment solution, immersing the wool knitted fabric in the anti-felting treatment solution, and performing an anti-felting treatment to obtain a subtractive anti-felting wool knitted fabric;

[0069] The anti-felting treatment solution contained 2.5 g / L keratinase and 15 g / L sodium 2-cyclohexylaminoethanesulfonate. The pH value was adjusted to 9 using a soda ash aqueous solution. The anti-felting treatment temperature was 60°C, the treatment time was 60 min, and the bath ratio was 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 polyphenol macromolecule grafted wool knitted fabric;

[0071] The grafting reaction solution had a horseradish peroxidase concentration of 5 g / L and a disulfide-bonded phenolic small molecule concentration of 10 g / L; the grafting reaction solution had a pH of 7.0; the immersion temperature was 40°C, the immersion time was 2 h, and the bath ratio was 1:12;

[0072] (4) Additive anti-felting: The polyphenol macromolecule grafted wool knitted fabric 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 according to step (2) of Example 1, except that sodium 2-cyclohexylaminoethanesulfonate was not added to the anti-felting treatment solution.

[0078] Comparative Example 3

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

[0080] Comparative Example 4

[0081] The wool woven fabric was treated according to 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 fabric.

[0088] Comparative Example 8

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

[0090] Comparative Example 9

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

[0092] Comparative Example 10

[0093] The wool knitted fabric was treated according to 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 fabrics prepared by the present invention (Example 1 and Example 2) is ≤6%, which meets the requirements of anti-shrinkage wool fabrics; the strength loss rate of the subtractive-additive anti-felting wool fabrics is less than 10%, indicating that the fibers are less damaged during the treatment; the drape coefficient of the prepared subtractive-additive anti-felting wool fabrics is similar to that of the wool fabrics of Comparative Example 1 or 7, and the hand feel is good.

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

[0103] The wool fabrics treated only with step (2) without the addition of sodium 2-cyclohexylaminoethanesulfonate (Comparative Examples 2 and 8) showed a certain degree of reduction in area felting compared to the untreated wool fabrics, but were still much higher than 6%, not yet meeting the standard for shrink-proof wool products. At the same time, the strength loss rates of the wool fabrics prepared in Comparative Examples 2 and 8 were both greater than 15%, indicating that the keratinase treatment alone hydrolyzed the intercellular components and cortical layer of the wool scales, causing damage to the wool fibers. This result indicates that it is difficult to meet the requirements for anti-felting wool using only keratinase.

[0104] Compared with the wool fabrics without the addition of sodium 2-cyclohexylaminoethanesulfonate (Comparative Example 2 and Comparative Example 8), the wool fabrics treated only by step (2) (Comparative Example 3 and Comparative Example 9) have a slightly lower area felting 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] The wool fabrics treated only by step (2) but using protease instead of keratinase (Comparative Examples 4 and 10) had similar felting shrinkage rates to those of the samples in Comparative Examples 3 and 9, respectively, under the same total enzyme activity conditions, but had higher strength loss rates, indicating that in the presence of sodium 2-cyclohexylaminoethanesulfonate, keratinase can more effectively hydrolyze keratin flakes with a higher disulfide bond content than protease, thereby reducing damage to the interior 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 phenolic small molecules are grafted and polymerized on the wool fiber surface by horseradish peroxidase, so that the wool fabrics obtain 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 surface of the fiber scales (i.e., fewer exposed tyrosine acids), which makes the number of polyphenolic macromolecules bound to the wool fiber surface by horseradish peroxidase less. Therefore, 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 not treated in step (4) (Comparative Examples 6 and 12) had lower felting rates, but still higher than the subtractive-additive anti-felting wool fabrics produced by the present invention (Examples 1 and 2). This is 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 temperatures to generate sulfhydryl groups. Further, through the bonding between the sulfhydryl groups, disulfide bonds are re-formed between the polyphenol macromolecules, forming a cross-linked network on the wool fiber surface, achieving an additive anti-felting effect and simultaneously increasing the strength of the wool fiber. The wool fabrics produced in Comparative Examples 6 and 12 were not treated with hot water, and no network structure was formed on the fiber surface. Therefore, 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, nor are the steps described to limit their execution order. Any obvious improvements to the present invention made by those skilled in the art in combination with existing common knowledge shall 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: Including steps: (1) Subtractive anti-felting: dissolve keratinase and sodium 2-cyclohexylaminoethanesulfonate in water, adjust the pH value to obtain an anti-felting treatment solution, immerse the wool fiber product in the anti-felting treatment solution, perform anti-felting treatment, and obtain a subtractive anti-felting wool fiber product; (2) Enzymatic grafting polymerization of phenolic small molecules: dissolve disulfide bond-containing phenolic small molecules and horseradish peroxidase in water to prepare a grafting reaction solution, and immerse the subtractive anti-felting wool fiber product in the grafting reaction solution to prepare a polyphenol macromolecule grafted wool fiber product; the structural formula of the disulfide bond-containing phenolic small molecule is as follows: Among them, -R1 is or ; (3) Additive anti-felting: The wool fiber products grafted with polyphenol macromolecules are immersed in hot water, washed and dried to obtain subtractive-additive anti-felting wool fiber products.

2. The method for anti-felting wool using biological enzymes according to claim 1, wherein: 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 soda ash aqueous solution.

4. The method for anti-felting wool using biological enzymes according to claim 1, wherein: 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 using biological enzymes according to claim 1, wherein: 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.

6. The method for anti-felting wool using biological enzymes according to claim 1, wherein: In step (2), the immersion temperature is 30-40° C., the immersion treatment time is 1-2 h, and the bath ratio is 1-8:1-12.

7. The method for anti-felting wool using biological enzymes according to claim 1, wherein: In step (3), the temperature of the hot water is 80-90°C, the pH value of the hot water is 6.5-7.5, and the immersion is carried out for 20-30 minutes.

8. Subtractive-additive anti-felting wool fiber products prepared by the wool bio-enzyme anti-felting finishing method according to claim 1.

9. Use of the subtractive-additive anti-felting wool fiber product according to claim 8 in the field of textiles.

Images