Low-temperature dyeing and antibacterial shrink-resistant composite processing method for wool

Abstract

The application discloses a low-temperature dyeing and antibacterial shrink-proof composite processing method for wool fabric, and belongs to the technical field of textile dyeing and finishing processing. Firstly, keratinase and protease are used for enzyme shrink-proof treatment of the wool fabric, wool scale keratin is decomposed by enzymolysis, and the wool is endowed with shrink-proof effect; then, low-temperature dyeing treatment is carried out on the wool fabric; finally, glutamine transaminase is used to catalyze amino macromolecules containing glutamine, and bio-enzyme addition composite finishing is carried out, so that the dyeing fastness is improved, the shrink-proof effect is increased, and the wool is endowed with antibacterial property. Compared with traditional chlorination or single enzyme method for wool shrink-proof finishing, the method has the advantages of process ecological environmental protection, low shrinkage rate, low strength loss, excellent antibacterial effect, high color depth and high color fastness.

Description

TECHNICAL FIELD

[0001] The present application relates to a low-temperature dyeing and antibacterial shrink-proof composite processing method for wool fabric, and belongs to the technical field of textile dyeing and finishing. BACKGROUND

[0002] Wool fiber is a high-grade textile fiber with excellent warmth retention and soft hand feeling. Due to the scale layer structure of wool fiber, after being subjected to mechanical force in a wet state, the sawtooth scale layers will cross and entangle, and interlock, resulting in the phenomenon of appearance felting and unclear lines of wool fabric during washing, which affects the wearability of wool fabric. Wool treatment by chlorination can effectively remove the scale cuticle of wool, not only improving the anti-felting effect of fiber products, but also being beneficial to low-temperature dyeing of wool fiber and realizing energy saving and consumption reduction in the production process, as the diffusion resistance of dye molecules is reduced due to the destruction of the integrity of the scale layer on the surface of wool. Although chlorination is beneficial to improving the anti-felting property of wool, a large amount of adsorbable organic halides are generated during the treatment, which is harmful to the human body and the environment, and the application in actual production is restricted to a certain extent.

[0003] Compared with the chlorination anti-felting processing method, the use of biological enzyme method for wool anti-felting processing has many advantages, including mild treatment conditions and soft fabric hand feeling after finishing. The most commonly used enzyme in wool enzyme anti-shrinkage finishing is protease, which hydrolyzes and destroys the scale layer structure of wool fiber by means of protease, so as to achieve the purpose of subtraction anti-felting. In actual application, due to the easy diffusion of protease molecules into the scale layer of fiber, catalyzing the hydrolysis of intercellular substance and cortex layer, wool fiber damage and strength loss are easily caused, so there is certain limitation in actual use. Although there are also studies on the use of cutinase, keratinase and protease in multi-enzyme combination, aiming to limit the enzymatic reaction in the scale layer of wool fiber and reduce the hydrolysis of cortex layer, but in actual application, this process is difficult to achieve satisfactory results, that is, if the enzyme treatment is insufficient, the scale layer removal effect is poor, and the anti-felting effect of wool fabric is poor; on the contrary, the enzyme treatment after reaching the low shrinkage rate requirement, the strength loss of the fabric is too large.

[0004] In order to solve the problem of wool enzyme anti-felting processing that wool damage is easily caused when meeting the requirement of low shrinkage rate, some researchers use biological enzyme method + resin method combination anti-felting process, that is, after biological enzyme anti-felting, a layer of resin macromolecules is deposited on the surface of wool fiber, aiming to make up for the fiber strength loss caused by biological enzyme method, and further improve the anti-felting effect. Biological enzyme method + resin method combination anti-felting finishing can give wool fabric low shrinkage rate and low strength loss, but due to the deposition of resin on the surface of fiber, the hand feeling of fiber product is easily deteriorated; and resin method addition anti-shrinkage finishing needs high temperature baking, which easily leads to yellowing of fiber or changes of color appearance of dyed wool.

[0005] Therefore, how to construct a wool fabric anti-felting method with low felting rate and low strength loss, while meeting the less influence on the color appearance and hand feeling of wool fabric, is a technical problem to be solved urgently. SUMMARY

[0006] In view of the problems of the chlorination method in the anti-felting processing of wool fabric, such as environmental unfriendliness, the wool fiber damage caused by the biological enzyme method, and the fabric hand feeling and appearance color change caused by the biological enzyme reduction method and resin addition method, the purpose of the present application is to provide a wool low-temperature dyeing and antibacterial anti-shrinkage composite processing method. The keratinase and protease are used to hydrolyze the scale layer of wool, destroy the integrity of the scale layer structure, and at the same time impart the wool fabric with anti-felting effect; on this basis, wool fiber low-temperature dyeing is carried out to realize low-energy-consumption dyeing; finally, with the help of glutamine transaminase, amino macromolecules containing glutamine are grafted to the wool fiber, and triple cross-linking between amino macromolecules, between amino macromolecules and wool fiber, and between wool fibers is formed on the surface of the fiber, so as to improve the dyeing fastness of wool fiber and enhance the anti-felting effect of wool fabric.

[0007] In order to achieve the above purpose, the present application first provides a wool fabric low-temperature dyeing and antibacterial anti-shrinkage composite processing method, comprising the following steps:

[0008] (1) Enzymatic anti-felting treatment: keratinase and protease are used to treat wool fabric, and the scale layer of wool fiber is subjected to anti-felting treatment by enzymatic hydrolysis;

[0009] (2) Low-temperature dyeing treatment: wool fabric treated in step (1) is subjected to low-temperature dyeing treatment with wool reactive dyes;

[0010] (3) Biological enzyme addition composite finishing: glutamine transaminase is used as a catalyst to catalyze the grafting of amino macromolecules containing glutamine on the surface of the wool fabric treated in step (2).

[0011] In an embodiment of the present application, in step (1), the enzyme anti-felting treatment is carried out by two-bath method, and the specific steps are as follows: first, the wool fabric is added to the keratinase solution for 30 min, then taken out and added to the protease solution for 30-60 min, and finally dried at 105 DEG C.

[0012] In an embodiment of the present application, in step (1), the enzyme activity of the keratinase is 10000-12000 U / mL, the concentration of the keratinase solution is 1-5 g / L, the enzyme activity of the protease is 10000-12000 U / mL, and the concentration of the protease solution is 0.5-2 g / L.

[0013] In one embodiment of the present application, in step (1), the temperature for keratinase treatment and protease treatment is 50-60℃, the pH range is 8.5-9, and the bath ratio is 1:20.

[0014] In one embodiment of the present application, in step (2), the dosage of the hair active dye is determined according to the color depth requirement, the dyeing temperature is 80-85℃, the pH range is 5-6, and the bath ratio is 1:30.

[0015] In one embodiment of the present application, in step (2), soda ash is added for fixation after dyeing for 30 min, the concentration of the soda ash is 2.5-5 g / L after addition, and the fixation time is 30 min; finally, the dyed wool fabric is washed with deionized water at 60℃ for 10 min.

[0016] In one embodiment of the present application, in step (3), the wool fabric treated in step (2) is immersed in a treatment solution containing transglutaminase and an amino macromolecule containing glutamine for 1-2 h, and the treated wool fabric is washed with deionized water at 60℃ for 10 min and dried at 105℃.

[0017] In one embodiment of the present application, in step (3), the temperature is 40-45℃, the pH range is 6.5-7, and the bath ratio is 1:20.

[0018] In one embodiment of the present application, in step (3), the enzyme activity of the transglutaminase in the treatment solution is 10000-15000 U / mL, the concentration is 0.5-2 g / L, and the concentration of the amino macromolecule containing glutamine is 2-10 g / L.

[0019] In one embodiment of the present application, the amino groups in the amino macromolecule containing glutamine are combined with the amino macromolecule by an amide bond, and the modification degree of the amino groups in the amino macromolecule is 15-20%.

[0020] In one embodiment of the present application, the amino macromolecule containing glutamine includes polylysine containing glutamine and polyethyleneimine containing glutamine, and the molecular weight is 3000-10000.

[0021] In one embodiment of the present application, in step (3), the preparation method of the amino macromolecule containing glutamine includes the following steps:

[0022] (1) dissolving 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide, N-hydroxysuccinimide, L-glutamine and an amino macromolecule in water to prepare a mixed solution, wherein the concentration of 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide in the mixed solution is 5 g / L, the concentration of N-hydroxysuccinimide is 5 g / L, the concentration of L-glutamine is 5 g / L, and the concentration of the amino macromolecule is 10 g / L, and reacting at a temperature of 25 DEG C and a pH of 5 for 24 h;

[0023] (2) dialyzing the mixed solution prepared in step (1) to remove 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide, N-hydroxysuccinimide and L-glutamine;

[0024] (3) freeze-drying the product obtained in step (2) to obtain a glutamine-containing amino macromolecule; wherein the amino macromolecule comprises polylysine and / or polyethyleneimine.

[0025] In an embodiment of the present application, the wool fabric includes wool fabrics of different gram weights, sizes and widths made of wool and cashmere.

[0026] The present application also provides a wool fabric finished by the above method.

[0027] Advantages of the present application

[0028] The present application first performs enzyme method anti-shrinking treatment on the wool fabric with keratinase and protease to hydrolyze the wool scale keratin and impart anti-shrinking effect to the wool; then performs dyeing treatment on the wool fabric at low temperature; finally, catalyzes the glutamine-containing amino macromolecule with glutamine transaminase to perform bio-enzyme finishing, which improves the dyeing fastness, increases the anti-shrinking effect and imparts antibacterial effect to the wool fabric. Compared with the traditional chlorination method, bio-enzyme + resin method or single protease method for anti-shrinking finishing of wool fabric, the present application has the following advantages:

[0029] (1) The finishing process is eco-friendly. Bio-enzyme belongs to biological agent and is a protein macromolecule itself, which has good ecology; no chlorine-containing oxidizing agent or resin finishing agent is used in the finishing of the wool fabric, so there is no risk of organic chlorine residue and free formaldehyde residue, and the eco-friendliness of the anti-shrinking finishing process of the wool fabric is realized.

[0030] (2) Low felting rate and low strength loss. Keratinase treatment can reduce and hydrolyze the outer layer structure of wool scales, promoting the removal of scale keratin by subsequent protease; in the bio-enzyme additive finishing complex, glutamine transaminase can catalyze the grafting of amino macromolecules containing glutamine onto wool, and at the same time, three reactions occur, including the reaction between wool fibers and amino macromolecules containing glutamine, the reaction between amino macromolecules containing glutamine, and the reaction between glutamine and amino groups on the wool fiber macromolecule; the above reactions promote the formation of a surface network cross-linking structure of the fiber, not only improving the anti-felting effect of wool products, but also achieving the repair of wool fiber damage, meeting the processing requirements of low felting rate and low strength loss;

[0031] (3) Excellent antibacterial effect. Glutamine transaminase can catalyze the grafting of amino macromolecules containing glutamine onto wool, introducing more amino macromolecules onto the fiber surface, and forming a multiple cross-linking network on the fiber surface, not only giving the wool fabric good additive anti-felting effect, but also giving the wool good antibacterial properties due to the rich amino groups.

[0032] (4) High color depth and high color fastness. After keratinase and protease treatment, the tightness of the surface structure of wool fibers is reduced, which is beneficial to the diffusion of dyes into the interior of the wool fibers, thereby achieving a high dyeing percentage at low temperature; glutamine transaminase can catalyze the grafting of amino macromolecules containing glutamine onto wool, forming a cross-linking network structure on the fiber surface, improving the dyeing fastness of wool fabric, and the fabric has good hand feeling. DETAILED DESCRIPTION

[0033] The preferred embodiments of the present application are described below, and it should be understood that the embodiments are for better explanation of the present application and are not used to limit the present application.

[0034] The following wool fabric is 230g / m 2 , width 44 inches; keratinase is purchased from Jinan Baisiji Biological Engineering Co., Ltd.; protease is Savinase 16L purchased from Novozymes; wool active dye is Lanasol Red CE provided by Huntsman Corporation, USA, and glutamine enzyme is purchased from Taizhou Yiming Biological Co., Ltd.

[0035] The preparation method of the polylysine containing glutamine involved in the examples and comparative examples of the present application includes the following steps:

[0036] (1) 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide, N-hydroxysuccinimide, L-glutamine, polylysine are dissolved in water to prepare a mixed solution, and the mixed solution is reacted at a temperature of 25°C and a pH of 5 for 24 hours, wherein the concentration of 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide in the mixed solution is 5 g / L, the concentration of N-hydroxysuccinimide is 5 g / L, the concentration of L-glutamine is 5 g / L, and the concentration of polylysine is 10 g / L;

[0037] (2) The mixed solution prepared in step (1) is dialyzed to remove 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide, N-hydroxysuccinimide, and L-glutamine;

[0038] (3) The product obtained in step (2) is freeze-dried to obtain glutamine-containing polylysine.

[0039] Example 1

[0040] A wool fabric low-temperature dyeing and antibacterial shrink-resistant composite processing method, specifically comprising the following steps:

[0041] (1) Enzymatic anti-felting treatment: keratinase and protease are used to treat wool fabric, and the specific process is as follows: first, the wool fabric is added to a keratinase solution for 30 minutes, then it is added to a protease solution for 30 minutes, and finally it is dried at 105°C; wherein the enzyme activity of keratinase in the keratinase solution is 10000 U / mL, and the concentration is 1 g / L; the enzyme activity of protease in the protease solution is 10000 U / mL, and the concentration is 0.5 g / L, the treatment temperature is 50°C, the pH is 8.5, and the bath ratio is 1:20;

[0042] (2) Low-temperature dyeing treatment: the wool fabric treated in step (1) is dyed with wool reactive dye Lanasol Red CE; wherein the concentration of Lanasol Red CE is 1 g / L, the dyeing temperature is 80°C, the pH is 5, and the bath ratio is 1:30; after dyeing for 30 minutes, soda ash is added for fixation, wherein the concentration of soda ash after adding is 2.5 g / L, and the fixation time is 30 minutes; finally, the dyed wool fabric is washed with deionized water at 60°C for 10 minutes;

[0043] (3) Bio-enzyme plus finishing: the wool fabric treated in step (2) is immersed in a treating solution containing transglutaminase and polylysine containing glutamine for 1 h, and then washed with deionized water at 60 ℃ for 10 min and dried at 105 ℃; wherein the enzyme activity of transglutaminase in the treating solution is 12000 U / mL, the concentration is 0.5 g / L, the concentration of polylysine containing glutamine is 2 g / L, the treating temperature is 40 ℃, the pH is 6.5, and the bath ratio is 1:20; the molecular weight of polylysine containing glutamine is 3000, and the modification degree of amino group in the molecule is 15%.

[0044] Example 2

[0045] (1) Enzyme anti-felting treatment: the wool fabric is treated with keratinase and protease, and the specific process is as follows: first, the wool fabric is added to a keratinase solution for 30 min, then added to a protease solution for 60 min, and finally dried at 105 ℃; wherein the enzyme activity of keratinase in the keratinase solution is 12000 U / mL, and the concentration is 5 g / L; the enzyme activity of protease in the protease solution is 12000 U / mL, and the concentration is 2 g / L, the treating temperature is 60 ℃, the pH is 9, and the bath ratio is 1:20.

[0046] (2) Low-temperature dyeing treatment: the wool fabric treated in step (1) is dyed with wool reactive dye Lanasol Red CE; wherein the concentration of Lanasol Red CE is 1 g / L, the dyeing temperature is 85 ℃, the pH is 6, and the bath ratio is 1:30; after dyeing for 30 min, soda ash is added for fixation, wherein the concentration of soda ash after adding is 5 g / L, and the fixation time is 30 min; finally, the dyed wool fabric is washed with deionized water at 60 ℃ for 10 min.

[0047] (3) Bio-enzyme plus finishing: the wool fabric treated in step (2) is immersed in a treating solution containing transglutaminase and polylysine containing glutamine for 2 h, and then washed with deionized water at 60 ℃ for 10 min and dried at 105 ℃; wherein the enzyme activity of transglutaminase in the treating solution is 12000 U / mL, the concentration is 2 g / L, the concentration of polylysine containing glutamine is 10 g / L, the treating temperature is 45 ℃, the pH is 7, and the bath ratio is 1:20; the molecular weight of polylysine containing glutamine is 10000, and the modification degree of amino group in the molecule is 20%.

[0048] Comparative Example 1

[0049] The difference between Comparative Example 1 and Example 1 is that the wool fabric is only treated in step (2) without treatment in steps (1) and (3), and the breaking strength of the fabric after dyeing is 512 N.

[0050] Comparative Example 2

[0051] Comparative Example 2 differs from Example 1 in that the wool fabric is treated only by steps (1)-(2) without step (3).

[0052] Comparative Example 3

[0053] Comparative Example 3 differs from Example 1 in that the wool fabric is treated by steps (1)-(3), but no polylysine containing glutamine is added in step (3).

[0054] Comparative Example 4

[0055] Comparative Example 4 differs from Example 1 in that the wool fabric is treated by steps (1)-(3), but no transglutaminase is added in step (3).

[0056] Comparative Example 5

[0057] Comparative Example 5 differs from Example 1 in that the wool fabric is treated by steps (1)-(3), but no keratinase is added in step (1) treatment.

[0058] Comparative Example 6

[0059] Comparative Example 6 differs from Example 1 in that the wool fabric is treated by steps (1)-(3), but no protease is added in step (1) treatment.

[0060] Comparative Example 7

[0061] Comparative Example 7 differs from Example 1 in that the wool fabric is treated by steps (1)-(3), but no two-bath method is used in step (1) treatment, i.e. keratinase and protease are added at the same time (i.e. one-bath method), and the treatment time is 60 min.

[0062] Comparative Example 8

[0063] Comparative Example 8 differs from Example 1 in that the wool fabric is treated by steps (1)-(3), but unmodified polylysine is used instead of polylysine containing glutamine in step (3) treatment, and the molecular weight of the polylysine used is 3000.

[0064] The properties of the wool fabric obtained in Examples 1-2 and Comparative Examples 1-7 were determined. The area shrinkage rate (%) of the wool fabric after finishing was determined according to GB / T 8628-2013; the breaking strength in the warp direction of the wool fabric was determined according to GB / T 3923.1-1997, and the relative strength change rate of different samples was calculated by taking only dyed wool fabric as a reference, and the strength loss rate (%) was calculated; the drape coefficient (%) of the wool fabric was determined according to GB / T 23329-2009; the dyeing percentage (%) was calculated by using a spectrophotometer according to the difference in absorbance of the solution before and after dyeing of the wool; the wet rubbing fastness grade of the dyed sample was determined according to GB 3920-2008; and the antibacterial rate (%) of the sample treated under different conditions against Staphylococcus aureus was evaluated according to GB / T 20944.3-2008, and the results are shown in Table 1.

[0065] Table 1

[0066]

[0067]

[0068] From Table 1, it can be seen that:

[0069] a. The area shrinkage rate of the wool fabric prepared by the method of the present application (Example 1, Example 2) is less than 4%, the strength loss rate of the sample in the warp direction is less than 12%, the sample has low shrinkage and low strength loss; the drape coefficient of the fabric after finishing is low, indicating that the sample has good hand feeling; the dyeing percentage of the wool fabric is high, the wet rubbing fastness grade is above 4, and the antibacterial rate against Staphylococcus aureus is high; the above results show that the sample has low shrinkage, low strength loss, high color fastness and antibacterial property.

[0070] b. The sample treated only by step (2) (Comparative Example 1) has high shrinkage (>20%), and poor anti-shrinkage effect; since the wool fiber surface scale layer structure is complete without keratinase and protease treatment, the dyeing percentage is low at low temperature, and the dye molecules cannot fully diffuse into the fiber, resulting in low color fastness grade; the fabric also has no antibacterial effect.

[0071] c. The sample treated only by steps (1)-(2) (Comparative Example 2) has a significant decrease in area shrinkage rate compared with the untreated sample, but is still higher than 6%, which still does not meet the standard requirements for shrink-proof wool; at the same time, the strength loss rate of the fabric is high (>20%), indicating that only keratinase / protease treatment can easily cause hydrolysis of the intercellular components and cortex layer of the wool scale cells in the fiber, resulting in serious fiber damage; in addition, the color fastness of the dyed wool fabric is also low, and has no antibacterial effect.

[0072] d. The sample treated by steps (1)-(3) but without adding polylysine containing glutamine in step (3) (Comparative Example 3) has an area shrinkage rate higher than 6%; although the fabric strength loss rate is lower than that of the fabric in Comparative Example 2, it is obviously higher than that of the sample in Example 1, because no polylysine containing glutamine is added, i.e., the transglutaminase can only catalyze the cross-linking between the accessible macromolecules of wool fibers, and it is difficult to form other multiple cross-linking on the fiber surface; because the enzyme catalyzed cross-linking network structure is not formed on the fiber surface, the wet rubbing fastness of the fabric is also low, and the antibacterial effect is not significant.

[0073] e. The sample treated by steps (1)-(3) but without adding transglutaminase in step (3) (Comparative Example 4) has an area shrinkage rate higher than 6%; the fabric strength loss rate is similar to that of the fabric in Comparative Example 2, because no transglutaminase is added in the treatment, and no multiple cross-linking is formed on the fiber surface; the wet rubbing fastness of the fabric after dyeing is also low, and the antibacterial effect is not significant.

[0074] f. The sample treated by steps (1)-(3) but without adding keratinase in step (1) (Comparative Example 5) has an area shrinkage rate meeting the requirements of the anti-shrinking wool standard; but the fabric strength loss rate is much higher than that of the fabric of the same specification in Comparative Example 1, because the lack of keratinase in the treatment for the loosening of the outer layer of the wool scale, and the protease is more likely to diffuse into the fiber interior to hydrolyze the intercellular matrix components and the cortex layer, causing greater fiber damage; the transglutaminase catalyzes the polylysine containing glutamine to form multiple cross-linking on the fiber surface, and the dyeing fastness and antibacterial effect of the fabric are both good.

[0075] g. The sample treated by steps (1)-(3) but without adding protease in step (1) (Comparative Example 6) has a relatively high area shrinkage rate, which does not meet the requirements of the anti-shrinking wool standard, because the keratinase in the treatment mainly acts on the outer layer of the wool scale with high sulfur content, and the lack of protease for further enzymatic hydrolysis of the loosened wool scale keratin structure makes the anti-shrinking effect of the wool fabric unsatisfactory.

[0076] h. The sample treated by steps (1)-(3) but without using the two-bath method, i.e., the keratinase and the protease are added at the same time in step (1) (Comparative Example 7) has an area shrinkage rate similar to that of the sample in Example 1, meeting the requirements of the anti-shrinking wool standard; but the fabric strength loss is significantly higher than that of the sample in Example 1, because when the keratinase and the protease are added at the same time in the treatment, the protease begins to diffuse into the fiber interior at the beginning of the treatment, and it is more likely to hydrolyze the intercellular matrix components and the cortex layer (rather than acting on the outer layer of the wool scale after the keratinase pretreatment); therefore, when the one-bath method is used in the enzymatic anti-shrinking treatment, because the keratinase has not yet loosened the structure of the outer layer of the scale with high sulfur content, the protease begins to diffuse into the fiber interior, thereby causing greater strength damage to the wool fabric.

[0077] i. The sample treated by steps (1)-(3) but using polylysine instead of glutamine-containing polylysine in step (3) (comparative example 8) has a slightly higher area shrinkage than that in example 1 and the fabric strength loss is also higher than that in example 1. The reason is that the use of polylysine can only cause transaminase catalyzed crosslinking on the surface of the fiber and cannot form glutamine-containing polylysine intermolecular enzymatic crosslinking on the surface of the wool. Therefore, the anti-shrinking finishing effect without the addition of glutamine-containing polylysine is not as good as that in example 1.

[0078] It can be seen that the samples in example 1 and example 2 treated by the method of the present application not only have a lower shrinkage and a good anti-shrinking effect, but also have a lower strength loss. The drape of the wool fabric is significantly improved compared with the untreated sample and the fabric has a good hand feeling. In addition, the dyeing at low temperature has a higher dye uptake percentage and good color fastness, and also has antibacterial properties.

[0079] The above examples provided are not intended to limit the scope covered by the present application, and the described steps are not intended to limit the execution order. Those skilled in the art can make obvious improvements to the present application in combination with the existing common knowledge, which also falls within the protection scope defined by the claims of the present application.

Claims

1. A method for low-temperature dyeing and antibacterial / shrinkage-resistant composite processing of wool fabrics, characterized in that, Includes the following steps: (1) Enzymatic anti-felting treatment: wool fabrics are treated with keratinase and protease to prevent felting by enzymatically hydrolyzing the scale layer of wool fibers. (2) Low-temperature dyeing treatment: The wool fabric treated in step (1) is dyed at low temperature with wool reactive dyes; (3) Bioenzyme addition composite finishing: using transglutaminase as a catalyst, glutamine-containing amino macromolecules are catalytically grafted onto the surface of wool fabric treated in step (2). The glutamine-containing amino macromolecules include polylysine containing glutamine and / or polyethyleneimine containing glutamine, with a molecular weight of 3000-10000. The method for preparing the glutamine-containing amino macromolecule includes the following steps: (1) Dissolve 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide, N-hydroxysuccinimide, L-glutamine, and amino macromolecules in water to prepare a mixed solution. React at 25℃ and pH=5 for 24h. The concentration of 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide in the mixed solution is 5g / L, the concentration of N-hydroxysuccinimide is 5g / L, the concentration of L-glutamine is 5g / L, and the concentration of amino macromolecules is 10g / L. (2) Dialyze the mixed solution prepared in step (1) to remove 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide, N-hydroxysuccinimide and L-glutamine; (3) The product obtained in step (2) is freeze-dried to obtain an amino macromolecule containing glutamine; wherein the amino macromolecule includes polylysine and / or polyethyleneimine.

2. The composite processing method according to claim 1, characterized in that, In step (1), the enzymatic anti-felting treatment is carried out using a two-bath method. The specific steps are as follows: first, the wool fabric is immersed in a keratinase solution for 30 minutes, then the wool fabric is removed and immersed in the protease solution again for 30-60 minutes, and finally dried at 105°C.

3. The composite processing method according to claim 1, characterized in that, In step (1), the keratinase activity is 10000-12000 U / mL, the concentration of the keratinase solution is 1-5 g / L, the protease activity is 10000-12000 U / mL, and the concentration of the protease solution is 0.5-2 g / L; the treatment temperature for both keratinase treatment and protease treatment is 50-60℃, the pH range is 8.5-9, and the bath ratio is 1:

20.

4. The composite processing method according to claim 1, characterized in that, In step (2), the dyeing temperature is 80-85℃, the pH range is 5-6, the liquor ratio is 1:30, and after dyeing for 30 minutes, soda ash is added to fix the color. The dyed wool fabric is then washed with deionized water at 60℃ for 10 minutes. After adding soda ash, the concentration of soda ash is 2.5-5g / L, and the color fixing time is 30 minutes.

5. The composite processing method according to claim 1, characterized in that, In step (3), the wool fabric obtained in step (2) is immersed in a treatment solution containing transglutaminase and amino macromolecules containing glutamin for 1-2 hours. The treated wool fabric is then washed with deionized water at 60°C for 10 minutes and dried at 105°C. The treatment temperature is 40-45°C, the pH range is 6.5-7, and the bath ratio is 1:

20.

6. The composite processing method according to claim 5, characterized in that, In step (3), the enzyme activity of glutamine transaminase in the treatment solution is 10000-15000 U / mL, the concentration is 0.5-2 g / L, and the concentration of amino macromolecules containing glutamine is 2-10 g / L.

7. The composite processing method according to any one of claims 1 to 6, characterized in that, In step (3), the glutamine group in the glutamine-containing amino macromolecule is bonded to the amino macromolecule by an amide bond, and the degree of modification of the amino group in the amino macromolecule is 15-20%.

8. Wool fabrics processed by the composite processing method according to any one of claims 1 to 7.

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