A method for anti-bacterial and shrink-proof finishing of wool fiber products based on catalytic grafting cross-linking

Abstract

The present application belongs to the field of textile dyeing and finishing technology, and provides an antibacterial and shrink-resistant finishing method for wool fiber products based on catalytic grafting and crosslinking, comprising the following steps: dissolving potassium hydroxide in ethanol to prepare an alkali-alcohol solution, immersing the wool fiber product in the alkali-alcohol solution to obtain a pretreated wool fiber product; synthesizing modified amino macromolecules containing disulfide bond side groups by using lipoic acid and amino macromolecules as main raw materials; immersing the pretreated wool fiber product in the modified amino macromolecule aqueous solution, and then immersing it in silver nitrate to obtain an antibacterial and shrink-resistant wool fiber product. The antibacterial and shrink-resistant finishing method forms a modified amino macromolecule crosslinking network layer on the surface of the wool fiber product, does not damage the fiber strength, and gives the wool a shrinkage-resistant effect; the modified amino macromolecule has antibacterial, reducing and coordination combination properties with nano-silver, promotes the reduction and deposition of silver ions on the surface of the wool fiber, and improves the antibacterial effect of the wool fiber product.

Description

TECHNICAL FIELD

[0001] The present application relates to a kind of wool fiber product based on catalytic grafting crosslinking antibacterial shrink-proof finishing method, belong to textile dyeing and finishing technology field. BACKGROUND

[0002] Wool is a kind of high-grade textile fiber with excellent warmth retention and soft hand feeling, but under the action of mechanical external force in the wet state, the sawtooth scale layer on the fiber surface is easy to cross and entangle and interlock, resulting in appearance size shrinkage and hand feeling change of wool fabric during washing, which seriously affects the wearing performance of wool fiber products.In addition, wool is a kind of protein fiber, which can easily become the nutrient of bacteria, mold and other microorganisms under appropriate temperature and humidity conditions, thus causing the mildew of fabric, and even possibly becoming the carrier of disease transmission.Therefore, in order to improve the wearing performance of wool fiber products, it is necessary to carry out finishing processing for the purpose of improving the anti-felting effect and antibacterial performance.

[0003] At present, wool anti-felting processing mostly adopts chlorination method, which can obtain good chlorination anti-felting effect at low temperature, but the disadvantage is that wool chlorination process can produce adsorbable organic halides, affecting the ecological safety of fiber products. Wool anti-felting processing using biological enzymes has many advantages, including mild processing conditions, soft hand feeling, etc., among which protease is more studied in wool anti-felting processing. Although there have been many reports on protease method for wool anti-felting processing, the anti-felting finishing effect based on protease in actual production is not ideal, because protease can easily diffuse into the interlaminar scale layer of fiber to hydrolyze the intercellular substance and cortex layer, thus causing great damage to the fiber.

[0004] For wool antibacterial finishing, available antibacterial finishing agents include silver ion, organic quaternary ammonium salt, halamine compound, etc., and the finishing process is mostly carried out by the method of padding and high-temperature baking, which can give the fiber products antibacterial effect, but also has the disadvantages of poor combination with fiber, easy release and migration from the surface of fiber to the surface of body skin, or damage to fiber strength during baking, and pollution of the environment by discharge of finishing waste liquid. In order to obtain durable and stable antibacterial effect, chemical crosslinking agents are also used to combine the antibacterial agent with cellulose or protein fiber under steaming or baking conditions, but improper treatment can affect the hand feeling of fabric, cause color change and strength decrease of fabric. Therefore, in the processing of wool fiber products, how to construct a finishing method with good shrink-proof and antibacterial effect, and long-lasting finishing effect and less fiber damage is an important topic to be explored at present. SUMMARY

[0005]

Technical problem

[0006] In the dyeing and finishing process of wool fiber products, using chlorination or protease for subtractive anti-shrinkage finishing can easily cause fiber damage; many wool antibacterial finishing processes have the disadvantages of complex finishing process, non-durable antibacterial effect and easy influence on the hand feeling of fiber products, which affects the processing of anti-shrinkage and antibacterial wool fiber products.

[0007]

Technical Scheme

[0008] To solve the above problems, the alkali alcohol solution is used for wool pretreatment to remove the lipid in the outer layer of the fiber scale and improve the accessibility of cystine in the wool scale layer; the modified amino macromolecule containing disulfide side groups is prepared by using thioctic acid and amino macromolecule as raw materials; the wool fiber product is immersed in the modified amino macromolecule aqueous solution for grafting treatment by using one-bath two-step method, the disulfide bond in the fiber scale layer and the modified amino macromolecule forms a reducing sulfydryl, and the modified amino macromolecule is further grafted and crosslinked on the fiber surface through disulfide bond reconstruction; then silver nitrate is added to the modified amino macromolecule aqueous solution, and the silver ion is reduced by the amino and sulfydryl in the modified amino macromolecule under heating to promote the deposition of nano-silver on the fiber surface and give the wool anti-shrinkage and antibacterial effect.

[0009] The first object of the present application is to provide an antibacterial and anti-shrinkage finishing method for wool fiber products based on catalytic grafting and crosslinking, comprising the following steps:

[0010] (1) Wool lipid layer removal: potassium hydroxide is dissolved in ethanol to prepare an alkali alcohol solution, and the wool fiber product is immersed in the alkali alcohol solution to obtain a pretreated wool fiber product;

[0011] (2) Preparation of modified amino macromolecule: thioctic acid, amino macromolecule, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide are dissolved in an ethanol aqueous solution to prepare a reaction solution, and the pH value is adjusted for reaction, after the reaction is completed, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxysuccinimide and unreacted thioctic acid are removed by dialysis, and the modified amino macromolecule containing disulfide side groups is prepared by freeze-drying;

[0012] (3) Construction of antibacterial layer on the fiber surface: the modified amino macromolecule containing disulfide side groups is dissolved in water to prepare a grafting finishing liquid, and the pretreated wool fiber product is subjected to grafting immersion treatment in the grafting finishing liquid; then silver nitrate is added to the grafting finishing liquid to obtain an antibacterial finishing liquid, and reduction immersion treatment is carried out, and the antibacterial and anti-shrinkage wool fiber product is prepared after water washing and drying;

[0013] Wherein, steps (1) and (2) have no sequence.

[0014] In one embodiment of the present application, in step (1), the wool fiber product is one or more of wool fabric, wool top, and wool loose fiber.

[0015] In one embodiment of the present application, in step (1), the mass concentration of potassium hydroxide in the alkali alcohol solution is 2.5-5 g / L.

[0016] In one embodiment of the present application, in step (1), the temperature of the dipping is 20-25℃, the treatment time of the dipping is 8-15 min, and the bath ratio is 1:8-10.

[0017] In one embodiment of the present application, in step (2), the molecular weight of the amino macromolecule is 1000-4000.

[0018] In one embodiment of the present application, in step (2), the amino macromolecule is one of polylysine, polyethyleneimine, and chitooligosaccharide.

[0019] In one embodiment of the present application, in step (2), the mass fraction of ethanol in the aqueous ethanol solution is 45-55%.

[0020] In one embodiment of the present application, in step (2), the mass concentration of lipoic acid in the reaction solution is 4-6 g / L, the mass concentration of the amino macromolecule is 15-25 g / L, the mass concentration of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride is 8-12 g / L, and the mass concentration of N-hydroxysuccinimide is 2.5-4 g / L.

[0021] In one embodiment of the present application, in step (2), the pH value is adjusted to 4-5.

[0022] In one embodiment of the present application, in step (2), the pH is adjusted with an aqueous acetic acid solution.

[0023] In one embodiment of the present application, in step (2), the temperature of the reaction is 20-30℃, and the reaction time is 8-12 h.

[0024] In one embodiment of the present application, in step (2), the dialysis conditions are as follows: using a dialysis bag with a molecular weight cut-off of 500 daltons to dialyze small molecules with deionized water at 25-30℃ until the solution conductivity is less than 4 μS / cm.

[0025] In one embodiment of the present application, in step (3), the mass concentration of the modified amino macromolecule in the grafting finishing solution is 4-8 g / L, and the mass concentration of silver nitrate in the antibacterial finishing solution is 2-4 g / L.

[0026] In one embodiment of the present application, in step (3), the pH of the grafting finishing solution is 5.5-6.5; the pH of the antibacterial finishing solution is 5.5-6.5.

[0027] In one embodiment of the present application, in step (3), the temperature of the grafting immersion treatment is 75-80℃, the time of the grafting immersion treatment is 10-15 min, and the bath ratio is 1:8-10; the temperature of the reduction immersion treatment is 75-80℃, and the time of the reduction immersion treatment is 10-15 min.

[0028] The bath ratio is the mass ratio of the fabric to the finishing solution.

[0029] A second object of the present application is to provide an antibacterial and shrink-resistant wool fiber product prepared by the above-mentioned antibacterial and shrink-resistant finishing method for wool fiber products.

[0030] A third object of the present application is the use of the above-mentioned antibacterial and shrink-resistant wool fiber product in the field of textiles.

[0031] Advantages:

[0032] An antibacterial and shrink-resistant finishing method for wool fiber products based on enzyme-catalyzed grafting and crosslinking. Compared with traditional chlorination or protease methods for anti-shrinkage, the present application has the following advantages:

[0033] (1) The finishing process is eco-friendly. In the method described in the present application, the wool fiber product is subjected to additive anti-shrinkage finishing using modified amino macromolecules, which avoids the potential AOX residue problem of traditional subtractive anti-shrinkage finishing of chlorination, and meets the dyeing and finishing processing requirements of ecological textiles.

[0034] (2) Low shrinkage rate and zero strength loss. After the lipid on the outer layer of the wool scale is removed, the accessibility of cystine in the scale layer increases. In the heating process, the disulfide bonds contained therein are broken to generate sulfhydryl groups, and the disulfide bonds in the modified amino macromolecules adsorbed on the surface of the fiber are also broken to generate sulfhydryl groups. In the oxidation process, sulfhydryl groups combine with each other to form disulfide bonds, and a crosslinked network layer of modified amino macromolecules is formed on the surface of the wool through grafting and crosslinking, which gives the wool additive anti-shrinkage effect, and the fiber is not damaged.

[0035] (3) High and persistent antibacterial effect. The modified amino macromolecules themselves have antibacterial properties. The disulfide bonds in the scale layer of the wool fiber and the modified amino macromolecules are broken to generate sulfhydryl groups. The amino and sulfhydryl groups in the modified amino macromolecules have reducing properties, which promote the reduction of silver nitrate to form nano-silver. The sulfhydryl groups on the wool and the modified amino macromolecules are combined through coordination bond with the nano-silver, which can realize the loading of nano-silver particles on the surface of the fiber, and give the fabric high and persistent antibacterial effect, and the hand feeling of the finished fabric is good. DETAILED DESCRIPTION

[0036] Test method

[0037] Shrinkage: The area shrinkage (%) of wool fabric was determined according to GB / T 8628-2013.

[0038] Strength change rate: The strength of wool fabric in warp direction was determined according to GB / T 3923.1-1997, and the strength loss rate was calculated according to the following formula:

[0039] Strength change rate (%) = (strength before finishing - strength after finishing) / strength before finishing x 100%.

[0040] Bacteriostatic rate: The antibacterial rate of wool fabric against Escherichia coli was determined according to GB / T 20944.3-2008.

[0041] Drape coefficient: The drape coefficient (%) of wool fabric was determined according to GB / T 23329-2009.

[0042] Example 1

[0043] An antibacterial and anti-shrinking finishing method for wool fiber products based on catalytic grafting crosslinking, comprising the steps of:

[0044] (1) Removing the lipid layer of wool: Dissolve potassium hydroxide in ethanol to prepare an alkali-alcohol solution, and immerse the full wool gabardine (a kind of wool fabric) in the alkali-alcohol solution to obtain a pretreated gabardine.

[0045] The mass concentration of potassium hydroxide in the alkali-alcohol solution is 2.5 g / L, the temperature of immersion is 20℃, the treatment time of immersion is 8 min, and the bath ratio is 1:8.

[0046] (2) Preparation of modified amino macromolecules: Dissolve lipoic acid, polylysine (molecular weight 1000), 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide in an ethanol aqueous solution to prepare a reaction solution, adjust the pH value for reaction, and after the reaction is completed, dialyze to remove 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxysuccinimide and unreacted lipoic acid, and freeze-dry to obtain modified polylysine containing disulfide side groups.

[0047] The mass fraction of ethanol in the ethanol aqueous solution is 50%; the mass concentration of lipoic acid in the reaction solution is 5 g / L, the mass concentration of polylysine is 15 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.

[0048] Adjust the pH value to 4 with an acetic acid aqueous solution, the reaction temperature is 25℃, and the reaction time is 8 h.

[0049] The dialysis conditions are as follows: using a dialysis bag with a molecular weight cut-off of 500 daltons to dialyze small molecules in deionized water at 25-30 DEG C until the solution conductivity is less than 4 muS / cm;

[0050] (3) Fiber surface antibacterial layer construction: dissolving the modified polylysine containing disulfide side groups in water to prepare a grafting finishing liquor, and performing grafting immersion treatment on the pretreated gabardine in the grafting finishing liquor; then adding silver nitrate in the grafting finishing liquor to obtain an antibacterial finishing liquor, and performing reduction immersion treatment, so that the amino groups and thiol groups in the modified amino macromolecules reduce silver ions to deposit nano-silver on the fiber surface, and after water washing and drying, the antibacterial and shrink-resistant gabardine is prepared;

[0051] The mass concentration of the modified polylysine in the grafting finishing liquor is 4 g / L, the pH value of the grafting finishing liquor is 5.5, and the mass concentration of silver nitrate in the antibacterial finishing liquor is 2 g / L; the pH value of the antibacterial finishing liquor is 5.5;

[0052] The temperature of the grafting immersion treatment is 75 DEG C, the grafting immersion treatment time is 10 min, and the bath ratio is 1:8; the temperature of the reduction immersion treatment is 75 DEG C, the reduction immersion treatment time is 10 min, and the bath ratio is 1:8.

[0053] Example 2

[0054] An antibacterial and shrink-resistant finishing method for wool fiber products based on catalytic grafting crosslinking, comprising the steps of:

[0055] (1) Lipid layer removal of wool: dissolving potassium hydroxide in ethanol to prepare an alkali-alcohol solution, and immersing the full wool serge (a kind of wool fabric) in the alkali-alcohol solution to obtain the pretreated serge;

[0056] The mass concentration of potassium hydroxide in the alkali-alcohol solution is 5 g / L, the temperature of the immersion is 25 DEG C, the treatment time of the immersion is 15 min, and the bath ratio is 1:10;

[0057] (2) Preparation of modified amino macromolecule: dissolving lipoic acid, chitooligosaccharide (molecular weight 4000), 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide in an ethanol aqueous solution to prepare a reaction solution, adjusting the pH value for reaction, dialyzing to remove 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxysuccinimide and unreacted lipoic acid after the reaction is completed, and freeze-drying to obtain modified chitooligosaccharide containing disulfide side groups;

[0058] The mass fraction of ethanol in the ethanol aqueous solution is 50%, the mass concentration of lipoic acid in the reaction solution is 5 g / L, the mass concentration of chitooligosaccharide is 25 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;

[0059] The pH is adjusted to 5 with aqueous acetic acid, the reaction temperature is 25℃, and the reaction time is 12h;

[0060] The dialysis conditions are as follows: the dialysis bag with a molecular weight cut-off of 500 daltons is used to remove small molecules by dialysis with deionized water at 25-30℃ until the solution conductivity is less than 4μS / cm;

[0061] (3) Fiber surface antibacterial layer construction: the modified chitosan oligosaccharide containing disulfide side groups and silver nitrate are dissolved in water to prepare a grafting finishing liquor, and the pretreated serge is subjected to grafting immersion treatment in the grafting finishing liquor; then silver nitrate is added to the grafting finishing liquor to obtain an antibacterial finishing liquor, and the reduction immersion treatment is performed, so that the amino groups and thiol groups in the modified amino macromolecules reduce silver ions to deposit nano-silver on the fiber surface, and the antibacterial shrink-resistant serge is prepared after water washing and drying;

[0062] The mass concentration of the modified chitosan oligosaccharide in the grafting finishing liquor is 8g / L, and the pH value of the grafting finishing liquor is 6.5; the mass concentration of silver nitrate in the antibacterial finishing liquor is 4g / L; and the pH value of the antibacterial finishing liquor is 6.5;

[0063] The temperature of the grafting immersion treatment is 80℃, the grafting immersion treatment time is 15min, and the bath ratio is 1:10; the temperature of the reduction immersion treatment is 80℃, the reduction immersion treatment time is 15min, and the bath ratio is 1:10.

[0064] Comparative Example 1

[0065] The full wool gabardine is not treated.

[0066] Comparative Example 2

[0067] The full wool gabardine is treated by steps (2) and (3) of Example 1.

[0068] Comparative Example 3

[0069] The difference from Example 1 is that silver nitrate is not added to the antibacterial finishing liquor in step (3).

[0070] Comparative Example 4

[0071] The full wool gabardine is treated by steps (1) and (3) of Example 1, but polylysine (molecular weight 1000) is used to replace the modified polylysine in step (3).

[0072] Comparative Example 5

[0073] The difference from Example 1 is that a two-bath method is used in step (3): the pretreated gabardine is subjected to grafting immersion treatment in the aqueous solution of the modified polylysine containing disulfide side groups, then taken out and washed, and then subjected to reduction immersion treatment in the silver nitrate solution.

[0074] The modified polylysine aqueous solution has a modified polylysine mass concentration of 4 g / L, a pH value of 5.5, a grafting immersion temperature of 75 ℃, an immersion time of 10 min, and a bath ratio of 1:8.

[0075] The silver nitrate solution has a silver nitrate mass concentration of 2 g / L, a pH value of 5.5, a reduction immersion temperature of 75 ℃, an immersion time of 10 min, and a bath ratio of 1:8.

[0076] Comparative Example 6

[0077] The wool serge is not treated.

[0078] Comparative Example 7

[0079] The wool serge is treated by steps (2) and (3) of Example 2.

[0080] Comparative Example 8

[0081] The difference from Example 2 is that no silver nitrate is added in the antibacterial finishing solution in step (3).

[0082] Comparative Example 9

[0083] The wool serge is treated by steps (1) and (3) of Example 2, but chitosan oligosaccharide (molecular weight 4000) is used to replace the modified chitosan oligosaccharide in step (3).

[0084] Comparative Example 10

[0085] The difference from Example 2 is that a two-bath method is used in step (3): the pretreated serge is subjected to grafting immersion treatment in the modified chitosan oligosaccharide aqueous solution containing disulfide side groups, then taken out and washed, and then subjected to reduction immersion treatment in the silver nitrate solution.

[0086] The modified chitosan oligosaccharide aqueous solution has a modified chitosan oligosaccharide mass concentration of 8 g / L, a pH value of 6.5, a grafting immersion temperature of 80 ℃, an immersion time of 15 min, and a bath ratio of 1:10.

[0087] The silver nitrate solution has a silver nitrate mass concentration of 4 g / L, a pH value of 6.5, a reduction immersion temperature of 80 ℃, an immersion time of 15 min, and a bath ratio of 1:10.

[0088] The wool fabrics obtained in Examples 1-2 and Comparative Examples 1-10 are respectively washed in water at 60 ℃ for 45 min to remove the modified amino macromolecules adsorbed on the surface and the nano-silver not firmly combined, and then performance determination is performed. The test results are shown in Table 1.

[0089] Table 1

[0090]

[0091] As can be seen from Table 1:

[0092] The anti-bacterial and anti-shrinkage wool fabric (Example 1, Example 2) prepared by the anti-bacterial and anti-shrinkage finishing method of the present application has the lowest shrinkage rate, and the strength and drape coefficient are similar to those of the untreated wool fabric (Comparative Example 1, Comparative Example 6); it is verified that the removal of the lipid structure on the surface of the wool by alkali alcohol can realize the grafting and cross-linking of the modified amino macromolecule containing disulfide bond on the fiber surface and the in-situ deposition of nano-silver, thereby imparting the wool with the effect of chemical anti-shrinkage and good antibacterial property.

[0093] The wool fabric without any treatment (Comparative Example 1, Comparative Example 6) has a high area shrinkage rate, and the fabric has poor anti-shrinkage effect.

[0094] The wool fabric treated only by steps (2) and (3) (Comparative Example 2, Comparative Example 7) has a lower shrinkage rate than the untreated wool fabric, but still higher than 6%, which is related to the lack of the removal of the lipid on the fiber surface in step (1), i.e., the lipid covers the surface of the wool scale, so that the sulfhydryl group of the modified amino macromolecule cannot form disulfide bond with the sulfhydryl group on the surface of the wool, and the modified amino macromolecule only cross-links with each other, but cannot directly graft and cross-link with the fiber, thereby resulting in that the polymer formed has a lower binding firmness or binding amount than the anti-bacterial and anti-shrinkage wool fabric prepared in Example 1 and Example 2; similarly, the antibacterial effect of the wool fabric prepared in Comparative Example 2 and Comparative Example 7 is also lower than that of the anti-bacterial and anti-shrinkage wool fabric prepared in Example 1 and Example 2.

[0095] The wool fabric treated only by steps (1) to (3) but without the addition of silver nitrate in step (3) (Comparative Example 3, Comparative Example 8) has good anti-shrinkage effect, which is similar to that of the anti-bacterial and anti-shrinkage wool fabric prepared in Example 1 and Example 2; the antibacterial rate is lower than that of the anti-bacterial and anti-shrinkage wool fabric prepared in Example 1 and Example 2, which is because silver nitrate is not added, and the reduction and deposition of nano-silver do not occur in the process of heating and breaking and rebuilding of disulfide bond.

[0096] The wool fabric treated only by steps (1) and (3) but using unmodified amino macromolecule in step (3) (Comparative Example 4, Comparative Example 9) has a shrinkage rate greater than 10%, which is because the unmodified amino macromolecule has only amino group as the reactive group, which cannot react with each other or form covalent bond with the surface of the wool fiber, and thus can only be adsorbed on the surface of the fiber in a small amount, and cannot form a continuous network cross-linking structure, so that the shrinkage rate is not significantly improved; in addition, the amino group in the amino macromolecule has weak reducing property, so that a small amount of nano-silver can be reduced and deposited on the surface of the fiber, thereby imparting the wool with certain antibacterial effect.

[0097] The area shrinkage of the wool fabric treated by step (1) (Comparative Example 5, Comparative Example 10) is similar to that of the corresponding examples, but the antibacterial rate of the fabric is slightly lower than that of the examples, because in the two-bath treatment, after the wool is immersed in the modified polylysine or modified chitosan oligosaccharide aqueous solution for treatment, the disulfide bond five-membered ring in the modified amino macromolecule on the surface of the fiber is opened at high temperature, and a cross-linked network is formed on the surface of the wool by reconstitution of the disulfide bond; when the fabric is immersed in silver nitrate solution after washing, the sulfhydryl group on the fiber is oxidized to disulfide bond, and in the reduction treatment, only the amino group reduces silver ions, and the deposition effect of nano-silver is not as good as that of nano-silver generated by the combined reduction of sulfhydryl and amino groups in the examples, so the antibacterial effect is slightly lower.

[0098] The above provided examples 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 make obvious improvements to the present application in combination with existing common knowledge, which also falls within the protection scope defined by the claims of the present application.

Claims

1. A method for antibacterial and shrink-resistant finishing of wool fiber products, characterized in that, Including the following steps: (1) Removal of wool lipid layer: Dissolve potassium hydroxide in ethanol to prepare an alkaline alcohol solution, and impregnate wool fiber products with the alkaline alcohol solution to obtain pretreated wool fiber products. (2) Preparation of modified amino macromolecules: Lipoic acid, amino macromolecules, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloric acid and N-hydroxysuccinimide were dissolved in an ethanol aqueous solution to prepare a reaction solution. The pH value was adjusted to carry out the reaction. After the reaction was completed, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloric acid, N-hydroxysuccinimide and unreacted lipoic acid were removed by dialysis. The modified amino macromolecules containing disulfide side groups were obtained by freeze drying. (3) Construction of antibacterial layer on fiber surface: The modified amino macromolecule containing disulfide bond side group is dissolved in water to prepare grafting solution. The pretreated wool fiber product is grafted and impregnated in the grafting solution. Then, silver nitrate is added to the grafting solution to obtain antibacterial solution, which is then subjected to reduction impregnation treatment. After washing and drying, antibacterial and shrink-resistant wool fiber product is obtained. Steps (1) and (2) are not in any particular order.

2. The method for antibacterial and shrink-resistant finishing of wool fiber products according to claim 1, characterized in that, In step (1), the mass concentration of potassium hydroxide in the alkaline alcohol solution is 2.5-5 g / L; the immersion temperature is 20-25℃; the immersion treatment time is 8-15 min; and the bath ratio is 1:8-10.

3. The method for antibacterial and shrink-resistant finishing of wool fiber products according to claim 1, characterized in that, In step (2), the molecular weight of the amino macromolecule is 1000-4000; the amino macromolecule is one of polylysine, polyethyleneimine, or chitosan oligosaccharide.

4. The method for antibacterial and shrink-resistant finishing of wool fiber products according to claim 1, characterized in that, In step (2), the ethanol aqueous solution has an ethanol mass fraction of 45-55%; the reaction solution has a lipoic acid mass concentration of 4-6 g / L, an amino macromolecular mass concentration of 15-25 g / L, a 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride mass concentration of 8-12 g / L, and an N-hydroxysuccinimide mass concentration of 2.5-4 g / L.

5. The method for antibacterial and shrink-resistant finishing of wool fiber products according to claim 1, characterized in that, In step (2), the pH value is adjusted to 4-5; the pH is adjusted with an aqueous acetic acid solution.

6. The method for antibacterial and shrink-resistant finishing of wool fiber products according to claim 1, characterized in that, In step (2), the reaction temperature is 20-30℃ and the reaction time is 8-12h.

7. The method for antibacterial and shrink-resistant finishing of wool fiber products according to claim 1, characterized in that, In step (3), the mass concentration of modified amino macromolecules in the grafting finishing solution is 4-8 g / L; the mass concentration of silver nitrate in the antibacterial finishing solution is 2-4 g / L.

8. The method for antibacterial and shrink-resistant finishing of wool fiber products according to claim 1, characterized in that, In step (3), the pH of the grafting solution is 5.5-6.5; the pH of the antibacterial solution is 5.5-6.5; the temperature of the grafting impregnation treatment is 75-80℃, the time of the grafting impregnation treatment is 10-15 min, and the bath ratio is 1:8-10; the temperature of the reduction impregnation treatment is 75-80℃, and the time of the reduction impregnation treatment is 10-15 min.

9. The antibacterial and shrink-resistant wool fiber product prepared by the antibacterial and shrink-resistant finishing method for wool fiber products according to claim 1.

10. The application of the antibacterial and shrink-resistant wool fiber product of claim 9 in the field of textiles.

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