Antibacterial and shrink-proof finishing method for wool fiber product based on catalytic grafting crosslinking

Abstract

The invention belongs to the technical field of textile dyeing and finishing, and provides a wool fiber product antibacterial shrink-proof finishing method based on catalytic grafting crosslinking, which comprises the following steps: dissolving potassium hydroxide in ethanol to prepare an alkali alcohol solution, and impregnating a wool fiber product with the alkali alcohol solution to obtain a pretreated wool fiber product; the preparation method comprises the following steps: synthesizing modified amino macromolecules containing disulfide bond side groups by taking lipoic acid and amino macromolecules as main raw materials; and impregnating the pretreated wool fiber product with the modified amino macromolecule aqueous solution, and then adding silver nitrate for impregnation to prepare the antibacterial shrink-proof wool fiber product. According to the antibacterial shrink-proof finishing method, a modified amino macromolecule cross-linked network layer is formed on the surface of the wool fiber product, the fiber strength is not damaged, and the wool is endowed with an anti-felting effect; and by adopting the modified amino macromolecules which have antibacterial property and reducibility and can be coordinated and combined with nano-silver, silver ions are promoted to be reduced and deposited on the surface of the wool fiber, and the antibacterial effect of the wool fiber product is improved.

Description

Technical Field

[0001] The invention relates to an antibacterial and shrinkage-resistant finishing method for wool fiber products based on catalytic grafting and cross-linking, and belongs to the technical field of textile dyeing and finishing. Background Art

[0002] Wool is a high-grade textile fiber with excellent warmth retention and soft feel. However, when it is wet and subjected to mechanical external forces, the jagged scales on the fiber surface are prone to cross-entanglement and interlocking, which causes the wool fabric to shrink in appearance and become hard during washing, seriously affecting the wearing performance of wool fiber products. In addition, wool is a protein fiber, which can easily become a nutrient for bacteria, mold and other microorganisms under appropriate temperature and humidity conditions, causing the fabric to mold and even become a carrier of disease transmission. Therefore, in order to improve the wearing performance of wool fiber products, it is necessary to perform finishing processing for the purpose of improving the anti-felting effect and antibacterial properties.

[0003] At present, the chlorination method is mostly used in wool anti-felting processing. It can achieve good chlorination anti-felting effect at low temperature. However, its disadvantage is that the wool chlorination process will produce adsorbable organic halides, which will affect the ecological safety of fiber products. The use of biological enzymes for wool anti-felting processing has many advantages, including mild treatment conditions and soft hand feel. Among them, proteases have been widely studied in wool anti-felting processing. Although there have been many research reports on protease-based wool anti-felting processing, the anti-felting finishing effect based on proteases in actual production is not ideal. The reason is that proteases can easily diffuse into the fiber scale layer to hydrolyze the intercellular matrix and cortex, thereby causing greater fiber damage.

[0004] In terms of wool antibacterial finishing, the available antibacterial finishing agents include silver ions, organic quaternary ammonium salts, halogenamine compounds, etc. The finishing process is mostly carried out by combining padding and high-temperature baking. While these finishing agents give fiber products antibacterial effects, they also have disadvantages such as weak bonding with fibers, easy release from the fiber surface and migration to the skin surface, or fiber strength damage during baking, and waste liquid discharge from finishing polluting the environment. In order to obtain a long-lasting and stable antibacterial effect, chemical cross-linking agents are also used to combine antibacterial agents with cellulose or protein fibers under steaming or baking conditions. However, improper handling can easily affect the feel of the fabric, causing the appearance of the fabric to change color and reduce strength. Therefore, in the processing of wool fiber products, how to construct a finishing method with better shrinkage prevention and antibacterial effects, long-lasting finishing effects, and less fiber damage is an important topic that needs to be explored. Summary of the invention

[0005]

Technical issues

[0006] In the dyeing and finishing of wool fiber products, the use of chlorination or protease for subtractive anti-felting finishing can easily cause fiber damage; many wool antibacterial finishing processes have the disadvantages of complex finishing procedures, short-lasting antibacterial effects, and easy impact on the feel of fiber products, which affects the processing of anti-shrinkage and antibacterial wool fiber products. A finishing method with better anti-shrinkage and antibacterial effects, long-lasting finishing effects, and less fiber damage is needed.

[0007]

Technical solution

[0008] In order to solve the above problems, the present invention adopts an alkaline alcohol solution to pretreat wool, removes lipids in the outer layer of fiber scales, and improves the accessibility of cystine in the wool scale layer; uses lipoic acid and amino macromolecules as raw materials to prepare modified amino macromolecules containing disulfide side groups; adopts a one-bath two-step method to immerse wool fiber products in an aqueous solution of modified amino macromolecules for grafting treatment, and the disulfide bonds in the fiber scale layer and the modified amino macromolecules form reducing thiol groups, and further realizes the grafting and mutual cross-linking of the modified amino macromolecules on the fiber surface through disulfide bond reconstruction; then, silver nitrate is added to the aqueous solution of modified amino macromolecules, and under heating, the silver ions are reduced by the amino and thiol groups in the modified amino macromolecules, thereby promoting the deposition of nanosilver on the fiber surface, and giving the wool anti-shrinkage and antibacterial effects.

[0009] The first object of the present invention is to provide a method for antibacterial and shrinkage-resistant finishing of wool fiber products based on catalytic grafting and cross-linking, comprising the steps of:

[0010] (1) Removal of wool lipid layer: potassium hydroxide is dissolved in ethanol to prepare an alkali-alcohol solution, and the alkali-alcohol solution is used to impregnate the wool fiber product to obtain a pretreated wool fiber product;

[0011] (2) Preparation of modified amino macromolecules: dissolving lipoic acid, amino macromolecules, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide in an ethanol aqueous solution to obtain a reaction solution, adjusting the pH value to react, dialyzing to remove 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxysuccinimide and unreacted lipoic acid after the reaction, and freeze-drying to obtain a modified amino macromolecule containing a disulfide bond side group;

[0012] (3) Construction of an antibacterial layer on the fiber surface: dissolving a modified amino macromolecule containing a disulfide side group in water to prepare a graft finishing solution, and performing a grafting immersion treatment on the pretreated wool fiber product in the graft finishing solution; then adding silver nitrate to the graft finishing solution to obtain an antibacterial finishing solution, performing a reduction immersion treatment, and washing and drying to obtain an antibacterial and shrink-resistant wool fiber product;

[0013] There is no order of precedence for steps (1) and (2).

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

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

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

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

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

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

[0020] In one embodiment of the present invention, in step (2), the mass concentration of lipoic acid in the reaction solution is 4-6 g / L, the mass concentration of amino macromolecules 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 invention, in step (2), the pH value is adjusted to 4-5.

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

[0023] In one embodiment of the present invention, in step (2), the reaction temperature is 20 to 30° C., and the reaction time is 8 to 12 hours.

[0024] In one embodiment of the present invention, in step (2), the dialysis conditions are: using a dialysis bag with a molecular weight cutoff of 500 Daltons to dialyze with deionized water at 25-30° C. to remove small molecules until the solution conductivity is less than 4 μS / cm.

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

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

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

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

[0029] The second object of the present invention is to provide an antibacterial and shrinkage-resistant wool fiber product produced by the above-mentioned antibacterial and shrinkage-resistant finishing method for wool fiber products.

[0030] The third object of the present invention is the application of the antibacterial and shrink-resistant wool fiber product in the field of textiles.

[0031] Beneficial effects:

[0032] A method for antibacterial and shrinkage-resistant finishing of wool fiber products based on enzyme-catalyzed graft cross-linking. Compared with the traditional chlorination method or protease method for shrinkage-resistant felting, the present invention has the following advantages:

[0033] (1) The finishing process is eco-friendly and environmentally friendly. In the method of the present invention, the wool fiber products are subjected to additive anti-felting finishing using modified amino macromolecules, thereby avoiding the potential AOX residue problem on the fibers caused by conventional chlorination-based subtractive anti-felting finishing, and meeting the dyeing and finishing requirements of ecological textiles.

[0034] (2) Low felt shrinkage and zero strength loss. After the outer layer of lipids in the wool scales are removed, the accessibility of cystine in the scale layer increases. During the heating process, the disulfide bonds contained therein break to form thiol groups, and the disulfide bonds in the modified amino macromolecules adsorbed on the fiber surface also break to form thiol groups. During oxidation, the thiol groups combine with each other to form disulfide bonds, and through grafting and cross-linking, a cross-linked network layer of modified amino macromolecules is formed on the wool surface, giving the wool an additive anti-felting effect without damaging the fiber.

[0035] (3) Highly effective and long-lasting antibacterial effect. The modified amino macromolecules themselves have antibacterial properties. The thiol groups generated by the rupture of disulfide bonds in the wool fiber scale layer and the modified amino macromolecules are reducing, which promotes the reduction of silver nitrate to generate nanosilver. The thiol groups on the wool and modified amino macromolecules are combined with nanosilver through coordination bonds to achieve the loading of nanosilver particles on the fiber surface, giving the fabric a high-efficiency and long-lasting antibacterial effect. The fabric also has a good feel after finishing. DETAILED DESCRIPTION

[0036] Test Method

[0037] Felting rate: refer to GB / T 8628-2013 to determine the area felting rate (%) of wool fabric.

[0038] Strength change rate: Determine the warp breaking strength of wool fabrics according to GB / T 3923.1-1997, and calculate the strength loss rate according to the following formula:

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

[0040] Antibacterial rate: Refer to GB / T 20944.3-2008 to determine the antibacterial rate of wool fabric against Escherichia coli.

[0041] Drape coefficient: refer to GB / T 23329-2009 to measure the drape coefficient (%) of wool fabric.

[0042] Example 1

[0043] A method for antibacterial and shrink-proof finishing of wool fiber products based on catalytic grafting and cross-linking, comprising the steps of:

[0044] (1) Removal of wool lipid layer: Potassium hydroxide is dissolved in ethanol to prepare an alkali-alcohol solution, and the alkali-alcohol solution is used to impregnate all-wool gabardine (a kind of wool fabric) to obtain pretreated gabardine;

[0045] The potassium hydroxide mass concentration of the alkaline alcohol solution is 2.5 g / L, the immersion temperature is 20°C, the immersion treatment time is 8 min, and the bath ratio is 1:8;

[0046] (2) Preparation of modified amino macromolecules: dissolving lipoic acid, polylysine (molecular weight 1000), 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide in an ethanol aqueous solution to obtain a reaction solution, adjusting the pH value to react, dialyzing to remove 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxysuccinimide and unreacted lipoic acid after the reaction, and freeze-drying 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] The pH value was adjusted to 4 with acetic acid aqueous solution, the reaction temperature was 25°C, and the reaction time was 8h;

[0049] The dialysis conditions were as follows: using a dialysis bag with a molecular weight cutoff of 500 Daltons to dialyze against deionized water at 25-30°C to remove small molecules until the solution conductivity was less than 4 μS / cm;

[0050] (3) Construction of an antibacterial layer on the fiber surface: Dissolve the modified polylysine containing disulfide side groups in water to obtain a graft finishing solution, and perform grafting and dipping treatment on the pretreated gabardine in the graft finishing solution; then add silver nitrate to the graft finishing solution to obtain an antibacterial finishing solution, and perform reduction dipping treatment to reduce silver ions through the amino and mercapto groups in the modified amino macromolecules, so that nanosilver is deposited on the fiber surface, and the antibacterial and shrink-proof gabardine is obtained after washing with water and drying;

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

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

[0053] Example 2

[0054] A method for antibacterial and shrink-proof finishing of wool fiber products based on catalytic grafting and cross-linking, comprising the steps of:

[0055] (1) Removal of wool lipid layer: Potassium hydroxide is dissolved in ethanol to prepare an alkali-alcohol solution, and the alkali-alcohol solution is used to impregnate the wool serge (a kind of wool fabric) to obtain the pretreated serge;

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

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

[0058] The ethanol mass fraction of the ethanol aqueous solution is 50%, the lipoic acid mass concentration of the reaction solution is 5 g / L, the chitosan oligosaccharide mass concentration is 25 g / L, the 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride mass concentration is 12 g / L, and the N-hydroxysuccinimide mass concentration is 4 g / L;

[0059] The pH value was adjusted to 5 with acetic acid aqueous solution, the reaction temperature was 25°C, and the reaction time was 12 h;

[0060] The dialysis conditions were as follows: using a dialysis bag with a molecular weight cutoff of 500 Daltons to dialyze against deionized water at 25-30°C to remove small molecules until the solution conductivity was less than 4 μS / cm;

[0061] (3) Construction of antibacterial layer on fiber surface: modified chitosan oligosaccharide containing disulfide side groups and silver nitrate are dissolved in water to prepare a graft finishing solution, and the pretreated serge is subjected to grafting and dipping treatment in the graft finishing solution; then silver nitrate is added to the graft finishing solution to obtain an antibacterial finishing solution, and reduction dipping treatment is performed to reduce silver ions through the amino and thiol groups in the modified amino macromolecules, so that nanosilver is deposited on the fiber surface, and the antibacterial and shrink-resistant serge is obtained after washing with water and drying;

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

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

[0064] Comparative Example 1

[0065] Untreated pure wool gabardine.

[0066] Comparative Example 2

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

[0068] Comparative Example 3

[0069] The difference from Example 1 is that in step (3), no silver nitrate is added to the antibacterial finishing liquid.

[0070] Comparative Example 4

[0071] The whole wool gabardine was treated by steps (1) and (3) of Example 1, except that in step (3), polylysine (molecular weight 1000) was used instead of modified polylysine.

[0072] Comparative Example 5

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

[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°C, 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° C., an immersion time of 10 min, and a bath ratio of 1:8.

[0076] Comparative Example 6

[0077] Untreated pure wool serge.

[0078] Comparative Example 7

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

[0080] Comparative Example 8

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

[0082] Comparative Example 9

[0083] The whole wool serge was treated by steps (1) and (3) of Example 2, except that in step (3), the modified chitosan oligosaccharide was replaced by chitosan oligosaccharide (molecular weight 4000).

[0084] Comparative Example 10

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

[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°C, 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° C., an immersion time of 15 min, and a bath ratio of 1:10.

[0088] The wool fabrics obtained in Examples 1 to 2 and Comparative Examples 1 to 10 were washed at 60° C. for 45 min to remove the modified amino macromolecules adsorbed on the surface and the nanosilver not firmly bound, and then the performance was measured. The test results are shown in Table 1.

[0089] Table 1

[0090]

[0091] From Table 1, we can see that:

[0092] The antibacterial shrinkage-resistant wool fabrics (Examples 1 and 2) prepared by the antibacterial shrinkage-resistant finishing method of the present invention have the lowest felt shrinkage rate, and the strength and drape coefficient are similar to those of the untreated wool fabrics (Comparative Examples 1 and 6); it is verified that the removal of the lipid structure on the surface of the wool by alkali alcohol can achieve the grafting and cross-linking of modified amino macromolecules containing disulfide bonds on the fiber surface and the in-situ deposition of nanosilver, giving the wool an additive anti-felting effect and at the same time giving the fabric better antibacterial properties.

[0093] The wool fabrics without any treatment (Comparative Example 1 and Comparative Example 6) have a high area felting rate and a poor anti-felting effect.

[0094] The felt shrinkage rate of the wool fabrics treated only by steps (2) and (3) (Comparative Example 2 and Comparative Example 7) is lower than that of the untreated wool fabrics, but is still higher than 6%. The reason is related to the lack of lipid removal treatment on the fiber surface in step (1), that is, lipids cover the surface of the wool scales, so that the thiol groups of the modified amino macromolecules cannot form disulfide bonds with the thiol groups on the wool surface, and the modified amino macromolecules only cross-link with each other and cannot directly graft cross-link with the fibers, resulting in the formed polymer bonding strength or bonding amount being lower than that of the antibacterial and shrinkage-resistant wool fabrics prepared in Examples 1 and 2; similarly, the antibacterial effect of the wool fabrics prepared in Comparative Examples 2 and 7 is also not as good as that of the antibacterial and shrinkage-resistant wool fabrics prepared in Examples 1 and 2.

[0095] The wool fabrics treated only by steps (1) to (3) but without adding silver nitrate in step (3) (Comparative Examples 3 and 8) have good anti-felting effects, which are similar to those of the antibacterial and shrink-proof wool fabrics prepared in Examples 1 and 2. The antibacterial rate is lower than that of the antibacterial and shrink-proof wool fabrics prepared in Examples 1 and 2 because no silver nitrate is added and nano-silver reduction deposition does not occur during the heating disulfide bond breaking and reconstruction process.

[0096] The wool fabrics treated only by steps (1) and (3) but using unmodified amino macromolecules in the treatment of step (3) (Comparative Examples 4 and Comparative Examples 9) had a felt shrinkage greater than 10%. The reason for this is that the reactive groups in the unmodified amino macromolecules are only amino groups, which cannot react with each other or form covalent bonds with the wool fiber surface. Therefore, they can only be adsorbed on the fiber surface in a small amount and cannot form a continuous network cross-linked structure. Therefore, the felt shrinkage is not significantly improved. In addition, since the amino groups in the amino macromolecules have weak reducing properties, a small amount of nanosilver can be reduced and deposited on the fiber surface, giving the wool a certain antibacterial effect.

[0097] The area felt shrinkage rate of the wool fabric treated by step (1) (Comparative Example 5, Comparative Example 10) is similar to that of the corresponding embodiment, but the antibacterial rate of the fabric is slightly lower than that of the embodiment. The reason is that in the two-bath method, after the wool is immersed in the modified polylysine or modified chitosan oligosaccharide aqueous solution, the disulfide bond five-membered ring in the modified amino macromolecule on the fiber surface has been opened at high temperature, and a cross-linked network is formed on the wool surface through disulfide bond reconstruction; when the fabric is washed and then immersed in a silver nitrate solution, the thiol group on the fiber has been oxidized to a disulfide bond. In the reduction treatment, only the amino group is relied on to reduce the silver ions. The nanosilver deposition effect is not as good as the nanosilver generated by the co-reduction of the thiol group and the amino group in the embodiment, so the antibacterial effect is slightly lower.

[0098] The embodiments provided above are not intended to limit the scope of the present invention, and the steps described are not intended to limit the execution order thereof. Those skilled in the art may make obvious improvements to the present invention in combination with existing common knowledge, which also fall within the scope of protection defined by the claims of the present invention.

Claims

1. A method for antibacterial and shrink-proof finishing of wool fiber products, characterized in that: Includes steps: (1) Removal of wool lipid layer: potassium hydroxide is dissolved in ethanol to prepare an alkali-alcohol solution, and the alkali-alcohol solution is used to impregnate the wool fiber product to obtain a pretreated wool fiber product; (2) Preparation of modified amino macromolecules: dissolving lipoic acid, amino macromolecules, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide in an ethanol aqueous solution to obtain a reaction solution, adjusting the pH value to react, dialyzing to remove 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxysuccinimide and unreacted lipoic acid after the reaction, and freeze-drying to obtain a modified amino macromolecule containing a disulfide bond side group; (3) Construction of an antibacterial layer on the fiber surface: dissolving a modified amino macromolecule containing a disulfide side group in water to prepare a graft finishing solution, and performing a grafting immersion treatment on the pretreated wool fiber product in the graft finishing solution; then adding silver nitrate to the graft finishing solution to obtain an antibacterial finishing solution, performing a reduction immersion treatment, and washing and drying to obtain an antibacterial and shrink-resistant wool fiber product; There is no order of precedence for steps (1) and (2).

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

3. The antibacterial and shrinkage-resistant finishing method for 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 and chitosan oligosaccharide.

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

5. The method for antibacterial and shrinkage-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 acetic acid aqueous solution.

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

7. The method for antibacterial and shrinkage-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 graft finishing solution is 4 to 8 g / L; and the mass concentration of silver nitrate in the antibacterial finishing solution is 2 to 4 g / L.

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

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

10. Use of the antibacterial and shrink-resistant wool fiber product according to claim 9 in the field of textiles.

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