Antibacterial warm-keeping fiber material for clothing and preparation method of antibacterial warm-keeping fiber material

Abstract

The invention discloses a preparation method of an antibacterial warm-keeping fiber material for clothing. The preparation method comprises the following steps: (1) preparing antibacterial matrix powder; (2) preparing a cyclodextrin dopamine polymer; (3) preparing gamma-aminopropyl triethoxy silane surface modified powder; and (4) adding the antibacterial matrix powder, the cyclodextrin dopamine polymer and the surface modified powder into a viscose spinning solution, stirring for more than 2 hours after charging, uniformly mixing, standing in a negative pressure environment to remove bubbles, then carrying out wet spinning and solidification forming, washing with deionized water after forming, and drying to obtain the fiber material. The fiber material prepared by adopting the method disclosed by the invention has good antibacterial property and certain strength, meets the standard requirement that the antibacterial rate is greater than or equal to 70%, and improves the pollution resistance and durability of the fiber material for clothing.

Description

Technical Field

[0001] The present invention relates to the technical field of antibacterial fiber fabrics, and particularly relates to an antibacterial and warm-keeping fiber material for clothing and a preparation method thereof. Background Art

[0002] Polyester fiber has excellent properties such as high breaking strength, good elasticity, heat resistance, wear resistance, and good light resistance, and is widely used in fiber fabrics for clothing. However, during daily wearing, polyester fabrics will be contaminated by human sweat, sebum secretions, and dandruff. These pollutants provide a breeding ground for the reproduction of microorganisms, which in turn leads to problems such as mildew growth and unpleasant odors, greatly affecting the wearing comfort. With the increasing attention of consumers to personal health, the requirements for the antibacterial effect and antibacterial persistence of polyester fiber are becoming more and more stringent. Therefore, developing polyester fiber with antibacterial ability is of increasing significance. Summary of the Invention

[0003] For this reason, the present invention provides a preparation method of an antibacterial and warm-keeping fiber material for clothing, and the steps include: (1) Pour deionized water into a reaction kettle, then add citric acid, glycine, and urea into the deionized water, and stir and dissolve under ultrasonic environment; seal the reaction kettle, heat it to 150-170 °C for hydrothermal insulation; after the insulation ends, naturally cool it to room temperature, and dialyze the product in a dialysis membrane to remove unreacted citric acid, glycine, and urea. The dialyzed solution is concentrated under reduced pressure and freeze-dried to obtain antibacterial matrix powder; (2) Dissolve cyclodextrin in Tris buffer solution to prepare a cyclodextrin solution, then add hydrochloric acid dopamine to the solution under stirring, after the addition is completed, heat it in a water bath to 35±5 °C, keep stirring for more than 5 h, then perform solid-liquid separation, and dry the solid phase to obtain cyclodextrin dopamine polymer; (3) Prepare an ethanol solution of γ-aminopropyltriethoxysilane, add cupric peroxide to the ethanol solution of γ-aminopropyltriethoxysilane under stirring, after the addition is completed, heat it in a water bath to 50±5 °C, keep stirring for more than 1 h, then perform solid-liquid separation, and dry the solid phase to obtain surface-modified powder; (4) Add the antibacterial matrix powder, cyclodextrin dopamine polymer, and surface-modified powder into the viscose spinning solution, stir for more than 2 h after the addition to mix evenly, let it stand in a negative pressure environment to remove bubbles, then perform wet spinning, solidify and form, wash with deionized water after forming, and dry to obtain the fiber material.

[0004] Furthermore, in the step (1), the amount ratio of citric acid, glycine, and urea added to deionized water is citric acid: glycine: urea: deionized water = 16-18 g: 2-4 g: 8-12 g: 100 mL; the hydrothermal insulation time at 150-170 °C is 3-4 h.

[0005] Further, in the step (2), in the cyclodextrin solution, the concentration of the cyclodextrin is 0.7 to 1.0 g / 100 mL; the addition amount of the dopamine hydrochloride to the amount of the cyclodextrin solution is dopamine hydrochloride:cyclodextrin solution = 0.1 to 0.2 g:100 mL.

[0006] Further, in the step (2), the concentration of the Tris buffer solution used is 50 mM, and pH = 8.5.

[0007] Further, in the step (3), in the ethanol solution of γ-aminopropyltriethoxysilane, the mass percentage of γ-aminopropyltriethoxysilane is 3% to 5%, and the solvent is ethanol; the mass ratio of adding cupric peroxide to the ethanol solution of γ-aminopropyltriethoxysilane is cupric peroxide:ethanol solution of γ-aminopropyltriethoxysilane = 1:50 to 100.

[0008] Further, in the step (4), the mass ratio of adding the antibacterial matrix powder, the cyclodextrin dopamine polymer, and the surface-modified powder to the viscose spinning solution is antibacterial matrix powder:cyclodextrin dopamine polymer:surface-modified powder:viscose spinning solution = 1 to 2:1 to 5:3 to 6:100.

[0009] The beneficial effects of the present invention are as follows: The fiber material prepared by the method of the present invention has good antibacterial properties and certain strength, meets the standard requirement of the bacteriostatic rate ≥ 70%, and improves the pollution resistance and durability of the fiber material for clothing. By comparing Example 3 with each comparative example, it can be seen that adding the antibacterial matrix powder, the cyclodextrin dopamine polymer, and the surface-modified powder prepared by the present invention to the traditional fiber material is the key to realizing the antibacterial property and improving the strength of the fiber material. This may be because: Loading the amino acid-based carbon quantum dot antibacterial matrix powder of the present invention on the surface of the fiber material, on the one hand, utilizes the characteristic that the surface functional groups of the carbon quantum dots can interact with the microbial cell membrane to destroy the integrity of the bacterial cell membrane, thereby playing the role of improving bactericidal performance. At the same time, adding glycine can significantly increase the number of amino groups and improve the adhesion strength between the antibacterial matrix powder and the fiber material. On the other hand, the amino acid-based carbon quantum dot antibacterial matrix powder can form a carbon layer on the fiber surface, playing the role of blocking heat and gas and improving the heat preservation performance of the fiber material. Secondly, adding the surface-modified cupric peroxide powder improves the binding force between the cupric peroxide powder, the cyclodextrin dopamine polymer, and the fiber material body; the cupric peroxide particles play a role in gradually decomposing and releasing hydroxyl radicals (·OH) and Cu 2+By adding cyclodextrin dopamine polymer, the binding force of antibacterial active substances on fiber materials can be significantly improved, and the antibacterial sustainability of fiber materials can be improved. At the same time, cyclodextrin dopamine polymer can include antibacterial active substances to a certain extent, and slowly and continuously release antibacterial free radicals or ions to maintain its long-term antibacterial ability. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] Figure 1 It is a comparison chart of the antibacterial rate of the fiber materials prepared in each embodiment and comparative example; Figure 2 The figure is a comparison chart of the breaking strength of the fiber materials prepared in each embodiment and comparative example. DETAILED DESCRIPTION

[0011] The present invention will be further described below in conjunction with the embodiments.

[0012] Example 1 A method for preparing an antibacterial thermal insulation fiber material for clothing, comprising the steps of: (1) Deionized water is poured into a reaction kettle, and then citric acid, glycine, and urea are added to the deionized water, wherein the ratio of citric acid, glycine, and urea added to the deionized water is citric acid: glycine: urea: deionized water = 16 g: 2 g: 8 g: 100 mL; stirring is performed under an ultrasonic environment for 30 min to completely dissolve; the reaction kettle is sealed, heated to 160° C. and hydrothermally insulated for 3 h; after the insulation is completed, the reaction kettle is naturally cooled to room temperature, the reaction kettle is opened, and the product in the kettle is dialyzed for 12 h in a dialysis membrane with a relative molecular mass cutoff of 1000 to remove unreacted citric acid, glycine, and urea, and the dialyzed liquid is concentrated under reduced pressure to half of its volume before concentration, and freeze-dried to obtain an antibacterial matrix powder; (2) Dissolving cyclodextrin in Tris buffer to prepare a cyclodextrin solution, wherein the concentration of cyclodextrin in the cyclodextrin solution is 0.7 g / 100 mL; the concentration of the Tris buffer is 50 mM, and the pH is 8.5; then, dopamine hydrochloride is added to the solution under stirring, and the ratio of the amount of dopamine hydrochloride added to the cyclodextrin solution is dopamine hydrochloride: cyclodextrin solution = 0.1 g: 100 mL; after the addition is completed, the mixture is heated to 35° C. in a water bath, stirred for 5 hours after reaching the temperature, and then the solid-liquid separation is performed, and the solid phase is dried at 60° C. for 3 hours to obtain a cyclodextrin dopamine polymer; (3) Prepare an ethanol solution of γ-aminopropyltriethoxysilane. In the ethanol solution of γ-aminopropyltriethoxysilane, the mass percentage of γ-aminopropyltriethoxysilane is 3%, and the solvent is ethanol. Add copper peroxide to the ethanol solution of γ-aminopropyltriethoxysilane under stirring. The mass ratio of copper peroxide added to the ethanol solution of γ-aminopropyltriethoxysilane is copper peroxide:ethanol solution of γ-aminopropyltriethoxysilane = 1:50. After the addition is completed, heat in a water bath to 50°C, stir constantly for 1 h, then perform solid-liquid separation, and dry the solid phase at 60°C for 2 h to obtain the surface-modified powder; (4) Add the antibacterial matrix powder, cyclodextrin dopamine polymer, and surface-modified powder to the viscose spinning solution. The mass ratio of the antibacterial matrix powder, cyclodextrin dopamine polymer, surface-modified powder to the viscose spinning solution is antibacterial matrix powder:cyclodextrin dopamine polymer:surface-modified powder:viscose spinning solution = 1:1:3:100. The mass percentage content of cellulose in the used viscose spinning solution is 9%. After adding the materials, stir for 2 h to mix evenly, let it stand for 5 h in a negative pressure environment (0.01 standard atmosphere) to remove air bubbles, and then perform wet spinning and solidify and form in a coagulation bath at 45°C. The wet spinning uses a spinneret with a pore diameter of 70 μm, and the spinning draw ratio is set to 1.6. The concentration of H2SO4 in the coagulation bath is 70 g / L, the concentration of Na2SO4 is 320 g / L, and the concentration of ZnSO4 is 16 g / L. After forming, wash with deionized water and dry to obtain the fiber material.

[0013] Example 2 A preparation method of an antibacterial and warm-keeping fiber material for clothing, the steps include: (1) Pour deionized water into a reaction kettle, and then add citric acid, glycine, and urea to the deionized water. The amount ratio of citric acid, glycine, urea added to the deionized water is citric acid:glycine:urea:deionized water = 17 g:3 g:10 g:100 mL. Stir under ultrasonic environment for 30 min to completely dissolve. Seal the reaction kettle and heat to 160°C for hydrothermal insulation for 3 h. After the insulation is completed, naturally cool to room temperature, open the reaction kettle, and dialyze the product in the kettle through a dialysis membrane with a cut-off molecular weight of 1000 for 12 h to remove unreacted citric acid, glycine, and urea. Concentrate the dialyzed solution under reduced pressure to half of the volume before concentration, and freeze-dry to obtain the antibacterial matrix powder; (2) Dissolve cyclodextrin in Tris buffer to prepare a cyclodextrin solution. In the cyclodextrin solution, the concentration of cyclodextrin is 0.8 g / 100 mL; the concentration of Tris buffer is 50 mM, and pH = 8.5. Then, add dopamine hydrochloride to the solution under stirring. The addition amount ratio of dopamine hydrochloride to the cyclodextrin solution is dopamine hydrochloride:cyclodextrin solution = 0.1 g:100 mL. After the feeding is completed, heat the solution in a water bath to 35°C, keep stirring for 5 h after reaching the temperature, then perform solid-liquid separation, and dry the solid phase at 60°C for 3 h to obtain cyclodextrin dopamine polymer; (3) Prepare an ethanol solution of γ-aminopropyltriethoxysilane. In the ethanol solution of γ-aminopropyltriethoxysilane, the mass percentage of γ-aminopropyltriethoxysilane is 4%, and the solvent is ethanol. Add copper peroxide to the ethanol solution of γ-aminopropyltriethoxysilane under stirring. The mass ratio of copper peroxide added to the ethanol solution of γ-aminopropyltriethoxysilane is copper peroxide:ethanol solution of γ-aminopropyltriethoxysilane = 1:50. After the feeding is completed, heat the solution in a water bath to 50°C, keep stirring at a constant temperature for 1 h, then perform solid-liquid separation, and dry the solid phase at 60°C for 2 h to obtain surface-modified powder; (4) Add the antibacterial matrix powder, cyclodextrin dopamine polymer, and surface-modified powder to the viscose spinning solution. The mass ratio of the antibacterial matrix powder, cyclodextrin dopamine polymer, surface-modified powder to the viscose spinning solution is antibacterial matrix powder:cyclodextrin dopamine polymer:surface-modified powder:viscose spinning solution = 1:2:4:100. The mass percentage content of cellulose in the used viscose spinning solution is 9%. After feeding, stir for 2 h to mix evenly, let it stand for 5 h in a negative pressure environment (0.01 standard atmosphere) to remove air bubbles, and then perform wet spinning and solidify and form in a coagulation bath at 45°C. The wet spinning uses a spinneret with a pore diameter of 70 μm, and the spinning draw ratio is set to 1.6. The concentration of H2SO4 in the coagulation bath is 70 g / L, the concentration of Na2SO4 is 320 g / L, and the concentration of ZnSO4 is 16 g / L. After forming, wash with deionized water and dry to obtain the fiber material.

[0014] Example 3 A preparation method of an antibacterial and warm-keeping fiber material for clothing, the steps include: (1) Pour deionized water into a reaction kettle, and then add citric acid, glycine, and urea into the deionized water. The amount ratio of citric acid, glycine, urea, and deionized water added into the deionized water is citric acid: glycine: urea: deionized water = 17 g: 3 g: 10 g: 100 mL; Stir for 30 min under ultrasonic environment until completely dissolved; Seal the reaction kettle, heat to 160 °C and keep it under hydrothermal condition for 3 h; After the heat preservation ends, naturally cool it to room temperature, open the reaction kettle, and dialyze the product in the kettle through a dialysis membrane with a cut-off relative molecular mass of 1000 for 12 h to remove unreacted citric acid, glycine, and urea. Concentrate the dialyzed solution under reduced pressure to half of its original volume before concentration, and then freeze-dry to obtain the antibacterial matrix powder; (2) Dissolve cyclodextrin in Tris buffer solution to prepare a cyclodextrin solution. In the cyclodextrin solution, the concentration of cyclodextrin is 0.9 g / 100 mL; the concentration of Tris buffer solution is 50 mM, and pH = 8.5; Then add dopamine hydrochloride to the solution under stirring. The amount ratio of dopamine hydrochloride added to the cyclodextrin solution is dopamine hydrochloride: cyclodextrin solution = 0.2 g: 100 mL; After the feeding is completed, heat it in a water bath to 35 °C, keep it warm and stir for 5 h after reaching the temperature, and then carry out solid-liquid separation. Dry the solid phase at 60 °C for 3 h to obtain the cyclodextrin dopamine polymer; (3) Prepare an ethanol solution of γ-aminopropyltriethoxysilane. In the ethanol solution of γ-aminopropyltriethoxysilane, the mass percentage of γ-aminopropyltriethoxysilane is 4%, and the solvent is ethanol; Add copper peroxide to the ethanol solution of γ-aminopropyltriethoxysilane under stirring. The mass ratio of copper peroxide added to the ethanol solution of γ-aminopropyltriethoxysilane is copper peroxide: ethanol solution of γ-aminopropyltriethoxysilane = 1:50; After the feeding is completed, heat it in a water bath to 50 °C, keep it at a constant temperature and stir for 1 h, and then carry out solid-liquid separation. Dry the solid phase at 60 °C for 2 h to obtain the surface-modified powder; (4) Add the antibacterial matrix powder, cyclodextrin dopamine polymer, and surface-modified powder into the viscose spinning solution. The mass ratio of the antibacterial matrix powder, cyclodextrin dopamine polymer, surface-modified powder, and viscose spinning solution added into the viscose spinning solution is antibacterial matrix powder: cyclodextrin dopamine polymer: surface-modified powder: viscose spinning solution = 2:3:5:100. The mass percentage content of cellulose in the used viscose spinning solution is 9%; After feeding, stir for 2 h to mix evenly, let it stand for 5 h in a negative pressure environment (0.01 standard atmosphere) to remove bubbles, and then carry out wet spinning and solidify and form in a coagulation bath at 45 °C; The spinneret used for wet spinning has a pore diameter of 70 μm, and the spinning draw ratio is set to 1.6; The concentration of H2SO4 in the coagulation bath is 70 g / L, the concentration of Na2SO4 is 320 g / L, and the concentration of ZnSO4 is 16 g / L; After forming, wash it with deionized water and dry it to obtain the fiber material.

[0015] Example 4 A preparation method of an antibacterial and heat - insulating fiber material for clothing, the steps include: (1) Pour deionized water into a reaction kettle, and then add citric acid, glycine, and urea into the deionized water. The amount ratio of citric acid, glycine, urea to deionized water is citric acid: glycine: urea: deionized water = 18g: 4g: 12g: 100mL; Stir for 30 min under ultrasonic environment until completely dissolved; Seal the reaction kettle, heat to 160 °C for hydrothermal insulation for 3 h; After the insulation is completed, cool naturally to room temperature, open the reaction kettle, and dialyze the product in the kettle through a dialysis membrane with a cut - off relative molecular mass of 1000 for 12 h to remove unreacted citric acid, glycine, and urea. Concentrate the dialyzed solution under reduced pressure to half of its original volume before concentration, and freeze - dry to obtain antibacterial matrix powder; (2) Dissolve cyclodextrin in Tris buffer solution to prepare a cyclodextrin solution. In the cyclodextrin solution, the concentration of cyclodextrin is 1.0 g / 100 mL; the concentration of Tris buffer solution is 50 mM, pH = 8.5; Then add dopamine hydrochloride to the solution under stirring. The amount ratio of dopamine hydrochloride to the cyclodextrin solution is dopamine hydrochloride: cyclodextrin solution = 0.2 g: 100 mL; After feeding, heat in a water bath to 35 °C, keep warm and stir for 5 h after reaching the temperature, then perform solid - liquid separation, and dry the solid phase at 60 °C for 3 h to obtain cyclodextrin - dopamine polymer; (3) Prepare an ethanol solution of γ - aminopropyltriethoxysilane. In the ethanol solution of γ - aminopropyltriethoxysilane, the mass percentage of γ - aminopropyltriethoxysilane is 5%, and the solvent is ethanol; Add cupric peroxide to the ethanol solution of γ - aminopropyltriethoxysilane under stirring. The mass ratio of cupric peroxide to the ethanol solution of γ - aminopropyltriethoxysilane is cupric peroxide: ethanol solution of γ - aminopropyltriethoxysilane = 1:50; After feeding, heat in a water bath to 50 °C, keep stirring at a constant temperature for 1 h, then perform solid - liquid separation, and dry the solid phase at 60 °C for 2 h to obtain surface - modified powder; (4) Add the antibacterial matrix powder, cyclodextrin dopamine polymer, and surface-modified powder to the viscose spinning solution. The mass ratio of the antibacterial matrix powder, cyclodextrin dopamine polymer, surface-modified powder, and viscose spinning solution is antibacterial matrix powder: cyclodextrin dopamine polymer: surface-modified powder: viscose spinning solution = 2:5:6:100. The mass percentage content of cellulose in the used viscose spinning solution is 9%; after adding the materials, stir for 2 h to mix evenly, stand for 5 h under a negative pressure environment (0.01 standard atmosphere) to remove air bubbles, and then perform wet spinning and solidify and form in a coagulation bath at 45°C; the wet spinning uses a spinneret with a pore size of 70 μm, and the spinning draw ratio is set to 1.6; the concentration of H2SO4 in the coagulation bath is 70 g / L, the concentration of Na2SO4 is 320 g / L, and the concentration of ZnSO4 is 16 g / L; after forming, wash with deionized water and dry to obtain the fiber material.

[0016] Comparative Example 1 A preparation method of an antibacterial and warm-keeping fiber material for clothing as a comparison, the steps include: (1) Pour deionized water into a reaction kettle, and then add citric acid and urea to the deionized water. The amount ratio of citric acid, urea, and deionized water added to the deionized water is citric acid: urea: deionized water = 17 g: 10 g: 100 mL; stir for 30 min in an ultrasonic environment to completely dissolve; seal the reaction kettle and heat to 160°C for hydrothermal insulation for 3 h; after the insulation is completed, naturally cool to room temperature, open the reaction kettle, and dialyze the product in the kettle in a dialysis membrane with a cut-off molecular weight of 1000 for 12 h to remove unreacted citric acid and urea. The dialyzed solution is concentrated under reduced pressure to half of the volume before concentration and freeze-dried to obtain the antibacterial matrix powder; (2) Dissolve cyclodextrin in Tris buffer solution to prepare a cyclodextrin solution. In the cyclodextrin solution, the concentration of cyclodextrin is 0.9 g / 100 mL; the concentration of Tris buffer solution is 50 mM, pH = 8.5; then add dopamine hydrochloride to the solution under stirring. The addition amount of dopamine hydrochloride and the amount of the cyclodextrin solution are in the ratio of dopamine hydrochloride: cyclodextrin solution = 0.2 g: 100 mL; after adding the materials, heat in a water bath to 35°C, keep warm and stir for 5 h after reaching the temperature, and then perform solid-liquid separation. The solid phase is dried at 60°C for 3 h to obtain the cyclodextrin dopamine polymer; (3) Prepare an ethanol solution of γ-aminopropyltriethoxysilane. In the ethanol solution of γ-aminopropyltriethoxysilane, the mass percentage of γ-aminopropyltriethoxysilane is 4%, and the solvent is ethanol. Add copper peroxide to the ethanol solution of γ-aminopropyltriethoxysilane under stirring. The mass ratio of copper peroxide added to the ethanol solution of γ-aminopropyltriethoxysilane is copper peroxide:ethanol solution of γ-aminopropyltriethoxysilane = 1:50. After the addition is completed, heat in a water bath to 50 °C, stir constantly for 1 h, then separate the solid and liquid. Dry the solid at 60 °C for 2 h to obtain the surface-modified powder. (4) Add the antibacterial matrix powder, cyclodextrin dopamine polymer, and surface-modified powder to the viscose spinning solution. The mass ratio of the antibacterial matrix powder, cyclodextrin dopamine polymer, surface-modified powder, and viscose spinning solution is antibacterial matrix powder:cyclodextrin dopamine polymer:surface-modified powder:viscose spinning solution = 2:3:5:100. The mass percentage of cellulose in the used viscose spinning solution is 9%. After adding the materials, stir for 2 h to mix evenly. Let it stand for 5 h under a negative pressure environment (0.01 standard atmosphere) to remove air bubbles, and then perform wet spinning and solidify and form in a coagulation bath at 45 °C. The wet spinning uses a spinneret with a pore size of 70 μm, and the spinning draw ratio is set to 1.6. The concentration of H2SO4 in the coagulation bath is 70 g / L, the concentration of Na2SO4 is 320 g / L, and the concentration of ZnSO4 is 16 g / L. After forming, wash with deionized water and dry to obtain the fiber material of this comparative example.

[0017] Comparative Example 2 A preparation method of an antibacterial and warm-keeping fiber material for clothing as a comparison, the steps include: (1) Pour deionized water into a reaction kettle, and then add citric acid, glycine, and urea to the deionized water. The amount ratio of citric acid, glycine, urea, and deionized water added is citric acid:glycine:urea:deionized water = 17 g:3 g:10 g:100 mL. Stir for 30 min in an ultrasonic environment to completely dissolve. Seal the reaction kettle and heat to 160 °C for hydrothermal insulation for 3 h. After the insulation is completed, naturally cool to room temperature, open the reaction kettle, and dialyze the product in the kettle in a dialysis membrane with a cut-off molecular weight of 1000 for 12 h to remove unreacted citric acid, glycine, and urea. Concentrate the dialyzed solution under reduced pressure to half of the volume before concentration, and freeze-dry to obtain the antibacterial matrix powder. (2) Prepare an ethanol solution of γ-aminopropyltriethoxysilane. In the ethanol solution of γ-aminopropyltriethoxysilane, the mass percentage of γ-aminopropyltriethoxysilane is 4%, and the solvent is ethanol. Add cupric peroxide to the ethanol solution of γ-aminopropyltriethoxysilane under stirring. The mass ratio of cupric peroxide added to the ethanol solution of γ-aminopropyltriethoxysilane is cupric peroxide:ethanol solution of γ-aminopropyltriethoxysilane = 1:50. After the feeding is completed, heat in a water bath to 50 °C, stir constantly for 1 h, then separate the solid and liquid. Dry the solid at 60 °C for 2 h to obtain the surface-modified powder. (3) Add the antibacterial matrix powder and the surface-modified powder to the viscose spinning solution. The mass ratio of the antibacterial matrix powder, the surface-modified powder, and the viscose spinning solution is antibacterial matrix powder:surface-modified powder:viscose spinning solution = 2:5:100. The mass percentage of cellulose in the used viscose spinning solution is 9%. After feeding, stir for 2 h to mix evenly, let stand for 5 h under a negative pressure environment (0.01 standard atmosphere) to remove bubbles, and then perform wet spinning and solidify and form in a coagulation bath at 45 °C. The wet spinning uses a spinneret with a pore diameter of 70 μm, and the spinning draw ratio is set to 1.6. The concentration of H2SO4 in the coagulation bath is 70 g / L, the concentration of Na2SO4 is 320 g / L, and the concentration of ZnSO4 is 16 g / L. After forming, wash with deionized water and dry to obtain the fiber material of this comparative example.

[0018] Comparative Example 3 A preparation method of an antibacterial and warm-keeping fiber material for clothing as a comparison, the steps include: (1) Pour deionized water into a reaction kettle, and then add citric acid, glycine, and urea to the deionized water. The amount ratio of citric acid, glycine, urea, and deionized water added is citric acid:glycine:urea:deionized water = 17 g:3 g:10 g:100 mL. Stir for 30 min under an ultrasonic environment to completely dissolve. Seal the reaction kettle and heat to 160 °C for hydrothermal insulation for 3 h. After the insulation is completed, naturally cool to room temperature, open the reaction kettle, and dialyze the product in the kettle in a dialysis membrane with a cut-off molecular weight of 1000 for 12 h to remove unreacted citric acid, glycine, and urea. Concentrate the dialyzed solution under reduced pressure to half of the volume before concentration, and freeze-dry to obtain the antibacterial matrix powder. (2) Dissolve cyclodextrin in Tris buffer to prepare a cyclodextrin solution. In the cyclodextrin solution, the concentration of cyclodextrin is 0.9 g / 100 mL; the concentration of Tris buffer is 50 mM, and pH = 8.5. Then, add dopamine hydrochloride to the solution under stirring. The addition amount of dopamine hydrochloride to the cyclodextrin solution is dopamine hydrochloride:cyclodextrin solution = 0.2 g:100 mL. After the feeding is completed, heat the solution in a water bath to 35 °C, keep stirring at the temperature for 5 h after reaching the temperature, then perform solid-liquid separation, and dry the solid phase at 60 °C for 3 h to obtain cyclodextrin dopamine polymer; (3) Add the antibacterial matrix powder, cyclodextrin dopamine polymer, and copper peroxide powder to the viscose spinning solution. The mass ratio of the antibacterial matrix powder, cyclodextrin dopamine polymer, copper peroxide powder to the viscose spinning solution is antibacterial matrix powder:cyclodextrin dopamine polymer:copper peroxide powder:viscose spinning solution = 2:3:5:100. The mass percentage content of cellulose in the used viscose spinning solution is 9%. After feeding, stir for 2 h to mix evenly, let it stand for 5 h under a negative pressure environment (0.01 standard atmosphere) to remove air bubbles, and then perform wet spinning and solidify and form in a coagulation bath at 45 °C. The wet spinning uses a spinneret with a pore diameter of 70 μm, and the spinning draw ratio is set to 1.6. The concentration of H2SO4 in the coagulation bath is 70 g / L, the concentration of Na2SO4 is 320 g / L, and the concentration of ZnSO4 is 16 g / L. After forming, wash with deionized water and dry to obtain the fiber material of this comparative example.

[0019] Example 5 Test the antibacterial rates of the fiber materials prepared by the methods of the above examples and comparative examples respectively according to the requirements of standard GB / T20944.3-2008 (oscillation method): First, cut the fiber material to be tested into pieces, sterilize by steaming, and then transfer it into a culture solution containing Staphylococcus aureus and culture it by shaking at 25 °C for 24 h. Dilute the cultured bacterial solution (dilute by 10 times, 10 2 times, 10 3 times, 10 4 times) according to the 10-fold dilution method, inoculate the diluted solution onto an agar plate, culture it at 37 °C for 24 h, and calculate the antibacterial rate by calculating the number of colonies. The results are as Figure 1 shown. In addition, according to the requirements of standard GB / T14337-2022, test the breaking strength of the fiber materials prepared by the methods of the above examples and comparative examples; before the test, condition the fiber material to be tested in an environment of 20 °C and 65% humidity for 18 h; test each group of samples 10 times and take the average value. The results are as Figure 2 shown.

[0020] From Figure 1 and Figure 2It can be seen that the fiber material prepared by the method of the present invention has good antibacterial properties and certain strength, meeting the standard requirement of an antibacterial rate of ≥ 70%, and improving the pollution resistance and durability of the fiber material for clothing. By comparing Example 3 with each comparative example, it can be seen that adding the antibacterial matrix powder, cyclodextrin dopamine polymer and surface-modified powder prepared by the present invention to the traditional fiber material is the key to achieving the antibacterial property and improving the strength of the fiber material. This may be because: loading the amino acid-based carbon quantum dot antibacterial matrix powder of the present invention on the surface of the fiber material, on the one hand, utilizes the characteristic that the surface functional groups of the carbon quantum dots can interact with the microbial cell membrane to destroy the integrity of the bacterial cell membrane, thus playing the role of improving bactericidal property. At the same time, adding glycine can significantly increase the number of amino groups and improve the adhesion strength between the antibacterial matrix powder and the fiber material. On the other hand, the amino acid-based carbon quantum dot antibacterial matrix powder can form a carbon layer on the fiber surface, playing the role of blocking heat and gas and improving the heat preservation performance of the fiber material. Secondly, adding the surface-modified cupric peroxide powder can improve the binding force between the cupric peroxide powder, the cyclodextrin dopamine polymer and the fiber material body; the cupric peroxide particles play a role in gradually decomposing and releasing hydroxyl radicals (·OH) and Cu 2+ , playing an antibacterial role. By adding the cyclodextrin dopamine polymer, the binding force of the antibacterial active substance on the fiber material can be significantly improved, and the persistence of the antibacterial property of the fiber material can be improved. At the same time, the cyclodextrin dopamine polymer can encapsulate the antibacterial active substance to a certain extent and slowly and continuously release antibacterial free radicals or ions to maintain its long-term antibacterial ability.

[0021] The technical solutions provided by the present invention have been introduced in detail above. For those of ordinary skill in the art, according to the idea of the embodiments of the present invention, there will be changes in the specific implementation manners and application scopes. In summary, the content of this specification should not be construed as a limitation to the present invention.

Claims

1. A preparation method of an antibacterial and warm-keeping fiber material for clothing, characterized in that the steps Including: (1) Pour deionized water into a reaction kettle, then add citric acid, glycine, and urea into the deionized water, and stir to dissolve under an ultrasonic environment; seal the reaction kettle, heat it to 150 - 170 °C for hydrothermal insulation; after the insulation is completed, naturally cool it to room temperature, dialyze the product in a dialysis membrane to remove unreacted citric acid, glycine, and urea, concentrate the dialyzed solution under reduced pressure, and freeze-dry to obtain antibacterial matrix powder; (2) Dissolve cyclodextrin in Tris buffer solution to prepare a cyclodextrin solution, then add dopamine hydrochloride to the solution under stirring, after the feeding is completed, heat it in a water bath to 35 ± 5 °C, keep stirring for more than 5 h, then perform solid-liquid separation, and dry the solid phase to obtain cyclodextrin dopamine polymer; (3) Prepare an ethanol solution of γ-aminopropyltriethoxysilane, add copper peroxide to the ethanol solution of γ-aminopropyltriethoxysilane under stirring, after the feeding is completed, heat it in a water bath to 50 ± 5 °C, keep stirring for more than 1 h, then perform solid-liquid separation, and dry the solid phase to obtain surface-modified powder; (4) Add the antibacterial matrix powder, cyclodextrin dopamine polymer, and surface-modified powder into the viscose spinning solution, stir for more than 2 h after feeding to mix evenly, stand in a negative pressure environment to remove bubbles, then perform wet spinning, solidify and form, wash with deionized water after forming, and dry to obtain the fiber material.

2. The preparation method of an antibacterial and warm-keeping fiber material for clothing according to claim 1, characterized in that In the step (1), the mass ratio of citric acid, glycine, and urea added into deionized water is citric acid: glycine: urea: deionized water = 16 - 18 g: 2 - 4 g: 8 - 12 g: 100 mL; the hydrothermal insulation time at 150 - 170 °C is 3 - 4 h.

3. The preparation method of an antibacterial and warm-keeping fiber material for clothing according to claim 1, characterized in that In the step (2), in the cyclodextrin solution, the concentration of cyclodextrin is 0.7 - 1.0 g / 100 mL; the mass ratio of the added amount of dopamine hydrochloride to the cyclodextrin solution is dopamine hydrochloride: cyclodextrin solution = 0.1 - 0.2 g: 100 mL.

4. The preparation method of an antibacterial and warm-keeping fiber material for clothing according to claim 3, characterized in that In the step (2), the concentration of the used Tris buffer solution is 50 mM, pH = 8.

5.

5. The preparation method of an antibacterial and warm-keeping fiber material for clothing according to claim 1, characterized in that In the step (3), in the ethanol solution of γ-aminopropyltriethoxysilane, the mass percentage of γ-aminopropyltriethoxysilane is 3% - 5%, and the solvent is ethanol; the mass ratio of copper peroxide added to the ethanol solution of γ-aminopropyltriethoxysilane is copper peroxide: ethanol solution of γ-aminopropyltriethoxysilane = 1: 50 - 100.

6. The preparation method of an antibacterial and warm-keeping fiber material for clothing according to claim 1, characterized in that In the step (4), the mass ratio of adding the antibacterial matrix powder, cyclodextrin dopamine polymer, and surface-modified powder into the viscose spinning solution is antibacterial matrix powder: cyclodextrin dopamine polymer: surface-modified powder: viscose spinning solution = 1 - 2: 1 - 5: 3 - 6: 100.

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