Preparation method of antibacterial fiber membrane containing composite nano antibacterial agent

Abstract

The invention belongs to the technical field of fiber membranes. The invention provides a preparation method of an antibacterial fiber membrane containing a composite nano antibacterial agent, which comprises the following steps: a, putting zinc oxide, modified titanium dioxide, a modified dispersant and water into a ball milling tank for ball milling to prepare the composite nano antibacterial agent; b, adding cellulose acetate into an organic solvent, and uniformly dispersing to obtain a cellulose acetate solution; adding the composite nano antibacterial agent in the step a into a cellulose acetate solution to prepare a spinning solution; c, the spinning solution prepared in the step b is transferred into a spinning needle tube for spinning, and the antibacterial fiber membrane containing the composite nano-antibacterial agent is prepared. The method provided by the invention can be used for preparing the composite nano antibacterial agent antibacterial fiber membrane, so that the fiber membrane not only has antibacterial performance, but also can improve the hydrophilic performance of the fiber membrane.

Description

Technical Field

[0001] This invention relates to the field of fiber membrane technology, and specifically to a method for preparing an antibacterial fiber membrane containing a composite nano-antibacterial agent. Background Technology

[0002] Cellulose acetate is hydrophilic and has good hygroscopic properties, as well as good biocompatibility, making it suitable for wound dressings. In the moist environment of a human wound, traditional cotton gauze dressings, if not changed frequently, are prone to bacterial growth, posing a risk of secondary infection. Cellulose acetate, with its excellent hygroscopicity and biocompatibility, avoids adhesion to the wound and secondary damage during dressing changes.

[0003] As people's living standards improve and their demands for health increase, cost-effective materials with strong antibacterial properties are receiving further extensive and in-depth research. Nano-zinc oxide and nano-titanium dioxide are semiconductor-type antibacterial agents. Even in the absence of light, they generate free electrons and holes, activating oxygen in the air into reactive oxygen species, which have a good inhibitory effect on bacteria. Furthermore, they are durable, stable, and non-toxic. Therefore, combining cellulose acetate, which has good water absorption, with composite nano-antibacterial agents endows the fibers with effective antibacterial properties. This avoids the risk of excessive moisture and bacterial infection during wound healing, thereby promoting wound healing. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide a method for preparing an antibacterial fiber membrane containing a composite nano antibacterial agent. This method can prepare an antibacterial fiber membrane with a composite nano antibacterial agent, so that the fiber membrane not only has antibacterial properties but also improves its hydrophilic properties.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0006] In a first aspect, the present invention provides a method for preparing an antibacterial fiber membrane containing a composite nano-antibacterial agent, the specific steps of which are as follows:

[0007] a. Zinc oxide, modified titanium dioxide, modified dispersant and water are added to a ball mill jar and ball-milled to obtain a composite nano antibacterial agent;

[0008] b. Add cellulose acetate to an organic solvent and disperse it evenly to obtain a cellulose acetate solution; add the composite nano antibacterial agent from step a to the cellulose acetate solution and disperse it evenly to obtain a spinning solution;

[0009] c. Transfer the spinning solution obtained in step b to a spinning needle for spinning to obtain an antibacterial fiber membrane containing composite nano antibacterial agents.

[0010] In a preferred embodiment of the first aspect, the mass ratio of the total amount of zinc oxide and modified titanium dioxide to the modified dispersant in step a is 8 to 20:1, and the mass ratio can also be any one of 8:1, 10:1, 12:1, 14:1, 18:1, 20:1 or a range between the two; the mass ratio of zinc oxide to modified titanium dioxide is 1 to 3:1, and the mass ratio can also be any one of 1:1, 2:1, 3:1 or a range between the two; The mass ratio of zinc oxide to water is 1:100 to 10000, and the mass ratio can be any one of the following or a range between two: 1:100, 1:250, 1:500, 1:1000, 1:1500, 1:2000, 1:2500, 1:3000, 1:3500, 1:4000, 1:5000, 1:6000, 1:7000, 1:7500, 1:8000, 1:9000, 1:10000.

[0011] In a preferred embodiment of the first aspect, the modified dispersant in step a is any one of the following composite dispersants:

[0012] 1) A combination of sodium hexametaphosphate and polyvinylpyrrolidone, wherein the mass ratio of sodium hexametaphosphate to polyvinylpyrrolidone is 4 to 2:1, and the mass ratio can also be any one of 4:1, 3:1, 2:1 or a range between the two. Preferably, the mass ratio is 3:1.

[0013] 2) A combination of sodium dodecylbenzenesulfonate and sodium tripolyphosphate, wherein the mass ratio of sodium dodecylbenzenesulfonate to sodium tripolyphosphate is 3:1;

[0014] 3) A combination of polyethylene glycol and polyvinylpyrrolidone, wherein the mass ratio of polyethylene glycol to polyvinylpyrrolidone is 3:1;

[0015] In a preferred embodiment of the first aspect, the ball milling in step a is performed at a rotation speed of 700 r / min for 4 h, and the average particle size of the composite nano antibacterial agent is 50-100 nm.

[0016] As a preferred embodiment of the first aspect, step a further includes adjusting the pH value to 5 using acetic acid.

[0017] In a preferred embodiment of the first aspect, the final concentration of cellulose acetate in step b is 5-15% (w / v), and the final concentration can also be any one of 5%, 8%, 10%, 12%, 14%, 15% or a range between two of them. Preferably, the final concentration of cellulose acetate is 10%.

[0018] In a preferred embodiment of the first aspect, the organic solvent in step b is a mixed solution of acetone, DMAc (dimethylacetamide) and water, and the mass ratio is acetone:DMAc:water = (8-5):(4-2):1 (w / w / w). The mass ratio can be any one of 8:4:1, 8:3:1, 7:4:1, 6:4:1, 5:2:1 or a range between two of them; preferably, the mass ratio is acetone:DMAc:water = 7:2:1.

[0019] In a preferred embodiment of the first aspect, the amount of composite nano-antibacterial agent added in step b is 0.1-2% (w / v), which can be any one or a range between two of 0.1%, 0.4%, 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, 1.5%, 1.6%, 1.8%, and 2.0%. Preferably, the amount added is 0.5%.

[0020] As a preferred embodiment of the first aspect, step b further includes ultrasonically dispersing the spinning solution under a constant temperature water bath at 60°C with stirring at 250 r / min for 30 min.

[0021] In a preferred embodiment of the first aspect, the spinning process parameters in step c are: voltage 15-25kV, receiving distance 15-20cm, injection pump flow rate 1-2ml / h, spinning temperature 20-30℃, relative humidity 45-55%, and rotation speed 80-100r / min. Preferably, the spinning process parameters are: voltage 17kV, receiving distance 18cm, injection pump flow rate 1ml / h, spinning temperature 25℃, relative humidity 45%, and rotation speed 90r / min.

[0022] In a second aspect, the present invention provides an antibacterial fiber membrane prepared by the method of the first aspect.

[0023] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0024] The antibacterial fiber membrane of this invention is made by adding a composite nano-antibacterial agent, which has undergone ball milling and small molecule dispersant coating, to cellulose acetate with good biocompatibility. Compared with existing traditional cotton gauze dressings, the cellulose acetate membrane containing nano-zinc oxide and nano-titanium dioxide is more suitable for use as a dressing. Simultaneously, by releasing free electrons and generating reactive oxygen species with oxygen, it exhibits a more stable antibacterial process and longer-lasting antibacterial effect. It can effectively promote the healing of human wounds without causing secondary damage to the wound during use. This method can prepare a composite nano-antibacterial agent antibacterial fiber membrane, making the fiber membrane not only possess antibacterial properties but also improve its hydrophilicity. Attached Figure Description

[0025] Figure 1The images are digital images of the antibacterial fiber membranes of Example 1 and Comparative Example 1, where (a) is the sample of Comparative Example 1 and (b) is the sample of Example 1. Detailed Implementation

[0026] To better illustrate the objectives, technical solutions, and advantages of this invention, the invention will be further described below with reference to specific embodiments. Those skilled in the art should understand that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

[0027] Unless otherwise specified, the experimental methods used in the examples are conventional methods; the materials and reagents used are commercially available unless otherwise specified. The zinc oxide involved is a commercially available agglomerate raw material with a purity of 99.98%; the sodium hexametaphosphate involved has a molecular weight of 611.77; the sodium dodecylbenzenesulfonate (SDS) involved has a molecular weight of 288.38; the polyethylene glycol involved has a CAS Registry Number of 25322-68-3; the sodium tripolyphosphate involved has a molecular weight of 367.864; and the polyvinylpyrrolidone involved has a molecular weight of 111.14200. The average particle size in the examples was obtained by particle size analyzer testing.

[0028] Example 1:

[0029] This embodiment provides a method for preparing an antibacterial fiber membrane containing a composite nano-antibacterial agent, the specific steps of which are as follows:

[0030] a. Weigh zinc oxide, titanium dioxide and modified dispersant, put them into a ball mill jar, add an appropriate amount of deionized water, add an appropriate amount of acetic acid to adjust the pH value to 5, and after ball milling at 700 r / min for 4 h, a composite nano antibacterial agent with an average particle size of 80 nm is obtained.

[0031] The total amount of zinc oxide and titanium dioxide is in a mass ratio of 10:1 to the modified dispersant, and the mass ratio of zinc oxide to titanium dioxide is 2:1. The amount of deionized water added is in a mass ratio of zinc oxide to deionized water of 1:100. The modified dispersant is a composite dispersant of sodium hexametaphosphate and polyvinylpyrrolidone, and the mass ratio of sodium hexametaphosphate to polyvinylpyrrolidone is 3:1.

[0032] b. Add cellulose acetate to an organic solvent to a final concentration of 10% (w / v) to obtain a cellulose acetate solution; weigh the above-mentioned composite nano antibacterial agent at an addition amount of 0.5% and add it to the prepared cellulose acetate solution, ultrasonically disperse for 30 min, stir and mix the system at 250 r / min for 1 h in a constant temperature water bath at 60℃, and after standing, obtain a bubble-free transparent spinning solution containing nano zinc oxide and nano titanium dioxide;

[0033] The organic solvent is a mixed solution of acetone, dimethylacetamide (DMAc), and water; and the mass ratio is acetone:DMAc:water = 7:2:1 (w / w / w).

[0034] c. Take the spinning solution prepared in the above steps, transfer it to the spinning needle tube, and set the spinning process parameters: yarn voltage 17kV, receiving distance 18cm, injection pump flow rate 1ml / h, spinning temperature 25℃, relative humidity 45%, receiving roller speed 90r / min. After spinning, an antibacterial fiber membrane containing composite nano antibacterial agent is obtained.

[0035] Example 2

[0036] This embodiment provides a method for preparing an antibacterial fiber membrane containing a composite nano-antibacterial agent, the specific steps of which are as follows:

[0037] a. Weigh zinc oxide, titanium dioxide and modified dispersant, put them into a ball mill jar, add an appropriate amount of deionized water, add an appropriate amount of acetic acid to adjust the pH value to 5, and after ball milling at 700 r / min for 3 h, a composite nano antibacterial agent with an average particle size of 50 nm is obtained.

[0038] The total amount of zinc oxide and titanium dioxide to the modified dispersant is in the mass ratio of 20:1, and the mass ratio of zinc oxide to titanium dioxide is 2:1; the amount of deionized water added is in the mass ratio of zinc oxide to deionized water of 1:100; the modified dispersant is a composite dispersant composed of sodium dodecylbenzenesulfonate and sodium tripolyphosphate, and the mass ratio of sodium dodecylbenzenesulfonate to sodium tripolyphosphate is 3:1.

[0039] b. Add cellulose acetate to an organic solvent to a final concentration of 5% (w / v) to obtain a cellulose acetate solution; weigh the above-mentioned composite nano antibacterial agent at a dosage of 1% and add it to the prepared cellulose acetate solution, ultrasonically disperse for 30 min, stir and mix the system at 250 r / min for 1 h in a constant temperature water bath at 60℃, and after standing, obtain a bubble-free transparent spinning solution containing nano zinc oxide and nano titanium dioxide;

[0040] The organic solvent is a mixed solution of acetone, dimethylacetamide (DMAc), and water; and the mass ratio is acetone:DMAc:water = 8:2:1 (w / w / w).

[0041] c. Take the spinning solution prepared in the above steps, transfer it to the spinning needle tube, and set the spinning process parameters: yarn voltage 15kV, receiving distance 20cm, injection pump flow rate 1ml / h, spinning temperature 20℃, relative humidity 55%, receiving roller speed 80r / min. After spinning, an antibacterial fiber membrane containing composite nano antibacterial agent is obtained.

[0042] Example 3

[0043] This embodiment provides a method for preparing an antibacterial fiber membrane containing a composite nano-antibacterial agent, the specific steps of which are as follows:

[0044] a. Weigh zinc oxide and titanium dioxide and the modified dispersant, put them into a ball mill jar, add an appropriate amount of deionized water, add an appropriate amount of acetic acid to adjust the pH value to 5, and after ball milling at 700 r / min for 6 h, a composite nano antibacterial agent with an average particle size of 100 nm is obtained.

[0045] The total amount of zinc oxide and titanium dioxide to the modified dispersant is in the mass ratio of 15:1, and the mass ratio of zinc oxide to titanium dioxide is 1:1; the amount of deionized water added is in the mass ratio of zinc oxide to deionized water of 1:100; the modified dispersant is a composite dispersant composed of polyethylene glycol and polyvinylpyrrolidone, and the mass ratio of polyethylene glycol to polyvinylpyrrolidone is 3:1.

[0046] b. Add cellulose acetate to an organic solvent to a final concentration of 8% (w / v) to obtain a cellulose acetate solution; weigh the above-mentioned composite nano antibacterial agent at an addition amount of 1.5% and add it to the prepared cellulose acetate solution, ultrasonically disperse for 30 min, stir and mix the system at 250 r / min for 1 h in a constant temperature water bath at 60℃, and after standing, obtain a bubble-free transparent spinning solution containing nano zinc oxide and nano titanium dioxide;

[0047] The organic solvent is a mixed solution of acetone, dimethylacetamide (DMAc), and water; and the mass ratio is acetone:DMAc:water = 6:3:1 (w / w / w).

[0048] c. Take the spinning solution prepared in the above steps, transfer it to the spinning needle tube, and set the spinning process parameters: filament voltage 20kV, receiving distance 16cm, injection pump flow rate 1ml / h, spinning temperature 30℃, relative humidity 50%, receiving roller speed 100r / min. After spinning, an antibacterial fiber membrane containing composite nano antibacterial agent is obtained.

[0049] Example 4

[0050] This embodiment provides a method for preparing an antibacterial fiber membrane containing a composite nano-antibacterial agent, the specific steps of which are as follows:

[0051] a. Weigh zinc oxide, titanium dioxide and modified dispersant, put them into a ball mill jar, add an appropriate amount of deionized water, add an appropriate amount of acetic acid to adjust the pH value to 5, and after ball milling at 700 r / min for 3.5 h, a composite nano antibacterial agent with an average particle size of 60 nm is obtained.

[0052] The total amount of zinc oxide and titanium dioxide is in a mass ratio of 8:1 to the modified dispersant, and the mass ratio of zinc oxide to titanium dioxide is 3:1. The amount of deionized water added is in a mass ratio of 1:100 to zinc oxide. The modified dispersant is a composite dispersant composed of sodium polyhexametaphosphate and polyvinylpyrrolidone, and the mass ratio of sodium polyhexametaphosphate to polyvinylpyrrolidone is 1:1.

[0053] b. Add cellulose acetate to an organic solvent to make a final concentration of 15% (w / v) to obtain a cellulose acetate solution; weigh the above composite nano antibacterial agent at an addition amount of 2% and add it to the prepared cellulose acetate solution. Disperse ultrasonically for 30 min, stir and mix the system at 250 r / min for 1 h in a constant temperature water bath at 60℃, and after standing, obtain a bubble-free transparent spinning solution containing nano zinc oxide and nano titanium dioxide.

[0054] The organic solvent is a mixed solution of acetone, dimethylacetamide (DMAc), and water; and the mass ratio is acetone:DMAc:water = 5:4:1 (w / w / w).

[0055] c. Take the spinning solution prepared in the above steps, transfer it to the spinning needle, and set the spinning process parameters: filament voltage 25kV, receiving distance 15cm, injection pump flow rate 2ml / h, spinning temperature 25℃, relative humidity 45%, receiving roller speed 70r / min. After spinning, an antibacterial fiber membrane containing composite nano antibacterial agent is obtained.

[0056] Example 5

[0057] This embodiment provides a method for preparing an antibacterial fiber membrane containing a composite nano-antibacterial agent, the specific steps of which are as follows:

[0058] a. Weigh zinc oxide, titanium dioxide and modified dispersant, put them into a ball mill jar, add an appropriate amount of deionized water, add an appropriate amount of acetic acid to adjust the pH value to 5, and after ball milling at 700 r / min for 4 h, a composite nano antibacterial agent with an average particle size of 80 nm is obtained.

[0059] The total amount of zinc oxide and titanium dioxide to the modified dispersant is in the mass ratio of 8:1, and the mass ratio of zinc oxide to titanium dioxide is 2:1; the amount of deionized water added is in the mass ratio of zinc oxide to deionized water of 1:100; the modified dispersant is a composite dispersant composed of sodium polyhexametaphosphate and polyvinylpyrrolidone, and the mass ratio of sodium polyhexametaphosphate to polyvinylpyrrolidone is 2:1.

[0060] b. Add cellulose acetate to an organic solvent to a final concentration of 12% (w / v) to obtain a cellulose acetate solution; weigh the above-mentioned composite nano antibacterial agent at an addition amount of 0.5% and add it to the prepared cellulose acetate solution, ultrasonically disperse for 30 min, stir and mix the system at 250 r / min for 1 h in a constant temperature water bath at 60℃, and after standing, obtain a bubble-free transparent spinning solution containing nano zinc oxide and nano titanium dioxide;

[0061] The organic solvent is a mixed solution of acetone, dimethylacetamide (DMAc), and water; and the mass ratio is acetone:DMAc:water = 5:3:1 (w / w / w).

[0062] c. Take the spinning solution prepared in the above steps, transfer it to the spinning needle tube, and set the spinning process parameters: yarn voltage 17kV, receiving distance 18cm, injection pump flow rate 1ml / h, spinning temperature 25℃, relative humidity 45%, receiving roller speed 90r / min. After spinning, an antibacterial fiber membrane containing composite nano antibacterial agent is obtained.

[0063] Comparative Example 1

[0064] The difference between Comparative Example 1 and Example 1 is that no composite nano-antibacterial agent was added; otherwise, they are the same as in Example 1. The preparation method of Comparative Example 1 is as follows:

[0065] a. Add cellulose acetate to an organic solvent to a final concentration of 10% (w / v) to prepare a transparent spinning solution;

[0066] The organic solvent is a mixed solution of acetone, dimethylacetamide (DMAc), and water; and the mass ratio is acetone:DMAc:water = 7:2:1 (w / w / w).

[0067] b. Take the spinning solution prepared in the above steps, transfer it to the spinning needle tube, and set the spinning process parameters: yarn voltage 17kV, receiving distance 18cm, injection pump flow rate 1ml / h, spinning temperature 25℃, relative humidity 45%, receiving roller speed 90r / min. After spinning, an antibacterial fiber membrane containing composite nano antibacterial agent is obtained.

[0068] Comparative Example 2

[0069] The difference between Comparative Example 2 and Example 1 is that the total amount of zinc oxide and titanium dioxide to the mass ratio of the modified dispersant is 22:1, and the rest is the same as in Example 1.

[0070] Comparative Example 3

[0071] The difference between Comparative Example 3 and Example 1 is that the total amount of zinc oxide and titanium dioxide to the mass ratio of the modified dispersant is 6:1, and the rest is the same as in Example 1.

[0072] Comparative Example 4

[0073] The difference between Comparative Example 4 and Example 1 is that the mass ratio of zinc oxide to titanium dioxide is 1:2, and the rest is the same as in Example 1.

[0074] Comparative Example 5

[0075] The difference between Comparative Example 5 and Example 1 is that the mass ratio of zinc oxide to titanium dioxide is 5:1, and the rest is the same as in Example 1.

[0076] Comparative Example 6

[0077] The difference between Comparative Example 6 and Example 1 is that, after ball milling at 900 r / min for 8 hours, a composite nano antibacterial agent with an average particle size of 30 nm was obtained. The rest is the same as in Example 1.

[0078] Comparative Example 7

[0079] The difference between Comparative Example 7 and Example 1 is that, after ball milling at 300 r / min for 2 h, a composite nano antibacterial agent with an average particle size of 250 nm was obtained. The rest is the same as in Example 1.

[0080] Comparative Example 8

[0081] The difference between Comparative Example 8 and Example 1 is that the final concentration of cellulose acetate is 4% (w / v), while the rest is the same as in Example 1.

[0082] Comparative Example 9

[0083] The difference between Comparative Example 9 and Example 1 is that the final concentration of cellulose acetate is 18% (w / v), while the rest is the same as in Example 1.

[0084] Comparative Example 10

[0085] The difference between Comparative Example 10 and Example 1 is that the mass ratio of acetone to DMAc and water in the organic solvent is: acetone:DMAc:water = 9:6:1 (w / w / w), and the rest is the same as in Example 1.

[0086] Comparative Example 11

[0087] The difference between Comparative Example 11 and Example 1 is that the mass ratio of acetone to DMAc and water in the organic solvent is acetone:DMAc:water = 4:1:1 (w / w / w), and the rest is the same as in Example 1.

[0088] Comparative Example 12

[0089] The difference between Comparative Example 12 and Example 1 is that the amount of composite nano antibacterial agent added is 0.05%, while the rest is the same as in Example 1.

[0090] Comparative Example 13

[0091] The difference between Comparative Example 13 and Example 1 is that the amount of composite nano antibacterial agent added is 3%, while the rest is the same as in Example 1.

[0092] Comparative Example 14

[0093] The difference between Comparative Example 14 and Example 1 is that the wire voltage in step c is 12kV, while the rest is the same as in Example 1.

[0094] Comparative Example 15

[0095] The difference between Comparative Example 15 and Example 1 is that the wire voltage in step c is 28kV, while the rest is the same as in Example 1.

[0096] Comparative Example 16

[0097] The difference between Comparative Example 16 and Example 1 is that the flow rate of the syringe pump in step c is 0.5 ml / h, while the rest is the same as in Example 1.

[0098] Comparative Example 17

[0099] The difference between Comparative Example 17 and Example 1 is that the flow rate of the syringe pump in step c is 3 ml / h, while the rest is the same as in Example 1.

[0100] Comparative Example 18

[0101] The difference between Comparative Example 18 and Example 1 is that the spinning temperature in step c is 15°C, while the rest is the same as in Example 1.

[0102] Comparative Example 19

[0103] The difference between Comparative Example 19 and Example 1 is that the spinning temperature in step c is 35°C, while the rest is the same as in Example 1.

[0104] Comparative Example 20

[0105] The difference between Comparative Example 20 and Example 1 is that the relative humidity in step c is 40%, while the rest is the same as in Example 1.

[0106] Comparative Example 21

[0107] The difference between Comparative Example 21 and Example 1 is that the relative humidity in step c is 60%, while the rest is the same as in Example 1.

[0108] Comparative Example 22

[0109] The difference between Comparative Example 22 and Example 1 is that the mass ratio of sodium hexametaphosphate to polyvinylpyrrolidone in step a is 5:1, while the rest is the same as in Example 1.

[0110] Comparative Example 23

[0111] The difference between Comparative Example 23 and Example 1 is that the mass ratio of sodium hexametaphosphate to polyvinylpyrrolidone in step a is 1:2, while the rest is the same as in Example 1.

[0112] Test case

[0113] 1. Antibacterial test: Take the antibacterial fiber membrane prepared in the above steps and test its antibacterial properties according to the standard "Evaluation of Antibacterial Properties of Textiles" (GB / T 20944, Part 2 Absorption Method). The test strains are: Escherichia coli ATCC 25922 and Staphylococcus aureus ATCC 29213.

[0114] 2. Water contact angle: The hydrophilicity of the fiber membrane was tested using a water contact angle tester. A water droplet was slowly and vertically dripped onto the fiber membrane from the needle tip, and the angle of water contact was recorded after 10 seconds. The number of parallel experimental groups was n = 3.

[0115] Table 1: Test Results of Examples and Comparative Examples

[0116]

[0117]

[0118] Note: Antibacterial performance against Staphylococcus aureus ≥99% is Grade I standard, ≥90% is Grade II standard; antibacterial performance against Escherichia coli ≥95% is Grade I standard, ≥85% is Grade II standard. Since the amount of compound antibacterial agent added, the mass ratio of total zinc oxide and titanium dioxide to modified dispersant, the mass ratio of zinc oxide to titanium dioxide, the average particle size of the antibacterial agent, and the ratio of sodium hexametaphosphate to polyvinylpyrrolidone have a significant impact on the antibacterial performance of cellulose membranes, the antibacterial performance of comparative examples 1–7, 12, 13, 22, and 23 was tested. Since the preparation of the cellulose acetate solution and the spinning process parameters have a significant impact on the hydrophilicity of the cellulose membranes, the water contact angle of comparative examples 8–11 and 14–21 was tested.

[0119] As shown in Table 1, Comparative Example 1 and Examples 1-5 demonstrate that the cellulose membrane with the added composite nano-antibacterial agent exhibits excellent antibacterial effects. When the amount of composite nano-antibacterial agent added is 0.5%, the coating achieves an antibacterial rate of 99.9% against Staphylococcus aureus and 97.2% against Escherichia coli, both meeting the Class I standard. The cellulose membrane without the added composite nano-antibacterial agent, however, shows no antibacterial properties. Comparative Examples 2 and 3 show that the total amount of zinc oxide and titanium dioxide added, relative to the mass ratio of the dispersant, significantly affects the antibacterial effect. In Comparative Example 2, the insufficient total mass of the dispersant prevented complete coating of the nano-zinc oxide and titanium dioxide, leading to agglomeration. In Comparative Example 3, excessive total mass of the dispersant resulted in a decrease in the absolute value of the Zeta potential, thereby reducing the stabilizing effect of electrostatic repulsion, affecting the stability of the slurry, and causing the viscosity of the suspension to rise, which also contributed to agglomeration. As shown in Comparative Examples 4 and 5, the mass ratio of zinc oxide to titanium dioxide has a significant impact on the antibacterial effect. Exceeding a certain mass ratio negatively affects the antibacterial effect. If the antibacterial agent particle size is too small, it is prone to agglomeration, making dispersion difficult. If the particle size is too large, it reduces the overall surface area of ​​the antibacterial agent particles, thus reducing the dust removal and antibacterial effect. Therefore, as shown in Comparative Example 6, the average particle size of the antibacterial agent is less than 50 nm, resulting in uneven dispersion and a decrease in its antibacterial activity. As shown in Comparative Example 7, the particle size of the antibacterial agent is greater than 200 nm, reducing the overall surface area of ​​the antibacterial agent particles and affecting its antibacterial performance. As shown in Comparative Examples 12 and 13, the amount of antibacterial agent added has a significant impact on the antibacterial effect of the fiber membrane. As shown in Comparative Example 13, excessive antibacterial agent addition prevents the antibacterial agent from being evenly distributed on the fiber membrane, thus affecting its antibacterial effect. Comparative Examples 22 and 23 show that the mass ratio of each component in the composite dispersant affects the antibacterial effect. When the mass ratio of sodium hexametaphosphate to polyvinylpyrrolidone exceeds the range of 4 to 2:1, it will affect the stability and dispersibility of the antibacterial agent, thereby reducing its antibacterial effect.

[0120] As shown in Comparative Examples 8-11 and 14-21, various parameters of the spinning process affect the hydrophilicity of the antibacterial fiber membrane. For example, the spinning solution concentration (Comparative Examples 8 and 9), the mass ratio of organic compounds in the organic solvent (Comparative Examples 10 and 11), the spinning voltage (Comparative Examples 14 and 15), the spinning solution flow rate (Comparative Examples 16 and 17), the spinning temperature (Comparative Examples 18 and 19), and the relative humidity (Comparative Examples 20 and 21) all have a certain influence on the fiber morphology. Different surface morphologies result in different water contact angles, thereby affecting the hydrophilicity of the fiber membrane. Therefore, this invention improves the hydrophilicity of the antibacterial fiber membrane by adjusting various parameters.

[0121] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A method for preparing an antibacterial fiber film containing a complex nano-antibacterial agent, characterized by, The specific steps are as follows: a. zinc oxide, modified titanium dioxide, modified dispersant and water are added into a ball mill tank for ball milling to prepare a composite nano antibacterial agent; b. cellulose acetate is added into an organic solvent and uniformly dispersed to obtain a cellulose acetate solution; the composite nano antibacterial agent of step a is added into the cellulose acetate solution to prepare a spinning solution; c. the spinning solution prepared in step b is transferred into a spinning needle tube for spinning to prepare an antibacterial fiber membrane containing the composite nano antibacterial agent.

2. The production method according to claim 1, wherein In step a, the mass ratio of the total amount of zinc oxide and modified titanium dioxide to the modified dispersant is 8-20:1; the mass ratio of zinc oxide to modified titanium dioxide is 1-3:1; and the mass ratio of zinc oxide to water is 1:100-10000.

3. The production method according to claim 2, wherein In step a, the modified dispersant is any one of the following composite dispersants: 1) a combination of sodium hexametaphosphate and polyvinylpyrrolidone, wherein the mass ratio of sodium hexametaphosphate to polyvinylpyrrolidone is 4-2:1; 2) a combination of sodium dodecyl benzene sulfonate and sodium tripolyphosphate, wherein the mass ratio of sodium dodecyl benzene sulfonate to sodium tripolyphosphate is 3:1; 3) a combination of polyethylene glycol and polyvinylpyrrolidone, wherein the mass ratio of polyethylene glycol to polyvinylpyrrolidone is 3:

1.

4. The production method according to claim 1, wherein In step a, the rotation speed of ball milling is 700 r / min, the ball milling time is 4 h, and the average particle size of the composite nano antibacterial agent is 50-100 nm.

5. The production method according to claim 1, wherein In step b, the final concentration of the cellulose acetate solution is 5-15% (w / v).

6. The production method according to claim 1, wherein In step b, the organic solvent is a mixed solution of acetone, dimethylacetamide and water, and the mass ratio is acetone: dimethylacetamide: water = (8-5):(4-2):1 (w / w / w).

7. The production method according to claim 1, wherein In step b, the addition amount of the composite nano antibacterial agent is 0.1-2% (w / v).

8. The production method according to claim 1, wherein In step b, the spinning solution is further subjected to ultrasonic dispersion at 60°C constant temperature water bath under stirring at 250 r / min for 30 min.

9. The production method according to claim 1, wherein In step c, the spinning process parameters are as follows: voltage 15-25 kV, receiving distance 15-20 cm, injection pump flow rate 1-2 ml / h, spinning temperature 20-30°C, relative humidity 45-55%, and rotation speed 80-100 r / min.

10. An antibacterial fiber membrane prepared by the preparation method of any one of claims 1-9.

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