Preparation method of antibacterial waterproof moisture-permeable clothing film

Abstract

The invention discloses a preparation method of an antibacterial waterproof moisture-permeable garment film. The preparation method comprises the following steps: S1, mixing materials to obtain a polyurethane dispersion liquid containing metal organic framework powder; s2, freeze drying: obtaining metal organic framework powder with the surface decorated with polyurethane; s3, ball milling is carried out, wherein metal organic framework superfine powder with the surface decorated with polyurethane is obtained; s4, preparing a film spraying liquid: mixing the metal organic framework ultrafine powder with the surface decorated with polyurethane with a hydrophilic polyurethane elastomer and a solvent according to a certain proportion to prepare the film spraying liquid; s5, soaking, pressing and drying to obtain the antibacterial, waterproof and moisture-permeable garment film. According to the invention, ZIF-67 (Co) is added into a polyurethane coating liquid, the ZIF-67 (Co) is utilized to absorb visible light, excite internal electrons and transition from a valence band to a conduction band to form electron-hole pairs, and the electron-hole pairs are further subjected to an oxidation-reduction reaction to generate hydroxyl free radicals and superoxide free radicals to kill microorganisms such as bacteria and viruses adsorbed on the waterproof and moisture-permeable film; the antibacterial effect is achieved.

Description

Technical Field

[0001] The invention relates to the technical field of clothing film preparation, and in particular to a method for preparing an antibacterial, waterproof and breathable clothing film. Background Art

[0002] The surface of polytetrafluoroethylene microporous film is hydrophobic and breathable. The polytetrafluoroethylene microporous film and textile fabric are laminated by lamination technology and can be applied to the textile field to give the product waterproof, moisture permeable, breathable, warm and other functions. However, due to the high porosity of the microporous film, it is easy to absorb salt and oil in human sweat. At the same time, during washing, some detergents will remain in the membrane pores, resulting in a decrease in the waterproof performance of the membrane itself. Therefore, as the wearing time increases, there will be problems of water seepage and reduced water pressure resistance of the fabric.

[0003] In order to solve the problem that the water pressure resistance of polytetrafluoroethylene laminated fabrics decreases after repeated washing, a layer of dense polyurethane is coated on the polytetrafluoroethylene microporous film, which can effectively improve the water washing resistance of the polytetrafluoroethylene microporous film. However, the polyurethane layer is a dense layer, which will cause the air permeability of the film to seriously decrease.

[0004] Metal organic framework materials are a type of organic-inorganic hybrid materials with an ordered network lattice structure, and are porous materials with a certain degree of crystallinity and porosity. Metal organic framework materials such as ZIF-67 (Co) produce hydroxyl radicals and superoxide radicals under visible light (absorption wavelength range of 450-650nm). These free radicals have strong oxidizing properties and can destroy the cell membrane structure and function of microorganisms such as bacteria and viruses, causing them to die; therefore, introducing ZIF-67 (Co) materials into waterproof and breathable membranes can improve the antibacterial properties of the membranes. Summary of the invention

[0005] The purpose of the present invention is to solve at least one of the technical problems existing in the prior art and provide a method for preparing an antibacterial, waterproof and breathable clothing membrane. ZIF-67(Co) is added to a polyurethane coating solution, and ZIF-67(Co) is used to absorb visible light, excite internal electrons, and transition from a valence band to a conduction band to form electron-hole pairs. The electron-hole pairs further undergo redox reactions to generate hydroxyl radicals and superoxide radicals, thereby killing microorganisms such as bacteria and viruses adsorbed on the waterproof and breathable membrane, thereby achieving an antibacterial effect.

[0006] The present invention also provides a method for preparing the above-mentioned antibacterial, waterproof and breathable clothing membrane, comprising the following steps:

[0007] S1. Mixing: mixing and dispersing the metal organic framework powder and the polyurethane aqueous emulsion to form a polyurethane dispersion containing the metal organic framework powder;

[0008] S2. Freeze drying: The polyurethane dispersion obtained in S1 is placed in an ultra-low temperature of -80°C and then placed in a freeze dryer for freeze drying to obtain a metal organic framework powder with a surface decorated with polyurethane;

[0009] S3. Ball milling: The metal organic framework powder obtained in S2 is placed in a ball mill, and after ball milling, a metal organic framework ultrafine powder with a surface decorated with polyurethane is formed;

[0010] S4. Configuring a coating solution: The metal organic framework ultrafine powder of the surface-decorated polyurethane obtained in S3 is mixed with a hydrophilic polyurethane elastomer and a solvent in a certain proportion to prepare a coating solution;

[0011] S5. Impregnation and drying: The polytetrafluoroethylene microporous membrane is impregnated in the coating solution obtained in S4, and after impregnation, it is pressed by a padder and then dried, and then rolled up to obtain an antibacterial, waterproof and breathable clothing membrane.

[0012] According to a method for preparing an antibacterial, waterproof and breathable clothing membrane provided by the present invention, the particle size of the metal organic framework powder in S1 is 300-800 nm, the polyurethane aqueous emulsion is one of polyurethane emulsion WPU-3015, polyurethane emulsion WPU-125, polyurethane emulsion FS-2040E, polyurethane emulsion AH-K100-1 and polyurethane emulsion WPU-1631, and the weight ratio of the metal organic framework powder to the polyurethane aqueous emulsion is 1:20-50.

[0013] According to the method for preparing an antibacterial, waterproof and breathable clothing membrane provided by the present invention, the dispersion in S1 is achieved by ultrasound, the ultrasonic dispersion time is 60 to 120 minutes, and the power of the ultrasound is 2400 watts.

[0014] According to a method for preparing an antibacterial, waterproof and breathable clothing membrane provided by the present invention, the freezing time in S2 is 24 hours, the temperature of the freeze dryer is minus 40° C., and the drying time is 48 hours.

[0015] According to a method for preparing an antibacterial, waterproof and breathable clothing membrane provided by the present invention, the weight ratio of the metal organic framework ultrafine powder with surface decorated polyurethane, the hydrophilic polyurethane elastomer and the solvent in S4 is 1:10 to 20:100, and the hydrophilic polyurethane elastomer is one of polyurethane TPU EHT-1190, polyurethane TPU EHT-1195, polyurethane TPU 1180A, polyurethane TPU 1185A, polyurethane TPU260D and polyurethane TPU270D.

[0016] According to a method for preparing an antibacterial, waterproof and breathable clothing membrane provided by the present invention, the immersion in S5 is carried out under vacuum conditions, the vacuum degree is 0.05-0.1 MPa, the gram weight of the polytetrafluoroethylene microporous membrane in S5 is 5-25 g / m2, and the immersion time is 30-60 minutes.

[0017] According to the method for preparing an antibacterial, waterproof and breathable clothing membrane provided by the present invention, the pressure of the rolling mill in S5 is 0.2-0.5 MPa, the drying temperature is 180° C.-200° C., and the drying time is 10-20 minutes.

[0018] According to a method for preparing an antibacterial, waterproof and breathable clothing membrane provided by the present invention, the solvent in S4 is one of N,N-dimethylacetamide, N,N-dimethylformamide and N-methylpyrrolidone.

[0019] Beneficial Effects

[0020] 1. The present invention adds ZIF-67(Co) to the polyurethane coating solution, utilizes ZIF-67(Co) to absorb visible light, excites internal electrons, and transitions from the valence band to the conduction band to form electron-hole pairs, and the electron-hole pairs further undergo redox reactions to generate hydroxyl radicals and superoxide radicals, thereby killing microorganisms such as bacteria and viruses adsorbed on the waterproof and breathable membrane, thereby achieving an antibacterial effect.

[0021] 2. The present invention mixes ZIF-67(Co) powder and polyurethane aqueous dispersion, ultrasonically disperses to form polyurethane aqueous dispersion containing ZIF-67(Co) powder, and then uses freeze drying technology and ball milling to prepare ZIF-67(Co) ultrafine powder with surface modified polyurethane. Since the surface of the ultrafine powder is polyurethane, it can be better dispersed uniformly in the polyurethane coating solution.

[0022] 3. The present invention immerses the polytetrafluoroethylene microporous film in a polyurethane coating liquid containing ZIF-67 (Co) material, and uses a vacuum treatment method to allow the coating liquid to evenly enter the polytetrafluoroethylene membrane pores instead of adhering to the membrane surface to form a dense polyurethane layer. While retaining the original microporous structure of the polytetrafluoroethylene membrane, the water-resistant performance and mechanical strength of the membrane are improved. The antibacterial, waterproof and breathable membrane of the present invention can be used in a variety of fields such as outdoor jacket fabrics, reusable surgical gowns, down clothing, etc., and has multiple functions such as waterproof, breathable, breathable, and antibacterial. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] The present invention is further described below in conjunction with the accompanying drawings and embodiments;

[0024] Figure 1 The figure is a schematic flow chart of the method for preparing the antibacterial, waterproof and breathable clothing membrane of the present invention;

[0025] Figure 2 This is a scanning electron microscope image of the method for preparing the antibacterial, waterproof and breathable clothing membrane of the present invention. DETAILED DESCRIPTION

[0026] This section will describe in detail the specific embodiments of the present invention. The preferred embodiments of the present invention are shown in the accompanying drawings. The purpose of the accompanying drawings is to supplement the description of the text part of the specification with graphics, so that people can intuitively and vividly understand each technical feature and the overall technical solution of the present invention, but it cannot be understood as a limitation on the scope of protection of the present invention.

[0027] Embodiment 1:

[0028] Reference Figure 1-2 The present invention provides a method for preparing an antibacterial, waterproof and breathable clothing membrane, which comprises the following steps:

[0029] S1. Mixing: Mix and disperse the metal organic framework (ZIF-67 (CO)) powder with a particle size of 800 nm and the polyurethane emulsion WPU-3015, the weight ratio of the metal organic framework (ZIF-67 (CO)) powder to the polyurethane emulsion WPU-3015 is 1:20, and disperse with ultrasound for 120 minutes at a power of 2400 watts to form a polyurethane dispersion containing the metal organic framework (ZIF-67 (CO)) powder;

[0030] S2. Freeze drying: The polyurethane dispersion obtained in S1 was placed in an ultra-low temperature freezer at -80°C for 24 hours, and then the frozen polyurethane dispersion was placed in a freeze dryer at -40°C for 48 hours to obtain a metal organic framework (ZIF-67(CO)) powder with a surface decorated polyurethane;

[0031] S3. Ball milling: The metal organic framework (ZIF-67 (CO)) powder obtained in S2 was placed in a ball mill and ball milled for 120 minutes at a speed of 700 r / min to form a metal organic framework (ZIF-67 (CO)) ultrafine powder with a surface decorated with polyurethane;

[0032] S4. Configuring a coating solution: The metal organic framework (ZIF-67 (CO)) ultrafine powder of the surface-decorated polyurethane obtained in S3 was mixed with a hydrophilic polyurethane elastomer TPU EHT-1190 and N,N-dimethylacetamide in a weight ratio of 1:10:100 to prepare a coating solution;

[0033] S5. Impregnation and drying: the weight is 5g / m 2The polytetrafluoroethylene microporous membrane is immersed in the coating solution obtained in S4, placed under a vacuum degree of 0.05MPa for 60 minutes, and then dried by a padding car. The padding pressure is 0.2MPa, the drying temperature is 180°C, the drying time is 20 minutes, and then rolled up to obtain an antibacterial, waterproof and breathable clothing membrane.

[0034] Example 2

[0035] A method for preparing an antibacterial, waterproof and breathable clothing membrane comprises the following steps:

[0036] S1. Mixing: Mix and disperse the metal organic framework (ZIF-67 (CO)) powder with a particle size of 300 nm and the polyurethane emulsion WPU-125, the weight ratio of the metal organic framework (ZIF-67 (CO)) powder to the polyurethane emulsion WPU-125 is 1:50, and disperse them by ultrasonic wave for 60 minutes at a power of 2400 watts to form a polyurethane dispersion containing the metal organic framework (ZIF-67 (CO)) powder;

[0037] S2. Freeze drying: The polyurethane dispersion obtained in S1 was placed in an ultra-low temperature freezer at -80°C for 24 hours, and then the frozen polyurethane dispersion was placed in a freeze dryer at -40°C for 48 hours to obtain a metal organic framework (ZIF-67(CO)) powder with a surface decorated polyurethane;

[0038] S3. Ball milling: The metal organic framework (ZIF-67 (CO)) powder obtained in S2 was placed in a ball mill and ball milled for 60 minutes at a speed of 1000 r / min to form a metal organic framework (ZIF-67 (CO)) ultrafine powder with a surface decorated polyurethane;

[0039] S4. Configuring a coating solution: The metal organic framework (ZIF-67 (CO)) ultrafine powder of the surface-decorated polyurethane obtained in S3 was mixed with a hydrophilic polyurethane elastomer TPU EHT-1190 and N,N-dimethylformamide in a weight ratio of 1:20:100 to prepare a coating solution;

[0040] S5. Dipping and drying: the weight is 25g / m 2 The polytetrafluoroethylene microporous membrane is immersed in the coating solution obtained in S4, placed under a vacuum degree of 0.1 MPa for 30 minutes, and then dried by a padding car. The padding pressure is 0.5 MPa, the drying temperature is 200°C, the drying time is 10 minutes, and then rolled up to obtain an antibacterial, waterproof and breathable clothing membrane.

[0041] Example 3

[0042] The present invention provides a method for preparing an antibacterial, waterproof and breathable clothing membrane, which comprises the following steps:

[0043] S1. Mixing: Mix and disperse the metal organic framework (ZIF-67 (CO)) powder with a particle size of 450 nm and the polyurethane emulsion FS-2040E, the weight ratio of the metal organic framework (ZIF-67 (CO)) powder to the polyurethane emulsion FS-2040E is 1:30, and disperse with ultrasound for 100 minutes at a power of 2400 watts to form a polyurethane dispersion containing the metal organic framework (ZIF-67 (CO)) powder;

[0044] S2. Freeze drying: The polyurethane dispersion obtained in S1 was placed in an ultra-low temperature freezer at -80°C for 24 hours, and then the frozen polyurethane dispersion was placed in a freeze dryer at -40°C for 48 hours to obtain a metal organic framework (ZIF-67(CO)) powder with a surface decorated polyurethane;

[0045] S3. Ball milling: The metal organic framework (ZIF-67 (CO)) powder obtained in S2 was placed in a ball mill and ball milled for 70 minutes at a speed of 900 r / min to form a metal organic framework (ZIF-67 (CO)) ultrafine powder with a surface decorated with polyurethane;

[0046] S4. Configuring a coating solution: The surface-decorated polyurethane metal organic framework (ZIF-67 (CO)) ultrafine powder obtained in S3 was mixed with a hydrophilic polyurethane elastomer TPU EHT-1180A and N-methylpyrrolidone in a weight ratio of 1:12:100 to prepare a coating solution;

[0047] S5. Impregnation and drying: the weight is 10g / m 2 The polytetrafluoroethylene microporous membrane is immersed in the coating solution obtained in S4, and placed under a vacuum degree of 0.06MPa for 50 minutes. After impregnation, it is rolled and dried by a padder with a pressure of 0.3MPa, a drying temperature of 185°C, and a drying time of 16 minutes. Then it is rolled up to obtain an antibacterial, waterproof and breathable clothing membrane.

[0048] Example 4

[0049] The present invention provides a method for preparing an antibacterial, waterproof and breathable clothing membrane, which comprises the following steps:

[0050] S1. Mixing: Mix and disperse the metal organic framework (ZIF-67 (CO)) powder with a particle size of 700 nm and the polyurethane emulsion AH-K100-1, the weight ratio of the metal organic framework (ZIF-67 (CO)) powder to the polyurethane emulsion AH-K100-1 is 1:40, and disperse with ultrasound for 90 minutes at a power of 2400 watts to form a polyurethane dispersion containing the metal organic framework (ZIF-67 (CO)) powder;

[0051] S2. Freeze drying: The polyurethane dispersion obtained in S1 was placed in an ultra-low temperature freezer at -80°C for 24 hours, and then the frozen polyurethane dispersion was placed in a freeze dryer at -40°C for 48 hours to obtain a metal organic framework (ZIF-67(CO)) powder with a surface decorated polyurethane;

[0052] S3. Ball milling: The metal organic framework (ZIF-67 (CO)) powder obtained in S2 was placed in a ball mill and ball milled for 90 minutes at a speed of 800 r / min to form a metal organic framework (ZIF-67 (CO)) ultrafine powder with a surface decorated with polyurethane;

[0053] S4. Configuring a coating solution: The surface-decorated polyurethane metal organic framework (ZIF-67 (CO)) ultrafine powder obtained in S3 was mixed with a hydrophilic polyurethane elastomer TPU EHT-1185A and N,N-dimethylformamide in a weight ratio of 1:18:100 to prepare a coating solution;

[0054] S5. Impregnation and drying: the weight is 20g / m 2 The polytetrafluoroethylene microporous membrane is immersed in the coating solution obtained in S4, and placed under a vacuum degree of 0.08MPa for 45 minutes. After impregnation, it is rolled and dried by a padder with a pressure of 0.35MPa, a drying temperature of 190°C, and a drying time of 14 minutes. Then it is rolled up to obtain an antibacterial, waterproof, and breathable clothing membrane.

[0055] Comparative Example 1

[0056] The difference between this comparative example and Example 1 is that there are no steps S1, S2, and S3. When preparing the coating solution, a metal organic framework (ZIF-67(CO)) powder with a particle size of 800 nm is mixed with a hydrophilic polyurethane elastomer TPU EHT-1190 and N,N-dimethylacetamide in a mass ratio of 1:10:100 to prepare the coating solution.

[0057] Comparative Example 2

[0058] The difference between this comparative example and Example 1 is that there is no S3 step, and when preparing the coating solution in S4, the metal organic framework (ZIF-67(CO)) powder of surface-modified polyurethane obtained by freeze-drying in S2 is mixed with the hydrophilic polyurethane elastomer TPU EHT-1190 and N,N-dimethylacetamide in a mass ratio of 1:10:100 to prepare the coating solution.

[0059] Comparative Example 3

[0060] The difference between this comparative example and Example 1 is that in step S5, the polytetrafluoroethylene microporous membrane is immersed in the laminating solution, placed under normal pressure for 60 minutes, then rolled by a padder and dried, and then rolled to prepare the antibacterial, waterproof and breathable clothing membrane.

[0061] Comparative Example 4

[0062] The difference between this comparative example and Example 1 is that there are no steps S1, S2 and S3, and when preparing the coating solution, the hydrophilic polyurethane elastomer TPU EHT-1190 and N,N-dimethylacetamide are mixed in a mass ratio of 1:10 to prepare the coating solution.

[0063] Comparative Example 5

[0064] This comparative example directly uses a polytetrafluoroethylene microporous membrane with a gram weight of 5 g / m2 as the waterproof and breathable clothing membrane.

[0065] The finished products obtained from Examples 1-4 and Comparative Examples 1-5 were subjected to performance tests:

[0066] 1. Water pressure resistance test

[0067] The YG(B)812T water permeability tester was used to test the hydrostatic pressure resistance of the membrane in accordance with the GB / T4744-2013 "Testing and evaluating the waterproof performance of textiles" test standard. The washing procedure was tested in accordance with the GB / T8629-2017 "Household washing and drying procedures for textile testing" test standard, using standard detergent 4 and A hanging drying conditions.

[0068] 2. Water vapor permeability test

[0069] The test was carried out in accordance with the test standard GB / T 12704.2-2009 “Test method for water vapor permeability of textile fabrics”.

[0070] 3. Antibacterial performance test

[0071] The present invention selects Escherichia coli, Staphylococcus aureus and Candida albicans as representatives, and performs the test with reference to the test standard FZ / T 73023-2006 "Antibacterial Knitwear".

[0072] 4. Mechanical properties test

[0073] The tensile properties and elongation at break of the antibacterial, waterproof and breathable clothing membrane in this application were tested according to the method in GB / T 1040.3-2006 "Determination of tensile properties of plastics". The test sample width was 20 mm, length was 100 mm, clamping distance was 50 mm, tensile speed was 100 mm / min, each group of samples was tested five times, and the average value was taken.

[0074] The test results are shown in the following table:

[0075] Table 1 Water pressure resistance and moisture permeability test results

[0076]

[0077] Table 2 Antibacterial performance test results

[0078]

[0079] Table 3 Mechanical properties test results

[0080] Average breaking strength (N) Average elongation (%) Example 1 11.65 90.61 Example 2 12.22 93.55 Example 3 12.19 90.73 Example 4 11.78 91.52 Comparative Example 1 11.50 93.38 Comparative Example 2 11.89 90.24 Comparative Example 3 7.34 90.80 Comparative Example 4 11.56 91.62 Comparative Example 5 6.20 90.07

[0081] Analysis of test results:

[0082] In combination with Example 1 and Comparative Example 1, the antibacterial performance of Example 1 is better than that of Comparative Example 1. The reason is that in Example 1, ZIF-67 (Co) powder is mixed with polyurethane emulsion WPU-3015, dispersed by ultrasonic wave, and a polyurethane dispersion containing ZIF-67 (Co) powder is formed. Then, ZIF-67 (Co) powder is prepared into ZIF-67 (Co) ultrafine powder with surface modified polyurethane by freeze drying and ball milling, which helps ZIF-67 (Co) powder to be evenly dispersed in polyurethane coating liquid. In Comparative Example 1, there are no steps such as ultrasonic dispersion, freeze drying and ball milling, and ZIF-67 (Co) powder is directly added to polyurethane coating liquid. Since the surface tension of ZIF-67 (Co) powder and the surface tension of polyurethane coating liquid are quite different, the compatibility of the two is poor, and ZIF-67 (Co) powder is unevenly dispersed in the coating liquid and agglomerated, resulting in a decrease in antibacterial performance.

[0083] Comparing Example 1 with Comparative Example 2, the antibacterial performance of Example 1 is better than that of Comparative Example 2. The reason is that in Comparative Example 2, the ZIF-67(Co) powder with surface modified polyurethane obtained by freeze-drying was not ball-milled into ultrafine powder. The large particle size of the powder will cause uneven dispersion and agglomeration in the coating solution, and the antibacterial performance is therefore reduced.

[0084] Comparing Example 1 with Comparative Example 3, the moisture permeability of Example 1 is higher than that of Comparative Example 3. The reason may be that under vacuum negative pressure conditions, the polyurethane coating liquid can penetrate into the interior of the polytetrafluoroethylene membrane and wrap on the fiber net. The micropores inside the membrane are not completely filled, and a part of the pores are retained. Water vapor can pass through the pores. The diffusion of water vapor belongs to the micropore diffusion mechanism, so the moisture permeability is large; while under normal pressure conditions, the surface tension of the polyurethane coating liquid of Comparative Example 1 is different from that of the polytetrafluoroethylene membrane, resulting in the polyurethane coating liquid can only adhere to the surface of the polytetrafluoroethylene membrane to form a dense polyurethane layer. The water vapor diffusion mechanism is dissolution diffusion, so the moisture permeability is small. Moreover, since the polyurethane coating liquid cannot penetrate into the pores of the polytetrafluoroethylene membrane, the tensile strength of the membrane is low.

[0085] Comparing Example 1 with Comparative Example 4, the antibacterial performance of Example 1 is much better than that of Comparative Example 4. This is because the ZIF-67 (Co) ultrafine powder with surface modified polyurethane added in Example 1 can absorb visible light, excite internal electrons, and jump from the valence band to the conduction band to form electron-hole pairs. The electron-hole pairs further undergo redox reactions to produce hydroxyl radicals and superoxide radicals, which can kill microorganisms such as bacteria and viruses adsorbed on the waterproof and breathable membrane, and have excellent antibacterial properties.

[0086] By comparing Example 1 with Comparative Example 5, the antibacterial performance, water pressure resistance and mechanical strength after washing of Example 1 are better than those of Comparative Example 5. The reason is that in Example 1, under vacuum negative pressure conditions, the polyurethane coating liquid can penetrate into the interior of the polytetrafluoroethylene membrane and wrap around the fiber net, thereby increasing the tensile strength of the polytetrafluoroethylene fiber net and greatly improving the mechanical strength of the polytetrafluoroethylene membrane. The improvement in the mechanical strength of the membrane can prevent it from breaking after 20 times of water washing and has a higher water pressure resistance. In addition, the addition of ZIF-67 (Co) ultrafine powder with surface-modified polyurethane to the coating liquid failed to improve the antibacterial performance of the waterproof and breathable membrane.

[0087] The embodiments of the present invention are described in detail above with reference to the accompanying drawings. However, the present invention is not limited to the above embodiments. Various changes can be made within the knowledge scope of ordinary technicians in the technical field without departing from the purpose of the present invention.

Claims

1. A method for preparing an antibacterial, waterproof and breathable clothing membrane, characterized in that: The following steps are involved: S1. Mixing: mixing and dispersing the metal organic framework powder and the polyurethane aqueous emulsion to form a polyurethane dispersion containing the metal organic framework powder; S2. Freeze drying: The polyurethane dispersion obtained in S1 is placed in an ultra-low temperature of -80°C and then placed in a freeze dryer for freeze drying to obtain a metal organic framework powder with a surface decorated with polyurethane; S3. Ball milling: The metal organic framework powder obtained in S2 is placed in a ball mill, and after ball milling, a metal organic framework ultrafine powder with a surface decorated with polyurethane is formed; S4. Configuring a coating solution: The metal organic framework ultrafine powder of the surface-decorated polyurethane obtained in S3 is mixed with a hydrophilic polyurethane elastomer and a solvent in a certain proportion to prepare a coating solution; S5. Impregnation and drying: The polytetrafluoroethylene microporous membrane is impregnated in the coating solution obtained in S4, and after impregnation, it is pressed by a padder and then dried, and then rolled up to obtain an antibacterial, waterproof and breathable clothing membrane.

2. The method for preparing an antibacterial, waterproof and breathable clothing membrane according to claim 1, characterized in that: The particle size of the metal organic framework powder in S1 is 300-800 nm, the polyurethane aqueous emulsion is one of polyurethane emulsion WPU-3015, polyurethane emulsion WPU-125, polyurethane emulsion FS-2040E, polyurethane emulsion AH-K100-1 and polyurethane emulsion WPU-1631, and the weight ratio of the metal organic framework powder to the polyurethane aqueous emulsion is 1:20-50.

3. The method for preparing an antibacterial, waterproof and breathable clothing membrane according to claim 1, characterized in that: The dispersion in S1 is achieved by ultrasound, the time of the ultrasound dispersion is 60 to 120 minutes, and the power of the ultrasound is 2400 watts.

4. The method for preparing an antibacterial, waterproof and breathable clothing membrane according to claim 1, characterized in that: The freezing time in S2 is 24 hours, the temperature of the freeze dryer is minus 40° C., and the drying time is 48 hours.

5. The method for preparing an antibacterial, waterproof and breathable clothing membrane according to claim 1, characterized in that: The weight ratio of the metal organic framework ultrafine powder of the surface decorated polyurethane in S4, the hydrophilic polyurethane elastomer and the solvent is 1:10 to 20:100, and the hydrophilic polyurethane elastomer is one of polyurethane TPU EHT-1190, polyurethane TPU EHT-1195, polyurethane TPU 1180A, polyurethane TPU 1185A, polyurethane TPU260D and polyurethane TPU270D.

6. The method for preparing an antibacterial, waterproof and breathable clothing membrane according to claim 1, characterized in that: The immersion in S5 is carried out under vacuum conditions, the vacuum degree is 0.05-0.1 MPa, and the weight of the polytetrafluoroethylene microporous membrane in S5 is 5-25 g / m 2 , the immersion time is 30 to 60 minutes.

7. The method for preparing an antibacterial, waterproof and breathable clothing membrane according to claim 1, characterized in that: The pressure of the rolling mill in S5 is 0.2-0.5 MPa, the temperature of the drying is 180° C.-200° C., and the drying time is 10-20 minutes.

8. The method for preparing an antibacterial, waterproof and breathable clothing membrane according to claim 1, characterized in that: The solvent in S4 is one of N,N-dimethylacetamide, N,N-dimethylformamide and N-methylpyrrolidone.

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