Breathable and moisture-permeable composite TPU material and preparation method thereof

Abstract

The application provides a breathable and moisture-permeable composite TPU material and a preparation method thereof, and comprises the following steps: taking TPU, adding mixed solvent and stirring, adding silicon oil to obtain an inner layer spinning solution; preparing an inner layer hydrophobic modified TPU film through an electrostatic spinning process; adding a mixture of hydrophilic polyacrylonitrile and TPU into N,N-dimethylformamide solvent and stirring to obtain a mixed solution; adding porous water-absorbing particles, syringopicroside and chitosan, and uniformly mixing to obtain an outer layer spinning solution; using an electrostatic spinning device to continuously spin the outer layer water-absorbing film on the surface of the hydrophobic modified TPU film to obtain a composite film; and finally obtaining the breathable and moisture-permeable composite TPU material through intermittent plasma treatment. The application adopts a double-layer structure, the inner layer is a hydrophobic modified TPU film, and the outer layer is a water-absorbing film; moisture can be transferred from the inner layer hydrophobic modified TPU film to the outer layer water-absorbing film in one direction; when applied to sports clothes, sweat can be guided out from the inside to the outside, the inside is kept dry and comfortable, and the outer layer absorbs the guided-out sweat and volatilizes and dries.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of functional materials, in particular to a breathable and moisture-permeable composite TPU material and a preparation method thereof. BACKGROUND

[0002] People's requirements for clothing are two aspects: aesthetics and function. To achieve these two requirements, there are only three elements: style, color and material. With the development of the times and the progress of culture, people's aesthetic concept has changed a lot. Cultural creativity has driven technological innovation, and clothing has gone through a development process from conservative to open, from open to practical, and from practical to scientific and technological integration. The function continues to improve. In terms of materials, what the current clothing material manufacturers are pursuing is not to replace the shortcomings of natural materials, but to create completely new materials to achieve functions and styles that any natural material cannot achieve. People's concern about sports clothes is also because of its great charm.

[0003] Whether it is professional or public sports, sports clothes are essential. People's concern for health makes sports not only a fashion, but also a necessity in life, and the status of sports clothes has also risen accordingly. With the improvement of people's living standards and the emphasis on sports, ordinary people have increasingly high requirements for sports clothes. Because of this, sports clothes have provided great business opportunities for the clothing industry. Sports clothes should meet the following requirements: 1. Keep dry (moisture-permeable and quick-drying); 2. Breathability (i.e. comfort); 3. Antibacterial property; 4. Meet the aesthetic needs. In order to meet the above requirements, research units and companies are making different research and development efforts. SUMMARY

[0004] The technical problem to be solved is to provide a breathable and moisture-permeable composite TPU material and a preparation method thereof, which adopts a double-layer structure, the inner layer is a hydrophobic modified TPU film, and the outer layer is a water-absorbing film. Water can be transferred from the inner hydrophobic modified TPU film to the outer water-absorbing film in one direction. When applied to sports clothes, sweat can be directed out from the inside, keeping the inside dry and comfortable, and the outer layer can absorb the directed-out sweat and volatilize dry.

[0005] The technical scheme is a breathable and moisture-permeable composite TPU material, characterized in that: the breathable and moisture-permeable composite TPU material is a double-layer structure, the inner layer is a hydrophobic modified TPU film, and the outer layer is a water-absorbing film.

[0006] Further, the pore size of the hydrophobic modified TPU film is ≤500 nm; and the pore size of the water-absorbing film is ≤70 nm.

[0007] Further, the hydrophilic film is composed of an antibacterial component, a hydrophilic polyacrylonitrile, and porous water-absorbing particles.

[0008] The preparation method of the breathable and moisture-permeable composite TPU material is characterized by comprising the following steps:

[0009] S1: Take 18 parts of TPU, add 80-90 parts of mixed solvent of N,N-dimethylformamide and tetrahydrofuran with a mass ratio of 1:1, stir for 2-4 h, add 1-3 parts of silicone oil, and obtain an inner layer spinning solution;

[0010] S2: Prepare an inner layer hydrophobic modified TPU film through an electrostatic spinning process;

[0011] S3: Add 10 parts of a mixture of hydrophilic polyacrylonitrile and TPU to 70-80 parts of N,N-dimethylformamide solvent, stir for 2-4 h, and obtain a mixed solution;

[0012] S4: Add 8-10 parts of porous water-absorbing particles, 1-2 parts of syringic acid, and 0.5 parts of chitosan, mix uniformly, and obtain an outer layer spinning solution;

[0013] S5: Use an electrostatic spinning device to continue spinning the outer layer water-absorbing film on the surface of the hydrophobic modified TPU film, and obtain a composite film;

[0014] S6: Take down the composite film, use an intermittent plasma treatment, the gas flow is 5 mL / min, the treatment power is 75 W, the treatment time is 10 s, the stop time is 10 s, and 5 cycles are performed, and finally obtain a breathable and moisture-permeable composite TPU material.

[0015] Further, the electrospinning conditions in S2 are as follows: the spinning voltage is 20 kV, the receiving distance is 18 cm, the receiving roller speed is 150 r / min, the flow rate is 0.08 mL / min, and the spinning time is 1-3 h.

[0016] Further, the mass ratio of the hydrophilic TPU and the polyacrylonitrile is 3:7.

[0017] Further, the preparation method of the porous water-absorbing particles is as follows:

[0018] S51: Mix 20 parts of polyacrylamide solution and straw cellulose solution with a mass fraction of 10% to obtain a mixed solution; S52: Take 2 parts of yeast and glucose with a mass ratio of 2:(2-4), add 10 parts of distilled water, and obtain a yeast activation solution; S53: Mix the yeast activation solution and the mixed solution, stir uniformly, place in a constant-temperature 32℃ water bath for foaming for 1-2 h, move to a low-temperature refrigerator for rapid shaping, and perform freeze-thaw cycling for 5 times and then perform dialysis with ultrapure water;

[0019] S54: Freeze-dry and crush to obtain the porous water-absorbing particles.

[0020] Further, the electrospinning condition in S5 is: spinning voltage 20kV, receiving distance 18cm, receiving roller rotating speed 100r / min, flow rate 0.1mL / min, and spinning time 1-3h.

[0021] Further, the mass ratio of the polyacrylamide solution and the straw cellulose solution is 5:(4-8).

[0022] Further, the porous water-absorbing particle has a particle size of ≤0.05μm.

[0023] Beneficial effects:

[0024] 1. The material of the application adopts a double-layer structure, the inner layer is a hydrophobic modified TPU film, and the outer layer is a water-absorbing film, water can be transferred from the inner layer of the hydrophobic modified TPU film to the outer layer of the water-absorbing film in one direction, when applied to sports clothes, sweat can be guided out from the inside to the outside, keeping the inside dry and comfortable, and the outer layer absorbs the guided-out sweat and volatilizes to dry.

[0025] 2. The application modifies TPU with low-surface-energy silicone oil and adopts an electrospinning structure to build a rough surface and improve the hydrophobic effect.

[0026] 3. The application adopts yeast to ferment a mixed solution of polyacrylamide solution and straw cellulose, the yeast cells form bubble nuclei, CO2 is produced by metabolism, the bubble holes grow, and new bubble nuclei are continuously formed, the adjacent bubble holes are extruded, polymerization and rupture occur, and finally a porous structure is formed; meanwhile, the hydrogen bond force between a large number of hydroxyl groups on the polyacrylamide and the straw cellulose is used to effectively crosslink them, the foaming matrix solution is gelled, the bubble holes are fixed, and finally a porous water-absorbing material is formed.

[0027] 4. The application adopts intermittent plasma treatment, and the air permeability effect is better than that of continuous plasma treatment, which may be because the continuous plasma treatment produces bombardment on the material, so that the material does not have an intermittent recovery process, thereby causing damage to the material and affecting its air permeability.

[0028] 5. The application adopts the form of natural antibacterial ingredient eugenol and chitosan compound, which is a natural ingredient and will not have adverse effects on the human body due to ingredient elution, and chitosan has antibacterial properties, can maintain the stability of eugenol, and has firmness in combination with the material, so the antibacterial effect is long-lasting. DETAILED DESCRIPTION

[0029] Example 1

[0030] The preparation method of the porous water-absorbing particle is as follows:

[0031] S51: 20 parts of polyacrylamide solution and straw cellulose solution with a mass fraction of 10% were mixed, the mass ratio of the polyacrylamide solution and the straw cellulose solution was 5:4, and a mixed solution was obtained;

[0032] S52: 2 parts of yeast and glucose with a mass ratio of 2:3 were taken, and 10 parts of distilled water was added to obtain a yeast activation solution;

[0033] S53: The yeast activation solution was blended with the mixed solution, stirred uniformly, placed in a constant-temperature 32°C water bath for foaming for 1.5 h, moved to a low-temperature refrigerator for rapid shaping, subjected to a freeze-thaw cycle for 5 times, and then subjected to dialysis with ultrapure water;

[0034] S54: Freeze-drying was performed, and the porous water-absorbing particles with a particle size of ≤0.05 μm were obtained by crushing.

[0035] Example 2

[0036] The preparation method of the porous water-absorbing particles is as follows:

[0037] S51: 20 parts of polyacrylamide solution and straw cellulose solution with a mass fraction of 10% were mixed, the mass ratio of the polyacrylamide solution and the straw cellulose solution was 5:6, and a mixed solution was obtained;

[0038] S52: 2 parts of yeast and glucose with a mass ratio of 2:3 were taken, and 10 parts of distilled water was added to obtain a yeast activation solution;

[0039] S53: The yeast activation solution was blended with the mixed solution, stirred uniformly, placed in a constant-temperature 32°C water bath for foaming for 1.5 h, moved to a low-temperature refrigerator for rapid shaping, subjected to a freeze-thaw cycle for 5 times, and then subjected to dialysis with ultrapure water;

[0040] S54: Freeze-drying was performed, and the porous water-absorbing particles with a particle size of ≤0.05 μm were obtained by crushing.

[0041] Example 3

[0042] The preparation method of the porous water-absorbing particles is as follows:

[0043] S51: 20 parts of polyacrylamide solution and straw cellulose solution with a mass fraction of 10% were mixed, the mass ratio of the polyacrylamide solution and the straw cellulose solution was 5:8, and a mixed solution was obtained;

[0044] S52: 2 parts of yeast and glucose with a mass ratio of 2:3 were taken, and 10 parts of distilled water was added to obtain a yeast activation solution;

[0045] S53: The yeast activation solution was blended with the mixed solution, stirred uniformly, placed in a constant-temperature 32°C water bath for foaming for 1.5 h, moved to a low-temperature refrigerator for rapid shaping, subjected to a freeze-thaw cycle for 5 times, and then subjected to dialysis with ultrapure water;

[0046] S54: Freeze-drying, broken to get porous water-absorbing particles with particle size ≤0.05 μm.

[0047] Example 4

[0048] The preparation method of the porous water-absorbing particles is as follows:

[0049] S51: Take 20 parts of polyacrylamide solution and straw cellulose solution with a mass fraction of 10%, and the mass ratio of polyacrylamide solution to straw cellulose solution is 5:6, to obtain a mixed solution;

[0050] S52: Take 2 parts of yeast and glucose with a mass ratio of 2:2, add 10 parts of distilled water, and obtain a yeast activation solution;

[0051] S53: Mix the yeast activation solution with the mixed solution, stir uniformly, place in a constant temperature water bath at 32°C for foaming for 1.5 h, move to a low-temperature refrigerator for rapid setting, and after 5 cycles of freeze-thaw, use ultrapure water for dialysis;

[0052] S54: Freeze-drying, broken to get porous water-absorbing particles with particle size ≤0.05 μm.

[0053] Example 5

[0054] The preparation method of the porous water-absorbing particles is as follows:

[0055] S51: Take 20 parts of polyacrylamide solution and straw cellulose solution with a mass fraction of 10%, and the mass ratio of polyacrylamide solution to straw cellulose solution is 5:6, to obtain a mixed solution;

[0056] S52: Take 2 parts of yeast and glucose with a mass ratio of 2:4, add 10 parts of distilled water, and obtain a yeast activation solution;

[0057] S53: Mix the yeast activation solution with the mixed solution, stir uniformly, place in a constant temperature water bath at 32°C for foaming for 1.5 h, move to a low-temperature refrigerator for rapid setting, and after 5 cycles of freeze-thaw, use ultrapure water for dialysis;

[0058] S54: Freeze-drying, broken to get porous water-absorbing particles with particle size ≤0.05 μm.

[0059] The porosity is determined by solvent displacement method;

[0060] Determination of water absorption: accurately weigh the porous water-absorbing particles (W d ), add deionized water at 25°C, and stand for water absorption, take out every certain time, and wipe the surface moisture with wet filter paper, and accurately weigh (W t), and this is repeated until the swelling equilibrium is reached, and the degree of swelling is calculated according to the following formula. The maximum degree of swelling is the degree of swelling at the swelling equilibrium, and is the same as the value of the equilibrium swelling degree.

[0061]

[0062] In the formula: W d - the dry weight of the sample, g; W t - the mass of the sample at time t, g.

[0063] Porosity (%) Swelling degree (%) Example 1 91.6 1614.09 Example 2 92.1 1643.57 Example 3 92.0 1629.77 Example 4 90.6 1629.46 Example 5 91.8 1636.38

[0064] The porosity and the degree of swelling of the above-mentioned examples are compared, and the porous water-absorbing particles prepared in Example 2 are used for subsequent tests.

[0065] Example 6

[0066] A breathable and moisture-permeable composite TPU material and a preparation method thereof, characterized by comprising the following steps:

[0067] S1: Take 18 parts of TPU, add 80 parts of a mixed solvent of N,N-dimethylformamide and tetrahydrofuran with a mass ratio of 1:1, stir for 3 h, and add 2 parts of silicon oil to obtain an inner layer spinning solution;

[0068] S2: Prepare an inner layer hydrophobic modified TPU film by an electrospinning process, and the electrospinning conditions are as follows: spinning voltage 20 kV, receiving distance 18 cm, receiving roller speed 150 r / min, flow rate 0.08 mL / min, and spinning time 3 h;

[0069] S3: Add 10 parts of a mixture of hydrophilic polyacrylonitrile and TPU to 75 parts of N,N-dimethylformamide solvent, stir for 3 h to obtain a mixed solution; wherein the mass ratio of hydrophilic TPU and polyacrylonitrile is 3:7;

[0070] S4: Add 10 parts of porous water-absorbing particles, 2 parts of syringic acid, and 0.5 parts of chitosan, and mix uniformly to obtain an outer layer spinning solution; S5: Use an electrospinning device to continue spinning the outer layer water-absorbing film on the surface of the hydrophobic modified TPU film, and the electrospinning conditions are as follows: spinning voltage 20 kV, receiving distance 18 cm, receiving roller speed 100 r / min, flow rate 0.1 mL / min, and spinning time 3 h, to obtain a composite film;

[0071] S6: Take down the composite film, and use an intermittent plasma treatment, with a gas flow rate of 5 mL / min, a treatment power of 75 W, a treatment time of 10 s, a stop time of 10 s, and 5 cycles, to finally obtain a breathable and moisture-permeable composite TPU material.

[0072] The pore size of the hydrophobic modified TPU film is ≤500 nm, and the pore size of the water-absorbing film is ≤70 nm.

[0073] Example 7

[0074] A breathable and moisture-permeable composite TPU material and a preparation method thereof, characterized by comprising the following steps:

[0075] S1: Take 18 parts of TPU, add 90 parts of mixed solvent of N,N-dimethylformamide and tetrahydrofuran with a mass ratio of 1:1 and stir for 3h, add 2 parts of silicon oil to obtain an inner layer spinning solution;

[0076] S2: Prepare the inner layer hydrophobic modified TPU film by electrospinning process, and the electrospinning conditions are: spinning voltage 20kV, receiving distance 18cm, receiving roller speed 150r / min, flow rate 0.08mL / min, and spinning time 3h;

[0077] S3: Add 10 parts of a mixture of hydrophilic polyacrylonitrile and TPU to 75 parts of N,N-dimethylformamide solvent, stir for 3h to obtain a mixed solution; wherein the mass ratio of hydrophilic TPU and polyacrylonitrile is 3:7;

[0078] S4: Add 10 parts of porous water-absorbing particles, 2 parts of syringic acid and 0.5 parts of chitosan, mix uniformly to obtain an outer layer spinning solution; S5: Use an electrospinning device to continue spinning the outer layer water-absorbing film on the surface of the hydrophobic modified TPU film, and the electrospinning conditions are: spinning voltage 20kV, receiving distance 18cm, receiving roller speed 100r / min, flow rate 0.1mL / min, and spinning time 3h to obtain a composite film;

[0079] S6: Take off the composite film, and use intermittent plasma treatment, gas flow 5mL / min, treatment power 75W, treatment 10s, stop 10s, 5 cycles, finally obtain a breathable and moisture-permeable composite TPU material.

[0080] The pore size of the hydrophobic modified TPU film is ≤500nm, and the pore size of the water-absorbing film is ≤70nm.

[0081] Example 8

[0082] A breathable and moisture-permeable composite TPU material and a preparation method thereof, characterized by comprising the following steps:

[0083] S1: Take 18 parts of TPU, add 80 parts of mixed solvent of N,N-dimethylformamide and tetrahydrofuran with a mass ratio of 1:1 and stir for 3h, add 1 part of silicon oil to obtain an inner layer spinning solution;

[0084] S2: Prepare the inner layer hydrophobic modified TPU film by electrospinning process, and the electrospinning conditions are: spinning voltage 20kV, receiving distance 18cm, receiving roller speed 150r / min, flow rate 0.08mL / min, and spinning time 3h;

[0085] S3: 10 parts of a mixture of hydrophilic polyacrylonitrile and TPU were added to 75 parts of N,N-dimethylformamide solvent, stirred for 3 h to obtain a mixed solution; wherein the mass ratio of hydrophilic TPU and polyacrylonitrile was 3:7;

[0086] S4: 10 parts of porous water-absorbing particles, 2 parts of syringic acid and 0.5 parts of chitosan were added and uniformly mixed to obtain an outer layer spinning solution; S5: an electrospinning device was used to continue spinning the outer layer water-absorbing film on the surface of the hydrophobic modified TPU film, and the electrospinning conditions were as follows: spinning voltage 20 kV, receiving distance 18 cm, receiving roller speed 100 r / min, flow rate 0.1 mL / min, spinning time 3 h, to obtain a composite film;

[0087] S6: the composite film was removed and treated by intermittent plasma, with a gas flow of 5 mL / min, a treatment power of 75 W, a treatment time of 10 s, a stop time of 10 s, and 5 cycles, to finally obtain a breathable and moisture-permeable composite TPU material.

[0088] The pore size of the hydrophobic modified TPU film was ≤500 nm, and the pore size of the water-absorbing film was ≤70 nm.

[0089] Example 9

[0090] A breathable and moisture-permeable composite TPU material and a method for preparing the same, characterized by comprising the following steps:

[0091] S1: 18 parts of TPU were taken and added to 80 parts of a mixed solvent of N,N-dimethylformamide and tetrahydrofuran with a mass ratio of 1:1, stirred for 3 h, and 3 parts of silicone oil were added to obtain an inner layer spinning solution;

[0092] S2: an inner layer hydrophobic modified TPU film was prepared by electrospinning process, and the electrospinning conditions were as follows: spinning voltage 20 kV, receiving distance 18 cm, receiving roller speed 150 r / min, flow rate 0.08 mL / min, and spinning time 3 h;

[0093] S3: 10 parts of a mixture of hydrophilic polyacrylonitrile and TPU were added to 75 parts of N,N-dimethylformamide solvent, stirred for 3 h to obtain a mixed solution; wherein the mass ratio of hydrophilic TPU and polyacrylonitrile was 3:7;

[0094] S4: 10 parts of porous water-absorbing particles, 2 parts of syringic acid and 0.5 parts of chitosan were added and uniformly mixed to obtain an outer layer spinning solution; S5: an electrospinning device was used to continue spinning the outer layer water-absorbing film on the surface of the hydrophobic modified TPU film, and the electrospinning conditions were as follows: spinning voltage 20 kV, receiving distance 18 cm, receiving roller speed 100 r / min, flow rate 0.1 mL / min, spinning time 3 h, to obtain a composite film;

[0095] S6: The composite film is peeled off, and intermittent plasma treatment is performed at a gas flow rate of 5 mL / min, a treatment power of 75 W, a treatment time of 10 s, a stop time of 10 s, and 5 cycles, to finally obtain the breathable and moisture-permeable composite TPU material.

[0096] The hydrophobic modified TPU film has a pore size of ≤500 nm, and the water absorption film has a pore size of ≤70 nm.

[0097] Example 10

[0098] A breathable and moisture-permeable composite TPU material and a preparation method thereof, characterized by comprising the following steps:

[0099] S1: Take 18 parts of TPU, add 80 parts of a mixed solvent of N,N-dimethylformamide and tetrahydrofuran with a mass ratio of 1:1, stir for 3 h, and add 2 parts of silicone oil to obtain an inner layer spinning solution;

[0100] S2: An inner layer hydrophobic modified TPU film is prepared by an electrospinning process, and the electrospinning conditions are as follows: a spinning voltage of 20 kV, a receiving distance of 18 cm, a receiving roller speed of 150 r / min, a flow rate of 0.08 mL / min, and a spinning time of 3 h;

[0101] S3: Add 10 parts of a mixture of hydrophilic polyacrylonitrile and TPU to 75 parts of N,N-dimethylformamide solvent, stir for 3 h, and obtain a mixed solution; wherein the mass ratio of hydrophilic TPU and polyacrylonitrile is 3:7;

[0102] S4: Add 8 parts of porous water absorption particles, 2 parts of syringic acid, and 0.5 parts of chitosan, and mix uniformly to obtain an outer layer spinning solution;

[0103] S5: An outer layer water absorption film is continuously spun on the surface of the hydrophobic modified TPU film by using an electrospinning device, and the electrospinning conditions are as follows: a spinning voltage of 20 kV, a receiving distance of 18 cm, a receiving roller speed of 100 r / min, a flow rate of 0.1 mL / min, and a spinning time of 3 h, to obtain a composite film;

[0104] S6: The composite film is peeled off, and intermittent plasma treatment is performed at a gas flow rate of 5 mL / min, a treatment power of 75 W, a treatment time of 10 s, a stop time of 10 s, and 5 cycles, to finally obtain the breathable and moisture-permeable composite TPU material.

[0105] The hydrophobic modified TPU film has a pore size of ≤500 nm, and the water absorption film has a pore size of ≤70 nm.

[0106] Example 11

[0107] A breathable and moisture-permeable composite TPU material and a preparation method thereof, characterized by comprising the following steps:

[0108] S1: Take 18 parts of TPU, add 80 parts of mixed solvent of N,N-dimethylformamide and tetrahydrofuran with a mass ratio of 1:1 and stir for 3h, add 2 parts of silicone oil to obtain an inner layer spinning solution;

[0109] S2: The inner layer hydrophobic modified TPU film is prepared by electrospinning process, and the electrospinning conditions are as follows: spinning voltage 20kV, receiving distance 18cm, receiving roller speed 150r / min, flow rate 0.08mL / min, and spinning time 3h;

[0110] S3: Add 10 parts of hydrophilic polyacrylonitrile and TPU mixture to 75 parts of N,N-dimethylformamide solvent, stir for 3h to obtain a mixed solution; wherein the mass ratio of hydrophilic TPU and polyacrylonitrile is 3:7;

[0111] S4: Add 10 parts of porous water-absorbing particles, 1 part of syringic acid and 0.5 part of chitosan, mix uniformly to obtain an outer layer spinning solution; S5: An electrospinning device is used to continue spinning the outer layer water-absorbing film on the surface of the hydrophobic modified TPU film, and the electrospinning conditions are as follows: spinning voltage 20kV, receiving distance 18cm, receiving roller speed 100r / min, flow rate 0.1mL / min, and spinning time 3h to obtain a composite film;

[0112] S6: The composite film is removed and treated by intermittent plasma, with a gas flow of 5mL / min, a treatment power of 75W, a treatment time of 10s, a stop time of 10s, and 5 cycles, to finally obtain a breathable and moisture-permeable composite TPU material.

[0113] The pore size of the hydrophobic modified TPU film is ≤500nm, and the pore size of the water-absorbing film is ≤70nm.

[0114] Comparative Example 1

[0115] The difference between this example and Example 6 is that no silicone oil is added, specifically:

[0116] A breathable and moisture-permeable composite TPU material and a preparation method thereof, characterized by comprising the following steps:

[0117] S1: Take 18 parts of TPU, add 80 parts of mixed solvent of N,N-dimethylformamide and tetrahydrofuran with a mass ratio of 1:1 and stir for 3h, to obtain an inner layer spinning solution;

[0118] S2: The inner layer hydrophobic modified TPU film is prepared by electrospinning process, and the electrospinning conditions are as follows: spinning voltage 20kV, receiving distance 18cm, receiving roller speed 150r / min, flow rate 0.08mL / min, and spinning time 3h;

[0119] S3: 10 parts of a mixture of hydrophilic polyacrylonitrile and TPU were added to 75 parts of N,N-dimethylformamide solvent, stirred for 3 h to obtain a mixed solution; wherein the mass ratio of hydrophilic TPU and polyacrylonitrile was 3:7;

[0120] S4: 10 parts of porous water-absorbing particles, 2 parts of syringic acid and 0.5 parts of chitosan were added and uniformly mixed to obtain an outer layer spinning solution; S5: an electrospinning device was used to continue spinning the outer layer water-absorbing film on the surface of the hydrophobically modified TPU film, and the electrospinning conditions were as follows: spinning voltage 20 kV, receiving distance 18 cm, receiving roller speed 100 r / min, flow rate 0.1 mL / min, spinning time 1-3 h, to obtain a composite film;

[0121] S6: The composite film was removed and subjected to intermittent plasma treatment, with a gas flow rate of 5 mL / min, a treatment power of 75 W, a treatment time of 10 s, a stop time of 10 s, and 5 cycles, to finally obtain a breathable and moisture-permeable composite TPU material.

[0122] The pore size of the hydrophobically modified TPU film was ≤500 nm, and the pore size of the water-absorbing film was ≤70 nm.

[0123] Comparative Example 2

[0124] The difference between this example and Example 6 is that no porous water-absorbing particles are added, and the specific process is as follows:

[0125] A breathable and moisture-permeable composite TPU material and a method for preparing the same, characterized by comprising the following steps:

[0126] S1: 18 parts of TPU were taken and added to 80 parts of a mixed solvent of N,N-dimethylformamide and tetrahydrofuran with a mass ratio of 1:1, stirred for 3 h, and 2 parts of silicone oil were added to obtain an inner layer spinning solution;

[0127] S2: An inner layer hydrophobically modified TPU film was prepared by electrospinning process, and the electrospinning conditions were as follows: spinning voltage 20 kV, receiving distance 18 cm, receiving roller speed 150 r / min, flow rate 0.08 mL / min, and spinning time 3 h;

[0128] S3: 10 parts of a mixture of hydrophilic polyacrylonitrile and TPU were added to 75 parts of N,N-dimethylformamide solvent, stirred for 3 h to obtain a mixed solution; wherein the mass ratio of hydrophilic TPU and polyacrylonitrile was 3:7;

[0129] S4: 2 parts of syringic acid and 0.5 parts of chitosan were added and uniformly mixed to obtain an outer layer spinning solution;

[0130] S5: The outer water-absorbing membrane is further spun on the surface of the hydrophobic modified TPU membrane using an electrospinning device. The electrospinning conditions are: spinning voltage 20kV, receiving distance 18cm, receiving roller speed 100r / min, flow rate 0.1mL / min, and spinning time 3h to obtain a composite membrane.

[0131] S6: Peel off the composite membrane and use intermittent plasma treatment with a gas flow rate of 5 mL / min, a treatment power of 75 W, a treatment time of 10 s, a stop time of 10 s, and repeat 5 cycles to finally obtain a breathable and moisture-permeable composite TPU material.

[0132] The hydrophobic modified TPU membrane has a pore size of ≤500nm, and the water-absorbing membrane has a pore size of ≤70nm.

[0133] Comparative Example 3

[0134] The difference between this embodiment and Embodiment 6 is that it does not use intermittent plasma treatment, but uses continuous plasma treatment for 60 seconds.

[0135] Comparative Example 4

[0136] The difference between this embodiment and Embodiment 6 is that eugenol is used instead of chitosan, 2.5 parts of eugenol are added, and chitosan is not added.

[0137] Comparative Example 5

[0138] The difference between this embodiment and Embodiment 6 is that chitosan is used instead of eugenol, and 2.5 parts of chitosan are added, while eugenol is not added.

[0139] The water absorption rate is determined using the following formula:

[0140]

[0141] In the formula: W WA m0 represents the water absorption rate (%); m0 represents the mass of the dried sample (g); and m1 represents the mass of the dried sample after equilibration in 10 mL of deionized water for 2 hours (g).

[0142] The moisture permeability was determined using a water vapor transmission rate tester and calculated using the following formula:

[0143]

[0144] In the formula: R WVT Moisture permeability, g / (m 2 ·d); t is the test time, h; m is the mass change of the permeation cup, g; A is the cup opening area, m². 2 .

[0145] Air permeability test: Using a fully automatic air permeability meter, 10 locations on the sample were randomly selected for testing, and the average value of the results was taken.

[0146] Table 1

[0147] Product name Water absorption rate (%) moisture permeability (g / (m 2 ·d)) Air permeability (mm / s) Example 6 1012 1356 153.6 Example 7 996 1339 150.2 Example 8 1035 1314 156.5 Example 9 984 1366 148.9 Example 10 968 1339 154.4 Example 11 1010 1355 153.4 Comparative Example 1 1046 1187 158.9 Comparative Example 2 814 1208 148.6 Comparative Example 3 1008 1349 64.2

[0148] Antibacterial test: Staphylococcus aureus, Escherichia coli and mold were selected as test bacteria, each example material was cut into a disc with a diameter of 0.5 cm, placed on a culture medium coated with bacterial solution, and placed in a 37°C incubator for 24 h, then the growth of colonies was observed.

[0149] Table 2 Antibacterial and air permeability performance

[0150]

[0151]

Claims

1. A breathable and moisture permeable composite TPU material, characterized in that: The air-permeable and moisture-permeable composite TPU material has a double-layer structure, the inner layer is a hydrophobic modified TPU film, and the outer layer is a water absorption film; The water absorption film is composed of an antibacterial component, hydrophilic polyacrylonitrile, and porous water absorption particles; The preparation method of the porous water absorption particles is as follows: S51: 20 parts of a polyacrylamide solution and a straw cellulose solution with a mass fraction of 10% are mixed to obtain a mixed solution; S52: 2 parts of yeast and glucose with a mass ratio of 2:(2-4) are taken, 10 parts of distilled water is added, and a yeast activation solution is obtained; S53: The yeast activation solution and the mixed solution are blended and uniformly stirred, and then placed in a constant-temperature 32 DEG C water bath for foaming for 1-2 h, and then moved to a low-temperature refrigerator for rapid setting, and then subjected to freeze-thaw cycles for 5 times and then subjected to dialysis with ultrapure water; S54: Freeze-drying and crushing to obtain the porous water absorption particles.

2. The breathable and moisture-permeable composite TPU material according to claim 1, characterized in that: The hydrophobic modified TPU film has a pore size of ≤500 nm, and the water absorption film has a pore size of ≤70 nm.

3. The breathable and moisture-permeable composite TPU material according to claim 1 or 2, characterized in that: The preparation method comprises the following steps: S1: 18 parts of TPU are taken, 80-90 parts of a mixed solvent of N,N-dimethylformamide and tetrahydrofuran with a mass ratio of 1:1 is added, stirring is carried out for 2-4 h, 1-3 parts of silicone oil is added, and an inner layer spinning solution is obtained; S2: An inner layer hydrophobic modified TPU film is prepared by an electrospinning process; S3: 10 parts of a mixture of hydrophilic polyacrylonitrile and TPU is added to 70-80 parts of N,N-dimethylformamide solvent, stirring is carried out for 2-4 h, and a mixed solution is obtained; S4: 8-10 parts of porous water absorption particles, 1-2 parts of syringic acid, and 0.5 parts of chitosan are added and uniformly mixed to obtain an outer layer spinning solution; S5: An electrospinning device is used to continue spinning the outer layer water absorption film on the surface of the hydrophobic modified TPU film to obtain a composite film; S6: The composite film is removed, intermittent plasma treatment is carried out, the gas flow is 5 mL / min, the treatment power is 75 W, the treatment time is 10 s, the stop time is 10 s, 5 cycles are carried out, and finally an air-permeable and moisture-permeable composite TPU material is obtained.

4. The breathable and moisture-permeable composite TPU material according to claim 3, characterized in that: In S2, the electrospinning conditions are as follows: the spinning voltage is 20 kV, the receiving distance is 18 cm, the receiving roller speed is 150 r / min, the flow rate is 0.08 mL / min, and the spinning time is 1-3 h.

5. The breathable and moisture permeable composite TPU material according to claim 3, characterized in that: In S3, the mass ratio of hydrophilic polyacrylonitrile to TPU is 3:

7.

6. The breathable and moisture-permeable composite TPU material according to claim 3, characterized in that: In S5, the electrospinning conditions are as follows: the spinning voltage is 20 kV, the receiving distance is 18 cm, the receiving roller speed is 100 r / min, the flow rate is 0.1 mL / min, and the spinning time is 1-3 h.

7. The breathable and moisture-permeable composite TPU material according to claim 1, characterized in that: In S51, the mass ratio of the polyacrylamide solution to the straw cellulose solution is 5:(4-8).

8. The breathable and moisture-permeable composite TPU material according to claim 1, characterized in that: The particle size of the porous water absorption particles is ≤0.05 μm.

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