Waterproof moisture-permeable heat-preservation durable film as well as preparation method and application thereof

Abstract

The invention relates to a waterproof moisture-permeable heat-preservation durable film as well as a preparation method and application thereof. The waterproof moisture-permeable heat-preservation durable film comprises an electrostatic spinning film and a coating, the electrostatic spinning membrane is obtained through silver stamping treatment. According to the waterproof and moisture-permeable heat-preservation durable film, silver stamping treatment and coating reinforcement are carried out on the electrostatic spinning film, so that the waterproof and moisture-permeable heat-preservation durable film has excellent durability and high practicability while having waterproof and moisture-permeable performance.

Description

Technical Field

[0001] This invention relates to the field of functional materials technology, and in particular to a waterproof, breathable, heat-insulating, and durable membrane, its preparation method, and its application. Background Technology

[0002] Waterproof and breathable membranes are commonly used functional materials, typically made from high-molecular waterproof materials, such as polyurethane (TPU, thermoplastic polyurethane elastomer rubber) as the main material, with hydrophilic groups incorporated. Additionally, waterproof and breathable membranes are also made from materials such as polytetrafluoroethylene (PTFE) and polyurethane (PU). Due to their unique performance characteristics, waterproof and breathable membranes are frequently used in the manufacture of outdoor sportswear (such as waterproof jackets, cold-weather clothing, and mountaineering clothing), work protective clothing, and medical surgical gowns. These garments not only effectively block the intrusion of external moisture and dirt but also maintain internal air circulation and moisture expulsion, thus providing optimal comfort and protection. Waterproof and breathable membranes are usually manufactured using coating, lamination, or electrospinning processes. However, when using electrospinning to prepare polyurethane-based electrospun membranes, due to the material's molding characteristics, they often suffer from poor durability and susceptibility to scratches.

[0003] The prior art CN2666223Y discloses a waterproof and breathable membrane material. Although the waterproof and breathable membrane sole of this patent has the advantages of being waterproof, odorproof, quick to wick away sweat and moisture, effectively keeping the inside of the shoe dry and hygienic, and having an attractive appearance and simple structure, it does not clearly explain its durability. The waterproof and breathable performance may decrease after long-term use.

[0004] Existing technology CN104513472A discloses a waterproof and breathable membrane and its applications. This waterproof and breathable membrane is mainly formed from water-based polyurethane resin and chitosan, and has high waterproof and breathable properties. Moreover, the raw materials are environmentally friendly and pollution-free, and it can be used in work clothes, sportswear, mountaineering clothing, etc. However, it does not focus on solving the problem of insufficient durability in practical applications, such as performance changes after long-term wear and washing.

[0005] Therefore, developing a thermal insulation membrane that combines good waterproof and breathable properties with excellent durability remains a pressing issue in this field. Summary of the Invention

[0006] To address the aforementioned technical problems, this invention provides a waterproof, breathable, heat-insulating, and durable membrane, its preparation method, and its applications. The waterproof, breathable, heat-insulating, and durable membrane is obtained by hot-stamping and coating reinforcement on an electrospun membrane, enabling it to possess both waterproof and breathable properties as well as excellent durability.

[0007] To achieve this objective, the present invention adopts the following technical solution:

[0008] In a first aspect, the present invention provides a waterproof, breathable, heat-insulating, and durable membrane, the waterproof, breathable, heat-insulating, and durable membrane comprising an electrospun membrane and a coating; the electrospun membrane is obtained by hot stamping.

[0009] The waterproof, breathable, heat-insulating, and durable membrane of this invention is obtained by hot-stamping and coating reinforcement on an electrospun membrane. This process enhances its durability while maintaining its waterproof and breathable properties, thereby improving its practicality. The hot-stamping treatment not only improves the heat reflectivity of the resulting membrane, thus enhancing its warmth retention, but also improves its waterproof and abrasion resistance, further enhancing its durability. Furthermore, the reinforcement coating after hot-stamping reduces the powder shedding rate of the hot-stamped membrane after washing, improving the abrasion resistance of the membrane and its surface, and also enhancing its waterproofness. This results in a waterproof, breathable, heat-insulating, and durable membrane with excellent durability.

[0010] Preferably, the thickness of the coating is 0.001-0.01μm, for example, it can be 0.001μm, 0.002μm, 0.003μm, 0.004μm, 0.005μm, 0.006μm, 0.007μm, 0.008μm, 0.009μm or 0.01μm, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0011] In this invention, setting a specific coating thickness can significantly improve the durability of the resulting electrospun membrane while ensuring its excellent waterproof and breathable properties. Furthermore, when the coating thickness is between 0.001 and 0.01 μm, the waterproof performance of the resulting waterproof, breathable, and heat-insulating durable membrane gradually increases with increasing thickness. However, when the thickness is below 0.001 μm, the durability of the membrane is affected, making it prone to wear and resulting in lower waterproof performance. When the thickness is above 0.01 μm, the breathability of the membrane deteriorates, affecting comfort.

[0012] Preferably, the raw material for the coating is adhesive.

[0013] Preferably, the adhesive comprises polyurethane adhesive.

[0014] Preferably, the viscosity of the polyurethane adhesive is 500-50000 mPa·s, for example, it can be 500 mPa·s, 1000 mPa·s, 5000 mPa·s, 10000 mPa·s, 20000 mPa·s, 30000 mPa·s, 40000 mPa·s or 50000 mPa·s, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0015] Preferably, the weight-average molecular weight of the polyurethane adhesive is 2000-50000 g / mol, for example, it can be 2000 g / mol, 4000 g / mol, 6000 g / mol, 8000 g / mol, 10000 g / mol, 20000 g / mol, 30000 g / mol, 40000 g / mol or 50000 g / mol, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0016] Preferably, the glass transition temperature of the polyurethane adhesive is -60 to 0°C, for example, it can be -60°C, -50°C, -40°C, -30°C, -20°C, -10°C or 0°C, and specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0017] Preferably, the vehicle speed during the coating preparation process is 15-30 m / min, for example, it can be 15 m / min, 16 m / min, 18 m / min, 20 m / min, 22 m / min, 24 m / min, 26 m / min, 28 m / min or 30 m / min, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0018] Preferably, the drying temperature during the coating preparation process is 150-170℃, for example, it can be 150℃, 152℃, 154℃, 156℃, 158℃, 160℃, 162℃, 164℃, 166℃, 168℃ or 170℃, as well as specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0019] Preferably, the drying time during the coating preparation process is 1-2 min, for example, it can be 1 min, 1.1 min, 1.2 min, 1.3 min, 1.4 min, 1.5 min, 1.6 min, 1.7 min, 1.8 min, 1.9 min or 2 min, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0020] Preferably, the drying temperature in the hot stamping process is 80-85℃, for example, it can be 80℃, 81℃, 82℃, 83℃, 84℃ or 85℃, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0021] In this invention, the drying temperature during the hot stamping process is preferably 80-85℃, which allows for secondary adhesion between the fibers in the electrospun film, thereby further improving its waterproof performance. When the drying temperature is below 80℃, the water-based acrylic emulsion is not dried sufficiently, and the fibers in the electrospun film cannot achieve good secondary adhesion, resulting in incomplete film formation and insufficient adhesion, thus reducing the waterproof performance of the obtained waterproof, breathable, heat-insulating, and durable film. When the drying temperature is too high, the water-based acrylic emulsion dries too quickly, causing defects (cracks, bubbles) in the electrospun film, which makes the obtained electrospun film layer brittle, also reducing the waterproof performance of the obtained waterproof, breathable, heat-insulating, and durable film.

[0022] Preferably, the raw material for the hot stamping treatment includes an aqueous acrylic emulsion.

[0023] Preferably, the aqueous acrylic emulsion includes acrylic emulsion and / or fluoroacrylic emulsion.

[0024] Preferably, the viscosity of the aqueous acrylic emulsion is 2000-3000 mPa·s, for example, it can be 2000 mPa·s, 2100 mPa·s, 2200 mPa·s, 2300 mPa·s, 2400 mPa·s, 2500 mPa·s, 2600 mPa·s, 2700 mPa·s, 2800 mPa·s, 2900 mPa·s or 3000 mPa·s, as well as specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0025] Preferably, the solid content of the aqueous acrylic emulsion is 1-5%, for example, it can be 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5%, and specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0026] Preferably, the electrospun membrane is prepared from an electrospun solution via an electrospun process.

[0027] Preferably, the electrospun film has a thickness of 10-100 μm, for example, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, or 100 μm. Specific values ​​within the above ranges are not exhaustively listed here for space limitations and for the sake of brevity.

[0028] Preferably, the electrospinning solution comprises polyurethane, a solvent, and inorganic particles.

[0029] Preferably, with the electrospinning solution having a mass percentage content of 100%, the polyurethane mass percentage content is 5-10%, for example, it can be 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5% or 10%, and specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0030] Preferably, with the electrospinning solution having a mass percentage content of 100%, the solvent mass percentage content is 85-95%, for example, it can be 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94% or 95%, and specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0031] Preferably, with the mass percentage of the electrospinning solution being 100%, the mass percentage of the inorganic particles is 0.01-2%, for example, it can be 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.2%, 1.4%, 1.6%, 1.8%, or 2%, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0032] In this invention, the addition of inorganic particles can significantly improve the thermal insulation performance of the resulting waterproof, breathable, and thermally insulating durable membrane. Further optimization of their content allows the resulting membrane to possess both excellent thermal insulation and durability. When the mass percentage of inorganic particles is too low, its thermal insulation performance decreases; conversely, when its mass percentage is too high, it affects the uniformity of the spun film. Furthermore, due to the higher impurity content, the membrane's toughness deteriorates, thus reducing the durability of the waterproof, breathable, and thermally insulating durable membrane.

[0033] Preferably, the solvent includes any one or a combination of at least two of N,N-dimethylformamide, tetrahydrofuran, or water.

[0034] Preferably, the solvent is a combination of N,N-dimethylformamide and tetrahydrofuran.

[0035] Preferably, the volume ratio of the combination of N,N-dimethylformamide and tetrahydrofuran is 1:4.

[0036] Preferably, the inorganic particles include any one or a combination of at least two of carbon nanotubes, rare earth materials, or ceramic powder.

[0037] Preferably, the electrospinning solution is used in a mixed manner.

[0038] Preferably, the mixing method includes stirring.

[0039] Preferably, the mixing temperature is 75-85℃, for example, it can be 75℃, 76℃, 77℃, 78℃, 79℃, 80℃, 81℃, 82℃, 83℃, 84℃ or 85℃, as well as specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0040] Preferably, the mixing time is 8-16 hours, for example, it can be 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours or 16 hours, as well as specific values ​​between the above-mentioned values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0041] Preferably, the electrospinning voltage in the electrospinning process is 10-25kV, for example, it can be 10kV, 12kV, 15kV, 18kV, 20kV, 22kV or 25kV, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0042] Preferably, the spinning rate in the electrospinning process is 0.05-1.5 mL / h, for example, it can be 0.05 mL / h, 0.08 mL / h, 0.1 mL / h, 0.3 mL / h, 0.5 mL / h, 0.8 mL / h, 1 mL / h, 1.2 mL / h or 1.5 mL / h, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0043] In a second aspect, the present invention provides a method for preparing a waterproof, breathable, heat-insulating, and durable membrane as described in the first aspect, the method comprising the following steps:

[0044] The electrospun film is subjected to hot stamping silver treatment and then composite coating to obtain the waterproof, breathable, heat-insulating, and durable film.

[0045] For example, the preparation method of the waterproof, breathable, heat-insulating, and durable membrane provided by the present invention specifically includes the following steps:

[0046] (1) Preparation of electrospun membrane:

[0047] Polyurethane particles were dissolved in a mixed solution of N,N-dimethylformamide (DMF) and tetrahydrofuran (THF), and optional inorganic particles were added. The mixture was stirred at 75-85°C for 8-16 hours to prepare an electrospinning solution. The electrospinning solution was then subjected to electrospinning at a voltage of 10-25 kV and a spinning rate of 0.05-1.5 mL / h to obtain the electrospinned film (10-100 μm thick).

[0048] (2) Hot stamping:

[0049] On the surface of the foil, a pattern roller is passed through a tank containing an aqueous acrylic emulsion, causing the emulsion to form a specific floral pattern on the hot stamping film. The hot stamping film with the floral pattern is then dried at a temperature controlled between 80-85°C to ensure the aqueous acrylic emulsion adheres firmly to the film and creates the desired pattern. Subsequently, the treated hot stamping film and the electrospun film described in step (1) are fed together between a hot roller and a rolling mill. Under the action of the hot roller and the pressure of the rolling mill, the hot stamping film and the electrospun film are tightly bonded together, ensuring a smooth and even bond.

[0050] (3) Preparation of coating:

[0051] Polyurethane adhesive is uniformly coated on one side of the electrospun film after hot stamping in step (2). During the coating process, the speed is controlled at 15-30 m / min, the drying temperature is controlled at 150-170℃, and the drying time is controlled at 1-2 min. The thickness of the coating is 0.001-0.01 μm, thus obtaining the waterproof, breathable, heat-insulating, and durable film.

[0052] Thirdly, the application of a waterproof, breathable, heat-insulating, and durable membrane as described in the first aspect in clothing.

[0053] Compared with the prior art, the present invention has at least the following beneficial effects:

[0054] (1) The waterproof, breathable, heat-insulating, and durable membrane provided by the present invention is made more durable while possessing excellent waterproof and breathable properties by hot-stamping and coating reinforcement on the electrospun membrane. Furthermore, the heat-insulating performance of the electrospun membrane of the present invention is also improved by adding inorganic particles that have both light absorption and heat generation and far-infrared temperature rise during the preparation process.

[0055] (2) The waterproof, breathable, heat-insulating, and durable membrane provided by this invention not only has excellent waterproof, breathable, and heat-insulating properties, but also has a waterproof performance of 100-110 kPa and a breathability performance of 7000-7120 g / m³. 2• 24-hour photothermal temperature rise is 12-13℃, far-infrared temperature rise is 2.8-3.1℃, and it also has good durability. After three washes, its waterproof performance is 89-96kPa and its moisture permeability is 7100-7200g / m³. 2 • The photothermal temperature rise is 12-13℃ in 24 hours and the far-infrared temperature rise is 2.8-3.1℃, without any silver foil peeling; at the same time, its wear resistance can be maintained at 25000r. Detailed Implementation

[0056] To facilitate understanding of the present invention, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of the invention.

[0057] Unless otherwise specified, all raw materials used in the following examples and comparative examples are commercially available. Some raw material information is as follows:

[0058] Polyurethane granules: purchased from BASF

[0059] Carbon nanotubes: purchased from OCSiAl's TUBALL TM ;

[0060] Both the nano-ceramic powder and rare earth materials were purchased from the Tianjin Rare Earth Research Institute.

[0061] Water-based acrylic emulsion: purchased from Henkel LDM 1876;

[0062] Polyurethane adhesive: purchased from 3M Scotch-Weld PU 560.

[0063] Example 1

[0064] This embodiment provides a waterproof, breathable, heat-insulating, and durable membrane, the preparation method of which includes the following steps:

[0065] (1) Preparation of electrospun membrane:

[0066] 5g of polyurethane particles were dissolved in a mixed solution of 20mL N,N-dimethylformamide (DMF) and 80mL tetrahydrofuran (THF), and 0.1g of carbon nanotubes were added. The mixture was stirred at 80°C for 12h to prepare an electrospinning solution. The electrospinning solution was then subjected to electrospinning at a voltage of 20kV and a spinning rate of 1.0mL / h to obtain the electrospinned film (50μm thick).

[0067] (2) Hot stamping:

[0068] On the surface of the foil, a pattern roller is passed through a tank containing an aqueous acrylic emulsion, causing the emulsion to form a specific floral pattern on the hot stamping film. The hot stamping film with the floral pattern is then dried at 83°C to ensure the aqueous acrylic emulsion adheres firmly to the film and creates the desired pattern. Subsequently, the treated hot stamping film and the electrospun film described in step (1) are fed together between a hot roller and a rolling mill. Under the action of the hot roller and the pressure of the rolling mill, the hot stamping film and the electrospun film are tightly bonded together, ensuring a smooth and even bond.

[0069] (3) Preparation of coating:

[0070] Polyurethane adhesive is uniformly coated on one side of the electrospun film after hot stamping in step (2). During the coating process, the speed is controlled at 22m / min, the drying temperature is 160℃, and the drying time is 1.5min. The thickness of the coating is 0.01μm, thus obtaining the waterproof, breathable, heat-insulating, and durable film.

[0071] Example 2

[0072] This embodiment provides a waterproof, breathable, heat-insulating, and durable membrane, the preparation method of which includes the following steps:

[0073] (1) Preparation of electrospun membrane:

[0074] 8g of polyurethane particles were dissolved in a mixed solution of 20mL DMF and 80mL THF, and 2g of nano-ceramic powder was added. The mixture was stirred at 75℃ for 16h to prepare an electrospinning solution. The electrospinning solution was then subjected to electrospinning at a voltage of 10kV and a spinning rate of 0.05mL / h to obtain the electrospinned film (10μm thick).

[0075] (2) Hot stamping:

[0076] On the surface of the foil, a pattern roller is passed through a tank containing an aqueous acrylic emulsion, causing the emulsion to form a specific floral pattern on the hot stamping film. The hot stamping film with the floral pattern is then dried at a temperature controlled between 80°C to ensure the aqueous acrylic emulsion adheres firmly to the film and creates the desired pattern. Subsequently, the treated hot stamping film and the electrospun film described in step (1) are fed together between a hot roller and a rolling mill. Under the action of the hot roller and the pressure of the rolling mill, the hot stamping film and the electrospun film are tightly bonded together, ensuring a smooth and even bond.

[0077] (3) Preparation of coating:

[0078] Polyurethane adhesive is uniformly coated on one side of the electrospun film after hot stamping in step (2). During the coating process, the speed is controlled at 15m / min, the drying temperature is 150℃, and the drying time is 2min. The thickness of the coating is 0.001μm, and the waterproof, breathable, heat-insulating and durable film is obtained.

[0079] Example 3

[0080] This embodiment provides a waterproof, breathable, heat-insulating, and durable membrane, the preparation method of which includes the following steps:

[0081] (1) Preparation of electrospun membrane:

[0082] 10g of polyurethane particles were dissolved in a mixed solution of 20mL DMF and 80mL THF. 0.02g of rare earth material was added, and the mixture was stirred at 85℃ for 8 hours to prepare an electrospinning solution. The electrospinning solution was then subjected to electrospinning at a voltage of 25kV and a spinning rate of 1.5mL / h to obtain the electrospinned membrane (100μm thick).

[0083] (2) Hot stamping:

[0084] On the surface of the foil, a pattern roller is passed through a tank containing an aqueous acrylic emulsion, causing the emulsion to form a specific floral pattern on the hot stamping film. The hot stamping film with the floral pattern is then dried at a temperature controlled between 85°C to ensure the aqueous acrylic emulsion adheres firmly to the film and creates the desired pattern. Subsequently, the treated hot stamping film and the electrospun film described in step (1) are fed together between a hot roller and a rolling mill. Under the action of the hot roller and the pressure of the rolling mill, the hot stamping film and the electrospun film are tightly bonded together, ensuring a smooth and even bond.

[0085] (3) Preparation of coating:

[0086] Polyurethane adhesive is uniformly coated on one side of the electrospun film after hot stamping in step (2). During the coating process, the speed is controlled at 30 m / min, the drying temperature is 170℃, and the drying time is 1 min. The thickness of the coating is 0.003 μm, thus obtaining the waterproof, breathable, heat-insulating, and durable film.

[0087] Example 4

[0088] This embodiment provides a waterproof, breathable, heat-insulating, and durable membrane. The only difference between this embodiment and Embodiment 1 is that the thickness of the coating obtained in step (3) is 0.005 μm. The other raw materials, contents, and preparation methods are the same as in Embodiment 1.

[0089] Example 5

[0090] This embodiment provides a waterproof, breathable, heat-insulating, and durable membrane. The only difference between this embodiment and Embodiment 1 is that the thickness of the coating obtained in step (3) is 0.008 μm. The other raw materials, contents, and preparation methods are the same as in Embodiment 1.

[0091] Example 6

[0092] This embodiment provides a waterproof, breathable, heat-insulating, and durable membrane. The only difference between this embodiment and Embodiment 1 is that the thickness of the coating prepared in step (3) is 0.012 μm. The other raw materials, contents, and preparation methods are the same as in Embodiment 1.

[0093] Example 7

[0094] This embodiment provides a waterproof, breathable, heat-insulating, and durable membrane. The only difference between this embodiment and Embodiment 1 is that the drying temperature in step (2) is adjusted from 83°C to 75°C. The other raw materials, contents, and preparation methods are the same as in Embodiment 1.

[0095] Example 8

[0096] This embodiment provides a waterproof, breathable, heat-insulating, and durable membrane. The only difference between this embodiment and Embodiment 1 is that the drying temperature in step (2) is adjusted from 83°C to 90°C. The other raw materials, contents, and preparation methods are the same as in Embodiment 1.

[0097] Comparative Example 1

[0098] This comparative example provides a waterproof, breathable, heat-insulating, and durable membrane. The only difference between this example and Example 1 is that the electrospun membrane obtained in step (1) is not subjected to the hot-stamping treatment in step (2), but the coating is prepared directly on one side in step (3). The raw materials, content, and preparation method are the same as those in Example 1.

[0099] Comparative Example 2

[0100] This comparative example provides a waterproof, breathable, heat-insulating, and durable membrane. The only difference between this example and Example 1 is that the coating preparation step (3) is omitted. Instead, the waterproof, breathable, heat-insulating, and durable membrane is obtained directly after the hot-stamping treatment in step (2). The raw materials, content, and preparation method are the same as those in Example 1.

[0101] Comparative Example 3

[0102] This comparative example provides a waterproof, breathable, heat-insulating, and durable membrane. The only difference between this membrane and Example 1 is that carbon nanotubes are not added to the electrospinning solution in step (1). The raw materials, content, and preparation method are the same as those in Example 1.

[0103] The waterproof, breathable, and thermally insulating durable membranes obtained in Examples 1-8 and Comparative Examples 1-3 were subjected to performance tests, and the corresponding test methods / standards are as follows:

[0104] Waterproof and moisture-permeable properties: The initial waterproof and moisture-permeable properties of the membrane and after three washes were tested in accordance with the test standard GB / T 40910-2021 Evaluation of Waterproof and Moisture-Permeable Properties of Textiles.

[0105] Photothermal storage temperature rise performance: The initial and three-wash photothermal storage temperature rise performance of the film were tested in accordance with the test standard GB / T 18319-2019 Test Method for Photothermal Storage Performance of Textiles.

[0106] Far-infrared temperature rise performance: The initial and three-wash far-infrared temperature rise performance of the film were tested in accordance with the test standard GB / T 30127-2013 Test and evaluation of far-infrared performance of textiles.

[0107] The washing method should be in accordance with GB / T 8629-2017 "Test Procedures for Household Washing and Drying of Textiles", and T3 indicates three washes.

[0108] Powder shedding rate of hot stamping after 3 washes: Visually observe the degree of powder shedding after 3 washes and calculate as a percentage.

[0109] Abrasion resistance: Refer to GB / T 21196.1~4-2007 Textiles - Martindale method for determination of abrasion resistance of fabrics.

[0110] The test results are shown in Table 1.

[0111] Table 1

[0112]

[0113] The test results show that:

[0114] (1) As can be seen from Examples 1 to 8, by performing hot stamping and coating reinforcement on the electrospun film, the present invention can make the film have excellent waterproof and breathable properties, as well as good heat retention and wear resistance.

[0115] (2) By comparing Example 1 with Examples 4-6, it can be seen that the coating thickness of the waterproof, breathable, heat-insulating and durable membranes obtained in Examples 1, 5 and 4 decreases in turn, and their measured waterproof performance decreases in turn. This indicates that when the coating thickness is between 0.001 and 0.01 μm, the waterproof performance of the obtained waterproof, breathable, heat-insulating and durable membrane gradually increases with the increase of its thickness. In Example 6, the coating thickness is greater than 0.01 μm, and the moisture permeability of the obtained waterproof, breathable, heat-insulating and durable membrane deteriorates. At the same time, the excessive coating thickness will affect the comfort of its actual use.

[0116] (3) By comparing Example 1 with Examples 7 and 8, it can be seen that the drying temperature in the hot stamping process in Example 7 is lower than 80°C. At this time, due to insufficient drying of the water-based acrylic emulsion, the fibers in the electrospun film cannot be well bonded together, resulting in incomplete film formation and insufficient adhesion. Consequently, the waterproof performance of the obtained waterproof, breathable, heat-insulating, and durable film deteriorates. In Example 8, the drying temperature in the hot stamping process is higher than 85°C. At this time, due to the excessively rapid drying of the water-based acrylic emulsion, defects (cracking, bubbles) appear in the electrospun film, causing the obtained electrospun film layer to become brittle, which in turn affects the waterproof performance of the obtained waterproof, breathable, heat-insulating, and durable film. This shows that by optimizing the drying temperature in the hot stamping process, the present invention can further improve the waterproof performance of the obtained waterproof, breathable, heat-insulating, and durable film.

[0117] (4) By comparing Example 1 and Comparative Example 1, it can be seen that Comparative Example 1 did not perform hot stamping silver treatment on the electrospun film. The initial value of the far-infrared temperature rise of the resulting waterproof, breathable, heat-insulating and durable film was only 1.5℃. The waterproof performance and wear resistance were significantly reduced. This shows that by performing hot stamping silver treatment on the electrospun film, the present invention can not only enhance the far-infrared temperature rise effect of the waterproof, breathable, heat-insulating and durable film, thereby achieving better heat retention, but also improve the waterproof performance and wear resistance of the waterproof, breathable, heat-insulating and durable film, thereby achieving the purpose of excellent durability.

[0118] (5) By comparing Example 1 and Comparative Example 2, it can be seen that Comparative Example 2 did not have a coating, and the waterproof and abrasion-resistant performance of the resulting waterproof, breathable and heat-insulating durable membrane was significantly reduced. At the same time, after three water washes, the powder removal rate of hot-stamping reached 60%, indicating that the present invention can obtain better waterproof and abrasion-resistant properties by setting a coating after hot-stamping the electrospun film.

[0119] (6) By comparing Example 1 and Comparative Example 3, it can be seen that when the waterproof, breathable, heat-insulating and durable membrane of Comparative Example 3 does not contain inorganic particles, its light heat storage temperature rise effect and far-infrared temperature rise effect are significantly reduced. This shows that by adding inorganic particles in the preparation process of electrospun membrane, the present invention can significantly enhance the heat preservation performance of the obtained waterproof, breathable, heat-insulating and durable membrane.

[0120] In summary, the waterproof, breathable, heat-insulating, and durable membrane provided by this invention is obtained by hot stamping and coating reinforcement on an electrospun membrane, enabling it to possess excellent waterproof and breathable properties while also being more durable. Furthermore, the heat-insulating performance of the electrospun membrane of this invention is also simultaneously improved by incorporating inorganic particles that possess both light absorption and heat generation properties, as well as far-infrared temperature rise, during the preparation process.

[0121] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A waterproof, breathable, heat-insulating, and durable membrane, characterized in that, The waterproof, breathable, heat-insulating, and durable membrane comprises an electrospun film and a coating; the electrospun film is obtained by hot stamping.

2. The waterproof, breathable, heat-insulating, and durable membrane according to claim 1, characterized in that, The thickness of the coating is 0.001-0.01 μm.

3. The waterproof, breathable, heat-insulating, and durable membrane according to claim 1, characterized in that, The raw material for the coating is adhesive; Preferably, the adhesive comprises polyurethane adhesive.

4. The waterproof, breathable, heat-insulating, and durable membrane according to any one of claims 1-3, characterized in that, The drying temperature during the hot stamping process is 80-85℃; Preferably, the raw material for the hot stamping treatment includes an aqueous acrylic emulsion; Preferably, the aqueous acrylic emulsion includes acrylic emulsion and / or fluoroacrylic emulsion; Preferably, the viscosity of the aqueous acrylic emulsion is 2000-3000 mPa·s; Preferably, the solid content of the aqueous acrylic emulsion is 1-5%.

5. The waterproof, breathable, heat-insulating, and durable membrane according to any one of claims 1-4, characterized in that, The electrospun membrane is prepared from an electrospun solution via an electrospun process. The preferred yarn is the electrospun film, which has a thickness of 10-100 μm.

6. The waterproof, breathable, heat-insulating, and durable membrane according to claim 5, characterized in that, The electrospinning solution comprises polyurethane, solvent, and inorganic particles; Preferably, the polyurethane content is 5-10% based on a mass percentage of 100% for the electrospinning solution; Preferably, the solvent content is 85-95% by mass, based on a 100% mass percentage of the electrospinning solution; Preferably, the inorganic particles have a mass percentage content of 0.01-2%, based on a mass percentage content of 100% for the electrospinning solution.

7. The waterproof, breathable, heat-insulating, and durable membrane according to claim 6, characterized in that, The solvent includes any one or a combination of at least two of N,N-dimethylformamide, tetrahydrofuran, or water; Preferably, the solvent is a combination of N,N-dimethylformamide and tetrahydrofuran; Preferably, the volume ratio of the combination of N,N-dimethylformamide and tetrahydrofuran is 1:4; Preferably, the inorganic particles include any one or a combination of at least two of carbon nanotubes, rare earth materials, or ceramic powder.

8. The waterproof, breathable, heat-insulating, and durable membrane according to any one of claims 5-7, characterized in that, The electrospinning voltage in the electrospinning process is 10-25kV; Preferably, the spinning rate in the electrospinning process is 0.05-1.5 mL / h.

9. A method for preparing a waterproof, breathable, heat-insulating, and durable membrane as described in any one of claims 1-8, characterized in that, The preparation method includes the following steps: The electrospun film is subjected to hot stamping silver treatment and then composite coating to obtain the waterproof, breathable, heat-insulating, and durable film.

10. The application of a waterproof, breathable, heat-insulating, and durable membrane as described in any one of claims 1-8 in clothing.

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