Highly efficient waterproof outdoor waterproof clothing

Abstract

The application relates to the field of waterproof clothes, and particularly discloses a high-efficiency waterproof outdoor waterproof clothes. The high-efficiency waterproof outdoor waterproof clothes is made of waterproof and moisture-permeable fabric, the waterproof and moisture-permeable fabric comprises fine denier polyester base cloth and a nanofiber membrane, the nanofiber membrane comprises the following components in parts by mass: 5-15 parts of modified metal organic framework material, 150-200 parts of modified polylactic acid and 250-300 parts of modified polyurethane. The waterproof clothes has excellent waterproof and moisture-permeable performance, and has ultraviolet resistance and antibacterial capacity, is softer and more skin-friendly, and is comfortable to wear.

Description

Technical Field

[0001] This application relates to the field of waterproof clothing, and more specifically, to a highly effective waterproof outdoor waterproof clothing. Background Technology

[0002] my country has a long history of producing waterproof clothing, evolving from coating fabrics with tung oil thousands of years ago to using organic fluorine-based processing for raincoats today. With the development of industrial and agricultural production, special functional protective clothing, including waterproof clothing, has attracted numerous professionals to engage in research and development.

[0003] Related technologies typically employ coating techniques to impart waterproof and breathable properties to waterproof clothing. The waterproof and breathable performance of coated fabrics varies depending on the coating thickness; relatively speaking, coated fabrics have lower moisture permeability and lower water pressure resistance. Furthermore, the coating on coated fabrics is prone to cracking during use, limiting their waterproof and breathable effectiveness, and therefore requires improvement. Summary of the Invention

[0004] In order to improve the waterproof and breathable performance of waterproof clothing, this application provides a highly effective waterproof outdoor waterproof clothing.

[0005] The technical solution for a highly effective waterproof outdoor waterproof garment provided in this application is as follows:

[0006] A highly effective waterproof outdoor waterproof garment, wherein the garment is made of a waterproof and breathable fabric comprising a fine denier polyester base fabric and a nanofiber membrane, the nanofiber membrane comprising the following components in parts by weight: 5-15 parts of modified metal-organic framework material.

[0007] 150-200 parts of modified polylactic acid

[0008] 250-300 parts of modified polyurethane.

[0009] The rich porous structure of modified metal-organic framework (MOF) materials helps transport moisture to the fabric surface, improving breathability. The synergistic effect of multi-metal coordination endows MOF materials with superior UV resistance and antibacterial properties. Modified polylactic acid (PLA) is a novel, environmentally friendly fiber with excellent UV resistance and biocompatibility; as a clothing fabric, it can wick away moisture and enhance comfort. The water-repellent properties of modified polyurethane are improved. A three-layer waterproof and breathable fabric with an outer layer of modified polyurethane and an inner layer of modified polylactic acid is obtained through coaxial electrospinning. The waterproof and breathable properties of the fabric are further enhanced by a nanofiber membrane, which exhibits good stability, is not easily cracked, and can maintain its waterproof and breathable properties for a long time. The MOF material is uniformly attached to the surface of each fiber; the synergistic effect of these three elements significantly improves the waterproof and breathable performance of waterproof clothing.

[0010] Preferably, the modified metal-organic framework material includes zirconium tetrachloride, zinc tetracarboxyphenylporphyrin, benzoic acid, dichlorodicyclopentadiene, and N,N-dimethylformamide.

[0011] The porphyrin structure of tetracarboxyphenylporphyrin zinc provides abundant electron-rich nitrogen atoms to coordinate with introduced zinc ions, activating oxygen molecules to generate singlet oxygen. Porphyrin molecules are photosensitive molecules that can absorb the energy of ultraviolet and blue light, becoming trimers and releasing singlet oxygen. Titanium ions can absorb and reflect ultraviolet light, and their incorporation further promotes the generation of singlet oxygen. The three metal ions and porphyrin work synergistically to improve the waterproof and breathable properties of the fabric while absorbing ultraviolet light and generating a large amount of singlet oxygen that diffuses along the porphyrin structure, interacting with biomolecules within bacteria and inducing bacterial death, thereby achieving anti-ultraviolet and antibacterial effects.

[0012] Preferably, the modified metal-organic framework material is prepared using the following steps:

[0013] (1) Zirconium tetrachloride, zinc tetracarboxyphenylporphyrin and benzoic acid were mixed and dispersed in N,N-dimethylformamide, reacted at 100-140℃, cooled, washed and dried to obtain metal-organic framework material A;

[0014] (2) Disperse metal-organic framework material A and titanium dichlorodecene in N,N-dimethylformamide, react at 100-140℃, cool, wash and dry to obtain modified metal-organic framework material.

[0015] Zirconium tetrachloride, zinc tetracarboxyphenylporphyrin, and benzoic acid coordinate and self-assemble in N,N-dimethylformamide to form a metal-organic framework material A with bimetallic coordination. Titanium dichlorophenocene is doped into metal-organic framework material A in N,N-dimethylformamide to obtain a modified metal-organic framework material with trimetallic coordination, which can improve the waterproof and breathable properties of the fabric. The synergistic effect of the three metal ions can also achieve better UV resistance and antibacterial effects.

[0016] Preferably, the reaction time required in step (2) of the preparation of the modified metal-organic framework material at 100-140°C is 21-27 hours.

[0017] Within this timeframe, modified metal-organic framework materials with good morphology and pore structure and high titanium doping rate can be obtained, exhibiting superior waterproof and breathable properties.

[0018] Preferably, the modified polylactic acid is prepared using the following steps:

[0019] Polylactic acid was pretreated by drying to obtain dried polylactic acid. The dried polylactic acid was then mixed and dispersed with tannic acid in N,N-dimethylformamide and stirred to obtain modified polylactic acid.

[0020] Tannic acid has good biocompatibility. When blended with polylactic acid (PLA), it can form strong van der Waals forces and hydrogen bonds, thereby further improving the hydrophilicity, thermal stability, and mechanical properties of PLA. Tannic acid has strong absorption in the ultraviolet region and has a significant inhibitory effect on a variety of bacteria, fungi, and microorganisms. Using tannic acid to modify PLA gives PLA that is in contact with the skin better moisture absorption properties. It can also synergistically enhance the waterproof and breathable properties, UV resistance, and antibacterial ability of fabrics with modified metal-organic framework materials.

[0021] Preferably, the mass ratio of tannic acid to polylactic acid is (0.05-0.15):1.

[0022] The modified polylactic acid obtained according to the above mass ratio can exhibit superior waterproof and breathable properties.

[0023] Preferably, the modified polyurethane is prepared using the following steps:

[0024] Polyurethane, methylhydrosiloxane and hydrophobic titanium dioxide were dispersed in N,N-dimethylformamide, stirred and allowed to stand to obtain modified polyurethane.

[0025] Methylhydrosiloxane possesses excellent weather resistance, hydrophobicity, and breathability; hydrophobic titanium dioxide can construct a rough micro-nano composite structure on the surface of polyurethane, enhancing its water-repellent properties. Furthermore, titanium dioxide molecules exhibit UV absorption and antibacterial properties, improving the polyurethane's UV resistance and antibacterial capabilities. Blending methylhydrosiloxane, hydrophobic titanium dioxide, and polyurethane can form a polymer cross-linked network structure, creating a highly dense and rough polysiloxane film that coats the fiber surface, thereby enhancing the waterproof and breathable properties, UV resistance, and antibacterial properties of the waterproof and breathable fabric.

[0026] Preferably, the waterproof and breathable fabric further includes tetrabutylammonium bromide and polyvinylpyrrolidone.

[0027] Tetrabutylammonium bromide can improve the conductivity of the spinning solution, allowing the spinning jet to split into finer branched fibers, thus forming a special dendritic morphology. This dendritic branching structure enhances the hydrophilic and hydrophobic properties of the fiber itself. The branched fibers can provide more contact sites, allowing more modified metal-organic framework materials to adhere to the fibers, thereby achieving better waterproof and breathable properties. Polyvinylpyrrolidone can improve the bonding strength between the nanofiber membrane and the fabric. Adding polyvinylpyrrolidone to the spinning solution can promote the bonding between the nanofiber membrane and the base fabric.

[0028] Preferably, the highly effective waterproof outdoor waterproof clothing is prepared using the following steps:

[0029] After pretreatment of fine denier polyester base fabric, an intermediate layer base fabric is obtained. Modified polylactic acid, polyvinylpyrrolidone and tetrabutylammonium bromide are mixed to obtain spinning solution A. Modified polyurethane, polyvinylpyrrolidone and tetrabutylammonium bromide are mixed to obtain spinning solution B. Modified metal-organic framework material is dispersed in N,N-dimethylformamide to obtain modified metal-organic framework material suspension.

[0030] Using the intermediate layer base fabric as the receiving screen, the spinning solution A and the modified metal-organic framework material suspension are coaxially electrospun to obtain fabric A with a modified polylactic acid nanofiber membrane on one side.

[0031] Using the side of fabric A away from the nanofiber membrane as a receiving screen, the spinning solution B and the modified metal-organic framework material suspension are coaxially electrospun to obtain fabric B with a modified polyurethane nanofiber membrane. Fabric B is then subjected to hot pressing treatment and washed to obtain a waterproof and breathable fabric.

[0032] Waterproof and breathable fabrics are cut, glued, spliced, and then hot-pressed. After cooling, highly effective waterproof outdoor clothing is obtained.

[0033] Using coaxial electrospinning, the modified metal-organic framework material can be uniformly attached to the modified polyurethane and modified polylactic acid fibers. By adding polyvinylpyrrolidone to increase the adhesion of the spinning solution, the interlayer force between the nanofiber membrane and the intermediate base fabric obtained by electrospinning is enhanced, which can exert better waterproof and breathable performance.

[0034] Preferably, the mass ratio of the tetrabutylammonium bromide to the modified polyurethane is 1:(0.1-0.15).

[0035] The waterproof and breathable fabric obtained according to the above mass ratio has a superior dendritic branching structure and good waterproof and breathable performance.

[0036] In summary, this application has the following beneficial effects:

[0037] 1. Through coaxial electrospinning, a three-layer waterproof and breathable fabric with high porosity is obtained. The nanofiber membrane obtained by electrospinning has good stability and is not easy to crack, so it can maintain its waterproof and breathable performance for a longer period of time. The hydrophilic modified polylactic acid has better biocompatibility and can achieve better moisture absorption and perspiration effect. The porous structure of the modified metal-organic skeleton material helps sweat to be transported to the fabric surface and discharged. The outermost modified polyurethane has the inherent water-repellent properties of synthetic fibers. The synergistic effect of the three can greatly improve the waterproof and breathable performance of the waterproof clothing.

[0038] 2. In modified metal-organic framework materials, zirconium, titanium, and zinc ions, along with porphyrin, work synergistically to absorb ultraviolet light, generating a large amount of singlet oxygen that interacts with biological macromolecules within bacteria, thereby inducing bacterial death. Tannic acid has strong absorption in the ultraviolet region and has a significant inhibitory effect on various bacteria, fungi, and microorganisms. It can work synergistically with modified metal-organic framework materials to enhance the fabric's UV resistance and antibacterial ability.

[0039] 3. Coaxial electrospinning gives the fibers a dendritic branching structure, while also allowing the modified metal-organic framework material to be uniformly coated on the surface of each fiber of modified polyurethane and modified polylactic acid. This reduces the impact of embedding the metal-organic framework material into the fibers on its performance and improves the waterproof and breathable properties of the fabric. Attached Figure Description

[0040] Figure 1 This is a cross-sectional view of the waterproof and breathable fabric of a highly effective waterproof outdoor waterproof garment according to an embodiment of this application.

[0041] Explanation of reference numerals in the attached figures: 1. Modified polyurethane nanofiber membrane; 2. Fine denier polyester base fabric; 3. Modified polylactic acid nanofiber membrane. Detailed Implementation

[0042] The present application will be further described in detail below with reference to the embodiments. In the embodiments of the present application, the waterproof and breathable fabric of the waterproof clothing includes a modified polyurethane nanofiber membrane 1, a fine denier polyester base fabric 2, and a modified polylactic acid nanofiber membrane 3. The modified polyurethane nanofiber membrane and the modified polylactic acid nanofiber membrane in the waterproof and breathable fabric of the waterproof clothing are obtained by electrostatic spinning and chemical bonding to the fine denier polyester base fabric.

[0043] Example

[0044] Example 1

[0045] Preparation of modified metal-organic framework materials

[0046] (1) Weigh 1.2 g of zirconium tetrachloride (CAS No.: 10026-11-6), 0.4 g of zinc tetracarboxyphenylporphyrin (CAS No.: 27647-84-3), and 16 g of benzoic acid (CAS No.: 65-85-0) and add them to a reaction vessel. Then add 80 mL of N,N-dimethylformamide (CAS No.: 68-12-2) to the reaction vessel. After ultrasonic dissolution, the reaction vessel is placed in an oven at 120 °C for 24 hours. After cooling to room temperature, the product obtained in the reaction vessel is washed three times with N,N-dimethylformamide, then washed three times with acetone, and dried in an oven at 80 °C for 8 hours to obtain metal-organic framework material A.

[0047] (2) 1.66 g of metal-organic framework material A, 5.5 g of titanium dichlorodichloropentane (CAS No.: 1271-19-8), and 100 mL of N,N-dimethylformamide were mixed in a reaction vessel and ultrasonically dispersed. The reaction vessel was then incubated in an oven at 120 °C for 21 hours. After cooling to room temperature, the product obtained in the reaction vessel was washed three times with N,N-dimethylformamide, followed by three times with alcohol, and dried in an oven at 80 °C for 8 hours to obtain the modified metal-organic framework material.

[0048] Preparation of modified polylactic acid

[0049] Polylactic acid powder (CAS No.: 26100-51-6) was dried in a vacuum oven at 80℃ for 2 hours to remove moisture and obtain dried polylactic acid. 7.3g of tannic acid powder (CAS No.: 1401-55-4) and 143g of dried polylactic acid were weighed and dispersed in 500mL of N,N-dimethylformamide. The mixture was placed in a constant temperature water bath and stirred at 500rpm for 2 hours to obtain a homogeneous solution. The homogeneous solution was then allowed to stand in a constant temperature 80℃ water bath for 2 hours to remove air bubbles and obtain modified polylactic acid.

[0050] Preparation of modified polyurethane

[0051] 31.3 g of methylhydrosiloxane (CAS No.: 1873-88-7) and 0.5 g of hydrophobic titanium dioxide (CAS No.: 1317-80-2) were dissolved in 500 mL of N,N-dimethylformamide. 218.8 g of polyurethane (CAS No.: 51852-81-4) powder was slowly added while stirring. The mixture was stirred at room temperature for 2 hours to obtain modified polyurethane.

[0052] Preparing waterproof clothing

[0053] After cleaning and drying the fine denier polyester base fabric, water-based polyurethane adhesive was sprayed onto it and cured for 6 hours to obtain the intermediate layer base fabric. 150g of modified polylactic acid, 7.6g of polyvinylpyrrolidone and 13.65g of tetrabutylammonium bromide were mixed to obtain spinning solution A. 250g of modified polyurethane, 12.6g of polyvinylpyrrolidone and 22.8g of tetrabutylammonium bromide were mixed to obtain spinning solution B. 5g of modified metal-organic framework material was dispersed in 500mL of N,N-dimethylformamide to obtain a suspension of modified metal-organic framework material.

[0054] Using the intermediate layer fabric as the receiving screen, coaxial electrospinning was performed with spinning solution A as the outer layer solution and modified metal-organic framework material suspension as the inner layer solution to obtain fabric A with a modified polylactic acid nanofiber membrane on one side. Using the side of fabric A away from the nanofiber membrane as the receiving screen, coaxial electrospinning was performed with spinning solution B as the outer layer solution and modified metal-organic framework material suspension as the inner layer solution to obtain fabric B with a modified polyurethane nanofiber membrane. The electrospinning voltage was 30kV, the receiving distance was 15cm, the syringe advance rate was 0.005mm / s, and the inner diameter of the inner nozzle of the coaxial nozzle was 0.4mm and the outer diameter was 0.5mm; the inner diameter of the outer nozzle was 0.9mm and the outer diameter was 1mm. Fabric B was hot-pressed using a flat vulcanizing machine for 2 minutes at a pressure of 2MPa and a temperature of 75℃. After washing, a waterproof and breathable fabric was obtained.

[0055] Waterproof and breathable fabric is cut, water-based polyurethane adhesive is applied to the seams, the seams are aligned, and then hot-pressed using a flat vulcanizing machine for 2 minutes at a pressure of 2 MPa and a temperature of 75°C. After cooling, a highly effective waterproof outdoor garment is obtained.

[0056] Example 2

[0057] Preparation of modified metal-organic framework materials

[0058] (1) Weigh 3.6 g of zirconium tetrachloride (CAS No.: 10026-11-6), 1.2 g of zinc tetracarboxyphenylporphyrin (CAS No.: 27647-84-3), and 48 g of benzoic acid (CAS No.: 65-85-0) and add them to a reaction vessel. Then add 240 mL of N,N-dimethylformamide (CAS No.: 68-12-2) to the reaction vessel. After ultrasonic dissolution, the reaction vessel is placed in an oven at 120 °C for 24 hours. After cooling to room temperature, the product obtained in the reaction vessel is washed three times with N,N-dimethylformamide, then washed three times with acetone, and dried in an oven at 80 °C for 8 hours to obtain metal-organic framework material A.

[0059] (2) 4.98 g of metal-organic framework material A, 16.5 g of titanium dichlorodicyclopentadiene (CAS No.: 1271-19-8), and 300 mL of N,N-dimethylformamide were mixed in a reaction vessel and ultrasonically dispersed. The reaction vessel was then incubated in an oven at 120 °C for 27 hours. After cooling to room temperature, the product obtained in the reaction vessel was washed three times with N,N-dimethylformamide, followed by three times with alcohol, and dried in an oven at 80 °C for 8 hours to obtain the modified metal-organic framework material.

[0060] Preparation of modified polylactic acid

[0061] Polylactic acid powder (CAS No.: 26100-51-6) was dried in an 80℃ vacuum oven for 2 hours to remove moisture and obtain dried polylactic acid. 8.8g of tannic acid powder (CAS No.: 1401-55-4) and 174g of dried polylactic acid were weighed and dispersed in 500mL of N,N-dimethylformamide. The mixture was placed in a constant temperature water bath and stirred at 500rpm for 2 hours to obtain a homogeneous solution. The homogeneous solution was then allowed to stand in an 80℃ water bath for 2 hours to remove air bubbles and obtain modified polylactic acid.

[0062] Preparation of modified polyurethane

[0063] 37.6 g of methylhydrosiloxane (CAS No.: 1873-88-7) and 0.6 g of hydrophobic titanium dioxide (CAS No.: 1317-80-2) were dissolved in 500 mL of N,N-dimethylformamide. 262.6 g of polyurethane (CAS No.: 51852-81-4) powder was slowly added while stirring. The mixture was stirred at room temperature for 2 hours to obtain modified polyurethane.

[0064] Preparing waterproof clothing

[0065] After cleaning and drying the fine denier polyester base fabric, water-based polyurethane adhesive was sprayed onto it and cured for 6 hours to obtain the intermediate layer base fabric. 200g of modified polylactic acid, 10.1g of polyvinylpyrrolidone and 26.1g of tetrabutylammonium bromide were mixed to obtain spinning solution A. 300g of modified polyurethane, 15.1g of polyvinylpyrrolidone and 37.6g of tetrabutylammonium bromide were mixed to obtain spinning solution B. 5g of modified metal-organic framework material was dispersed in 500mL of N,N-dimethylformamide to obtain a suspension of modified metal-organic framework material.

[0066] Using the intermediate layer fabric as the receiving screen, coaxial electrospinning was performed with spinning solution A as the outer layer solution and modified metal-organic framework material suspension as the inner layer solution to obtain fabric A with a modified polylactic acid nanofiber membrane on one side. Using the side of fabric A away from the nanofiber membrane as the receiving screen, coaxial electrospinning was performed with spinning solution B as the outer layer solution and modified metal-organic framework material suspension as the inner layer solution to obtain fabric B with a modified polyurethane nanofiber membrane. The electrospinning voltage was 30kV, the receiving distance was 15cm, the syringe advance rate was 0.005mm / s, and the inner diameter of the inner nozzle of the coaxial nozzle was 0.4mm and the outer diameter was 0.5mm; the inner diameter of the outer nozzle was 0.9mm and the outer diameter was 1mm. Fabric B was hot-pressed using a flat vulcanizing machine for 2 minutes at a pressure of 2MPa and a temperature of 75℃. After washing, a waterproof and breathable fabric was obtained.

[0067] Waterproof and breathable fabric is cut, water-based polyurethane adhesive is applied to the seams, the seams of the fabric are aligned and then hot-pressed using a flat vulcanizing machine for 2 minutes at a pressure of 2 MPa and a temperature of 75°C. After cooling, a highly effective waterproof outdoor garment is obtained.

[0068] Example 3

[0069] Preparation of modified metal-organic framework materials

[0070] (1) Weigh 2.4 g of zirconium tetrachloride (CAS No.: 10026-11-6), 0.8 g of zinc tetracarboxyphenylporphyrin (CAS No.: 27647-84-3), and 32 g of benzoic acid (CAS No.: 65-85-0) and add them to a reaction vessel. Then add 160 mL of N,N-dimethylformamide (CAS No.: 68-12-2) to the reaction vessel. After ultrasonic dissolution, the reaction vessel is placed in an oven at 120 °C for 24 hours. After cooling to room temperature, the product obtained in the reaction vessel is washed three times with N,N-dimethylformamide, then washed three times with acetone, and dried in an oven at 80 °C for 8 hours to obtain metal-organic framework material A.

[0071] (2) 3.32 g of metal-organic framework material A, 11 g of titanium dichlorodicyclopentadiene (CAS No.: 1271-19-8), and 200 mL of N,N-dimethylformamide were mixed in a reaction vessel and ultrasonically dispersed. The reaction vessel was then incubated in an oven at 120 °C for 24 hours. After cooling to room temperature, the product obtained in the reaction vessel was washed three times with N,N-dimethylformamide, followed by three times with alcohol, and dried in an oven at 80 °C for 8 hours to obtain the modified metal-organic framework material.

[0072] Preparation of modified polylactic acid

[0073] Polylactic acid powder (CAS No.: 26100-51-6) was dried in an 80℃ vacuum oven for 2 hours to remove moisture and obtain dried polylactic acid. 16g of tannic acid powder (CAS No.: 1401-55-4) and 160g of dried polylactic acid were weighed and dispersed in 500mL of N,N-dimethylformamide. The mixture was placed in a constant temperature water bath and stirred at 500rpm for 2 hours to obtain a homogeneous solution. The homogeneous solution was then allowed to stand in an 80℃ water bath for 2 hours to remove air bubbles and obtain modified polylactic acid.

[0074] Preparation of modified polyurethane

[0075] 34.5 g of methylhydrosiloxane (CAS No.: 1873-88-7) and 0.55 g of hydrophobic titanium dioxide (CAS No.: 1317-80-2) were dissolved in 500 mL of N,N-dimethylformamide. 241 g of polyurethane (CAS No.: 51852-81-4) powder was slowly added while stirring. The mixture was stirred at room temperature for 2 hours to obtain modified polyurethane.

[0076] Preparing waterproof clothing

[0077] After cleaning and drying the fine denier polyester base fabric, water-based polyurethane adhesive was sprayed onto it and cured for 6 hours to obtain the intermediate layer base fabric. 175g of modified polylactic acid, 8.8g of polyvinylpyrrolidone and 19.5g of tetrabutylammonium bromide were mixed to obtain spinning solution A. 275g of modified polyurethane, 13.8g of polyvinylpyrrolidone and 34.4g of tetrabutylammonium bromide were mixed to obtain spinning solution B. 10g of modified metal-organic framework material was dispersed in 500mL of N,N-dimethylformamide to obtain a suspension of modified metal-organic framework material.

[0078] Using the intermediate layer fabric as the receiving screen, coaxial electrospinning was performed with spinning solution A as the outer layer solution and modified metal-organic framework material suspension as the inner layer solution to obtain fabric A with a modified polylactic acid nanofiber membrane on one side. Using the side of fabric A away from the nanofiber membrane as the receiving screen, coaxial electrospinning was performed with spinning solution B as the outer layer solution and modified metal-organic framework material suspension as the inner layer solution to obtain fabric B with a modified polyurethane nanofiber membrane. The electrospinning voltage was 30kV, the receiving distance was 15cm, the syringe advance rate was 0.005mm / s, and the inner diameter of the inner nozzle of the coaxial nozzle was 0.4mm and the outer diameter was 0.5mm; the inner diameter of the outer nozzle was 0.9mm and the outer diameter was 1mm. Fabric B was hot-pressed using a flat vulcanizing machine for 2 minutes at a pressure of 2MPa and a temperature of 75℃. After washing, a waterproof and breathable fabric was obtained.

[0079] Waterproof and breathable fabric is cut, water-based polyurethane adhesive is applied to the seams, the seams of the fabric are aligned and then hot-pressed using a flat vulcanizing machine for 2 minutes at a pressure of 2 MPa and a temperature of 75°C. After cooling, a highly effective waterproof outdoor garment is obtained.

[0080] Example 4

[0081] Example 4 is based on Example 3. The only difference between Example 4 and Example 3 is that the reaction time of step (2) in preparing the modified metal-organic framework material is 18 hours.

[0082] Example 5

[0083] Example 5 is based on Example 3. The only difference between Example 5 and Example 3 is that the reaction time of step (2) in preparing the modified metal-organic framework material is 30 hours.

[0084] Example 6

[0085] Example 6 is based on Example 3. The only difference between Example 6 and Example 3 is that the mass ratio of tannic acid to polylactic acid is 0.02:1, the amount of tannic acid is 3.45g, and the amount of polylactic acid is 171.6g.

[0086] Example 7

[0087] Example 7 is based on Example 3. The only difference between Example 7 and Example 3 is that in Example 7, the mass ratio of tannic acid to polylactic acid is 0.3:1, the amount of tannic acid is 40.5g, and the amount of polylactic acid is 134.7g.

[0088] Example 8

[0089] Example 8 is based on Example 3. The only difference between Example 8 and Example 3 is that the mass ratio of tetrabutylammonium bromide to modified polyurethane in Example 8 is 0.02:1, and the amount of tetrabutylammonium bromide is 4.9g.

[0090] Example 9

[0091] Example 9 is based on Example 3. The only difference between Example 9 and Example 3 is that in Example 9, the mass ratio of tetrabutylammonium bromide to modified polyurethane is 0.2:1, and the amount of tetrabutylammonium bromide is 41.7g.

[0092] Comparative Example

[0093] Comparative Example 1

[0094] Comparative Example 1 is based on Example 3. The only difference between Comparative Example 1 and Example 3 is that tannic acid is replaced with carvacrol in Comparative Example 1.

[0095] Comparative Example 2

[0096] Comparative Example 2 is based on Example 3. The only difference between Comparative Example 2 and Example 3 is that tetrabutylammonium bromide is replaced with ammonium bromide in Comparative Example 2.

[0097] Comparative Example 3

[0098] Comparative Example 3 is based on Example 3. The only difference between Comparative Example 3 and Example 3 is that the modified metal-organic framework material in Comparative Example 3 is replaced with nano-titanium dioxide.

[0099] Performance testing

[0100] (1) Select GB / T4744-2013 Test and evaluation of waterproof performance of textiles by hydrostatic pressure method as the standard. Take five 10cm×10cm samples from different parts of the waterproof clothing, record the pressure value when the third seepage point appears, test each sample three times, take the average value after measurement, and fill in the measurement results in Table 1.

[0101] (2) Select GB / T12704.2-2009 Textiles - Test Method for Moisture Permeability of Fabrics - Part 2: Evaporation Method as the standard. Take three samples with a diameter of 70 cm from different parts of the waterproof clothing. Under the conditions of 38℃ temperature and 50% humidity, use the inverted cup method to calculate the moisture permeability of the samples. After measurement, take the average value of the three samples and fill in the measurement results in Table 1.

[0102] (3) Select GB / T18830-2009 Evaluation of UV protection performance of textiles as the standard, select four parts on the waterproof clothing to cut 10cm×10cm samples, record the transmittance between 290nm and 400nm, record once every five minutes, calculate the UPF value and UVA transmittance, and record the results in Table 2.

[0103] (4) Select GB / T20944.2-2007 Evaluation of antibacterial properties of textiles - Part 2: Absorption method as the standard, cut 6 samples of 0.4g each, incubate and wash them, calculate the antibacterial rate and fill in the measurement results in Table 2.

[0104] Table 1. Test results of the waterproof and breathable properties of waterproof clothing

[0105]

[0106]

[0107] Table 2. Test results of UV resistance and antibacterial properties of waterproof clothing

[0108] Test content UPF value UVA transmittance / % Escherichia coli inhibition rate / % Example 1 53.5 0.47 99.5 Example 2 54.2 0.54 99.3 Example 3 56.9 0.23 99.8 Example 4 51.3 0.69 98.9 Example 5 48.9 0.98 97.3 Example 6 45.9 1.13 95.9 Example 7 46.3 1.11 95.3 Example 8 42.5 1.56 93.1 Example 9 41.7 1.83 92.8 Comparative Example 1 34.8 5.9 87.2 Comparative Example 2 37.1 5.37 88.5 Comparative Example 3 30.3 6.42 81.4

[0109] As shown in Table 1, the hydrostatic pressure resistance of Examples 1-3 all reached over 161.2 kPa, and the moisture permeability reached 9937 g / (m³). 2 The results show that the high-efficiency waterproof outdoor waterproof clothing prepared in this application has good waterproof and breathable properties (24h and above). The UPF values ​​of Examples 1-3 are greater than 53.5, the UVA transmittance is all below 0.54%, and the antibacterial rate is greater than 99.3%. It can be seen that the high-efficiency waterproof outdoor waterproof clothing prepared in this application has excellent UV resistance and antibacterial properties.

[0110] As shown in Table 1, compared with Example 3, the waterproof and breathable properties of Example 4 were weakened, and the UV resistance and antibacterial properties were reduced. This is because the reaction time was too short, the doping rate of titanium ions in the modified metal-organic framework material was low, and the pore structure, UV resistance and antibacterial properties of the modified metal-organic framework material did not reach the optimal state. As a result, the synergistic effect of the modified metal-organic framework material with the modified polylactic acid and modified polyurethane was weakened, thus resulting in a decrease in the waterproof and breathable properties, UV resistance and antibacterial properties of the waterproof clothing.

[0111] As shown in Table 1, compared with Example 3, Example 5 showed an improvement in water repellency but a decrease in moisture permeability, UV resistance, and antibacterial properties. This is because the reaction time was too long, which affected the topological structure of the modified metal-organic framework material. At the same time, the doping rate of titanium ions was not further improved. The excessively long reaction time reduced the porosity of the modified metal-organic framework material, weakening its UV resistance and antibacterial properties. This weakened the synergistic effect between the modified metal-organic framework material, modified polylactic acid, and modified polyurethane, resulting in an improvement in the water repellency of the waterproof garment, but a decrease in moisture permeability, UV resistance, and antibacterial properties.

[0112] As shown in Table 1, compared with Example 3, Example 6 exhibits a weakened waterproof and breathable performance, and a decrease in UV resistance and antibacterial properties. This is because the amount of tannic acid was reduced, resulting in insufficient modification of polylactic acid and a decrease in the hydrophilicity of the modified polylactic acid, thus weakening its waterproof and breathable performance. The reduction in tannic acid also reduced the UV resistance and antibacterial properties of the modified polylactic acid. Furthermore, the synergistic effect between the modified polylactic acid, the modified metal-organic framework material, and the modified polyurethane was weakened, leading to a decrease in UV resistance and antibacterial properties.

[0113] As shown in Table 1, compared with Example 3, the waterproof and breathable properties of Example 7 were weakened, and the UV resistance and antibacterial properties were reduced. This is because the amount of tannic acid was increased. Excessive tannic acid will lead to a decrease in the mechanical properties of modified polylactic acid and a reduction in the thermal stability of polylactic acid. This may affect the performance of modified polylactic acid in subsequent hot pressing processes, thereby weakening the synergistic effect of modified polylactic acid with modified metal-organic framework materials and modified polyurethane. As a result, the waterproof and breathable properties, UV resistance, and antibacterial properties were all reduced.

[0114] As shown in Table 1, compared with Example 3, the waterproof and breathable properties of Example 8 were weakened, and the UV resistance and antibacterial properties were reduced. This is because the amount of tetrabutylammonium bromide was reduced, the conductivity of the spinning solution was reduced, the charge density on the fiber surface was reduced during the jet stretching process, and not enough fine branched fibers were formed. As a result, the hydrophobic properties of the modified polyurethane were not enhanced. At the same time, the reduction of branched fibers reduced the number of attachment sites, and the modified metal-organic skeleton material was not fully attached to the surface of the modified polyurethane. As a result, the waterproof and breathable properties, UV resistance, and antibacterial properties of the waterproof garment were all reduced to varying degrees.

[0115] As shown in Table 1, compared with Example 3, the waterproof and breathable properties of Example 9 were weakened, and the UV resistance and antibacterial properties were reduced. This is because the amount of tetrabutylammonium bromide was increased. The excessive addition of tetrabutylammonium bromide made the conductivity of the spinning solution too high, causing instability in the spinning process, resulting in a large amount of adhesion between fibers, and damage to the microporous structure of the fibers. At the same time, the adhesion rate of the modified metal-organic framework material was reduced, thus leading to a decrease in the waterproof and breathable properties, UV resistance, and antibacterial properties of the waterproof garment.

[0116] As shown in Table 1, compared with Comparative Example 1 and Example 3, the waterproof and breathable properties decreased significantly, as did the UV resistance and antibacterial properties. This is because although carvacrol also has certain UV resistance and antibacterial capabilities, its hydrophilicity is poor, which limits its effect on modifying the hydrophilicity of polylactic acid. Consequently, the breathable properties of the modified polylactic acid decreased significantly, and the synergistic effect between the modified polylactic acid, the metal-organic framework material, and the modified polyurethane weakened. As a result, the waterproof and breathable properties, UV resistance, and antibacterial properties of the waterproof garment all decreased significantly.

[0117] As shown in Table 1, compared with Comparative Example 2 and Example 3, the waterproof and breathable properties, UV resistance, and antibacterial properties of the waterproof garment were significantly reduced. This is because the conductivity of ammonium bromide in the spinning solution is lower than that of tetrabutylammonium bromide, the charge density on the fiber surface decreases during jet stretching, and the number of fine branched fiber structures in the waterproof garment decreases. This weakens the enhancing effect on the hydrophilic and hydrophobic properties of modified polylactic acid. At the same time, the reduction of branched fibers means that the modified metal-organic framework material does not fully adhere to the surface of modified polylactic acid and modified polyurethane, thus resulting in a significant decrease in the waterproof and breathable properties, UV resistance, and antibacterial properties of the waterproof garment.

[0118] As shown in Table 1, compared with Comparative Example 3, the waterproof and breathable properties, UV resistance, and antibacterial properties of the waterproof garment were significantly reduced. This is because nano-titanium dioxide lacks a porous structure, which reduces the breathability of the waterproof garment. The UV resistance and antibacterial properties exerted by the only titanium atoms in nano-titanium dioxide are limited. Therefore, the waterproof and breathable properties, UV resistance, and antibacterial properties of the waterproof garment are significantly reduced when nano-titanium dioxide is used.

[0119] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A highly effective waterproof outdoor waterproof garment, characterized in that: The highly effective waterproof outdoor waterproof clothing is made of a waterproof and breathable fabric, which comprises a fine denier polyester base fabric and a nanofiber membrane. The nanofiber membrane comprises the following components in parts by weight: 5-15 parts of modified metal-organic framework material 150-200 parts of modified polylactic acid 250-300 parts of modified polyurethane; The modified metal-organic framework material includes zirconium tetrachloride, zinc tetracarboxyphenylporphyrin, benzoic acid, dichlorodicyclopentadiene, and N,N-dimethylformamide; The modified metal-organic framework material is prepared using the following steps: (1) Zirconium tetrachloride, zinc tetracarboxyphenylporphyrin and benzoic acid were mixed and dispersed in N,N-dimethylformamide, reacted at 100-140℃, cooled, washed and dried to obtain metal-organic framework material A; (2) Disperse metal-organic framework material A and titanium dichlorodecene in N,N-dimethylformamide, react at 100-140℃, cool, wash and dry to obtain modified metal-organic framework material; The modified polylactic acid was prepared using the following steps: Polylactic acid was pretreated by drying to obtain dried polylactic acid. The dried polylactic acid was then mixed and dispersed with tannic acid in N,N-dimethylformamide and stirred to obtain modified polylactic acid. The mass ratio of tannic acid to polylactic acid is (0.05-0.15):1; The nanofiber membrane also includes tetrabutylammonium bromide and polyvinylpyrrolidone; The highly effective waterproof outdoor waterproof clothing is prepared using the following steps: After pretreatment of fine denier polyester base fabric, an intermediate layer base fabric is obtained. Modified polylactic acid, polyvinylpyrrolidone and tetrabutylammonium bromide are mixed to obtain spinning solution A. Modified polyurethane, polyvinylpyrrolidone and tetrabutylammonium bromide are mixed to obtain spinning solution B. Modified metal-organic framework material is dispersed in N,N-dimethylformamide to obtain modified metal-organic framework material suspension. Using the intermediate layer base fabric as the receiving screen, the spinning solution A and the modified metal-organic framework material suspension are coaxially electrospun to obtain fabric A with a modified polylactic acid nanofiber membrane on one side. Using the side of fabric A away from the nanofiber membrane as a receiving screen, the spinning solution B and the modified metal-organic framework material suspension are coaxially electrospun to obtain fabric B with a modified polyurethane nanofiber membrane. Fabric B is then subjected to hot pressing treatment and washed to obtain a waterproof and breathable fabric. Waterproof and breathable fabrics are cut, glued, spliced, and then hot-pressed and cooled to obtain highly waterproof outdoor clothing. The mass ratio of the tetrabutylammonium bromide to the modified polyurethane is (0.1-0.15):

1.

2. The highly efficient waterproof outdoor waterproof clothing according to claim 1, characterized in that: The reaction time required in step (2) of the preparation of the modified metal-organic framework material at 100-140℃ is 21-27 hours.

3. The highly efficient waterproof outdoor waterproof clothing according to claim 1, characterized in that: The modified polyurethane is prepared using the following steps: Polyurethane, methylhydrosiloxane and hydrophobic titanium dioxide were dispersed in N,N-dimethylformamide, stirred and allowed to stand to obtain modified polyurethane.

Images