Waterproof clothing coating and preparation method thereof

Abstract

The invention belongs to the technical field of coating compositions, and relates to a waterproof clothing coating and a preparation method thereof. The invention provides a waterproof clothing coating, the waterproof clothing coating is formed by coating, drying and cooling a waterproof composite emulsion, the waterproof composite emulsion is formed by mixing and emulsifying a water phase and an oil phase, and the water phase is composed of a pretreated fluorocarbon-silane composite dispersion liquid, ethylene glycol and 1, 2-propylene glycol; the oil phase is prepared from an acrylate-organosilicon copolymer, isododecane, isopropyl myristate, hydrogenated polydecene and microcrystalline wax. The waterproof clothing coating provided by the invention realizes synchronous improvement of waterproofness and stability.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of coating compositions, and relates to a waterproof garment coating and a preparation method thereof. BACKGROUND

[0002] The waterproof performance of garments is crucial for outdoor sports, field operations and daily rain and snow weather protection. Traditional garment waterproof coatings mostly rely on polytetrafluoroethylene (PTFE) film lamination or fluorocarbon coating finishing, which can provide initial waterproof effect, but generally have the problem of insufficient durability. After long-term use or repeated washing, the waterproof effect of the coating will rapidly decay due to physical wear, chemical degradation or surface microstructure damage, resulting in failure of the waterproof performance of the garment.

[0003] To improve durability, existing technologies often add inorganic nanoparticles (such as silicon dioxide, zinc oxide) to the coating to build a rough structure. However, the compatibility of inorganic fillers with the organic coating matrix is poor, and they are prone to agglomeration or precipitation from the coating, which not only affects the uniformity of the coating, but also the rough structure built by them is easily damaged during friction and washing.

[0004] Therefore, there is an urgent need in the current industry for a new solution to garment waterproof coating. This solution needs to overcome the contradiction of existing technologies, that is, to impart excellent waterproofness to garments while significantly improving their long-term stability against washing and friction. Developing a waterproof coating with high performance, high durability and good practicality has become a key technical requirement for promoting the upgrading of the functional garment industry. SUMMARY

[0005] The present application provides an improved waterproof garment coating and a preparation method thereof to overcome the shortcomings of the prior art and achieve simultaneous improvement of waterproofness and stability.

[0006] To achieve this technical purpose, the present application adopts the following technical solutions:

[0007] In a first aspect, the present application provides a waterproof garment coating formed by coating, drying and cooling of a waterproof composite emulsion, wherein the waterproof composite emulsion is formed by mixing and emulsifying an aqueous phase and an oil phase, and wherein the aqueous phase is composed of a pretreated fluorocarbon-silane composite dispersion, ethylene glycol and 1,2-propanediol; the oil phase is composed of an acrylate-silicone copolymer, isododecane, isopropyl myristate, hydrogenated polydecene and microcrystalline wax; The preparation method of the pretreated fluorocarbon-silane composite dispersion is as follows: The 10% fluorocarbon-silane composite aqueous dispersion liquid is mixed with 10 mM phosphate buffer (pH 7.0-7.5) at a volume ratio of 1:1-1:2, and a uniform dispersion liquid is obtained by magnetic stirring (stirring speed: 300-500 rpm, stirring time: 30-60 min); the uniform dispersion liquid is dialyzed with a dialysis bag with a molecular weight cut-off of 8-14 kDa and deionized water (dialysis time: 24-48 h, water change every 6-8 h), and a dialyzed dispersion liquid is obtained; 3% (mass percent) trehalose, 2.0 mM ascorbic acid glucoside, and 0.5% (mass percent) polyglycerol-3 diisostearate are added to the dialyzed dispersion liquid, and oxygen is removed by inert gas (such as nitrogen or argon) blowing (blowing time: 15-30 min) to obtain a modified dispersion liquid. Lecithin, polyglycerol-6 distearate, and stearamidopropyl dimethylamine are mixed at a mass ratio of 4:3:3, deionized water is added (the mass ratio of the total mass of lecithin, polyglycerol-6 distearate, and stearamidopropyl dimethylamine to the mass of deionized water is 1:10-1:20), and an ultrasonic emulsion is obtained by ultrasonic emulsification (ultrasonic power: 200-400 W, ultrasonic time: 10-20 min, working mode: ultrasonic 2 s / intermittent 2 s) under ice bath conditions. The modified dispersion liquid and the composite micelle emulsion are mixed at a volume ratio of 7:1-9:1, and the mixture is incubated (time: 2-4 h) at 20-30°C by gentle shaking (shaking frequency: 80-120 times / min, shaking amplitude: 2-4 cm) to obtain the pretreated fluorocarbon-silane composite dispersion liquid.

[0008] Preferably, the preparation method of the 10% fluorocarbon-silane composite aqueous dispersion liquid is as follows: Fluorocarbon emulsion (solid content: 40-60%) and alkoxysilane hydrolysate are mixed at a mass ratio of 2:1, deionized water is added (the amount of deionized water is added to make the solid content of the primary dispersion liquid 5-8%), and the primary dispersion liquid is obtained by stirring; 0.3% (mass percent) sodium polyacrylate is added to the primary dispersion liquid, and the dispersion liquid is obtained by high-speed shearing dispersion (shearing speed: 8000-12000 rpm, time: 5-10 min); the dispersion liquid is treated by circulating through a high-pressure homogenizer (homogenization pressure: 80-120 MPa, circulation times: 3-5 times); and finally, the dispersion liquid is concentrated to a solid content of 10% (mass percent) by ultrafiltration to obtain the 10% fluorocarbon-silane composite aqueous dispersion liquid.

[0009] Preferably, the alkoxysilane hydrolysate is obtained by hydrolysis of methyltrimethoxysilane, ethanol, water, and an acidic catalyst at a mass ratio of 10:50:40:0.5.

[0010] More preferably, the acidic catalyst is selected from at least one of hydrochloric acid, acetic acid and p-toluene sulfonic acid.

[0011] Preferably, the water phase is composed of 70-90 parts of pretreated fluorocarbon-silane composite dispersion liquid, 5-15 parts of ethylene glycol and 2-8 parts of 1,2-propylene glycol by mass fraction.

[0012] Preferably, the oil phase is composed of 10-20 parts of acrylate-silicone copolymer (silicone-acrylate copolymer), 8-14 parts of isododecane, 4-10 parts of isopropyl myristate, 3-7 parts of hydrogenated polydecene and 0.5-2 parts of microcrystalline wax by mass fraction.

[0013] More preferably, the water phase is composed of 80 parts of pretreated fluorocarbon-silane composite dispersion liquid, 10 parts of ethylene glycol and 5 parts of 1,2-propylene glycol by mass fraction.

[0014] More preferably, the oil phase is composed of 15 parts of acrylate-silicone copolymer, 11 parts of isododecane, 7 parts of isopropyl myristate, 5 parts of hydrogenated polydecene and 1.2 parts of microcrystalline wax by mass fraction.

[0015] Preferably, the water-repellent composite emulsion is O / W type, with a median particle size (D50) of 150-300 nm and a particle size distribution index (PDI) ≤0.25.

[0016] Preferably, the mass ratio of the water phase to the oil phase is 4:1-7:1.

[0017] In the second aspect, a preparation method of the water-repellent clothing coating is provided, which comprises the following steps: The pretreated fluorocarbon-silane composite dispersion liquid, ethylene glycol and 1,2-propylene glycol are mixed and stirred at 25-35℃ (stirring speed: 200-400 rpm, time: 20-40 min) until uniform and transparent, to obtain the water phase; The microcrystalline wax is heated and melted at 72-75℃, and the acrylate-silicone copolymer, isododecane, isopropyl myristate and hydrogenated polydecene are added and stirred uniformly at 75-80℃ (stirring speed: 400-600 rpm, time: 30-45 min), to obtain the oil phase; cooling circulation system (keeping the material temperature below 40℃), control the median particle size (D50) of the emulsion to 150-300 nm, then cool down to 25-30℃ and low-speed stirring (stirring speed is 50-100 rpm, time is 2-4 h) to mature, forming the emulsion (waterproof composite emulsion) ; coat the emulsion on the surface of the garment substrate with a coating amount of 20-30 g / m 2 of dry weight gain, and after drying at 100-120℃ for 1-3 min and natural cooling, the waterproof garment coating is obtained.

[0018] It should be noted that the dry weight gain refers to the mass of solid coating deposited on the unit area of the garment substrate after drying and curing.

[0019] In a third aspect, the application provides the use of the waterproof garment coating described in the application in improving the waterproofness, wash resistance and / or rubbing resistance of the garment.

[0020] Compared with the prior art, the technical solution provided by the application has at least the following beneficial effects or advantages: ‌(1) The modification system composed of trehalose, ascorbic acid glucoside and polyglycerol-3 diisostearate in the application can regulate the strong hydrophobic surface of fluorocarbon-silane composite water dispersion to a moderate hydrophilic state after removing oxygen by inert gas blowing, which not only retains its ultra-low surface energy characteristics to maintain waterproof performance, but also significantly improves the compatibility with water-based systems, avoiding the interface phase separation caused by traditional physical mixing. The modification system provides stable chemical anchoring points for subsequent composite micelle encapsulation through dynamic hydrogen bond network and electrostatic interaction, which is the key interface modification technology to endow the waterproof garment coating of the application with wash resistance.‌

[0021] ‌(2) The composite micelle emulsion formed by lecithin, polyglycerol-6 distearate and stearamidopropyl dimethylamine in a specific ratio, which is a dynamic nanocarrier constructed under ice bath ultrasonic conditions, can provide a strong and tough interface stabilization network for the modified fluorocarbon-silane dispersion. The composite micelle can deeply wrap the modified fluorocarbon-silane particles in the micellar core or anchor them in the interface membrane, forming a nanoscale protective unit resistant to shear and high temperature, which is the core structure to ensure that the waterproof garment coating of the application resists mechanical damage and water washing damage during coating, drying and use.‌

[0022] (3) The present application incubates the modified dispersion liquid and the composite micelle emulsion in a specific ratio, realizes molecular level coupling and structure reorganization through 20-30℃ gentle oscillation, and finally forms a pretreated fluorocarbon-silane composite dispersion liquid which is a functional composite unit, and the fluorocarbon chain segment and the silane group in the unit are stably realized by the space steric hindrance of the composite micelle network. The structure can effectively inhibit the particle migration, aggregation and interface precipitation caused by shear force, temperature fluctuation or water washing during the subsequent emulsification, coating and high temperature drying process, and is the fundamental reason for giving the coating excellent friction resistance, washing resistance and long-term waterproof stability.

[0023] (4) The present application combines the dispersion of sodium polyacrylate and the hydrolysis of alkoxy silane, and through high pressure homogenization and ultrafiltration concentration process, an initial dispersion system with high solid content and low agglomeration is constructed in the pretreatment stage. The composite dispersion liquid forms a fluorocarbon-silane hybrid network through silane hydrolysis and condensation reaction, provides a uniform matrix interface for subsequent composite micelle encapsulation, and further optimizes the particle size distribution through high pressure homogenization circulation treatment, ensuring the uniformity, density and mechanical strength of the waterproof network structure in the final coating.

[0024] (5) The water phase and the oil phase are combined to form a waterproof composite emulsion through O / W type emulsification process. The waterproof composite emulsion system realizes the balance between waterproofness and air permeability through precise control of the mass ratio of water phase to oil phase and particle size distribution, meeting the harsh use requirements of outdoor clothing. DETAILED DESCRIPTION

[0025] In the following, the technical solutions of the present application will be described in conjunction with examples. However, the present application is not limited to the following examples. The experimental methods and detection methods described in each example are conventional methods unless otherwise specified. The reagents and materials described are commercially available unless otherwise specified.

[0026] Example 1 The present embodiment provides a waterproof clothing coating, which is formed by coating, drying and cooling of a waterproof composite emulsion (O / W type, D50 is 150-300 nm, particle size distribution index is ≤0.25). The waterproof composite emulsion is formed by mixing and emulsifying a water phase and an oil phase, and the mass ratio of the water phase to the oil phase is 4:1; the mass fraction is as follows: The water phase is composed of 70 parts of pretreated fluorocarbon-silane composite dispersion liquid, 5 parts of ethylene glycol and 2 parts of 1,2-propanediol. The oil phase is composed of 10 parts of acrylate-silicone copolymer (silicone-acrylate copolymer), 8 parts of isododecane, 4 parts of isopropyl myristate, 3 parts of hydrogenated polydecene and 0.5 parts of microcrystalline wax.

[0027] The preparation method of the pretreated fluorocarbon-silane composite dispersion liquid is as follows: 10% (mass percentage) fluorocarbon-silane composite aqueous dispersion liquid was mixed with 10 mM phosphate buffer (pH 7.0-7.5) at a volume ratio of 1:1, and a uniform dispersion liquid was obtained by magnetic stirring (stirring speed was 300 rpm, and stirring time was 30 min). The uniform dispersion liquid was dialyzed with a dialysis bag with a molecular weight cut-off of 8-14 kDa and deionized water (dialysis time was 24 h, and water was changed every 6 h), and a post-dialysis dispersion liquid was obtained. 3% (mass percentage) trehalose, 2.0 mM ascorbic acid glucoside, and 0.5% (mass percentage) polyglycerol-3 diisostearate were added to the post-dialysis dispersion liquid, and oxygen was removed by nitrogen blowing (blowing time was 15 min), and a modified dispersion liquid was obtained. Lecithin, polyglycerol-6 distearate, and stearamidopropyl dimethylamine were mixed at a mass ratio of 4:3:3, deionized water was added (the mass ratio of the total mass of lecithin, polyglycerol-6 distearate, and stearamidopropyl dimethylamine to the mass of deionized water was 1:10), and an ultrasonic emulsion was obtained by ultrasonic emulsification (ultrasonic power was 200 W, ultrasonic time was 10 min, and working mode was ultrasonic 2 s / intermittent 2 s) under ice bath conditions. The modified dispersion liquid and the composite micelle emulsion were mixed at a volume ratio of 7:1, and the mixture was incubated (time was 2 h) at 20°C under gentle oscillation (oscillation frequency was 80 times / min, and amplitude was 2 cm) to obtain the pretreated fluorocarbon-silane composite dispersion liquid.

[0028] The preparation method of the 10% fluorocarbon-silane composite aqueous dispersion liquid is as follows: Fluorocarbon emulsion (solid content was 40-60%) and alkoxysilane hydrolyzate (obtained by stirring hydrolysis of methyltrimethoxysilane, ethanol, water, and glacial acetic acid at a mass ratio of 10:50:40:0.5 at 25°C for 24 h) were mixed at a mass ratio of 2:1, deionized water was added (the amount of deionized water was added to make the solid content of the primary dispersion liquid 5%), and the mixture was stirred to obtain a primary dispersion liquid. 0.3% (mass percentage) sodium polyacrylate was added to the primary dispersion liquid, and the mixture was dispersed at a high speed (shear speed was 8000 rpm, and time was 5 min) to obtain a dispersion liquid. The dispersion liquid was treated by circulating through a high-pressure homogenizer (homogenization pressure was 80 MPa, and circulation number was 3 times). Finally, the dispersion liquid was concentrated by ultrafiltration to a solid content of 10% (mass percentage) to obtain the 10% fluorocarbon-silane composite aqueous dispersion liquid.

[0029] Example 2 The embodiment provides a waterproof garment coating, the waterproof garment coating is formed after waterproof composite emulsion (O / W type, D50 is 150-300 nm, and the particle size distribution index is less than or equal to 0.25) is coated, dried and cooled, the waterproof composite emulsion is formed after water phase and oil phase are mixed and emulsified, and the mass ratio of the water phase to the oil phase is 7:1, according to mass fraction; The water phase is composed of 90 parts of pretreated fluorocarbon-silane composite dispersion liquid, 15 parts of ethylene glycol and 8 parts of 1,2-propylene glycol; The oil phase is composed of 20 parts of acrylate-silicone copolymer (silicone-acrylate copolymer), 14 parts of isododecane, 10 parts of isopropyl myristate, 7 parts of hydrogenated polydecene and 2 parts of microcrystalline wax.

[0030] The preparation method of the pretreated fluorocarbon-silane composite dispersion liquid is as follows: 10% (mass percent) fluorocarbon-silane composite water dispersion liquid is mixed with 10 mM phosphate buffer (pH 7.0-7.5) at a volume ratio of 1:2, and a uniform dispersion liquid is obtained by magnetic stirring (stirring speed is 500 rpm, and stirring time is 60 min); the uniform dispersion liquid is dialyzed with a dialysis bag with a molecular weight cut-off of 8-14 kDa and deionized water (dialysis time is 48 h, and water is changed every 8 h), and a dialyzed dispersion liquid is obtained; 3% (mass percent) trehalose, 2.0 mM ascorbic acid glucoside and 0.5% (mass percent) polyglycerol-3 diisostearate are added to the dialyzed dispersion liquid, oxygen is removed by nitrogen blowing (blowing time is 30 min), and a modified dispersion liquid is obtained; Lecithin, polyglycerol-6 distearate and stearamidopropyl dimethylamine are mixed at a mass ratio of 4:3:3, deionized water is added (the mass ratio of the total mass of lecithin, polyglycerol-6 distearate and stearamidopropyl dimethylamine to the mass of deionized water is 1:20), and ultrasonic emulsification is performed under ice bath conditions (ultrasonic power is 400 W, ultrasonic time is 20 min, and the working mode is ultrasonic 2 s / intermittent 2 s), and a composite micelle emulsion is obtained; The modified dispersion liquid and the composite micelle emulsion are mixed at a volume ratio of 9:1, incubated (time is 4 h) at 30 DEG C under gentle oscillation (oscillation frequency is 120 times / min, and amplitude is 4 cm), and the pretreated fluorocarbon-silane composite dispersion liquid is obtained.

[0031] The preparation method of the 10% fluorocarbon-silane composite water dispersion liquid is as follows: The fluorocarbon emulsion (solid content of 40-60%) and the alkoxysilane hydrolysis solution (obtained by stirring methyltrimethoxysilane, ethanol, water and glacial acetic acid at a mass ratio of 10:50:40:0.5 at 25°C for 24 h) are mixed at a mass ratio of 2:1, deionized water is added (the amount of addition is such that the solid content of the primary dispersion is 8%), and stirring is performed to obtain a primary dispersion; 0.3% (mass percentage) of sodium polyacrylate is added to the primary dispersion, high-speed shearing dispersion (shearing speed of 12000 rpm, time of 10 min) is performed to obtain a dispersion; the dispersion is treated by circulating through a high-pressure homogenizer (homogenization pressure of 120 MPa, circulation number of 5 times); and finally, ultrafiltration concentration is performed to obtain a 10% fluorocarbon-silane composite water dispersion with a solid content of 10% (mass percentage).

[0032] Example 3 The present example provides a waterproof garment coating, which is formed after the waterproof composite emulsion (O / W type, D50 of 150-300 nm, particle size distribution index ≤0.25) is coated, dried and cooled, and the waterproof composite emulsion is formed after the water phase and the oil phase are mixed and emulsified, and the mass ratio of the water phase to the oil phase is 6:1, and the proportions are calculated by mass; The water phase is composed of 80 parts of pretreated fluorocarbon-silane composite dispersion, 10 parts of ethylene glycol and 5 parts of 1,2-propanediol; The oil phase is composed of 15 parts of acrylate-silicone copolymer, 11 parts of isododecane, 7 parts of isopropyl myristate, 5 parts of hydrogenated polydecene and 1.2 parts of microcrystalline wax.

[0033] The preparation method of the pretreated fluorocarbon-silane composite dispersion is as follows: The 10% (mass percentage) fluorocarbon-silane composite water dispersion is mixed with 10 mM phosphate buffer (pH 7.0-7.5) at a volume ratio of 1:1, and magnetic stirring (stirring speed of 300 rpm, time of 50 min) is performed to obtain a uniform dispersion; the uniform dispersion is dialyzed (dialysis time of 36 h, water change every 6 h) with a dialysis bag with a molecular weight cut-off of 8-14 kDa and deionized water to obtain a post-dialysis dispersion; 3% (mass percentage) of trehalose, 2.0 mM of ascorbic acid glucoside and 0.5% (mass percentage) of polyglycerol-3 diisostearate are added to the post-dialysis dispersion, and oxygen is removed by nitrogen blowing (blowing time of 20 min) to obtain a modified dispersion; Lecithin, polyglycerol-6 distearate, and stearamide propyl dimethylamine were mixed in a mass ratio of 4:3:3, and deionized water was added (the total mass of lecithin, polyglycerol-6 distearate, and stearamide propyl dimethylamine was in a mass ratio of 1:15 to deionized water). The mixture was then subjected to ultrasonic emulsification under ice bath conditions (ultrasonic power of 200 W, ultrasonic time of 10 min, working mode of ultrasonic 2 s / intermittent 2 s) to obtain a composite micelle emulsion. The modified dispersion and the composite micelle emulsion were mixed at a volume ratio of 8:1 and incubated at 30°C with gentle shaking (oscillation frequency of 80 times / min and amplitude of 4 cm) for 4 h to obtain the pretreated fluorocarbon-silane composite dispersion.

[0034] The preparation method of the 10% fluorocarbon-silane composite aqueous dispersion is as follows: Fluorocarbon emulsion (solid content 40-60%) was mixed with alkoxysilane hydrolysate (obtained by hydrolyzing methyltrimethoxysilane, ethanol, water and glacial acetic acid in a mass ratio of 10:50:40:0.5 at 25°C for 24 h by stirring) at a mass ratio of 2:1. Deionized water was added (to make the initial dispersion solid content 5%) and stirred to obtain an initial dispersion. 0.3% (mass percentage) sodium polyacrylate was added to the initial dispersion and dispersed by high-speed shearing (shear speed 8000 rpm, time 7 min) to obtain a dispersion. The dispersion was circulated through a high-pressure homogenizer (homogenization pressure 80 MPa, number of cycles 3 times). Finally, it was concentrated by ultrafiltration to a solid content of 10% (mass percentage) to obtain the 10% fluorocarbon-silane composite aqueous dispersion.

[0035] Example 4 This embodiment provides a method for preparing a waterproof clothing coating, including the following steps: The pretreated fluorocarbon-silane composite dispersion, ethylene glycol, and 1,2-propanediol were mixed and stirred at a constant temperature of 25-35°C (stirring speed of 200-400 rpm, time of 20-40 min) until homogeneous and transparent to obtain the aqueous phase. Microcrystalline wax was heated and melted at 72-75℃, and acrylate-organosilicon copolymer, isododecane, isopropyl myristate and hydrogenated polydecene were added. The mixture was stirred evenly at 75-80℃ (stirring speed 400-600 rpm, time 30-45 min) to obtain the oil phase. The oil phase is cooled to 65-70℃ and slowly (at a rate of 1-3 drops / s) added to the preheated aqueous phase at the same temperature. High-speed homogenization and emulsification are then performed at 65-70℃ (homogenization speed 10000-15000 rpm, time 3-6 min) to form a primary emulsion. This primary emulsion is then circulated through a high-pressure homogenizer connected to a cooling circulation system (maintaining the material temperature below 40℃) (homogenization pressure 100-150 MPa, number of cycles 4-8), controlling the median particle size (D50) to 150-300 nm. Subsequently, the temperature is lowered to 25-30℃ and slowly stirred (stirring speed 50-100 rpm, time 2-4 h) to mature the emulsion, forming a dry weight gain of 20-30 g / m³. 2 The coating is applied to the surface of the garment substrate, dried at 100-120℃ for 1-3 minutes, and then naturally cooled to obtain the waterproof garment coating.

[0036] Comparative Example 1 This comparative example is the same as Example 3, except that in the preparation method of the pretreated fluorocarbon-silane composite dispersion, trehalose is replaced with sucrose.

[0037] Comparative Example 2 This comparative example is the same as Example 3, except that in the preparation method of the pretreated fluorocarbon-silane composite dispersion, lecithin is replaced with phosphatidylcholine.

[0038] Comparative Example 3 This comparative example is the same as Example 3, except that in the preparation method of the pretreated fluorocarbon-silane composite dispersion, the volume ratio of the modified dispersion to the composite micelle emulsion is adjusted to 6:1.

[0039] Effect verification Experimental subjects: (1) Clothing base material: Polyester-cotton blended fabric (65% polyester content, 35% cotton content, 180 g / m²) 2 After desizing, bleaching, and pre-treatment, the samples were cut into 200 mm × 200 mm specimens.

[0040] (2) Test samples: The waterproof clothing coatings prepared according to Example 4 for Examples 1-3 and Comparative Examples 1-3 were respectively applied to the same clothing substrate, with a coating amount (dry weight gain) of 25 g / m². 2 Dry at 110℃ for 2 min, then allow to cool and solidify naturally. Prepare 3 parallel samples for each group of samples.

[0041] Experimental methods: (1) Static water resistance (hydrostatic pressure resistance) test: Referring to GB / T 4744-2013 "Test and evaluation of water resistance performance of textiles by hydrostatic pressure method", a hydrostatic pressure tester was used to uniformly increase the pressure at a rate of 60 cmH2O / min. The pressure value when the third water droplet seeps out of the sample surface was recorded. The average value of 3 parallel samples was taken as the final hydrostatic pressure data (initial hydrostatic pressure value). The larger the value, the better the water resistance performance.

[0042] (2) Washability test: The test was conducted according to the 4N procedure in GB / T 8629-2017 "Test Procedures for Household Washing and Drying of Textiles". The detergent was ECE phosphate-free standard detergent, and the dosage was 4 g / L. The sample and the accompanying cloth were placed in the washing machine together and washed at 40°C with standard detergent. After 0, 5, 10 and 20 washes, the sample was taken out and dried at 60°C or below. After rebalancing, the hydrostatic pressure retention rate was tested according to the method in (1) above. The hydrostatic pressure retention rate (%) = (hydrostatic pressure value after washing / initial hydrostatic pressure value) × 100%. The higher the hydrostatic pressure retention rate, the better the washability.

[0043] (3) Abrasion resistance test: Refer to GB / T 3920-2008 "Color fastness test of textiles - color fastness to rubbing" and use standard cotton rubbing cloth (dry state) to rub back and forth 1000 times with a vertical pressure of 9 N and a frequency of 1 time per second. After rubbing, test the waterproof performance according to the above method (1) and calculate the hydrostatic pressure retention rate. Hydrostatic pressure retention rate (%) = (hydrostatic pressure after rubbing / hydrostatic pressure before rubbing) × 100%.

[0044] (4) Coating surface condition (observation with a 20x magnifying glass): A 20x magnifying glass is used to systematically observe the friction contact center area of ​​the sample after the friction resistance test. The observation area covers at least three different locations. The focus is on examining the continuity, smoothness and integrity of the coating, including whether there are defects such as peeling, particle shedding, scratches, cracks, exposed substrate and uneven gloss.

[0045] Experimental results: The results of static water resistance (hydrostatic pressure resistance) and washability tests are shown in Table 1, and the results of static water resistance (hydrostatic pressure resistance), abrasion resistance and coating surface condition are shown in Table 2.

[0046] Table 1

[0047] As shown in Table 1, the initial hydrostatic pressure of Examples 1-3 (538.6-675.2 cm H2O) was significantly higher than that of the comparative examples (367.2-433.5 cm H2O). The core reason is that the present invention forms a uniform and dense waterproof network. Example 3 showed the best effect, as the aqueous phase, oil phase, and dispersion-micelle ratio were the optimal combination, resulting in the best continuity and density of the waterproof network, thus achieving the highest hydrostatic pressure. In Comparative Example 1, sucrose could not form a dynamic hydrogen bond network, the fluorocarbon-silane surface modification effect was insufficient, and the waterproof components were unevenly dispersed. The micelles formed in Comparative Example 2 had a higher curvature and insufficient stability during dynamic emulsification, leading to a worse initial encapsulation effect and a decrease in coating density. In Comparative Example 3, the amount of micelles was insufficient (volume ratio 6:1), failing to form a complete and stable interfacial network, resulting in micropores in the coating and a significant decrease in hydrostatic pressure.

[0048] The hydrostatic retention rates of Examples 1-3 (82.2-89.4% after 20 washes) were significantly higher than those of the comparative examples (57.2-65.1%), with Example 3 exhibiting the highest retention rate. This is because the functionalized composite units formed by the modified system and the composite micelles in this invention resist shear forces and water molecule erosion during washing, effectively inhibiting the migration and precipitation of fluorocarbon-silane particles. Inert gas purging removes oxygen, preventing oxidative degradation of the modified system and further enhancing its wash resistance stability. In contrast, the sucrose hydroxyl groups in Comparative Example 1 readily combine with water molecules, leading to swelling and detachment of the modified layer; the phosphatidylcholine micelles in Comparative Example 2 have lower mechanical strength and are more prone to rupture under shear forces and water molecule swelling during washing, resulting in accelerated loss of the encapsulated waterproof particles; and the micelle network in Comparative Example 3 is incomplete, failing to fix the waterproof particles, leading to significant particle loss during washing and the lowest retention rate.

[0049] Table 2

[0050] As shown in Table 2, the hydrostatic pressure retention rates of Examples 1-3 (88.1-90.5%) were significantly higher than those of the comparative examples (68.6-73.9%), and the coating structures remained intact. The core reason for this is that the dynamic nanocarrier constructed by the composite micelles of this invention provides strong interfacial protection for the fluorocarbon-silane particles, resisting frictional mechanical damage; the dynamic hydrogen bond network formed by the modification system synergistically enhances the adhesion between the coating and the substrate, preventing coating peeling due to friction. In contrast, the sucrose-modified surface in Comparative Example 1 lacked sufficient wear resistance, leading to damage to the modified layer after friction; the interfacial protective layer provided by phosphatidylcholine in Comparative Example 2 lacked sufficient mechanical strength and wear resistance, making the micelle structure more prone to breakage during friction, failing to effectively anchor the particles, resulting in severe particle detachment; and the micelle dosage in Comparative Example 3 was insufficient, failing to completely encapsulate the particles, leading to particle precipitation after friction, disrupting the coating continuity, and resulting in the lowest hydrostatic pressure retention rate.

[0051] The embodiments described above are some, but not all, of the embodiments of the present invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the claimed invention, but rather to illustrate selected embodiments of the invention. All other embodiments obtained by those skilled in the art through related deductions and substitutions based on the inventive concept, without inventive effort, are within the scope of protection of the present invention.

Claims

1. A waterproof clothing coating, characterized in that, The waterproof garment coating is formed by coating, drying, and cooling a waterproof composite emulsion, which is formed by emulsifying an aqueous phase and an oil phase. The aqueous phase consists of a pretreated fluorocarbon-silane composite dispersion, ethylene glycol, and 1,2-propanediol. The oil phase is composed of acrylate-organosilicon copolymer, isododecane, isopropyl myristate, hydrogenated polydecene, and microcrystalline wax. The preparation method of the pretreated fluorocarbon-silane composite dispersion is as follows: A 10% fluorocarbon-silane composite aqueous dispersion was mixed with a 10 mM phosphate buffer solution and magnetically stirred to obtain a homogeneous dispersion. The homogeneous dispersion was dialyzed with deionized water to obtain a post-dialysis dispersion. 3% trehalose, 2.0 mM ascorbate glucoside, and 0.5% polyglycerol-3 diisostearate were added to the post-dialysis dispersion, and oxygen was removed by inert gas purging to obtain a modified dispersion. Lecithin, polyglycerol-6 distearate and stearamide dimethylamine were mixed in a mass ratio of 4:3:3, deionized water was added, and ultrasonic emulsification was performed under ice bath conditions to obtain a composite micelle emulsion. The modified dispersion and the composite micelle emulsion were mixed at a volume ratio of 7:1 to 9:1 and gently shaken and incubated at 20-30°C to obtain the pretreated fluorocarbon-silane composite dispersion.

2. The waterproof clothing coating according to claim 1, characterized in that, The preparation method of the 10% fluorocarbon-silane composite aqueous dispersion is as follows: Fluorocarbon emulsion and alkoxysilane hydrolysate were mixed at a mass ratio of 2:1, and deionized water was added and stirred to obtain a preliminary dispersion. 0.3% sodium polyacrylate was added to the preliminary dispersion and dispersed by high-speed shearing to obtain a final dispersion. The dispersion was then circulated through a high-pressure homogenizer. Finally, it was concentrated to a solid content of 10% by ultrafiltration to obtain the 10% fluorocarbon-silane composite aqueous dispersion.

3. The waterproof clothing coating according to claim 1, characterized in that, The aqueous phase, by mass, consists of 70-90 parts of pretreated fluorocarbon-silane composite dispersion, 5-15 parts of ethylene glycol, and 2-8 parts of 1,2-propanediol.

4. The waterproof clothing coating according to claim 1, characterized in that, The oil phase, by weight, consists of 10-20 parts of acrylate-organosilicon copolymer, 8-14 parts of isododecane, 4-10 parts of isopropyl myristate, 3-7 parts of hydrogenated polydecene, and 0.5-2 parts of microcrystalline wax.

5. The waterproof clothing coating according to claim 3, characterized in that, The aqueous phase, by mass, consists of 80 parts of pretreated fluorocarbon-silane composite dispersion, 10 parts of ethylene glycol, and 5 parts of 1,2-propanediol.

6. The waterproof clothing coating according to claim 4, characterized in that, The oil phase, by weight, consists of 15 parts acrylate-organosilicon copolymer, 11 parts isododecane, 7 parts isopropyl myristate, 5 parts hydrogenated polydecene, and 1.2 parts microcrystalline wax.

7. The waterproof clothing coating according to claim 1, characterized in that, The waterproof composite emulsion is of the O / W type, with a median particle size of 150-300 nm and a particle size distribution index ≤0.

25.

8. The waterproof clothing coating according to claim 1, characterized in that, The mass ratio of the aqueous phase to the oil phase is 4:1 to 7:

1.

9. The method for preparing the waterproof clothing coating according to any one of claims 1-8, characterized in that, Includes the following steps: The pretreated fluorocarbon-silane composite dispersion, ethylene glycol, and 1,2-propanediol were mixed and stirred at a constant temperature until homogeneous and transparent to obtain the aqueous phase. Microcrystalline wax was heated to 72-75℃ and melted. Acrylate-organosilicon copolymer, isododecane, isopropyl myristate and hydrogenated polydecene were added and stirred evenly to obtain the oil phase. The oil phase is cooled to 65-70°C, and the aqueous phase, preheated to the same temperature, is slowly added. After high-speed homogenization and emulsification, a primary emulsion is formed. The primary emulsion is then circulated through a high-pressure homogenizer to control the emulsion particle size. Subsequently, it is cooled and matured by low-speed stirring to obtain a stable waterproof composite emulsion. The waterproof composite emulsion is coated onto the surface of a garment substrate, and after drying and cooling, the waterproof garment coating is obtained.

10. The use of the waterproof garment coating according to any one of claims 1-8 in improving the waterproofness, washability and / or abrasion resistance of garments.

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