Fluorine-free silicon wax waterproof finishing method of textile fabric and waterproof textile fabric

Abstract

The present application belongs to the field of textile functional finishing technology, and relates to a fluorine-free silicon wax waterproof finishing method for textile fabric and waterproof textile fabric. The method is as follows: components A and B are compounded into working solution before use, and the fabric is immersed and rolled, then pre-dried and cured. Component A is a fluorine-free silicon wax waterproof mother liquor containing hydroxyl silicone oil, long-chain polyhydroxy hydrophobic component, catalyst and emulsifier in the form of water-based emulsion, component B is a cationic blocked isocyanate crosslinking agent water dispersion, and n(C-OH) / n(Si-OH) satisfies 2.2-5.0. The present application can improve the waterproofness, wash resistance, durability and construction stability of the fabric, and is suitable for waterproof finishing of polyester, nylon, cotton and blended fabrics.

Description

Technical Field

[0001] This invention belongs to the field of functional finishing technology of textiles, specifically relating to a method for fluorine-free silicone wax waterproof finishing of textiles and a waterproof textile. Background Technology

[0002] Textile waterproofing agents mainly fall into two categories: fluorinated and fluorine-free. With increasingly stringent environmental regulations, fluorine-free waterproofing systems are receiving growing attention. Among existing fluorine-free waterproofing technologies, silicone-based waterproofing agents are widely used in fabric waterproofing due to their advantages such as softness, smoothness, and good breathability; however, their wash resistance and durability often have room for further improvement. Currently, publicly available information relates to fabric waterproofing agent systems containing silicone components such as hydroxyl silicone oil.

[0003] To improve the wash resistance of fluorine-free waterproofing finishes, existing technologies have proposed introducing blocked isocyanates into silicone waterproofing systems. For example, it has been published that blocked isocyanate-modified silicone waxes can be used for textile waterproofing, and that they can achieve better waterproofing and wash resistance when combined with fluorine-free waterproofing agents.

[0004] In addition, existing technologies also disclose cationic blocked isocyanate crosslinking agents and their formulations with waterproofing agents for waterproofing fabric finishing. Related commercial data also indicate that waterborne blocked polyisocyanate crosslinking agents can be used as latent crosslinking agents in cationic or other waterborne 1K systems.

[0005] However, existing technologies still have the following problems: Firstly, pre-introducing blocked isocyanates into silicone wax or pre-mixing them in waterproof mother liquor for a long period of time may complicate the system design and make it difficult to form a stable and clear application window. Secondly, existing technologies focus more on introducing the crosslinking agent itself, and less on formula design based on the balance between the construction of the organosilicon framework and the retention of subsequent crosslinking sites; Thirdly, there is still room for improvement in how to ensure initial waterproofness while also taking into account washability, durability, system storage stability, and fabric feel.

[0006] Therefore, it is necessary to provide a high-durability fluorine-free silicone wax waterproofing finishing system and its finishing method with a clearer structural logic and a process more suitable for industrial implementation. Summary of the Invention

[0007] The purpose of this invention is to provide a fluorine-free silicone wax waterproof finishing method for textiles and a waterproof textile, so as to solve the problems of existing fluorine-free waterproof finishing systems in terms of washability, process complexity and system logic consistency.

[0008] To achieve the above objectives, the present invention adopts the following technical solution: This invention provides a method for applying a fluorine-free silicone wax waterproofing finish to textiles, comprising the following steps: (1) Before use, component A and component B are compounded into a working solution; wherein, component A and component B are stored separately; component A is an aqueous emulsion type fluorine-free silicone wax waterproof mother liquor, which includes, by weight: 1~5 parts hydroxyl silicone oil, 15~22 parts long-chain polyhydroxy hydrophobic component, 0.5~2 parts catalyst, 1~3 parts emulsifier, and the remainder is water; The long-chain polyhydroxy hydrophobic component contains at least one C18 or higher hydrophobic segment and contains no less than two free hydroxyl groups that can react with isocyanates. The molar number of hydroxyl end hydroxyl groups in hydroxyl silicone oil is denoted as n(Si-OH), and the molar number of reactive hydroxyl groups in the long-chain polyhydroxy hydrophobic component is denoted as n(C-OH), satisfying 2.2≤n(C-OH) / n(Si-OH)≤5.0; Component B is an aqueous dispersion of a cationic blocked isocyanate crosslinking agent. (2) Immerse the fabric in the working solution and roll it out, controlling the liquid carry-over rate to 60-80%; (3) Pre-dry the fabric after rinsing with liquid at a temperature of 100~115℃ for 2~4 min; (4) Curing the pre-dried fabric at a temperature of 150~160℃ for 1~3 minutes.

[0009] Through the above technical solutions, hydroxyl silicone oil, long-chain polyhydroxy hydrophobic components, and component B synergistically construct a waterproof finishing layer on the fabric surface. This application is not limited to a specific mechanism of action. The inventors believe that the long-chain polyhydroxy hydrophobic components, on the one hand, provide C18 and above hydrophobic segments, which helps reduce the surface energy of the finishing layer; on the other hand, they provide reactive hydroxyl sites, which facilitate further reaction with the unsealed isocyanate groups during the curing stage. Therefore, a finishing layer with hydrophobicity, adhesion, and wash resistance can be formed on the fabric surface, thereby improving the overall waterproof finishing effect.

[0010] Preferably, the working solution is used up within 8 hours after being compounded.

[0011] Preferably, based on the working solution, the amount of component A is 20~80 g / L and the amount of component B is 5~30 g / L.

[0012] Preferably, the hydroxyl silicone oil is α,ω-dihydroxy-terminated polydimethylsiloxane with a number-average molecular weight of 160-300.

[0013] Preferably, the long-chain polyhydroxy hydrophobic component is selected from one or more of 1,18-octadecanediol, 1,2-octadecanediol, and 3-octadecoxypropane-1,2-diol.

[0014] Preferably, the catalyst is selected from one or more of benzenesulfonic acid, p-toluenesulfonic acid, and dodecylbenzenesulfonic acid.

[0015] Preferably, the emulsifier is selected from one or more of high-carbon fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ester, dehydrated sorbitan ester, and alkylphenol polyoxyethylene ether.

[0016] Preferably, n(Si-OH) is calculated using the following formula: n(Si-OH)=2m1 / Mn; where m1 is the mass of hydroxyl silicone oil and Mn is the number-average molecular weight of hydroxyl silicone oil.

[0017] When the long-chain polyhydroxy hydrophobic component is of one type: n(C-OH) = f·m2 / M; Where f is the free hydroxyl functionality of the long-chain polyhydroxy hydrophobic component, m2 is its mass, and M is its molecular weight.

[0018] When the long-chain polyhydroxy hydrophobic component consists of two or more types: n(C-OH) = Σ(fi·mi / Mi); Where fi is the free hydroxyl functionality of the i-th long-chain polyhydroxy hydrophobic component, mi is the mass of the i-th long-chain polyhydroxy hydrophobic component, and Mi is the molecular weight of the i-th long-chain polyhydroxy hydrophobic component.

[0019] The values ​​of Mn, M, Mi, and functionality f and fi mentioned above should be calculated based on the theoretical values ​​of pure substances. When using industrial raw materials, the values ​​can be converted based on the average molecular weight, purity, or measured hydroxyl value provided by the supplier.

[0020] Preferably, component A is prepared by the following method: hydroxyl silicone oil, long-chain polyhydroxy hydrophobic component, emulsifier and water are mixed and heated to 60~80℃ for pre-emulsification, then homogenized under high pressure of 20~50MPa 2~3 times, and then the catalyst is added after cooling to below 40℃.

[0021] Preferably, the emulsion D50 of component A is 100~500nm, more preferably 200~300nm.

[0022] Preferably, component B is a cationic blocked isocyanate crosslinking agent aqueous dispersion, which can be prepared by existing methods, with a solid content of 25~40wt%, a viscosity of 20~500mPa·s at 25℃, a pH of 3.5~6.5, and an emulsion D50 of 50~300nm.

[0023] Preferably, component B has an isocyanate backbone of IPDI trimer, HDI trimer or a combination thereof, contains cationic hydrophilic structural units that have been neutralized into salts by organic acids, and the blocking agent is an oxime blocking agent.

[0024] Preferably, the oxime blocking agent is at least one of 2-propanone oxime and methyl ethyl ketone oxime.

[0025] The present invention also provides a waterproof textile fabric, obtained by the above method, having a static water contact angle of 130~150° and a static water pressure resistance of 20~50kPa.

[0026] Preferably, the weight gain of the surface finishing layer of the waterproof textile fabric is 0.5-4.0% relative to the unfinished fabric, and the amount of finishing agent adhering to the fabric surface per unit area is 0.2-2.5 g / m². 2 .

[0027] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are: 1. The present invention adopts the method of storing component A and component B separately and recombining them before use, which avoids the long-term contact between the blocked isocyanate crosslinking agent and the active hydroxyl component in the waterproof mother liquor during the storage stage. This is beneficial to improving the storage stability and construction applicability of the system, and reducing the risk of significant flocculation, sedimentation, stratification or abnormal viscosity increase of the working liquid.

[0028] 2. This invention controls the n(C-OH) / n(Si-OH) ratio within the range of 2.2 to 5.0, enabling long-chain polyhydroxy hydrophobic components and hydroxyl silicone oil to jointly participate in the construction of the finishing layer. The long-chain hydrophobic segments facilitate the formation of a low surface energy hydrophobic layer on the fabric surface, while the retained reactive hydroxyl sites in the system facilitate subsequent cross-linking with component B, thus achieving both initial water resistance and durable finishing effects.

[0029] 3. This invention employs a two-stage heat treatment method combining pre-drying and curing. The pre-drying stage facilitates the spreading, dehydration, and initial film formation of the working solution on the fabric surface, while the curing stage promotes the unsealing of the blocked isocyanate crosslinking agent and its further participation in the crosslinking reaction, thereby enhancing the bonding between the finishing layer and the fibers, as well as within the finishing layer itself. Compared to single heat treatment conditions, this invention is more advantageous in achieving a balance between waterproof performance and durability.

[0030] 4. The finishing method of the present invention is applicable to polyester, nylon, cotton and their blended fabrics, and has good process adaptability and application versatility, making it easy to promote and apply in the finishing processes of different textile substrates.

[0031] 5. Waterproof textiles treated with the method of this invention can obtain a high static water contact angle and good hydrostatic pressure resistance. At the same time, the weight gain rate of its surface finishing layer and the amount of finishing agent attached per unit area are controlled within a reasonable range. This invention does not rely on excessive dosage to simply pile up to obtain waterproof performance, but achieves good finishing effect and durability under moderate finishing load. Attached Figure Description

[0032] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0033] Figure 1 The image shows the Fourier transform infrared spectrum of the system obtained in Example 1; in the image: 3429.83cm -1 The absorption peak for hydroxyl groups is located nearby; 2981.03 cm⁻¹ -1 and 2851.23cm -1 These correspond to the stretching vibration peaks of the methyl and methylene groups in long-chain alkyl groups, respectively; 1086.16 cm⁻¹ -1 and 1042.21cm -1 The nearby peak is related to silicon-oxygen bonds; 938.18 cm⁻¹ -1 The nearby area shows absorption peaks related to silanol groups. Detailed Implementation

[0034] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0035] Unless otherwise stated, the hydroxyl silicone oils used in Examples 1-5 are all α,ω-dihydroxy-terminated polydimethylsiloxanes with a number-average molecular weight Mn=200. Component B used in the examples is a cationic blocked isocyanate crosslinking agent aqueous dispersion with a solid content of 30-35wt%, a viscosity of 80-200 mPa·s at 25°C, a pH of 4.0-5.5, an emulsion D50 of 80-180 nm, an isocyanate backbone of IPDI trimer, HDI trimer, or a combination thereof, and a blocking agent of methyl ethyl ketone oxime and / or 2-acetone oxime. Example 1

[0036] Mix 3g of hydroxyl silicone oil, 15g of 1,18-octadecanediol, 2g of emulsifier and 79g of water, heat to 70℃ and stir at 200rpm for 25min for pre-emulsification; then homogenize under high pressure at 30MPa 3 times; after cooling to below 40℃, add 1g of p-toluenesulfonic acid and stir evenly to obtain component A.

[0037] Before use, prepare the working solution by mixing component A at 40 g / L and component B at 10 g / L. Polyester, nylon, and woven cotton fabrics are treated using a two-dip, two-nip process, with the liquid retention rate controlled at 70%. The fabrics are then pre-dried at 110℃ for 3 minutes and then cured at 150℃ for 2 minutes to obtain the finished fabrics.

[0038] n(C-OH) / n(Si-OH)=3.50. Example 2

[0039] 3g of hydroxyl silicone oil, 18g of 1,2-octadecanediol, 2g of emulsifier and 76g of water were mixed and pre-emulsified, homogenized under high pressure and cooled and acidified in the same manner as in Example 1 to obtain component A.

[0040] Before use, prepare a working solution by mixing component A at 50 g / L and component B at 10 g / L. Impregnate, pre-dry, and cure polyester, nylon, and woven cotton fabrics respectively in the same manner as in Example 1 to obtain finished fabrics. n(C-OH) / n(Si-OH) = 4.20. Example 3

[0041] 3g of hydroxyl silicone oil, 10g of 1,18-octadecanediol, 8g of 1,2-octadecanediol, 2g of emulsifier and 76g of water were mixed and pre-emulsified, homogenized under high pressure and cooled and acidified in the same manner as in Example 1 to obtain component A.

[0042] Before use, prepare a working solution by mixing component A at 40 g / L and component B at 15 g / L. Impregnate polyester, nylon, and woven cotton fabrics in the same manner as in Example 1, pre-dry at 110°C for 3 min, and then cure at 155°C for 2 min to obtain the finished fabric.

[0043] n(C-OH) / n(Si-OH)=4.20. Example 4

[0044] 5g of hydroxyl silicone oil, 20g of 1,18-octadecanediol, 2g of emulsifier and 72g of water were mixed and pre-emulsified, homogenized under high pressure and cooled and acidified in the same manner as in Example 1 to obtain component A.

[0045] Before use, prepare a working solution by mixing component A at 60 g / L and component B at 10 g / L. Impregnate polyester, nylon, and woven cotton fabrics in the same manner as in Example 1, pre-dry at 115°C for 3 min, and then cure at 150°C for 2 min to obtain the finished fabric.

[0046] n(C-OH) / n(Si-OH)=2.80. Example 5

[0047] Component A was prepared according to the method in Example 3. Before use, a working solution was prepared by mixing component A at 45 g / L and component B at 15 g / L. The nylon / cotton blended fabric was treated by a two-dip, two-nip process, with the liquid retention rate controlled at 72%. It was pre-dried at 110°C for 3 min and then cured at 160°C for 2 min to obtain the treated fabric.

[0048] n(C-OH) / n(Si-OH)=4.20.

[0049] Comparative Example 1 3g of hydroxyl silicone oil, 1.5g of 1,18-octadecanediol, 2g of emulsifier and 92.5g of water were mixed and treated in the same manner as in Example 1 to obtain component A.

[0050] Before use, prepare a working solution by mixing component A at 40 g / L and component B at 10 g / L. The remaining procedures are the same as in Example 1.

[0051] n(C-OH) / n(Si-OH)=0.35.

[0052] Comparative Example 2 Except for the absence of component B in the working solution, the other formulations and process conditions are the same as in Example 1.

[0053] Comparative Example 3 First, component A and component B obtained in Example 1 were premixed according to the usage ratio. After being placed in a sealed container at 25°C for 14 days, the fabric was then treated according to the method in Example 1. The initial D50 of the premixed system was 184 nm. After 14 days, the D50 increased to 398 nm, and slight oil floating and thickening of the system were observed.

[0054] Comparative Example 4 Mix 3g of hydroxyl silicone oil, 22g of 1,18-octadecanediol, 2g of emulsifier and 72g of water, heat to 70℃ and stir at 200rpm for 25min for pre-emulsification; then homogenize under high pressure at 30MPa 3 times; after cooling to below 40℃, add 1g of p-toluenesulfonic acid and stir evenly to obtain component A.

[0055] Before use, prepare a working solution by mixing component A at 40 g / L and component B at 10 g / L.

[0056] n(C-OH) / n(Si-OH) = 5.13, which is higher than the range defined in this invention.

[0057] Comparative Example 5 Comparative Example 5 uses only a single-stage heat treatment, as detailed below: Component A was prepared according to the method of Example 1, and working solutions were prepared by dispensing Component A at 40 g / L and Component B at 10 g / L in the same manner as in Example 1. Polyester, nylon, and woven cotton fabrics were treated by a two-dip, two-nip process, with the liquid retention rate controlled at 70%. Instead of pre-drying at 110°C, the fabrics were directly baked at 150°C for 5 minutes to obtain the finished fabrics.

[0058] Test method: (1) Spray water repellency test: The spray test was conducted in accordance with GB / T 4745-2012 "Test and evaluation of water-repellent properties of textiles - water-wetting method" to evaluate the finishing effect based on the surface wettability of the fabric. The test results were expressed using a visual rating of 1 to 5. Level 1 indicates that the surface was completely wetted; Level 2 indicates that half of the surface was wetted; Level 3 indicates that only a small, discontinuous area of ​​the surface was wetted; Level 4 indicates that the surface was not wetted but had water droplets on it; Level 5 indicates that the surface was not wetted and had no water droplets on it. For boundary samples between adjacent levels, + or - can be used for further subdivision and recording, where 4+ indicates a state between level 4 and level 5 and closer to level 5, and 5- indicates a state between level 4 and level 5 and close to level 5 but not reaching the typical level 5 standard pattern.

[0059] (2) Wash resistance test: The wash resistance test was conducted in accordance with GB / T8629-2017. The wash resistance result is expressed as the spray water repellency level after washing; in the durability evaluation after multiple washes, the spray water repellency level and hydrostatic pressure resistance changes were examined after 5, 10, 15 and 25 washes respectively.

[0060] (3) Contact angle test: The contact angle test shall be conducted in accordance with GB / T42694-2023. The test shall be conducted using a contact angle measuring instrument, and at least 5 different locations shall be measured for each sample. The average value shall be taken as the result.

[0061] (4) Static water pressure resistance test: The finished fabric was subjected to a static water pressure test in accordance with GB / T4744-2013, and the result was expressed in kPa.

[0062] (5) Storage stability test of component A: Component A of Example 1 was stored at 25°C for 30 days and at 40°C for 7 days. The emulsion D50, pH and viscosity were measured periodically, and it was observed whether layering, floating oil, precipitation or obvious thickening occurred.

[0063] (6) Working solution stability test: Component A and component B are prepared into a working solution according to the usage ratio. After standing at room temperature for 4h and 8h, D50, pH, viscosity and appearance changes are measured and observed. At the same time, the A / B premixed system is sealed at 25℃ for 14d and then the same test is performed.

[0064] The test results are shown in Tables 1 to 5: Table 1

[0065] Table 2 Durability of Polyester

[0066] Table 3 Storage stability and working fluid stability of component A

[0067] Table 4. Effects of n(C-OH) / n(Si-OH) range and heat treatment method on finishing effect (polyester)

[0068] Table 5. Weight gain and amount of finishing agent adhering per unit area of ​​the finished fabric.

[0069] As shown in Table 1, the finished fabrics obtained in Examples 1-5 all exhibited good initial water repellency and water repellency retention after washing on polyester, nylon, woven cotton, and nylon / cotton blended substrates, indicating that the finishing system of the present invention has good applicability to different textile substrates. Among them, Examples 1, 3, and 4 showed superior spray water repellency, contact angle, and hydrostatic pressure resistance on polyester substrates, indicating that within the scope of the present invention, appropriately adjusting the type of long-chain polyhydroxy hydrophobic component, the amount of crosslinking agent, and the curing conditions can further improve the finishing effect.

[0070] Table 2 shows that, on polyester substrates, Examples 1 and 3 maintained high spray water repellency and hydrostatic pressure resistance after multiple washes, significantly better than Comparative Examples 1, 2, 3, 4, and 5. This indicates that the system of the present invention not only has good initial waterproofing effect but also good wash durability. Comparative Example 2 shows that when component B is not added to the working solution, the wash resistance retention of the finishing layer decreases significantly, indicating that the cationic blocked isocyanate crosslinking agent plays an important role in improving the bonding strength between the finishing layer and the fiber, as well as within the finishing layer. Comparative Example 3 shows that long-term premixing of components A and B before use leads to a decrease in the finishing effect, indicating that separate storage and recombining before use are more beneficial for maintaining system stability and final finishing performance. Comparative Example 4 shows that when n(C-OH) / n(Si-OH) exceeds the range defined in this invention, although the proportion of hydrophobic components in the finishing layer further increases, the overall performance does not continue to improve but instead decreases. Comparative Example 5 shows that when only a single-stage heat treatment is used, the waterproof and durability properties of the finished fabric are lower than those of the two-stage heat treatment method combining pre-drying and curing used in this invention.

[0071] Table 3 shows that after storing component A at 25℃ for 30 days and at 40℃ for 7 days, the emulsion D50, pH, and viscosity of component A obtained in Example 1 showed little change, with no stratification, no floating oil, and no significant thickening. The working solution prepared from components A and B maintained good homogeneity after being placed at room temperature for 4 hours and 8 hours. In contrast, after being placed in a sealed container at 25℃ for 14 days, the D50 of the A / B premixed system increased from 184 nm to 398 nm, and slight floating oil and significant thickening were observed. These results indicate that the method of storing components A and B separately and recombining them before use in this invention helps reduce the risk of system instability during storage and improves construction stability and process applicability.

[0072] Table 4 shows that when n(C-OH) / n(Si-OH) is controlled within the range of 2.2 to 5.0, the finished fabric exhibits good overall performance in terms of initial spray water repellency, post-wash spray water repellency, contact angle, and hydrostatic pressure resistance. Specifically, Examples 1, 3, and 4, corresponding to ratios of 3.50, 4.20, and 2.80 respectively, all achieved optimal results. Comparative Example 1 indicates that when n(C-OH) / n(Si-OH) is too low, the long-chain polyhydroxy hydrophobic components in the system are insufficient, which is detrimental to the formation of a finishing layer with both hydrophobicity and subsequent cross-linking ability. Comparative Example 4 shows that when n(C-OH) / n(Si-OH) is too high, the overall performance of the finished fabric decreases. This indicates that controlling n(C-OH) / n(Si-OH) within the range of 2.2 to 5.0 is beneficial for achieving a good balance between initial water resistance, wash durability, and the uniformity of the finishing layer. Meanwhile, a comparison between Example 1 and Comparative Example 5 shows that, with essentially the same formulation, the two-stage heat treatment process of pre-drying at 100~115℃ and curing at 150~160℃ resulted in a finished fabric with better initial spray water repellency, post-wash spray water repellency, contact angle, and hydrostatic pressure resistance than the sample that only underwent single-stage heat treatment. This indicates that two-stage heat treatment is more conducive to the spreading and film formation of the finished layer and subsequent cross-linking and curing.

[0073] As shown in Table 5, the finished fabrics obtained in the embodiments of the present invention have a weight gain rate of 0.5-4.0% and a finishing agent adhesion amount of 0.2-2.5 g / m². 2 Within a reasonable range, a higher contact angle and better hydrostatic pressure resistance can be obtained, indicating that the present invention does not rely on excessive dosage to simply pile up to obtain waterproof performance. Instead, under a moderate finishing load, through the synergistic effect of component A and component B, the control of the n(C-OH) / n(Si-OH) range, and the combination of two heat treatment processes, a better waterproof finishing effect and durability are achieved.

[0074] In summary, by storing component A and component B separately and recombining them before use, and by combining the preferred n(C-OH) / n(Si-OH) range and a two-stage heat treatment process, this invention can achieve a waterproof finishing effect with good initial water resistance, washability, durability, and construction stability on different textile substrates.

[0075] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

[0076] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to specific implementations. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A method for applying a fluorine-free silicone wax waterproofing finish to textiles, characterized in that, Includes the following steps: (1) Before use, component A and component B are compounded into a working solution; wherein, component A and component B are stored separately; Component A is an aqueous emulsion-type fluorine-free silicone wax waterproofing mother liquor, which, by weight, includes: 1-5 parts hydroxyl silicone oil, 15-22 parts long-chain polyhydroxy hydrophobic component, 0.5-2 parts catalyst, 1-3 parts emulsifier, and the balance being water; The long-chain polyhydroxy hydrophobic component contains at least one C18 or higher hydrophobic segment and contains at least two free hydroxyl groups that can react with isocyanates. The molar number of hydroxyl end hydroxyl groups in hydroxyl silicone oil is denoted as n(Si-OH), and the molar number of reactive hydroxyl groups in the long-chain polyhydroxy hydrophobic component is denoted as n(C-OH), satisfying 2.2≤n(C-OH) / n(Si-OH)≤5.0; Component B is an aqueous dispersion of a cationic blocked isocyanate crosslinking agent. (2) Immerse the fabric in the working solution and roll it in, controlling the liquid carry-over rate to be 60-80%; (3) Pre-dry the fabric after rinsing with liquid at a temperature of 100-115℃ for 2-4 minutes; (4) Curing the pre-dried fabric at a temperature of 150~160℃ for 1~3 min; The catalyst is selected from one or more of benzenesulfonic acid, p-toluenesulfonic acid, and dodecylbenzenesulfonic acid; The working solution should be used within 8 hours after preparation.

2. The method according to claim 1, characterized in that, Based on the working solution, the dosage of component A is 20~80g / L, and the dosage of component B is 5~30g / L.

3. The method according to claim 1, characterized in that, The hydroxyl silicone oil is α,ω-dihydroxy-terminated polydimethylsiloxane with a number-average molecular weight of 160-300.

4. The method according to claim 1, characterized in that, The long-chain polyhydroxy hydrophobic component is selected from one or more of 1,18-octadecanediol, 1,2-octadecanediol, and 3-octadecoxypropane-1,2-diol.

5. The method according to claim 1, characterized in that, The n(Si-OH) is calculated using the following formula: n(Si-OH)=2m1 / Mn; where m1 is the mass of the hydroxyl silicone oil and Mn is the number-average molecular weight of the hydroxyl silicone oil. When the long-chain polyhydroxy hydrophobic component is of one type, n(C-OH) = f·m2 / M; Where f is the free hydroxyl functionality of the long-chain polyhydroxy hydrophobic component, m2 is its mass, and M is its molecular weight. When there are two or more long-chain polyhydroxy hydrophobic components, n(C-OH) = Σ(fi·mi / Mi); Where fi is the free hydroxyl functionality of the i-th long-chain polyhydroxy hydrophobic component, mi is the mass of the i-th long-chain polyhydroxy hydrophobic component, and Mi is the molecular weight of the i-th long-chain polyhydroxy hydrophobic component.

6. The method according to claim 1, characterized in that, Component A is prepared by the following method: hydroxyl silicone oil, long-chain polyhydroxy hydrophobic component, emulsifier and water are mixed and heated to 60~80℃ for pre-emulsification, then homogenized under high pressure of 20~50MPa 2~3 times, and then the catalyst is added after cooling to below 40℃.

7. The method according to claim 1, characterized in that, Component B has an isocyanate backbone of IPDI trimer, HDI trimer or a combination thereof, and contains cationic hydrophilic structural units that have been neutralized into salts by organic acids; the blocking agent is an oxime blocking agent.

8. A waterproof textile fabric, characterized in that, It is obtained by the method described in any one of claims 1 to 7, and its static water contact angle is 130 to 150° and its static water pressure resistance is 20 to 50 kPa.

9. The waterproof textile fabric according to claim 8, characterized in that, Compared to the unfinished textile fabric, the weight gain of the surface finishing layer of the waterproof textile fabric is 0.5% to 4.0%, and the amount of finishing agent adhering to the fabric surface per unit area is 0.2 to 2.5 g / m². 2 .

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