Bio-based all-cotton fluoride-free waterproof fabric for high-performance sports cap and preparation method of bio-based all-cotton fluoride-free waterproof fabric

Abstract

The invention discloses a bio-based all-cotton fluoride-free waterproof fabric for a high-performance sports cap and a preparation method of the bio-based all-cotton fluoride-free waterproof fabric, and relates to the field of biochemical treatment and preparation of textile fabrics. The garment body is made of fabric, the fabric comprises a bio-based all-cotton base material, a compound enzyme treatment layer, a bio-based modified layer and a fluoride-free waterproof layer, compound enzyme is composed of cellulase, pectinase and lipase, the raw material of the bio-based modified layer is bio-based polyol, and the raw material of the fluoride-free waterproof layer is a polycaprolactone fluoride-free waterproof agent. The preparation method comprises the following steps: firstly cleaning and drying the base material, then carrying out compound enzyme biochemical treatment and bio-based polyol grafting reaction, and finally padding and curing through a fluoride-free waterproof agent. The fabric and the method meet the fluoride-free and environment-friendly requirements and meet the use requirements of high-performance sports caps, and the comprehensive performance of the fabric is improved by means of a biochemical treatment process.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of textile fabric biochemical treatment and preparation, and particularly relates to a bio-based full-cotton fluorine-free waterproof fabric for high-performance sports hats and a preparation method thereof. BACKGROUND

[0002] High-performance sports hats have high requirements for the waterproofness, air permeability and environmental protection of the used fabric. Full-cotton fabric has become one of the preferred substrates for sports hat fabric due to its good skin-friendliness, moisture absorption and air permeability. However, natural full-cotton fibers have no waterproof structure on the surface, and need to be treated to have waterproof performance. With the popularization of environmental protection concept, fluorine-containing waterproof agents are gradually restricted in use due to the possible environmental accumulation risk, and the development of fluorine-free waterproof treatment technology has become an important research direction in the field of textiles for sports fabric.

[0003] At present, fluorine-free waterproof treatment for full-cotton fabric mostly adopts the method of combining chemical modifiers with substrates, but such process often requires high reaction temperature or a large amount of auxiliary agents, which easily damages the natural structure of full-cotton fibers, resulting in decreased air permeability and hard hand feeling of the fabric. Some technologies attempt to introduce biochemical treatment to improve the surface properties of the substrate, but the existing biochemical treatment mostly uses single enzyme preparation, which can only achieve a small amount of impurity removal or mild etching on the fiber surface, and cannot provide stable binding sites for subsequent fluorine-free waterproof layer, resulting in poor waterproof effect durability and difficulty in balancing the mechanical strength and waterproof performance of the fabric.

[0004] In addition, in the preparation process of the existing sports hat fabric, the compatibility of the waterproof treatment with the pretreatment and subsequent modification of the substrate is insufficient. For example, the conventional pretreatment does not consider the interface bonding requirement with fluorine-free waterproof agents, and the surface active group of the substrate after biochemical treatment is not properly regulated, which easily leads to poor adhesion of the waterproof layer, and rapid decay of the waterproof performance after multiple washes or outdoor use. The above problems make it difficult for the existing full-cotton fluorine-free waterproof fabric to meet the comprehensive requirements of environmental protection, function and durability of high-performance sports hats, and there is obvious room for technical improvement. SUMMARY

[0005] In order to overcome the above-mentioned defects of the prior art, the embodiments of the present application provide a bio-based full-cotton fluorine-free waterproof fabric for high-performance sports hats and a preparation method thereof, which solves the problems of easy damage to the natural structure of fibers in the fluorine-free waterproof treatment of full-cotton fabric in the prior art and poor waterproof durability caused by the single enzyme biochemical treatment which cannot provide stable binding sites.

[0006] To solve the above problems, the present application provides the following technical solutions:

[0007] A bio-based full-cotton fluorine-free waterproof fabric for high-performance sports hats, comprising a bio-based full-cotton base material, a composite enzyme treatment layer, a bio-based modification layer, and a fluorine-free waterproof layer; the composite enzyme treatment layer is formed on the surface and internal fiber gap of the bio-based full-cotton base material, the composite enzyme is composed of cellulase, pectinase, and lipase; the bio-based modification layer is covered on the surface of the composite enzyme treatment layer, the raw material of the bio-based modification layer is bio-based polyol; the fluorine-free waterproof layer is covered on the surface of the bio-based modification layer, and the raw material of the fluorine-free waterproof layer is polycaprolactone-based fluorine-free waterproof agent.

[0008] Further, the mass ratio of cellulase, pectinase, and lipase in the composite enzyme is 3-5:1-2:1-2. Here, cellulase can etch the fiber surface of the bio-based full-cotton base material to form a microporous structure, pectinase can remove residual pectin impurities on the fiber surface, and lipase can remove oil stains. By limiting the specific mass ratio of the three, not only can the limitations of single enzyme treatment that can only achieve single cleaning or etching be avoided, but also the imbalance of enzyme ratio that can cause excessive damage to the fiber or incomplete treatment can be prevented, ultimately providing uniform and stable surface active sites for the subsequent attachment of the bio-based modification layer, ensuring the structural integrity of the fabric and the bonding strength of the subsequent functional layer.

[0009] Further, the bio-based polyol is castor oil-based polyol or soybean oil-based polyol. Here, the multiple hydroxyl groups contained in the molecular structure of the bio-based polyol can efficiently undergo grafting reactions with the hydroxyl, carboxyl, and other groups exposed on the fiber surface after composite enzyme treatment. Compared with other types of polyols, it can be more firmly combined on the surface of the composite enzyme treatment layer to form a stable bio-based modification layer, and at the same time provide an adaptive chemical structure for the subsequent fluorine-free waterproof layer, reducing the risk of interfacial peeling between the two layers and improving the overall functional stability of the fabric.

[0010] Further, the solid content of the polycaprolactone-based fluorine-free waterproof agent is 20-30wt%. By limiting the specific solid content, a fluorine-free waterproof film with appropriate thickness and continuous integrity can be formed, achieving excellent waterproof performance while maintaining the skin-friendliness and breathability of the bio-based full-cotton fabric, adapting to the use scenario requirements of high-performance sports hats.

[0011] The bio-based full-cotton fluorine-free waterproof fabric of the present application takes the comprehensive needs of skin-friendliness, breathability, waterproofness and environmental protection of sports hats as the core, first selects bio-based full-cotton as the base material to ensure basic comfort performance; then designs a composite enzyme treatment layer, through the synergistic effect of cellulase, pectinase and lipase, moderately etches the surface of the base material fiber and removes impurities in the biochemical treatment process, creating stable surface conditions for the subsequent functional layer attachment; then sets a bio-based modification layer, uses bio-based polyols to build a transition structure, not only continues the environmental protection property, but also strengthens the combination with the composite enzyme treatment layer through molecular level grafting reaction, and at the same time provides a suitable binding site for the fluorine-free waterproof layer; finally, a polycaprolactone-based fluorine-free waterproof agent is used to form a waterproof layer to avoid environmental risks of fluorine-containing substances, and through the synergistic design of the four-layer structure, the balance of environmental protection, functionality and durability of the fabric is realized, meeting the needs of the use scene of high-performance sports hats.

[0012] As a general inventive concept, the present application provides a preparation method of a bio-based full-cotton fluorine-free waterproof fabric for high-performance sports hats as described above, comprising the following steps,

[0013] S1. Selecting bio-based full-cotton gray cloth as the base material, placing the base material in deionized water for ultrasonic cleaning, the cleaning power is 300-500W, the cleaning time is 15-25min, after cleaning, taking out the base material and placing it in a 60-80℃ oven for drying;

[0014] S2. Placing the dried base material of step S1 into a composite enzyme solution for biochemical treatment, the composite enzyme solution is made by mixing cellulase, pectinase, lipase and deionized water, the mass concentration of the composite enzyme in the solution is 2-5g / L, the treatment temperature is controlled at 45-55℃, the treatment time is 60-90min, after treatment, taking out the base material and washing it with water to neutral;

[0015] S3. Placing the washed base material of step S2 into a bio-based polyol solution, the mass concentration of the bio-based polyol solution is 8-12g / L, carrying out grafting reaction in a protective gas atmosphere, after reaction, taking out the base material and placing it in a 70-90℃ oven for drying;

[0016] S4. Placing the dried base material of step S3 into a polycaprolactone-based fluorine-free waterproof agent solution for pad-drying treatment, then placing the base material into an oven for curing treatment, forming a fluorine-free waterproof layer, obtaining a bio-based full-cotton fluorine-free waterproof fabric.

[0017] Further, the pH value of the composite enzyme solution in step S2 is controlled at 6.0-7.0. Here, by controlling the pH value, the three enzymes can maintain high-efficiency catalytic state at the same time, ensuring that the composite enzyme treatment can uniformly form fiber surface micropores and active sites, laying a good foundation for the subsequent grafting combination of the bio-based modification layer.

[0018] Further, the temperature of the grafting reaction in step S3 is 60-70℃, and the reaction time is 40-60min. If the grafting reaction temperature is too low, the reaction rate of the polyol and the active group on the surface of the substrate is slow, and the grafting is insufficient, and the modified layer is not firmly attached. If the temperature is too high, the molecular structure of the polyol may be damaged or the all-cotton substrate may be damaged. If the reaction time is too short, the grafting degree is insufficient, and if the reaction time is too long, side reactions may occur.

[0019] Further, the protective gas in step S3 is nitrogen or argon. Nitrogen and argon are both inert gases, which can effectively isolate oxygen and prevent side reactions from occurring, ensuring the purity and bonding strength of the bio-based modified layer.

[0020] Further, the pick-up rate of the padding treatment in step S4 is 70-80%. If the pick-up rate is too low, the fabric will not carry enough waterproof agent, and a continuous and complete waterproof film cannot be formed after solidification. If the pick-up rate is too high, the waterproof agent will accumulate on the surface of the fabric, and during drying and solidification, it is easy to cause sagging, uneven film thickness, and a hard hand feeling and reduced air permeability of the fabric, which does not meet the use requirements of sports hats.

[0021] Further, the temperature of the solidification treatment in step S4 is 110-130℃, and the solidification time is 15-25min. The limitation can ensure that the waterproof agent is fully crosslinked to form a stable and strongly adhered fluorine-free waterproof layer, so that the fabric has durable waterproof performance, and at the same time, the high temperature does not cause damage to the all-cotton substrate.

[0022] The preparation method of the bio-based all-cotton fluorine-free waterproof fabric of the application first pretreats the bio-based all-cotton substrate by ultrasonic cleaning and drying to remove impurities and unify the substrate state, laying a foundation for subsequent treatment. Then, a composite enzyme composed of cellulase, pectinase and lipase is used for biochemical treatment to etch the fiber surface to form active sites and remove residual impurities, solving the problem of limited effect of single enzyme treatment. Subsequently, a bio-based polyol is introduced for grafting reaction to construct a modified interface on the surface of the composite enzyme treatment layer, which not only relies on bio-based raw materials to improve the environmental protection properties, but also enhances the compatibility with the subsequent fluorine-free waterproof agent. Finally, a stable waterproof layer is formed on the surface of the modified layer by fluorine-free waterproof agent padding and solidification, realizing the use requirements of fluorine-free waterproof, skin-friendly and breathable, and adapting to sports scenarios.

[0023] Compared with the prior art, the application has the following advantages:

[0024] (1) The fabric of the present application takes bio-based full cotton as a base material, adopts bio-based polyols to construct a modified layer, and a fluorine-free waterproof agent based on polycaprolactone to form a waterproof layer, and replaces traditional chemical pretreatment through biochemical treatment of composite enzymes, avoids the use of fluorine-containing substances and high-pollution chemical additives throughout the process, reduces environmental burden from raw material selection to process links, and meets the environmental protection development trend of high-performance sports equipment;

[0025] (2) In the preparation process of the present application, the uniform active sites are provided for the bio-based modified layer through the synergistic treatment of the composite enzymes, and then the transition layer is formed by grafting the bio-based polyols, so that the interfacial bonding force between the transition layer and the fluorine-free waterproof layer is enhanced, the waterproof layer is prevented from peeling or falling off, and the stable waterproof effect of the fabric can be maintained after long-term use and washing, and the poor waterproof durability caused by single enzyme treatment is overcome.

[0026] (3) The present application takes full cotton as a base material, and the composite enzyme treatment only moderately optimizes the fiber surface structure without damaging the fiber body, and the thickness of the bio-based modified layer and the fluorine-free waterproof layer is controllable (controlled by the roll-off rate and curing parameters), so that the skin-friendliness and moisture absorption and air permeability of the full cotton fabric are retained, and the waterproof function is also given, the problems of hard fabric and reduced air permeability caused by traditional waterproof treatment are avoided, and the sports hat is suitable for close-fitting wearing and outdoor use scenarios.

[0027] (4) The composite enzyme biochemical treatment of the present application removes impurities and weak structures on the surface of the base material fiber, while avoiding excessive etching damage to the fiber; the bio-based modified layer forms stable chemical bonds with the fiber during grafting, which can enhance the bonding force between the fibers, to a certain extent, improve the tensile and wear resistance of the fabric, and cooperate with the protection of the waterproof layer to the fiber, so that the sports hat fabric is not easy to break in frequent outdoor use, prolonging the service life of the product. BRIEF DESCRIPTION OF DRAWINGS

[0028] Figure 1 is a flowchart of a bio-based full cotton fluorine-free waterproof fabric for high-performance sports hats and a preparation method thereof. DETAILED DESCRIPTION

[0029] In order to facilitate the understanding of the present application, the present application will be described more fully, specifically and concretely below with reference to the drawings and preferred embodiments, but the scope of protection of the present application is not limited to the following specific embodiments.

[0030] Unless otherwise defined, all professional terms used herein have the same meaning as generally understood by those skilled in the art. The professional terms used herein are only for the purpose of describing specific embodiments, and are not intended to limit the scope of protection of the present application.

[0031] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present application can be purchased from the market or can be prepared by existing methods.

[0032] Embodiment 1

[0033] Reference Figure 1 A bio-based full-cotton fluorine-free waterproof fabric for high-performance sports hats of the present application comprises a bio-based full-cotton base material, a composite enzyme treatment layer, a bio-based modification layer, and a fluorine-free waterproof layer; the composite enzyme treatment layer is formed on the surface and internal fiber gaps of the bio-based full-cotton base material, the composite enzyme is composed of cellulase, pectinase, and lipase, and the mass ratio of the three is 3:1:1; the bio-based modification layer is covered on the surface of the composite enzyme treatment layer, and the raw material of the bio-based modification layer is castor oil-based polyol; the fluorine-free waterproof layer is covered on the surface of the bio-based modification layer, and the raw material of the fluorine-free waterproof layer is polycaprolactone-based fluorine-free waterproof agent, and the solid content thereof is 20wt%.

[0034] The preparation method of the bio-based full-cotton fluorine-free waterproof fabric for high-performance sports hats of the present application comprises the following steps,

[0035] S1. Select a bio-based full-cotton gray cloth as a base material, and place the base material in deionized water for ultrasonic cleaning, with a cleaning power of 300W and a cleaning time of 15min. After cleaning, the base material is taken out and dried in a 60℃ oven;

[0036] S2. The base material dried after step S1 is placed in a composite enzyme solution for biochemical treatment. The composite enzyme solution is prepared by mixing cellulase, pectinase, lipase, and deionized water. The mass concentration of the composite enzyme in the solution is 2g / L. The treatment temperature is controlled at 45℃, and the treatment time is 60min. After treatment, the base material is taken out and washed with water until it is neutral. The pH value of the composite enzyme solution is controlled at 6.0;

[0037] S3. The base material washed after step S2 is placed in a bio-based polyol solution with a mass concentration of 8g / L, and a grafting reaction is carried out in a nitrogen atmosphere. The reaction temperature is 60℃, and the reaction time is 40min. After the reaction is completed, the base material is taken out and dried in a 70℃ oven;

[0038] S4. The base material dried after step S3 is placed in a polycaprolactone-based fluorine-free waterproof agent solution for padding treatment, with a padding rate of 70%. Then the base material is placed in an oven for curing treatment, with a curing temperature of 110℃ and a curing time of 15min. A fluorine-free waterproof layer is formed, and a bio-based full-cotton fluorine-free waterproof fabric is obtained.

[0039] Embodiment 2

[0040] The difference between this embodiment and embodiment 1 is that the mass ratio of cellulase, pectinase and lipase in the complex enzyme is 5:2:2, the mass concentration of the complex enzyme in the complex enzyme solution is 5 g / L, the temperature of the complex enzyme treatment in S2 is 55°C, and the treatment time is 90 min, and the rest of the fabric composition and preparation step parameters are consistent with embodiment 1.

[0041] Example 3

[0042] The difference between this embodiment and embodiment 1 is that the raw material of the bio-based modified layer is a soybean oil-based polyol, the mass concentration of the bio-based polyol solution in S3 is 12 g / L, the protective gas of the grafting reaction is argon, and the rest of the fabric composition and preparation step parameters are consistent with embodiment 1.

[0043] Example 4

[0044] The difference between this embodiment and embodiment 1 is that the raw material of the fluorine-free waterproof layer is a polycaprolactone-based fluorine-free waterproof agent with a solid content of 30 wt%, the pick-up rate of the padding treatment in S4 is 80%, and the concentration of the fluorine-free waterproof agent solution is adjusted synchronously with the solid content to meet the padding requirements, and the rest of the fabric composition and preparation step parameters are consistent with embodiment 1.

[0045] Example 5

[0046] The difference between this embodiment and embodiment 1 is that the temperature of the grafting reaction in S3 is 70°C, the reaction time is 60 min, and the substrate drying temperature is adjusted to 90°C to meet the moisture removal requirements after the grafting reaction, and the rest of the fabric composition and preparation step parameters are consistent with embodiment 1.

[0047] Example 6

[0048] The difference between this embodiment and embodiment 1 is that the temperature of the curing treatment in S4 is 130°C, the curing time is 25 min, the power of the ultrasonic cleaning in S1 is 500 W, the cleaning time is 25 min, and the substrate drying temperature after cleaning is 80°C to improve the consistency of the initial state of the substrate for subsequent processing, and the rest of the fabric composition and preparation step parameters are consistent with embodiment 1.

[0049] Comparative Example 1

[0050] The difference between this comparative example and embodiment 1 is that the complex enzyme composed of cellulase, pectinase and lipase is replaced by a single cellulase, the complex enzyme solution is replaced by a cellulase solution, and the mass concentration of the cellulase in the solution is still 2 g / L, the temperature of the biochemical treatment in S2 is still 45°C, the treatment time is still 60 min, and the pH value of the solution is still controlled at 6.0, and the rest of the fabric composition and preparation step parameters are consistent with embodiment 1.

[0051] Comparative Example 2

[0052] The difference between the present comparative example and Example 1 is that the S3 bio-based polyol grafting reaction step is omitted, the S2 rinsed substrate is directly placed in a 70°C oven for drying, and then directly subjected to the padding treatment of S4, the padding treatment still has a pick-up rate of 70%, the curing treatment still has a temperature of 110°C, the curing time still has 15 min, the solid content of the fluorine-free waterproof agent still has 20wt%, and the rest of the fabric composition and preparation step parameters are consistent with Example 1.

[0053] Comparative Example 3

[0054] The difference between the present comparative example and Example 1 is that the bio-based modified layer raw material is replaced by traditional petroleum-based chemical modifier ethylene glycol diglycidyl ether, the bio-based polyol solution in S3 is replaced by ethylene glycol diglycidyl ether solution and the mass concentration is still 8g / L, the grafting reaction atmosphere is still nitrogen, the reaction temperature is still 60°C, the reaction time is still 40 min, the substrate drying temperature after reaction is still 70°C, and the rest of the fabric composition and preparation step parameters are consistent with Example 1.

[0055] The fabrics of Examples 1-6 and Comparative Examples 1-3 were tested, and the results are shown in Table 1.

[0056] 1. Waterproofing grade according to GB / T4744-2013 “Determination and Evaluation of Waterproof Performance of Textiles by Hydrostatic Pressure Method”, with 5 being the highest;

[0057] 2. Air permeability according to GB / T5453-2025 “Determination of Air Permeability of Textile Fabrics”;

[0058] 3. Breaking strength according to GB / T3923.1-2013 “Textile Fabrics Tensile Properties Part 1: Determination of Breaking Strength and Elongation at Break Strip Method”;

[0059] 4. Hand feeling grade: according to the scoring standard of 1-5 levels (5 being the softest), the fabric softness and skin friendliness were blindly evaluated and the average grade was taken.

[0060] Table 1: Experimental results of Examples 1-6 and Comparative Examples 1-3

[0061] Case Initial waterproofing level Waterproofing level after 50 washes Air permeability (mm / s) Breaking strength (N) Hand feel level Example 1 4 3 280 320 4 Example 2 5 4 295 335 4 Example 3 4 3 290 325 4.5 Example 4 5 4 270 340 3.5 Example 5 4.5 3.5 285 330 4 Example 6 5 4 288 338 4 Comparative Example 1 2 1 260 300 3.5 Comparative Example 2 3 1 292 310 4 Comparative Example 3 4 2.5 275 328 3.5

[0062] In summary, from Table 1, the initial waterproofing grade, waterproofing grade after 50 washes, air permeability, breaking strength, and hand feeling score of the examples are significantly better than those of the comparative examples, and the core difference is due to the process innovation of using composite enzyme for synergistic biochemical treatment, constructing a bio-based modified layer, and using a fluorine-free waterproof system.

[0063] Comparative Example 1 uses single cellulase treatment, only achieving mild etching and impurity removal on the fiber surface, failing to fully expose active groups, resulting in insufficient subsequent bio-based modification layer grafting, weak fluorine-free waterproof layer bonding, thus low initial waterproof grade and severe attenuation after washing, and lower air permeability and breaking strength due to insufficient treatment effect; Comparative Example 2 omits the bio-based modification layer, and the fluorine-free waterproof agent is directly combined with the substrate treated by the composite enzyme, lacking interface transition and adaptive structure, and the waterproof layer has poor adhesion stability, and the waterproof performance decreases rapidly after washing, although the air permeability is not significantly affected, but the overall functional durability is insufficient; Comparative Example 3 uses traditional petroleum-based chemical modifier, which has poor interface compatibility with the full cotton substrate and fluorine-free waterproof agent, and cannot form a stable bonding system, resulting in significant attenuation of waterproof grade after washing, and lower hand feeling due to the rigidity of the chemical modifier than the bio-based polyol in the examples.

[0064] Example 1 uses the reference process parameters, and the composite enzyme is synergistically treated, the bio-based modification and the fluorine-free waterproof system form effective cooperation, and all performances are balanced and good.

[0065] Example 2 optimizes the composite enzyme ratio and improves the treatment concentration and temperature, the synergistic effect of enzyme hydrolysis is enhanced, and the active sites on the fiber surface are more abundant, so the waterproof grade, air permeability and breaking strength are all better than the reference example.

[0066] Example 3 uses soybean oil-based polyol, which has better compatibility with full cotton fiber in molecular structure, and the flexibility of the bio-based modification layer is improved, so the hand feeling grade is the highest.

[0067] Example 4 improves the solid content and mill yield of the fluorine-free waterproof agent, and the waterproof layer film is more complete and dense, and the waterproof performance is the best, but excessive waterproof agent causes slight decrease in air permeability and hand feeling.

[0068] Example 5 optimizes the grafting reaction temperature and time, the bio-based polyol grafting efficiency is improved, the modification layer is more firmly bonded, and all performances are slightly optimized compared with the reference example.

[0069] Example 6 adjusts the curing temperature, time and pretreatment parameters, the initial state of the substrate is more stable, and the waterproof layer is more fully crosslinked, so the waterproof grade and breaking strength are excellent.

Claims

1. A bio-based, fluorine-free, waterproof cotton fabric for high-performance sports caps, characterized in that: The product comprises a bio-based cotton substrate, a composite enzyme-treated layer, a bio-based modified layer, and a fluorine-free waterproof layer. The composite enzyme-treated layer is formed on the surface and in the interfiber spaces of the bio-based cotton substrate, and the composite enzyme is composed of cellulase, pectinase, and lipase. The bio-based modified layer covers the surface of the composite enzyme-treated layer, and the raw material of the bio-based modified layer is a bio-based polyol. The fluorine-free waterproof layer covers the surface of the bio-based modified layer, and the raw material of the fluorine-free waterproof layer is a polycaprolactone-based fluorine-free waterproofing agent.

2. The bio-based, fluorine-free, waterproof cotton fabric for high-performance sports caps according to claim 1, characterized in that: The mass ratio of cellulase, pectinase and lipase in the complex enzyme is 3-5:1-2:1-2.

3. The bio-based, fluorine-free, waterproof cotton fabric for high-performance sports caps according to claim 1, characterized in that: The bio-based polyol is castor oil-based polyol or soybean oil-based polyol.

4. The bio-based, fluorine-free, waterproof cotton fabric for high-performance sports caps according to claim 1, characterized in that: The solid content of the polycaprolactone-based fluorine-free waterproofing agent is 20-30 wt%.

5. A method for preparing a bio-based, fluorine-free, waterproof cotton fabric for high-performance sports caps, characterized in that: Includes the following steps, S1. Select bio-based cotton fabric as the substrate, immerse the substrate in deionized water for ultrasonic cleaning, with a cleaning power of 300-500W and a cleaning time of 15-25 minutes. After cleaning, take out the substrate and dry it in an oven at 60-80℃. S2. The substrate dried in step S1 is placed in a compound enzyme solution for biochemical treatment. The compound enzyme solution is made by mixing cellulase, pectinase, lipase and deionized water. The mass concentration of the compound enzyme in the solution is 2-5 g / L. The treatment temperature is controlled at 45-55℃ and the treatment time is 60-90 min. After the treatment is completed, the substrate is taken out and rinsed with water until neutral. S3. Place the substrate rinsed in step S2 into a bio-based polyol solution with a mass concentration of 8-12 g / L, and carry out the grafting reaction under a protective gas atmosphere. After the reaction is completed, take out the substrate and dry it in an oven at 70-90°C. S4. The substrate dried in step S3 is immersed in a polycaprolactone-based fluorine-free waterproofing agent solution for padding treatment. Then, the substrate is placed in an oven for curing treatment to form a fluorine-free waterproof layer, thus obtaining a bio-based all-cotton fluorine-free waterproof fabric.

6. The method for preparing a bio-based, fluorine-free, waterproof cotton fabric for a high-performance sports cap according to claim 5, characterized in that: In step S2, the pH value of the complex enzyme solution is controlled to be 6.0-7.

0.

7. The method for preparing a bio-based, fluorine-free, waterproof cotton fabric for a high-performance sports cap according to claim 5, characterized in that: The grafting reaction in step S3 is carried out at a temperature of 60-70°C for 40-60 minutes.

8. The method for preparing a bio-based, fluorine-free, waterproof cotton fabric for a high-performance sports cap according to claim 5, characterized in that: The protective gas in step S3 is nitrogen or argon.

9. The method for preparing a bio-based, fluorine-free, waterproof cotton fabric for a high-performance sports cap according to claim 5, characterized in that: The rolling allowance in step S4 is 70-80%.

10. The method for preparing a bio-based, fluorine-free, waterproof cotton fabric for a high-performance sports cap according to claim 5, characterized in that: The curing temperature in step S4 is 110-130℃, and the curing time is 15-25 min.

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