Radiation-proof antibacterial and deodorant fabric and preparation method thereof

Abstract

This invention provides a radiation-proof, antibacterial, and deodorizing fabric and its preparation method, belonging to the field of fabric preparation technology. This invention constructs a bio-crosslinking network using a chitosan / polyethylene glycol composite gel and the natural crosslinking agent genipin. Combined with a gradient pore design of an inner high-porosity bio-reservoir layer and an outer sparse porous radiation-proof functional layer, it achieves an integrated and stable bond between the radiation-proof coating and Bacillus subtilis spore capsules. The invention utilizes the biofilm densification formed by in-situ germination of spores and the dual antibacterial system of plant-derived antibacterial agents to avoid the risk of drug resistance. Simultaneously, a pore-forming agent is added to the coating solution to balance the density of the radiation-proof layer and the breathability of the biofilm growth. This solves the technical problems in existing technologies, such as the functional conflict between the density of the radiation-proof coating and the breathability of the antibacterial components, insufficient long-term stability, and the imbalance between function and practicality. It is suitable for daily protection, medical protection, special protection, and high-end civilian applications.

Description

Technical Field

[0001] This invention belongs to the field of fabric preparation technology, specifically relating to a radiation-proof, antibacterial, and deodorizing fabric and its preparation method. Background Technology

[0002] Clothing is the object that comes into most contact with the human body in daily life. As people become more aware of health protection, the demand for functional clothing fabrics is also gradually increasing. Modern society is filled with various radiation hazards, such as radiation from electronic devices, ultraviolet radiation, and medical X-rays. Furthermore, since clothing is worn close to the skin for extended periods, it is prone to bacterial growth and odors, affecting wearing comfort and hygiene. Therefore, clothing fabrics that combine radiation protection and antibacterial / deodorizing functions have become a market necessity.

[0003] Currently, most functional fabrics on the market focus on achieving a single function. For example, anti-radiation fabrics often use metal coatings or metal fiber blends, which can effectively shield electromagnetic waves, but often suffer from problems such as being heavy, having poor breathability, and not being washable, and lacking hygiene functions such as antibacterial and deodorizing properties. Antibacterial and deodorizing fabrics often add antibacterial agents such as silver and zinc in the finishing process, which can inhibit bacteria, but their durability is insufficient and they are easily rendered ineffective by washing, and they do not consider the needs of radiation protection. CN120367058A discloses an anti-radiation fabric and its preparation method, which achieves the functions of anti-radiation, flame retardancy, and anti-photoaging by coating modified bismuth powder and polyurethane coating containing flame retardant and anti-aging structures onto the surface of polyester base fabric, and introduces an antibacterial crosslinking agent to give it a certain degree of antibacterial properties. However, its antibacterial performance mainly depends on the crosslinking agent in the coating, and its antibacterial spectrum and durability are limited. Moreover, the coating process may cause the fabric to harden and reduce its breathability, which conflicts with the comfort requirements of close-fitting clothing. CN120592042B discloses an antibacterial and deodorizing nylon fabric and its preparation method. By blending modified nano-titanium dioxide, polyhexamethylene guanidine and other antibacterial components with nylon 56 and spinning them, followed by polyacrylic acid treatment and antibacterial finishing liquid impregnation, the fabric achieves high-efficiency antibacterial and wash-resistant properties. However, its functionality depends on multiple chemical modifications and post-treatment impregnation, which is a relatively complicated process and may affect the original softness and breathability of the fabric, making it difficult to meet the comprehensive protection needs in complex environments.

[0004] In summary, the development of anti-radiation, antibacterial, and deodorizing fabrics still faces some challenges. Therefore, there is an urgent need to develop a new type of anti-radiation, antibacterial, and deodorizing fabric that can ensure the anti-radiation effect while achieving stable fixation and long-lasting effect of antibacterial components, and also take into account the breathability and wearing comfort of the fabric, so as to meet the application needs of daily protection, medical protection, special protection and high-end civilian fields. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide a radiation-proof, antibacterial, and deodorizing fabric and its preparation method. This invention constructs a bio-crosslinking network using a chitosan / polyethylene glycol composite gel and the natural crosslinking agent genipin. Combined with a gradient-channel dual-layer design of an inner high-porosity bio-reservoir layer and an outer sparsely porous radiation-proof functional layer, it achieves an integrated and stable bond between the radiation-proof coating and Bacillus subtilis spore capsules. The densification of the biofilm formed by in-situ germination of spores and the dual antibacterial system of plant-derived antibacterial agents avoid the risk of drug resistance. Simultaneously, sodium chloride is added to the coating solution as a pore-forming agent to balance the density of the radiation-proof layer with the breathability of the biofilm growth. This solves the technical problems in existing technologies, such as the functional conflict between the density of the radiation-proof coating and the breathability of the antibacterial components, insufficient long-term stability, and the imbalance between function and practicality.

[0006] This invention discloses a method for preparing a radiation-proof, antibacterial, and deodorizing fabric, such as... Figure 1 As shown, the specific technical solution is as follows: Step 1: Enzymatically hydrolyze cellulose fibers with neutral cellulase, and simultaneously modify the surface of bismuth oxide with a silane coupling agent under acidic conditions.

[0007] Step 2: Prepare a chitosan / polyethylene glycol composite gel as the inner layer matrix. Mix it with Bacillus subtilis spore capsules, a pore-forming agent, a plant-derived antibacterial and deodorizing agent, and spore-specific germination inducer microspheres to form an inner layer coating liquid. Apply the inner layer coating liquid to the fiber surface through a padding process. After pre-curing and cleaning to create pores, a stable porous coating is formed. Simultaneously prepare a radiation-resistant particle / waterborne polyurethane composite coating liquid as the outer layer coating liquid. Disperse the pore-forming agent in the outer layer coating liquid. Apply the outer layer coating liquid to the inner layer surface through a spraying process. After pre-curing and subsequent cleaning to create pores, an outer layer coating is formed.

[0008] Step 3: The fibers coated with the double coating are subjected to low-temperature synergistic curing to promote cross-linking and fixation of the inner and outer layers, and then rinsed and dried.

[0009] Step 4: Weave the fibers into fabric, then soak it in a softener to obtain a fabric that has both anti-radiation and antibacterial and deodorizing functions, as well as being soft, skin-friendly, and comfortable to wear.

[0010] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. By constructing a bio-crosslinking network through chitosan / polyethylene glycol composite gel and genipin, a stable bond is achieved between the composite gel and the hydroxyl groups on the fiber surface. Simultaneously, the covalent reaction between genipin and the amino groups of the extracellular polysaccharides in the biofilm prevents coating peeling and spore loss. Furthermore, the stress-resistant structure of the spores and their metabolic dormancy mechanism in dry environments ensure that the spores remain active after multiple washes and can re-germinate and form a biofilm upon contact with sweat. This provides core support for the dual-function long-lasting effect, enabling the anti-radiation coating and the antibacterial biofilm to form a strong bond, which helps to improve the structural stability and durability of the product.

[0011] 2. By inducing in situ growth through sweat, Bacillus subtilis forms a dense biofilm within the fiber pores. The three-dimensional network of extracellular polysaccharides in the biofilm forms a physical barrier. At the same time, the biofilm encapsulates the antimicrobial peptides secreted by the strain, achieving immediate and highly effective antibacterial action. Combined with naringenin, which has UV resistance and sweat degradation resistance, as a long-term backup, it compensates for the activity decay of the antimicrobial peptides after long-term use. This avoids the risk of cross-resistance caused by multiple antimicrobial agents and ensures the long-term stability of the antimicrobial effect.

[0012] 3. Sodium chloride is added to the coating solution as a pore-forming agent. After cleaning, it forms a uniformly distributed breathable channel. This does not affect the radiation protection density of bismuth oxide, but provides oxygen and nutrient delivery pathways for the germination of Bacillus subtilis spores and the formation of biofilm. The release of the inducer is controlled by slow-release microspheres to avoid pore blockage, thus achieving a balance between the density of the radiation protection coating, the breathability of biofilm growth, and the comfort of the fabric. Attached Figure Description

[0013] Figure 1 This is a flowchart illustrating the preparation process of the radiation-proof, antibacterial, and deodorizing fabric of the present invention. Figure 2 This is a cryo-electron microscopy schematic diagram of the sample in Example 1 of the present invention; Figure 3 This is a schematic diagram of a confocal laser scanning microscope used for the sample in Example 1 of the present invention. Detailed Implementation

[0014] The following embodiments further explain and illustrate the technical solutions of the present invention. It should be specifically noted that each specific embodiment is a concretization and explanation of the technical solution and should not be considered as a limitation on the scope of protection of the present invention. Those skilled in the art still have the right to modify the technical solutions of these embodiments and make equivalent substitutions for some or all of the technical features, and these modifications or substitutions do not change the essence of the corresponding technical solutions, nor do they cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions described in the present invention.

[0015] This invention proposes a method for preparing a radiation-proof, antibacterial, and deodorizing fabric, such as... Figure 1 As shown, the specific technical solution is as follows: 1. Fiber pore-forming treatment and bismuth oxide modification Cellulose fibers are enzymatically hydrolyzed, washed, and dried. Simultaneously, the radiation-shielding particles are surface-modified with a silane coupling agent, then dried, sealed, and stored for later use. Due to the specific catalytic action of cellulase, enzyme molecules can precisely identify amorphous structural regions on the fiber surface, selectively hydrolyzing them without destroying the fiber's crystalline structure. This gentle etching method forms a uniformly distributed microporous structure on the fiber surface, avoiding excessive damage to the fiber's mechanical framework while significantly increasing the fiber's specific surface area. This enzymatic treatment provides abundant physical anchoring points for the subsequent adhesion of the inner functional coating, allowing functional components to bind more firmly to the fiber surface and preventing detachment during use. Furthermore, it creates a suitable spatial environment for the subsequent growth of antibacterial biofilms, facilitating the formation of a dense biofilm network and enhancing the long-lasting antibacterial effect. As a core component of radiation protection, the radiation protection effect of anti-radiation particles relies on the principle of physical shielding. Effective scattering and absorption of X-rays is achieved through the localized dense packing of particles. If the particles are excessively uniformly dispersed, the packing density per unit area decreases, allowing rays to easily penetrate through the gaps between particles, leading to a decline in protective effectiveness. Unmodified particles have strong surface polarity and poor compatibility with organic film-forming agents, making them prone to irregular agglomeration. This can cause excessive local particle aggregation, leading to stress concentration cracking in the coating, and can also create voids, resulting in protective gaps and severely affecting the stability and consistency of radiation protection performance. The organic modification layer formed on the surface of radiation-protective particles by silane coupling agents can effectively regulate the particle dispersion state. This reduces excessive attraction between particles to avoid large-size agglomeration and improves interfacial compatibility with water-based polyurethane coating liquid. It guides the particles to form a locally dense but overall continuous distribution, ensuring the packing density per unit area to block ray penetration while avoiding coating defects caused by agglomeration. Ultimately, this results in a dense radiation-protective layer with uniform protection and a stable structure.

[0016] 2. Preparation and pre-curing of the double-layer coating A chitosan / polyethylene glycol composite gel was prepared as the inner layer matrix. This gel was mixed with functional components to form the inner layer gel, which was then coated, pre-cured, and pore-forming to form a stable porous coating. An outer layer coating liquid loaded with modified radiation-shielding particles was then applied to the inner layer surface. Genipin was used to crosslink the outer and inner layers. Chitosan, as a natural polysaccharide, contains a large number of amino and hydroxyl groups, forming a bio-crosslinking network with genipin. This ensures both coating stability and good biocompatibility. Polyethylene glycol is inserted into the chitosan molecular chain, which reduces the crosslinking density and improves the fabric's softness. Bacillus subtilis spores are encapsulated in microcapsules, which effectively isolates the spores from the influence of the external environment, prevents premature germination, and endows them with structural integrity and activity retention under stress conditions such as washing and drying. The pore-forming agent is a water-soluble salt that leaves no residue after washing. The formed through-pores provide sufficient oxygen and nutrient delivery pathways for spore germination and biofilm growth, while improving fabric breathability. The specific germination inducer is encapsulated in microspheres to prevent premature contact with Bacillus subtilis spores. The outer shell of the microspheres is a water-soluble polymer. When the fabric comes into contact with a humid environment, the moisture permeates and causes the polymer microspheres to swell, thereby slowly releasing the inducer from the inside of the microspheres. It accumulates in the confined and moisturizing microenvironment formed by the inner porous structure, and after reaching an effective concentration, it specifically induces the germination of Bacillus subtilis spores, thereby forming a stable biofilm and realizing on-demand triggering and long-term maintenance of antibacterial function. Plant-derived antibacterial agents possess broad-spectrum antibacterial properties, rapidly inhibiting bacterial growth and forming a synergistic antibacterial system with biofilms. This avoids the risk of drug resistance and ensures long-term stability of the antibacterial effect. The inner layer pad-coating, through pressure, allows the gel to fully penetrate the microporous structure of the fiber surface, achieving uniform loading of functional components. Through a combination of physical anchoring and chemical cross-linking, coating adhesion is enhanced. The outer layer spray coating allows for precise control of coating thickness, strengthening the coating's radiation protection capabilities and preventing radiation-proof gaps. To achieve a balance in material exchange between the outer radiation-proof layer and the inner bioactive microenvironment, a small amount of pore-forming agent is added to the outer coating solution, but at a much lower level than the inner layer, ensuring that the radiation-proof particles can still form an effective, locally dense accumulation network to block X-rays. After the inner coating is pre-cured, the pore-forming agent in the inner layer is dissolved and washed away through a cleaning step. Then, the outer coating is applied. After the outer layer is pre-cured, the pore-forming agent in the outer layer is also dissolved and washed away through a cleaning step. Through cleaning and pore-forming, the inner layer forms a through-hole porous gel network to load biological components, while the outer layer forms a uniform, sparse micron-sized pore structure. This structure can maintain high radiation protection performance externally, while allowing water vapor and oxygen to slowly pass through by diffusion internally. This provides the necessary gas and humidity conditions for the activation of Bacillus subtilis and the growth of biofilm in the inner layer, while effectively blocking the large-scale intrusion of external liquid water and protecting the functional components.

[0017] 3. Curing, rinsing, and drying The double-layered coated fibers loaded with spore capsules are cured, then rinsed and dried. Mild curing conditions achieve a stable bond between the double-layer coating and the fibers, while protecting the structural integrity and potential activity of the spore capsules, allowing for effective activation in humid environments during subsequent use. This mild environment promotes the bio-crosslinking reaction between genipin and chitosan, enabling the inner gel to form a stable three-dimensional network structure, enhancing its bonding strength with the fibers. It also promotes interfacial fusion between the outer waterborne polyurethane coating and the inner gel, making the double-layer structure a robust whole, preventing coating peeling or functional layer separation during subsequent use. This mild curing environment ensures the full progress of the crosslinking reaction while avoiding damage to spore activity from high temperatures, ensuring the spores retain their germination ability upon subsequent contact with sweat. The rinsing step after curing removes unreacted free substances and potentially irritating residues, resulting in a cleaner and safer fabric surface. The drying process further fixes the fabric structure and ensures that the Bacillus subtilis spores remain dormant under the protection of the microcapsules. Because the spores have a multi-layered stress-resistant structure, they can withstand conventional detergents and medium-low temperature drying. Their biofilm can enter dormancy or form new spores through metabolic regulation in a dry environment. When they come into contact with a humid environment again, the spores are induced to germinate rapidly by a Bacillus subtilis spore-specific germination inducer and reform the biofilm, thereby achieving functional regeneration after the washing-drying cycle and making the bond between the double coating and the fiber more stable.

[0018] 4. Blended fabrics and comfort-enhancing post-treatments After cross-linked and cured modified fibers are mixed with unmodified fibers in a certain proportion and spun into a greige fabric, it undergoes softener soaking and low-temperature setting treatment to obtain a functionally stable and comfortable anti-radiation, antibacterial, and deodorizing fabric. When modified and unmodified natural fibers are mixed in a certain proportion, the modified fibers, which carry the functions of radiation protection and antibacterial properties, are evenly distributed within the fiber aggregate. The unmodified natural fibers form a moisture-wicking and breathable basic structure within the aggregate. This complementary combination of the two fibers allows the aggregate to retain the component density required for the core function while possessing the flexibility and breathability of natural fibers, avoiding performance imbalances caused by a single fiber type. Subsequently, the greige fabric is soaked in a softener. During the soaking process, the softener molecules adsorb onto the fiber surface, forming a uniform lubricating film. This reduces the frictional resistance between fibers and between fibers and skin, thereby alleviating the rough feel that modified fibers may cause. This gives the fabric a soft and skin-friendly quality. Furthermore, the softener's action is gentle and does not damage the bio-crosslinked network already formed on the fiber surface, nor does it affect the structure or spore activity of bismuth oxide. Low-temperature setting fixes the fiber arrangement and fabric structure of the fabric, reducing shape deformation during subsequent wearing and washing. At the same time, it further enhances the structural stability of the yarn and the fabric, preventing the functional components from falling off due to mechanical action. In addition, the low-temperature environment can retain the functional activity of the anti-radiation components and spores to the greatest extent, ensuring that the fabric can continue to perform its core functions stably during long-term use.

[0019] The following are some specific embodiments of the present invention, and Table 1 shows the raw material information used in the embodiments.

[0020] Table 1 Raw Material Information Table Example 1 S1: Take 10g of cotton fiber and immerse it in 100mL of 1.5g / L neutral cellulase solution. At the same time, add acetate-sodium acetate buffer to adjust the pH of the system to 6.0. Treat the fiber with enzyme in a 45℃ water bath for 60min, stirring once every 15min. After the reaction, rinse the fiber with 60℃ deionized water 4 times for 5min each time. Then dry it in an oven at 60℃ until the moisture content is 9% to obtain the enzyme-treated fiber. Meanwhile, add 0.1g of silane coupling agent KH-550 to 50mL of ethanol-water mixed solvent with a volume ratio of 95:5. Adjust the pH to 4.5 with glacial acetic acid. Let it stand at room temperature for 30min for hydrolysis. Add 5g of bismuth oxide and stir in an oil bath at 60℃ at 400rpm for 90min. After the reaction, centrifuge at 8000rpm for 10min. Collect the precipitate, wash it twice with anhydrous ethanol, and dry it in a vacuum drying oven at 60℃ for 4h to obtain silane-modified bismuth oxide.

[0021] S2: Take 100 mL of 1% acetic acid solution, add 3 g of chitosan, stir at 50℃ for 30 min until completely dissolved, cool to room temperature, add 20 g of polyethylene glycol, stir for 10 min, then add 0.2 g of sodium chloride, 0.05 g of naringenin, and 0.1 g of L-alanine sustained-release microspheres in sequence, stir at 300 rpm for 20 min, disperse under 20 kHz, 150 W ultrasonication for 30 min, stirring once every 5 min during this period, to prepare the inner layer gel solution; immerse the enzyme-treated fiber obtained in S1 into the inner layer gel solution, perform padding at a speed of 0.3 m / min, control the padding rate to 60%, pre-cur at room temperature for 40 min; then rinse with 60℃ deionized water 4 times, 5 min each time, and dry to a moisture content of 9%; take 6 g of water-soluble polyurethane resin, add 2 g of modified bismuth oxide, 0.05 g sodium chloride and 10 mL anhydrous ethanol were ultrasonically dispersed at 20 kHz and 150 W for 30 min, and sprayed onto the inner layer surface at a speed of 0.3 m / min. The mixture was pre-cured at room temperature for 40 min, then rinsed four times with 60 °C deionized water for 10 min each time, and dried to a moisture content of 9%. 1 g genipin was dissolved in 20 mL deionized water and sprayed evenly onto the fiber surface with the double-layer coating. The mixture was reacted at room temperature for 20 min to allow the genipin to fully penetrate into the inner layer gel, thus obtaining a double-layer functional coated fiber with complete inner layer cross-linking.

[0022] S3: The pre-cured fiber was placed in a Class 10,000 cleanroom incubation tunnel and cured for 2 hours at 40°C and 75% humidity. Then it was rinsed twice with phosphate buffer for 1 minute each time and dried in a forced-air dryer at 60°C for 30 minutes to obtain the modified functional fiber.

[0023] S4: The treated functional fibers are mixed with untreated ordinary cotton fibers at a mass ratio of 7:3, spun on a ring spinning machine at 8000 rpm, and woven into a plain weave fabric. The fabric is then immersed in a 3g / L neutral softener solution at 30℃ for 20 minutes, during which it is stirred three times at 150 rpm for 1 minute each time. After immersion, it is removed and drained, and placed in an 80℃ oven for setting for 10 minutes. After naturally cooling to room temperature, a comfortable, functionally stable anti-radiation, antibacterial, and deodorizing fabric is obtained.

[0024] The functional fibers obtained from S3 were immersed in liquid nitrogen for 60 seconds to completely freeze and brittle them. Then, using pre-cooled tweezers, the fibers were quickly broken off underwater. The broken fibers, with the cut surface facing upwards, were vertically attached to a sample stage coated with conductive adhesive. An ion sputtering technique was used to spray a Pt conductive layer under vacuum conditions for 60 seconds. The sample was then placed in a field emission scanning electron microscope (FET) with an accelerating voltage of 5 kV and a detector mode of SE+BSE hybrid mode to observe its microscopic surface morphology. The results are as follows: Figure 2As shown, the sample exhibits a sandwich structure of fiber substrate, porous inner layer, and dense outer layer. The inner layer, due to the significant leaching of sodium chloride, contains numerous interconnected pores with large diameters, providing space for biofilm growth. The outer layer, on the other hand, should exhibit a denser structure containing a small number of uniformly dispersed micropores. Bismuth oxide particles are mainly concentrated in the outer layer, with bismuth oxide distributed both inside and on the surface of the outer substrate. This indicates that the dual-coating process successfully loaded the radiation-shielding layer and the antibacterial layer onto the fiber surface.

[0025] Example 2 The preparation method according to Example 1 differs in that: S1: The enzyme treatment temperature in the water bath is 43℃, the treatment time is 50min, bismuth oxide is replaced with barium sulfate, the silane coupling agent is hydrolyzed and the pH is adjusted to 4.3, the oil bath temperature is 55℃, and the stirring time is 80min. S2: Chitosan dissolution temperature is 45℃, dissolution time is 25min; inner layer gel liquid stirring time is 15min, ultrasonic dispersion time is 25min, padding rate is 50%, room temperature pre-curing time is 35min; the mass of sodium chloride added to the outer layer coating liquid is 0.1g, ultrasonic dispersion time is 25min, outer layer pre-curing time is 35min; after adding genipin, stirring time is 15min; naringenin is replaced with tea polyphenols; L-alanine sustained-release microspheres are replaced with L-valine sustained-release microspheres. S3: Curing temperature is 40℃, curing time is 1h, rinsing time is 1min, and drying time is 20min; S4: The blending ratio of functional fiber to ordinary cotton fiber is 6:4, the softener concentration is 2g / L, the soaking temperature is 25℃, the soaking time is 15min, the setting temperature is 70℃, the setting time is 5min, and the remaining steps are the same.

[0026] Example 3 The preparation method according to Example 1 differs in that: S1: The enzyme treatment temperature in the water bath is 48℃, the treatment time is 70min, bismuth oxide is replaced with tin oxide, the pH of the silane coupling agent is adjusted to 4.8, the oil bath temperature is 65℃, and the stirring time is 110min. S2: Chitosan dissolution temperature is 55℃, dissolution time is 35min, inner layer gel stirring time is 25min, ultrasonic dispersion time is 35min, padding rate is 70%, room temperature pre-curing time is 45min, sodium chloride added to outer layer coating liquid is 0.04g, ultrasonic dispersion time is 35min, outer layer pre-curing time is 45min, after adding genipin, stirring time is 25min, naringenin is replaced with citral, and L-alanine sustained-release microspheres are replaced with L-leucine sustained-release microspheres; S3: Curing temperature is 45℃, curing time is 2.5h, rinsing time is 2min, and drying time is 40min; S4: The blending ratio of functional fiber to ordinary cotton fiber is 8:2, the softener concentration is 5g / L, the soaking temperature is 35℃, the soaking time is 30min, the setting temperature is 85℃, the setting time is 12min, and the remaining steps are the same.

[0027] Example 4 The preparation method according to Example 1 differs in that: S1: The enzyme treatment temperature in the water bath is 46℃, the treatment time is 62min, the pH adjustment for silane coupling agent hydrolysis is 4.6, the oil bath temperature is 61℃, and the stirring time is 95min. S2: Chitosan dissolution temperature is 52℃, dissolution time is 32min, inner layer gel stirring time is 18min, ultrasonic dispersion time is 32min, padding rate is 58%, room temperature pre-curing time is 42min, the mass of sodium chloride added to the outer coating liquid is 0.08g, ultrasonic dispersion time is 32min, outer layer pre-curing time is 42min, and stirring time after adding genipin is 18min; S3: Curing temperature is 43℃, curing time is 1.8h, rinsing time is 1.5min, and drying time is 28min; S4: The blending ratio of functional fiber to ordinary cotton fiber is 6.5:3.5, the softener concentration is 3.5g / L, the soaking temperature is 31℃, the soaking time is 22min, the setting temperature is 78℃, the setting time is 9min, and the remaining steps are the same.

[0028] Comparative Example 1 The preparation method according to Example 1 differs in that: S2: No genipin is added to the inner gel solution; all other steps are the same.

[0029] This comparative example shows a fabric coated with a conventional chitosan / polyethylene glycol composite coating that has not undergone biocrosslinking.

[0030] Comparative Example 2 The preparation method according to Example 1 differs in that: S2: L-alanine sustained-release microspheres are not added to the inner gel solution; all other steps are the same.

[0031] This comparative study prepared functional fabrics whose spores cannot be activated by sweat.

[0032] Comparative Example 3 The preparation method according to Example 1 differs in that: S2: No sodium chloride is added to the inner gel solution; all other steps are the same.

[0033] This comparative example prepares a dense, double-layer coated fabric without any breathable pores.

[0034] Experimental Example 1 Referring to GBZ / T147-2002 "Determination of Attenuation Performance of X-ray Protective Materials", the radiation protection of the prepared coated fabric was tested using an X-ray air kerma (protection level) standard device, with a measurement range of 1.0 × 10⁻⁶. -5 At a speed of ~1.0 Gy / h, with the geometric center of the radiation emitter and the center of the detector remaining unchanged, the air-to-energy release rate (H0) without shielding material was obtained. Subsequently, fabrics prepared in Examples 1-4 and Comparative Examples 1-3 were placed between the radiation source and the detector, respectively, to obtain the air-to-energy release rate (H) with shielding material. The X-ray shielding efficiency η of the fabric was calculated using the following formula: The fabrics prepared in Examples 1-4 and Comparative Examples 1-3 were placed in Staphylococcus aureus and Escherichia coli bacterial solutions, respectively, and the antimicrobial properties of the fabrics were determined according to GB / T20944.3-2008 "Evaluation of antimicrobial properties of textiles - Part 3: Shaking method".

[0035] The fabrics prepared in Examples 1-4 and Comparative Examples 1-3 were cut into 100×100mm sizes. After adsorption for 2 hours at a temperature of 20°C and a humidity of 65%, the deodorization performance of the fabrics was tested according to the standard "ISO 17299-2-2014 Determination of deodorization properties of textiles - Part 2: Test tube method". The test gases were ammonia and acetic acid.

[0036] The test results are shown in Table 2.

[0037] Table 2 Radiation protection, antibacterial and deodorizing performance of the examples and comparative samples As shown in Table 2, the fabric products prepared in the examples are significantly superior to the comparative samples in terms of radiation protection and antibacterial and deodorizing performance. Especially after multiple washes, they maintain good performance, indicating that the fabrics prepared in the examples have more stable functionality. Comparative Example 1 sample did not contain genipin, and therefore did not form a genipin-mediated three-dimensional bio-crosslinking network. This not only resulted in poor adhesion between the coating and the fiber but also affected the continuity and cohesion of the coating itself. Due to the loose structure of the coating, its ability to encapsulate and fix the modified bismuth oxide was weak, leading to easy detachment or uneven distribution of the radiation-protective filler, resulting in a low X-ray shielding rate. Furthermore, this unstable coating structure is more easily damaged during washing, exacerbating the loss of all functional components, causing a significant deterioration in all aspects of the fabric's performance after washing. Comparative Example 2 fabric did not contain L-alanine, so the spores could not be activated by sweat and remained in a dormant state, unable to form a biofilm. It could only rely on naringenin for a short-term effect, and the chemical adsorption and reaction efficiency of the naringenin-only system for deodorization was far lower than that of the naringenin / biofilm system. The synergistic effect of the membrane system, and the continuous dissolution and loss of naringenin during repeated washing, as well as the potential degradation of its molecular structure, lead to rapid performance degradation. The lack of biomembrane-assisted film formation also slightly affects the uniformity of the bismuth oxide coating, resulting in a decrease in shielding efficiency. Comparative Example 3, without the addition of sodium chloride pore-forming agent, cannot form interconnected breathable channels in the inner layer, resulting in a dense double-layer coated fabric. This dense coating not only hinders sweat penetration and oxygen flow, making it difficult for subsequent spores to contact the inducing agent and significantly reducing germination efficiency, but also affects the wetting and spreading of the coating liquid on the fiber surface, leading to poor adhesion between the coating and fiber and uneven distribution of bismuth oxide. This results in a significant decrease in radiation protection performance. Furthermore, the hot and stuffy environment further affects the antibacterial function, ultimately resulting in extremely poor antibacterial and deodorizing capabilities that cannot be maintained for long periods.

[0038] Experiment Example 2 The fabrics prepared in Examples 1-4 and Comparative Examples 1-3 were cut into 200×50mm sizes and equilibrated for 24 hours at a temperature of 20℃ and a humidity of 65%. The average tear strength of the fabrics was tested in both the radial and weft directions according to GB / T 3917 "Textiles - Tear Properties of Fabrics" to evaluate the tear resistance of the fabrics. The results are shown in Table 3.

[0039] Table 3. Tear resistance of the examples and comparative samples As shown in Table 3, the fabrics prepared in the examples all exhibited higher tear resistance, indicating that the three-dimensional bio-crosslinked network formed by genipin and chitosan can effectively enhance the durability of the fabric. Comparative Example 1, without the addition of genipin, could not form a genipin-mediated bio-crosslinked network, relying solely on physical entanglement and van der Waals forces to adhere to the fiber surface. Therefore, the bonding force was weak, and the cohesive strength after film formation was far lower than that of the bio-crosslinked network. When torn, it was prone to large-area cracking and peeling, failing to effectively transfer and disperse stress. The fabric prepared in Comparative Example 2 did not contain L-alanine, so the spores could not be activated to form a biofilm. Lacking the binding effect of the biofilm on the coating, the mechanical properties of the product relied solely on the genipin-mediated crosslinking effect. Therefore, the products prepared in the comparative examples are all weaker; Comparative Example 3 did not add sodium chloride pore-forming agent, and the inner layer has no interconnected breathable pores. The dense coating hinders the penetration of sweat and the flow of oxygen, and at the same time affects the wetting and spreading of the coating liquid on the fiber surface, resulting in extremely weak bonding between the cured coating and the fiber. Moreover, the dense structure makes it easy for voids and defects to be generated inside the coating, forming a fragile layered structure. The cohesive strength of this structure itself is extremely low. When subjected to tearing force, the damage can be easily initiated from the fragile interface between the coating and the fiber or from the defects in the coating itself and spread rapidly.

[0040] Experimental Example 3 The finished fabric prepared in Example 1 was cut into 1cm × 1cm squares and rinsed three times with sterile PBS buffer to remove surface impurities. Then, it was placed in a sterile confocal culture dish. Simulated sweat was prepared according to the ISO 105-E04 standard artificial sweat formulation, with 10 mmol / L L-alanine added as a spore germination inducer, and the pH adjusted to 6.5. 2 mL of the L-alanine-containing simulated sweat was added to the culture dish containing the fabric, and the dish was placed in a constant temperature and humidity incubator at 37°C and 90% relative humidity. Samples were taken after 0 h, 12 h, and 24 h of incubation. After sampling, the culture medium was aspirated, and the samples were rinsed twice with sterile NaCl solution to remove airborne bacteria, retaining attached bacteria. SYTO 9 dye and PI dye were mixed in a 1:1 ratio and diluted 1000 times with sterile water to prepare the staining working solution. 200 μL of the staining working solution was added to each sample after sampling, and the samples were incubated at room temperature in the dark for 15 min. Excess staining solution was then aspirated, and an anti-fluorescence quenching mounting medium was added. The samples were then covered with coverslips and placed under a confocal microscope for observation. The confocal microscope channel parameters were set as follows: Channel 1 used an Argon Laser 488nm laser with a detection range of 500–540 nm, using green to observe live bacteria; Channel 2 used a DPSS Laser 561nm laser with a detection range of 600–700 nm, using red to observe dead bacteria; Channel 3 was adjusted to reflective mode to observe fiber structure or reflected light; the overall resolution was 1024 × 1024 pixels, the scanning speed was 400 Hz, and the scan was performed in 0.5 μm increments, scanning downwards from the fabric surface to a depth of 30–40 μm to reconstruct 3D biofilm images.

[0041] The results are as follows Figure 3As shown, the uncultured sample exhibits an interwoven structure of two types of fibers. On the surface of the functional fibers, scattered, faint green specks caused by dormant spores are visible, while the surface of the ordinary fibers is very clean with no fluorescence or red signal. In contrast, in the sample cultured for 12 hours, bright green rod-shaped fluorescent signals appeared on the surface of the functional fibers, with obvious cell division observed. This indicates that with L-alanine induction, the spores began to germinate into vegetative cells, leading to a sharp increase in green fluorescence intensity and the observation of bacterial division and proliferation. The surface of the ordinary fibers remained sterile or showed only a very small amount of non-specific adsorption. The appearance of sporadic red fluorescent dots in the field of view indicates that a very small number of bacteria died due to metabolic stress or natural apoptosis during germination. In the sample cultured for 24 hours, the functional fibers were wrapped by thick green fluorescent clumps, indicating that the biofilm formed by spore germination adhered to the fiber surface, while the surface of ordinary fibers remained relatively clean. Compared with the 12-hour sample, the red fluorescent signal increased slightly and was mainly located at the bottom layer of the biofilm, indicating that bacteria died due to hypoxia or nutrient depletion. The 3D reconstructed Z-axis view shows that the biofilm thickness is about 15~25μm, filling the micropores on the surface of the functional fibers and presenting a three-dimensional protective layer structure.

Claims

1. A radiation-proof, antibacterial, and deodorizing fabric, woven from fibers with a surface coated with a double-layer functional material coating, characterized in that: The fiber is a fiber treated with neutral cellulase to create pores. The bilayer functional material coating includes an inner layer and an outer layer. The inner layer is a chitosan / polyethylene glycol composite gel coating, and the outer layer is a radiation-resistant particle / waterborne polyurethane composite coating. The inner layer is loaded with Bacillus subtilis spore capsules, a pore-creating agent, a plant-derived antibacterial agent, and a Bacillus subtilis spore-specific germination inducer. The outer layer is loaded with a pore-creating agent and modified radiation-resistant particles. The inner layer and the hydroxyl groups on the fiber surface are covalently cross-linked through genipin, and the outer layer is interfacially bonded to the inner layer through a silane coupling agent.

2. The anti-radiation, antibacterial, and deodorizing fabric according to claim 1, characterized in that: The specific germination inducer is used to induce the in situ germination of Bacillus subtilis spore capsules to form an antibacterial biofilm structure; the biofilm grows in the porous channels of the inner coating layer and forms a three-dimensional network structure with the inner coating layer through extracellular polysaccharides.

3. The anti-radiation, antibacterial, and deodorizing fabric according to claim 1, characterized in that: The fabric has an X-ray shielding rate of >50%, an antibacterial rate of >90% against Staphylococcus aureus and Escherichia coli, and a removal rate of >85% for ammonia and acetic acid; the average tear strength of the fabric in both the radial and weft directions is >20N.

4. A method for preparing a radiation-proof, antibacterial, and deodorizing fabric according to any one of claims 1 to 3, characterized in that, It is prepared according to the following method: S1. The fiber is treated with neutral cellulase to construct a surface microporous structure. Simultaneously, a silane coupling agent is used to organically modify the surface of the radiation-shielding particles. The treated fiber is washed and dried, and the modified particles are separated and dried for use as independent raw materials. S2. Prepare a chitosan / polyethylene glycol composite gel as the inner layer matrix, mix it with Bacillus subtilis spore capsules, a pore-forming agent, a plant-derived antibacterial and deodorizing agent, and spore-specific germination inducing microspheres to form an inner layer coating liquid. Apply the inner layer coating liquid to the fiber surface through a padding process, and form a stable porous coating after pre-curing and cleaning to create pores. Simultaneously prepare a radiation-proof particle / waterborne polyurethane composite coating liquid as the outer layer coating liquid, disperse a pore-forming agent in it, and apply it to the inner layer surface through a spraying process. After pre-curing and subsequent cleaning to create pores, an outer layer coating is formed. S3. Co-cur the fibers with double coating to promote cross-linking and fixation of the inner and outer layers, and then rinse and dry. S4. The functional fibers obtained in S3 are blended with ordinary cellulose fibers in a certain proportion and woven into fabric. The fabric is then soaked in a softener solution and heated to set, resulting in a finished fabric that combines protective function with good wearability.

5. The method for preparing a radiation-proof, antibacterial, and deodorizing fabric according to claim 4, characterized in that: The radiation-shielding particles mentioned in S1 are one or more of bismuth oxide, barium sulfate, and tin oxide.

6. The method for preparing a radiation-proof, antibacterial, and deodorizing fabric according to claim 4, characterized in that: The enzyme treatment temperature in S1 is 43~48℃, and the treatment time is 50~70min; the reaction temperature of the silane-modified bismuth oxide is 55~65℃, and the stirring time is 80~110min.

7. The method for preparing a radiation-proof, antibacterial, and deodorizing fabric according to claim 4, characterized in that: The pore-forming agent in S2 is one or more of sodium chloride, potassium chloride, and ammonium chloride; the plant-derived antibacterial and deodorizing agent is one or more of naringenin, tea polyphenols, and citral; and the Bacillus subtilis spore-specific germination inducer is one or more of L-alanine, L-valine, and L-leucine.

8. The method for preparing a radiation-proof, antibacterial, and deodorizing fabric according to claim 4, characterized in that: The temperature for preparing the chitosan / polyethylene glycol composite gel as described in S2 is 45~55℃, and the stirring and dissolving time is 25~35min; the stirring time of the inner layer gel liquid is 15~25min, and the ultrasonic dispersion time is 25~35min; the padding rate is 50%~70%; the pre-curing time is 35~45min, the ultrasonic dispersion time of the outer layer coating liquid is 25~35min, and the outer layer pre-curing time is 35~45min; the stirring time after adding genipin is 15~25min; the mass ratio of the pore-forming agent in the inner layer coating liquid to the pore-forming agent in the outer layer coating liquid is (2:1)~(5:1).

9. The method for preparing a radiation-proof, antibacterial, and deodorizing fabric according to claim 4, characterized in that: The curing temperature of S3 is 40~45℃, and the curing time is 1~2.5h; the rinsing time is 1~2min; the drying temperature is 60℃, and the drying time is 20~40min.

10. The method for preparing a radiation-proof, antibacterial, and deodorizing fabric according to claim 4, characterized in that: The ratio of the functional fiber to the ordinary cotton fiber in S4 is (6:4) to (8:2); the concentration of the softener solution is 2 to 5 g / L; the soaking temperature is 25 to 35°C and the soaking time is 15 to 30 min; the temperature for heat setting is 70 to 85°C and the setting time is 5 to 12 min.

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