An antibacterial lace fabric and its preparation method

Abstract

This invention discloses an antibacterial lace fabric and its preparation method, relating to the field of functional fiber fabric technology. The preparation method includes first coating the lower surface of an antibacterial layer with a water-based polyurethane adhesive, then stacking a cotton support layer below the antibacterial layer, performing hot-pressing lamination, and then laying nylon 66 lace trim on both sides of the antibacterial layer, fixing it with hot-melt adhesive strips to obtain the antibacterial lace fabric. The lace fabric prepared by this invention has excellent antibacterial properties and long-lasting antibacterial activity.

Description

Technical Field

[0001] This invention relates to the field of functional fiber fabric technology, specifically to an antibacterial lace fabric and its preparation method. Background Technology

[0002] Lace fabric, with its exquisite three-dimensional patterns, light and flowing texture, and excellent decorative properties, occupies an irreplaceable position in clothing, home textiles, underwear, and wedding dresses. Its penetration rate is particularly high in women's underwear, making it a core material for enhancing product fashion and added value. With the upgrading of consumption and the comprehensive improvement of health awareness, consumers' demands for lace fabric have shifted from simple aesthetics to functionality and comfort. Antibacterial properties have become a core requirement for products that come into direct contact with the skin (such as underwear, loungewear, and infant home textiles). In these scenarios, the fabric is in prolonged contact with skin secretions and sweat, making it prone to the growth of pathogenic bacteria such as E. coli and Staphylococcus aureus. This can not only produce odors but also cause skin itching, inflammation, and other health problems, seriously affecting the wearing experience and product competitiveness. Summary of the Invention

[0003] The purpose of this invention is to provide an antibacterial lace fabric and its preparation method to solve the technical problems mentioned in the background.

[0004] To achieve the above objectives, the present invention provides the following technical solution:

[0005] A method for preparing an antibacterial lace fabric includes the following steps:

[0006] The lower surface of the antibacterial layer is coated with water-based polyurethane adhesive, and then a cotton support layer is stacked under the antibacterial layer. After hot pressing and laminating, nylon 66 lace trim is laid on both sides of the antibacterial layer and fixed with hot melt adhesive strips to obtain antibacterial lace trim fabric.

[0007] The method for preparing the antibacterial layer includes the following steps:

[0008] S1. Disperse silver-loaded zirconium phosphate and graphene quantum dots in deionized water, add a treatment solution prepared with KH-560 silane coupling agent and KH-550 silane coupling agent for surface treatment, and obtain activated composite antibacterial powder after reaction and post-treatment.

[0009] S2. After mixing and preheating PET chips with activated composite antibacterial powder, melt granulation is performed to obtain core layer raw material; nano silver is ultrasonically dispersed and pretreated, then melt-mixed with PBAT resin to obtain sheath layer raw material; the core layer raw material and the sheath layer raw material are respectively fed into a composite spinning machine, extruded through a composite spinneret, and then cooled, hot-stretched and heat-set in sequence to obtain a core-sheath structure antibacterial fiber precursor;

[0010] S3. The antibacterial fiber precursor with a core-sheath structure is subjected to plasma treatment and KH-570 silane coupling agent grafting treatment in sequence to obtain methacryloyloxy functionalized fiber.

[0011] S4. Dissolve antimicrobial peptide LL-37 and polyethylene glycol diglycidyl ether in a mixed solution of ethanol and deionized water to prepare a modification solution; immerse methacryloyloxy functionalized fibers in the modification solution and carry out a constant temperature shaking reaction under an inert atmosphere; after the reaction is completed, wash and dry to obtain antimicrobial fibers.

[0012] S5. The antibacterial fibers are spun into yarn and then woven into fabric to obtain the antibacterial layer.

[0013] In this invention, the antibacterial properties of the antibacterial lace fabric are achieved synergistically from two aspects. Firstly, the antibacterial fiber core layer uses PET as a matrix to load activated composite antibacterial powder of silver-loaded zirconium phosphate and graphene quantum dots. The silver-loaded zirconium phosphate can release silver ions slowly and effectively, achieving long-lasting sterilization by destroying bacterial DNA and enzyme activity. The graphene quantum dots, with their micro-nano size physical puncture effect and photocatalytically generated active oxygen, rapidly kill bacteria and inhibit fungal growth. The two work synergistically to broaden the antibacterial spectrum. Secondly, the outer layer uses PBAT copolyester to load silver nanoparticles. The small particle size and large specific surface area of ​​the silver nanoparticles allow for rapid release of silver ions to exert an immediate sterilization effect, compensating for the slower onset of action of the antibacterial agent in the core layer. Meanwhile, the antibacterial powder modified by ultrasonic dispersion and coupling agent is evenly dispersed in the fiber, avoiding the loss of antibacterial sites caused by agglomeration. The core-sheath structure realizes the time-series synergy of rapid sterilization in the sheath layer and long-term antibacterial effect in the core layer, ensuring that the antibacterial layer can maintain a high level of antibacterial effect at different stages of use. Moreover, the antibacterial agent is encapsulated by the fiber matrix, reducing the loss caused by direct exposure.

[0014] On the other hand, plasma treatment firstly bombards the fiber surface with active particles, etching micro- and nano-grooves, significantly increasing the fiber's specific surface area. Simultaneously, it introduces a large number of active groups, providing ample sites for subsequent functionalization and antimicrobial peptide grafting. After KH-570 functionalization and polyethylene glycol diglycidyl ether treatment, the fiber can stably bind to the antimicrobial peptide LL-37, ensuring strong grafting and uniform distribution. As a broad-spectrum antimicrobial agent, antimicrobial peptide LL-37 adsorbs onto the bacterial cell membrane surface through cationic affinity, thereby forming pores and disrupting cell membrane integrity. This complements the mechanism of inorganic antimicrobial agents that disrupt the internal structure of bacteria, achieving highly efficient killing of pathogenic bacteria such as Escherichia coli, Staphylococcus aureus, and Candida albicans, especially showing significant inhibitory effects on some drug-resistant bacteria resistant to inorganic antimicrobial agents. In addition, the grafted antimicrobial peptides form a cross-linked network through polyethylene glycol diglycidyl ether, making them less prone to detachment due to external forces such as washing or friction. At the same time, the excellent biocompatibility of the antimicrobial peptides also avoids the risk of skin irritation that may be caused by inorganic antimicrobial agents.

[0015] Preferably, in step S1, the mass ratio of silver-loaded zirconium phosphate to graphene quantum dots is 7:(1-3).

[0016] Preferably, in step S1, the mass ratio of KH-560 silane coupling agent to KH-550 silane coupling agent is 3:(1-2).

[0017] Preferably, in step S2, the mass ratio of PET slices to activated composite antibacterial powder is 25:(2-5).

[0018] Preferably, in step S2, the mass ratio of PBAT resin to nano-silver is 108:(10-15).

[0019] Preferably, in step S3, the core-sheath structure antibacterial fiber precursor undergoes the following modification treatment after plasma treatment:

[0020] The plasma-treated fiber was immersed in an aqueous solution of potassium 3-sulfopropyl methacrylate, and the photoinitiator Irgacure2959 was added. The reaction was carried out under ultraviolet light irradiation, and the fiber was washed and dried to obtain the final product.

[0021] In this invention, research revealed that cationic silver ions exist in the sheath layer of the core-sheath structure antibacterial fiber precursor, while the antibacterial peptide LL-37 used for subsequent modification is a cationic polypeptide. Due to their identical charge properties, these two molecules exhibit significant electrostatic repulsion on the fiber surface, making it difficult for the antibacterial peptide to effectively bind to the fiber surface, severely limiting the synergistic antibacterial efficacy of the dual modification. To further address this technical problem, the fiber is functionalized using zwitterionic potassium 3-sulfopropyl methacrylate. The potassium 3-sulfopropyl methacrylate molecule possesses both cationic (methacryloyloxy) and anionic (sulfonate) structures. The anionic group can neutralize the excess positive charge remaining on the fiber surface due to the presence of silver ions in the sheath layer, fundamentally eliminating the electrostatic repulsion between cationic silver ions and the cationic antibacterial peptide LL-37. This removes the charge barrier for the binding of the antibacterial peptide to the fiber surface, significantly improving the grafting density and distribution uniformity of the antibacterial peptide, and further enhancing the antibacterial performance of the fabric.

[0022] Preferably, the mass concentration of the potassium salt 3-sulfopropyl methacrylate aqueous solution is 5-8%.

[0023] Preferably, in step S4, the mass ratio of antimicrobial peptide LL-37 to polyethylene glycol diglycidyl ether is 5:(2-3).

[0024] Preferably, in step S4, the reaction temperature is 40–45°C and the reaction time is 4–6 h.

[0025] An antibacterial lace fabric is prepared by the method described above.

[0026] Compared with the prior art, the beneficial effects of the present invention are:

[0027] 1. By combining the core-sheath structure inside the fiber (rapid sterilization by nano-silver and long-lasting antibacterial effect by silver-loaded composite powder) with the grafting of antimicrobial peptides on the fiber surface (biophysical membrane breaking mechanism), the complementary effects of immediate and long-lasting, inorganic and biological antibacterial mechanisms are achieved, significantly broadening the antibacterial spectrum and improving the effect against drug-resistant bacteria.

[0028] 2. The core-sheath structure encapsulates the antibacterial agent inside the fiber, reducing direct exposure losses. At the same time, through surface chemical modification and cross-linking technology, the antibacterial peptides are firmly grafted and are not easily detached due to washing or friction, thus ensuring the long-term stability of antibacterial performance.

[0029] 3. The use of zwitterionic treatment solves the problem of charge repulsion on the fiber surface, which greatly improves the uniformity and density of antimicrobial peptide grafting. In addition, the biocompatible antimicrobial peptides partially replace inorganic silver agents, reducing the potential risk of skin irritation and making the fabric safer and more comfortable. Attached Figure Description

[0030] Figure 1 This is a SEM image of the antibacterial layer fabric prepared in Example 4 of the present invention.

[0031] Figure 2 This is the XPS spectrum of the antibacterial layer fabric prepared in Example 4 of the present invention. Detailed Implementation

[0032] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0033] Example 1

[0034] A method for preparing an antibacterial lace fabric includes the following steps:

[0035] At 60g / m² on the lower surface of the antibacterial layer 2 Coating amount: Apply water-based polyurethane adhesive at a rate of 130 g / m². 2 A cotton support layer is placed underneath, and hot-pressed at 105℃ and 0.3MPa for 50 seconds; 60g / m 2 Nylon 66 lace trim is laid on both sides of the antibacterial layer, hot melt adhesive strips are placed, and it is fixed by hot pressing at 95℃ and 0.1MPa for 20 seconds to obtain antibacterial lace trim fabric.

[0036] The method for preparing the antibacterial layer includes the following steps:

[0037] Step 1: Weigh 140g of silver-loaded zirconium phosphate and 50g of graphene quantum dots (particle size 8nm), stir at room temperature using a high-speed mixer (3000r / min) for 15min until uniform, add 900mL of deionized water directly, and disperse using a 900W ultrasonic cell disruptor for 50min to obtain a uniformly dispersed antibacterial powder suspension.

[0038] Weigh 6g of KH-560 silane coupling agent and 3.5g of KH-550 silane coupling agent, slowly add 200mL of ethanol-deionized water mixed solution, stir to dissolve, and adjust the pH to 5.0 with 1mol / L acetic acid solution to prepare the treatment solution; spray the treatment solution evenly into the above suspension at a rate of 6mL / min using a high-pressure sprayer, and maintain stirring at 300r / min during the spraying process. After spraying, transfer to a constant temperature water bath and react at 50℃ for 3.5h. After the reaction, filter using a vacuum filter, wash the filter cake with deionized water until the pH of the washing liquid is 7.0, and then dry it to constant weight in a vacuum drying oven at 108℃. After pulverizing by an ultra-micro pulverizer, pass through a 300-mesh standard sieve to obtain activated composite antibacterial powder.

[0039] Step 2: Weigh 250g of PET chips (intrinsic viscosity 0.68dL / g) and 40g of activated composite antibacterial powder, place them in a high-speed mixer, preheat and mix at 120℃ for 20min (speed 2500r / min), then add them to a twin-screw extruder (zone 1 240℃, zone 2 255℃, zone 3 265℃, zone 4 260℃, zone 5 255℃, screw speed 180r / min) for melt granulation to obtain core layer raw material (total core layer mass 280g); weigh 108g PBAT (number average molecular weight 25000) and 14g of nano-silver (particle size 20nm) were mixed. The nano-silver was added to 10mL of deionized water and pretreated by ultrasonic dispersion at 900W for 20min. Then, it was added together with PBAT into a single-screw extruder and melt-mixed at 215℃ (screw speed 150r / min) to obtain the sheath material (total sheath mass 120g, sheath-core mass ratio 30:70). The core and sheath materials were fed separately into a composite spinning machine and extruded through a composite spinneret at 260℃. Side blowing cooling was used (wind speed 1.0m / s, temperature 23℃, wind distance 15cm). Then, it was subjected to 4.0 times hot stretching on a 90℃ hot roller and finally kept at 115℃ for 35s to obtain the sheath-core structure antibacterial fiber precursor.

[0040] Step 3: The antibacterial fiber precursor with a core-sheath structure is evenly wound onto a quartz support and placed into a plasma treatment device. After closing the chamber door, the vacuum is evacuated to 18 Pa. An argon-oxygen mixture (volume ratio 2:1) is introduced, and the inlet valve is adjusted to maintain the gas pressure inside the device at 50 Pa. The radio frequency power is set to 200 W, and after processing for 5 minutes, the gas supply is stopped. The device is allowed to cool naturally to room temperature and then the plasma-activated fiber is obtained.

[0041] The plasma-activated fiber was immersed in a 7% (w / w) aqueous solution of potassium 3-sulfopropyl methacrylate, and 0.5 wt% of photoinitiator Irgacure2959 was added. The fiber was then irradiated with 365 nm ultraviolet light at 30°C for 15 min (light intensity 10 mW / cm²). 2 The fibers were washed with deionized water until their conductivity stabilized, and then vacuum dried at 65°C for 1 hour to obtain the modified fibers.

[0042] Prepare a 5% KH-570 ethanol solution, add 1 mol / L acetic acid solution to adjust the pH to 3.5, completely immerse the modified fiber in the solution, place it in a constant temperature water bath shaker, and shake at 40℃ and 150 r / min for 2.5 h. After the reaction is complete, remove the fiber, wash it three times with anhydrous ethanol, and dry it in a vacuum drying oven at 65℃ for 1.5 h to obtain methacryloyloxy functionalized fiber.

[0043] Step 4: Weigh 5g of antimicrobial peptide LL-37 (purity 96%, molecular weight 4500Da) and 2.8g of polyethylene glycol diglycidyl ether (molecular weight 400Da), dissolve them in 1000mL of ethanol-deionized water mixed solution (volume ratio 1:1), stir to dissolve, and then add 1mol / L sodium hydroxide solution to adjust the pH to 8.0; completely immerse the methacryloyloxy functionalized fiber in the solution, purge the air in the system with nitrogen three times, seal it, and place it in a constant temperature water bath shaker at 43℃ and 180r / min for 5h; after the reaction, take out the fiber, wash it 4 times with PBS buffer solution (pH=7.4), then wash it with deionized water until the pH of the washing solution is 7.0, and place it in a vacuum drying oven at 50℃ to dry to constant weight to obtain antimicrobial fiber.

[0044] Step 5: Feed the antibacterial fiber into a ring spinning machine, set the spinning speed to 120m / min and the twist to 800 twists / m, to produce 30-count yarn. Then, use an air-jet loom to weave the yarn in a plain weave, controlling the fabric weight to be 90g / m². 2 , thus obtaining an antibacterial layer fabric.

[0045] Example 2

[0046] A method for preparing an antibacterial lace fabric includes the following steps:

[0047] At 60g / m² on the lower surface of the antibacterial layer2 Coating amount: Apply water-based polyurethane adhesive at a rate of 130 g / m². 2 A cotton support layer is placed underneath, and hot-pressed at 105℃ and 0.3MPa for 50 seconds; 60g / m 2 Nylon 66 lace trim is laid on both sides of the antibacterial layer, hot melt adhesive strips are placed, and it is fixed by hot pressing at 95℃ and 0.1MPa for 20 seconds to obtain antibacterial lace trim fabric.

[0048] The method for preparing the antibacterial layer includes the following steps:

[0049] Step 1: Weigh 140g of silver-loaded zirconium phosphate and 30g of graphene quantum dots (particle size 8nm), stir at room temperature using a high-speed mixer (3000r / min) for 15min until uniform, add 900mL of deionized water directly, and disperse using a 900W ultrasonic cell disruptor for 50min to obtain a uniformly dispersed antibacterial powder suspension.

[0050] Weigh 6g of KH-560 silane coupling agent and 2.5g of KH-550 silane coupling agent, slowly add 200mL of ethanol-deionized water mixed solution, stir to dissolve, and adjust the pH to 5.0 with 1mol / L acetic acid solution to prepare the treatment solution; spray the treatment solution evenly into the above suspension at a rate of 6mL / min using a high-pressure sprayer, and maintain stirring at 300r / min during the spraying process. After spraying, transfer to a constant temperature water bath and react at 50℃ for 3.5h. After the reaction, filter using a vacuum filter, wash the filter cake with deionized water until the pH of the washing solution is 7.0, and then dry it to constant weight in a vacuum drying oven at 108℃. After pulverizing with an ultra-micro pulverizer, pass through a 300-mesh standard sieve to obtain activated composite antibacterial powder.

[0051] Step 2: Weigh 250g of PET chips (intrinsic viscosity 0.68dL / g) and 30g of activated composite antibacterial powder, place them in a high-speed mixer, preheat and mix at 120℃ for 20min (speed 2500r / min), then add them to a twin-screw extruder (zone 1 240℃, zone 2 255℃, zone 3 265℃, zone 4 260℃, zone 5 255℃, screw speed 180r / min) for melt granulation to obtain core layer raw material (total core layer mass 280g); weigh 108g PBAT (number average molecular weight 25000) and 12g of nano-silver (particle size 20nm) were mixed. The nano-silver was added to 10mL of deionized water and pretreated by ultrasonic dispersion at 900W for 20min. Then, it was added to a single-screw extruder and melt-mixed at 215℃ (screw speed 150r / min) to obtain the sheath material (total sheath mass 120g, sheath-core mass ratio 30:70). The core and sheath materials were fed separately into a composite spinning machine and extruded through a composite spinneret at 260℃. Side blowing cooling was used (wind speed 1.0m / s, temperature 23℃, wind distance 15cm). Then, it was subjected to 4.0 times hot stretching on a 90℃ hot roller and finally kept at 115℃ for 35s to obtain the sheath-core structure antibacterial fiber precursor.

[0052] Step 3: The antibacterial fiber precursor with a core-sheath structure is evenly wound onto a quartz support and placed into a plasma treatment device. After closing the chamber door, the vacuum is evacuated to 18 Pa. An argon-oxygen mixture (volume ratio 2:1) is introduced, and the inlet valve is adjusted to maintain the gas pressure inside the device at 50 Pa. The radio frequency power is set to 200 W, and after processing for 5 minutes, the gas supply is stopped. The device is allowed to cool naturally to room temperature and then the plasma-activated fiber is obtained.

[0053] The plasma-activated fiber was immersed in a 6% (w / w) aqueous solution of potassium 3-sulfopropyl methacrylate, and 0.5 wt% of photoinitiator Irgacure2959 was added. The fiber was then irradiated with 365 nm ultraviolet light at 30°C for 15 min (light intensity 10 mW / cm²). 2 The fibers were washed with deionized water until their conductivity stabilized, and then vacuum dried at 65°C for 1 hour to obtain the modified fibers.

[0054] Prepare a 5% KH-570 ethanol solution, add 1 mol / L acetic acid solution to adjust the pH to 3.5, completely immerse the modified fiber in the solution, place it in a constant temperature water bath shaker, and shake at 40℃ and 150 r / min for 2.5 h. After the reaction is complete, remove the fiber, wash it three times with anhydrous ethanol, and dry it in a vacuum drying oven at 65℃ for 1.5 h to obtain methacryloyloxy functionalized fiber.

[0055] Step 4: Weigh 5g of antimicrobial peptide LL-37 (purity 96%, molecular weight 4500Da) and 2.3g of polyethylene glycol diglycidyl ether (molecular weight 400Da), dissolve them in 1000mL of ethanol-deionized water mixed solution (volume ratio 1:1), stir to dissolve, and then add 1mol / L sodium hydroxide solution to adjust the pH to 8.0; completely immerse the methacryloyloxy functionalized fiber in the solution, purge the air in the system with nitrogen three times, seal it, and place it in a constant temperature water bath shaker at 43℃ and 180r / min for 5h; after the reaction, take out the fiber, wash it four times with PBS buffer solution (pH=7.4), then wash it with deionized water until the pH of the washing solution is 7.0, and dry it in a vacuum drying oven at 50℃ until constant weight to obtain antimicrobial fiber.

[0056] Step 5: Feed the antibacterial fiber into a ring spinning machine, set the spinning speed to 120m / min and the twist to 800 twists / m, to produce 30-count yarn. Then, use an air-jet loom to weave the yarn in a plain weave, controlling the fabric weight to be 90g / m². 2 , thus obtaining an antibacterial layer fabric.

[0057] Example 3

[0058] A method for preparing an antibacterial lace fabric includes the following steps:

[0059] At 60g / m² on the lower surface of the antibacterial layer 2 Coating amount: Apply water-based polyurethane adhesive at a rate of 130 g / m². 2 A cotton support layer is placed underneath, and hot-pressed at 105℃ and 0.3MPa for 50 seconds; 60g / m 2 Nylon 66 lace trim is laid on both sides of the antibacterial layer, hot melt adhesive strips are placed, and it is fixed by hot pressing at 95℃ and 0.1MPa for 20 seconds to obtain antibacterial lace trim fabric.

[0060] The method for preparing the antibacterial layer includes the following steps:

[0061] Step 1: Weigh 140g of silver-loaded zirconium phosphate and 40g of graphene quantum dots (particle size 8nm), stir at room temperature using a high-speed mixer (3000r / min) for 15min until uniform, add 900mL of deionized water directly, and disperse using a 900W ultrasonic cell disruptor for 50min to obtain a uniformly dispersed antibacterial powder suspension.

[0062] Weigh 6g of KH-560 silane coupling agent and 3g of KH-550 silane coupling agent, slowly add 200mL of ethanol-deionized water mixed solution, stir to dissolve, and adjust the pH to 5.0 with 1mol / L acetic acid solution to prepare the treatment solution; spray the treatment solution evenly into the above suspension at a rate of 6mL / min using a high-pressure sprayer, and maintain stirring at 300r / min during the spraying process. After spraying, transfer to a constant temperature water bath and react at 50℃ for 3.5h. After the reaction, filter using a vacuum filter, wash the filter cake with deionized water until the pH of the washing solution is 7.0, and then dry it to constant weight in a vacuum drying oven at 108℃. After pulverizing by an ultra-micro pulverizer, pass through a 300-mesh standard sieve to obtain activated composite antibacterial powder.

[0063] Step 2: Weigh 250g of PET chips (intrinsic viscosity 0.68dL / g) and 35g of activated composite antibacterial powder, place them in a high-speed mixer, preheat and mix at 120℃ for 20min (speed 2500r / min), then add them to a twin-screw extruder (zone 1 240℃, zone 2 255℃, zone 3 265℃, zone 4 260℃, zone 5 255℃, screw speed 180r / min) for melt granulation to obtain core layer raw material (total core layer mass 280g); weigh 108g PBAT (number average molecular weight 25000) and 13g of nano-silver (particle size 20nm) were mixed. The nano-silver was added to 10mL of deionized water and pretreated by ultrasonic dispersion at 900W for 20min. Then, it was added together with PBAT to a single-screw extruder and melt-mixed at 215℃ (screw speed 150r / min) to obtain the sheath material (total sheath mass 120g, sheath-core mass ratio 30:70). The core and sheath materials were fed separately into a composite spinning machine and extruded through a composite spinneret at 260℃. Side-blowing cooling was used (wind speed 1.0m / s, temperature 23℃, wind distance 15cm). Then, it was subjected to 4.0 times hot stretching on a 90℃ hot roller and finally kept at 115℃ for 35s to obtain the sheath-core structure antibacterial fiber precursor.

[0064] Step 3: The antibacterial fiber precursor with a core-sheath structure is evenly wound onto a quartz support and placed into a plasma treatment device. After closing the chamber door, the vacuum is evacuated to 18 Pa. An argon-oxygen mixture (volume ratio 2:1) is introduced, and the inlet valve is adjusted to maintain the gas pressure inside the device at 50 Pa. The radio frequency power is set to 200 W, and after processing for 5 minutes, the gas supply is stopped. The device is allowed to cool naturally to room temperature and then the plasma-activated fiber is obtained.

[0065] The plasma-activated fiber was immersed in a 6.5% (w / w) aqueous solution of potassium 3-sulfopropyl methacrylate, and 0.5 wt% of photoinitiator Irgacure2959 was added. The fiber was then irradiated with 365 nm ultraviolet light at 30°C for 15 min (light intensity 10 mW / cm²). 2The fibers were washed with deionized water until their conductivity stabilized, and then vacuum dried at 65°C for 1 hour to obtain the modified fibers.

[0066] Prepare a 5% KH-570 ethanol solution, add 1 mol / L acetic acid solution to adjust the pH to 3.5, completely immerse the modified fiber in the solution, place it in a constant temperature water bath shaker, and shake at 40℃ and 150 r / min for 2.5 h. After the reaction is complete, remove the fiber, wash it three times with anhydrous ethanol, and dry it in a vacuum drying oven at 65℃ for 1.5 h to obtain methacryloyloxy functionalized fiber.

[0067] Step 4: Weigh 5g of antimicrobial peptide LL-37 (purity 96%, molecular weight 4500Da) and 2.5g of polyethylene glycol diglycidyl ether (molecular weight 400Da), dissolve them in 1000mL of ethanol-deionized water mixed solution (volume ratio 1:1), stir to dissolve, and then add 1mol / L sodium hydroxide solution to adjust the pH to 8.0; completely immerse the methacryloyloxy functionalized fiber in the solution, purge the air in the system with nitrogen three times, seal it, and place it in a constant temperature water bath shaker at 43℃ and 180r / min for 5h; after the reaction, take out the fiber, wash it four times with PBS buffer solution (pH=7.4), then wash it with deionized water until the pH of the washing solution is 7.0, and dry it in a vacuum drying oven at 50℃ until constant weight to obtain antimicrobial fiber.

[0068] Step 5: Feed the antibacterial fiber into a ring spinning machine, set the spinning speed to 120m / min and the twist to 800 twists / m, to produce 30-count yarn. Then, use an air-jet loom to weave the yarn in a plain weave, controlling the fabric weight to be 90g / m². 2 , thus obtaining an antibacterial layer fabric.

[0069] Example 4

[0070] A method for preparing an antibacterial lace fabric includes the following steps:

[0071] At 60g / m² on the lower surface of the antibacterial layer 2 Coating amount: Apply water-based polyurethane adhesive at a rate of 130 g / m². 2 A cotton support layer is placed underneath, and hot-pressed at 105℃ and 0.3MPa for 50 seconds; 60g / m 2 Nylon 66 lace trim is laid on both sides of the antibacterial layer, hot melt adhesive strips are placed, and it is fixed by hot pressing at 95℃ and 0.1MPa for 20 seconds to obtain antibacterial lace trim fabric.

[0072] The method for preparing the antibacterial layer includes the following steps:

[0073] Step 1: Weigh 140g of silver-loaded zirconium phosphate and 60g of graphene quantum dots (particle size 8nm), stir at room temperature using a high-speed mixer (3000r / min) for 15min until uniform, add 900mL of deionized water directly, and disperse using a 900W ultrasonic cell disruptor for 50min to obtain a uniformly dispersed antibacterial powder suspension.

[0074] Weigh 6g of KH-560 silane coupling agent and 4g of KH-550 silane coupling agent, slowly add 200mL of ethanol-deionized water mixed solution, stir to dissolve, and adjust the pH to 5.0 with 1mol / L acetic acid solution to prepare the treatment solution; spray the treatment solution evenly into the above suspension at a rate of 6mL / min using a high-pressure sprayer, and maintain stirring at 300r / min during the spraying process. After spraying, transfer to a constant temperature water bath and react at 50℃ for 3.5h. After the reaction, filter using a vacuum filter, wash the filter cake with deionized water until the pH of the washing liquid is 7.0, and then dry it to constant weight in a vacuum drying oven at 108℃. After pulverizing by an ultra-micro pulverizer, pass it through a 300-mesh standard sieve to obtain activated composite antibacterial powder.

[0075] Step 2: Weigh 250g of PET chips (intrinsic viscosity 0.68dL / g) and 50g of activated composite antibacterial powder, place them in a high-speed mixer, preheat and mix at 120℃ for 20min (speed 2500r / min), then add them to a twin-screw extruder (zone 1 240℃, zone 2 255℃, zone 3 265℃, zone 4 260℃, zone 5 255℃, screw speed 180r / min) for melt granulation to obtain core layer raw material (total core layer mass 280g); weigh 108g PBAT (number average molecular weight 25000) and 15g of nano-silver (particle size 20nm) were mixed. The nano-silver was added to 10mL of deionized water and pretreated by ultrasonic dispersion at 900W for 20min. Then, it was added to a single-screw extruder and melt-mixed at 215℃ (screw speed 150r / min) to obtain the sheath material (total sheath mass 120g, sheath-core mass ratio 30:70). The core and sheath materials were fed separately into a composite spinning machine and extruded through a composite spinneret at 260℃. Side-blowing cooling was used (wind speed 1.0m / s, temperature 23℃, wind distance 15cm). Then, it was subjected to 4.0 times hot stretching on a 90℃ hot roller and finally kept at 115℃ for 35s to obtain the sheath-core structure antibacterial fiber precursor.

[0076] Step 3: The antibacterial fiber precursor with a core-sheath structure is evenly wound onto a quartz support and placed into a plasma treatment device. After closing the chamber door, the vacuum is evacuated to 18 Pa. An argon-oxygen mixture (volume ratio 2:1) is introduced, and the inlet valve is adjusted to maintain the gas pressure inside the device at 50 Pa. The radio frequency power is set to 200 W, and after processing for 5 minutes, the gas supply is stopped. The device is allowed to cool naturally to room temperature and then the plasma-activated fiber is obtained.

[0077] The plasma-activated fiber was immersed in an 8% (w / w) aqueous solution of potassium 3-sulfopropyl methacrylate, and 0.5 wt% of photoinitiator Irgacure2959 was added. The fiber was then irradiated with 365 nm ultraviolet light at 30°C for 15 min (light intensity 10 mW / cm²). 2 The fibers were washed with deionized water until their conductivity stabilized, and then vacuum dried at 65°C for 1 hour to obtain the modified fibers.

[0078] Prepare a 5% KH-570 ethanol solution, add 1 mol / L acetic acid solution to adjust the pH to 3.5, completely immerse the modified fiber in the solution, place it in a constant temperature water bath shaker, and shake at 40℃ and 150 r / min for 2.5 h. After the reaction is complete, remove the fiber, wash it three times with anhydrous ethanol, and dry it in a vacuum drying oven at 65℃ for 1.5 h to obtain methacryloyloxy functionalized fiber.

[0079] Step 4: Weigh 5g of antimicrobial peptide LL-37 (purity 96%, molecular weight 4500Da) and 3g of polyethylene glycol diglycidyl ether (molecular weight 400Da), dissolve them in 1000mL of ethanol-deionized water mixed solution (volume ratio 1:1), stir to dissolve, and then add 1mol / L sodium hydroxide solution to adjust the pH to 8.0; completely immerse the methacryloyloxy functionalized fiber in the solution, purge the air in the system with nitrogen three times, seal it, and place it in a constant temperature water bath shaker at 45℃ and 180r / min for 6h; after the reaction, take out the fiber, wash it 4 times with PBS buffer solution (pH=7.4), then wash it with deionized water until the pH of the washing solution is 7.0, and dry it in a vacuum drying oven at 50℃ until constant weight to obtain antimicrobial fiber.

[0080] Step 5: Feed the antibacterial fiber into a ring spinning machine, set the spinning speed to 120m / min and the twist to 800 twists / m, to produce 30-count yarn. Then, use an air-jet loom to weave the yarn in a plain weave, controlling the fabric weight to be 90g / m². 2 , thus obtaining an antibacterial layer fabric.

[0081] Example 5

[0082] A method for preparing an antibacterial lace fabric includes the following steps:

[0083] At 60g / m² on the lower surface of the antibacterial layer 2 Coating amount: Apply water-based polyurethane adhesive at a rate of 130 g / m². 2 A cotton support layer is placed underneath, and hot-pressed at 105℃ and 0.3MPa for 50 seconds; 60g / m 2 Nylon 66 lace trim is laid on both sides of the antibacterial layer, hot melt adhesive strips are placed, and it is fixed by hot pressing at 95℃ and 0.1MPa for 20 seconds to obtain antibacterial lace trim fabric.

[0084] The method for preparing the antibacterial layer includes the following steps:

[0085] Step 1: Weigh 140g of silver-loaded zirconium phosphate and 20g of graphene quantum dots (particle size 8nm), stir at room temperature using a high-speed mixer (3000r / min) for 15min until uniform, add 900mL of deionized water directly, and disperse using a 900W ultrasonic cell disruptor for 50min to obtain a uniformly dispersed antibacterial powder suspension.

[0086] Weigh 6g of KH-560 silane coupling agent and 2g of KH-550 silane coupling agent, slowly add 200mL of ethanol-deionized water mixed solution, stir to dissolve, and adjust the pH to 5.0 with 1mol / L acetic acid solution to prepare the treatment solution; spray the treatment solution evenly into the above suspension at a rate of 6mL / min using a high-pressure sprayer, and maintain stirring at 300r / min during the spraying process. After spraying, transfer to a constant temperature water bath and react at 50℃ for 3.5h. After the reaction, filter using a vacuum filter, wash the filter cake with deionized water until the pH of the washing solution is 7.0, and then dry it to constant weight in a vacuum drying oven at 108℃. After pulverizing with an ultra-micro pulverizer, pass through a 300-mesh standard sieve to obtain activated composite antibacterial powder.

[0087] Step 2: Weigh 250g of PET chips (intrinsic viscosity 0.68dL / g) and 20g of activated composite antibacterial powder, place them in a high-speed mixer, preheat and mix at 120℃ for 20min (speed 2500r / min), then add them to a twin-screw extruder (zone 1 240℃, zone 2 255℃, zone 3 265℃, zone 4 260℃, zone 5 255℃, screw speed 180r / min) for melt granulation to obtain core layer raw material (total core layer mass 280g); weigh 108g PBAT (number average molecular weight 25000) and 10g of nano-silver (particle size 20nm) were mixed. The nano-silver was added to 10mL of deionized water and pretreated by ultrasonic dispersion at 900W for 20min. Then, it was added together with PBAT to a single-screw extruder and melt-mixed at 215℃ (screw speed 150r / min) to obtain the sheath material (total sheath mass 120g, sheath-core mass ratio 30:70). The core and sheath materials were fed separately into a composite spinning machine and extruded through a composite spinneret at 260℃. Side-blowing cooling was used (wind speed 1.0m / s, temperature 23℃, wind distance 15cm). Then, it was subjected to 4.0 times hot stretching on a 90℃ hot roller and finally kept at 115℃ for 35s to obtain the sheath-core structure antibacterial fiber precursor.

[0088] Step 3: The antibacterial fiber precursor with a core-sheath structure is evenly wound onto a quartz support and placed into a plasma treatment device. After closing the chamber door, the vacuum is evacuated to 18 Pa. An argon-oxygen mixture (volume ratio 2:1) is introduced, and the inlet valve is adjusted to maintain the gas pressure inside the device at 50 Pa. The radio frequency power is set to 200 W, and after processing for 5 minutes, the gas supply is stopped. The device is allowed to cool naturally to room temperature and then the plasma-activated fiber is obtained.

[0089] The plasma-activated fiber was immersed in a 5% (w / w) aqueous solution of potassium 3-sulfopropyl methacrylate, and 0.5 wt% of photoinitiator Irgacure2959 was added. The fiber was then irradiated with 365 nm ultraviolet light at 30°C for 15 min (light intensity 10 mW / cm²). 2 The fibers were washed with deionized water until their conductivity stabilized, and then vacuum dried at 65°C for 1 hour to obtain the modified fibers.

[0090] Prepare a 5% KH-570 ethanol solution, add 1 mol / L acetic acid solution to adjust the pH to 3.5, completely immerse the modified fiber in the solution, place it in a constant temperature water bath shaker, and shake at 40℃ and 150 r / min for 2.5 h. After the reaction is complete, remove the fiber, wash it three times with anhydrous ethanol, and dry it in a vacuum drying oven at 65℃ for 1.5 h to obtain methacryloyloxy functionalized fiber.

[0091] Step 4: Weigh 5g of antimicrobial peptide LL-37 (purity 96%, molecular weight 4500Da) and 2g of polyethylene glycol diglycidyl ether (molecular weight 400Da), dissolve them in 1000mL of ethanol-deionized water mixed solution (volume ratio 1:1), stir to dissolve, and then add 1mol / L sodium hydroxide solution to adjust the pH to 8.0; completely immerse the methacryloyloxy functionalized fiber in the solution, purge the air in the system with nitrogen three times, seal it, and place it in a constant temperature water bath shaker at 40℃ and 180r / min for 4h; after the reaction, take out the fiber, wash it 4 times with PBS buffer solution (pH=7.4), then wash it with deionized water until the pH of the washing solution is 7.0, and dry it in a vacuum drying oven at 50℃ until constant weight to obtain antimicrobial fiber.

[0092] Step 5: Feed the antibacterial fiber into a ring spinning machine, set the spinning speed to 120m / min and the twist to 800 twists / m, to produce 30-count yarn. Then, use an air-jet loom to weave the yarn in a plain weave, controlling the fabric weight to be 90g / m². 2 , thus obtaining an antibacterial layer fabric.

[0093] Comparative Example 1: The difference between Comparative Example 1 and Example 1 is that step 1 is omitted and activated composite antibacterial powder is not added in step 2.

[0094] Comparative Example 2: The difference between Comparative Example 2 and Example 1 is that steps 3 and 4 are omitted, and the antibacterial fiber in step 5 is replaced with a core-sheath structure antibacterial fiber precursor.

[0095] Comparative Example 3: The difference between Comparative Example 3 and Example 1 is that the plasma-activated fiber in step 3 is not modified with potassium 3-sulfopropyl methacrylate.

[0096] Performance testing:

[0097] 1. Antibacterial Rate Test: Referring to GB / T 20944.3-2008 "Evaluation of Antibacterial Properties of Textiles - Part 3: Shaking Method", *Escherichia coli* (ATCC 25922), *Staphylococcus aureus* (ATCC 6538), and *Candida albicans* (ATCC 10231) were selected as test strains. Fabric samples from the examples and comparative examples were cut into 25mm × 25mm pieces, sterilized by high-pressure steam at 121℃ for 20 minutes, and then treated with an additive containing 1 × 10⁻⁶ bacteria. 6 A bacterial suspension of CFU / mL was incubated at 37℃ with shaking at 150 rpm for 18 h. The antibacterial rate was calculated using the plate count method. Simultaneously, following GB / T 8629-2017 "Home Washing and Drying Procedures for Textile Testing", the samples were washed 50 times and the antibacterial rate was tested using the same method. Each group of samples was tested three times, and the average value was taken. The test results are shown in Table 1.

[0098] Table 1:

[0099]

[0100] 2. Mechanical property testing: Referring to GB / T 3923.1-2013 "Textiles - Tensile properties of fabrics - Part 1: Determination of breaking strength and elongation at break (strip method)", strips of 50mm × 200mm were cut from the main body of the antibacterial layer of the fabric without lace trim (length direction consistent with warp direction). A universal testing machine was used, with the clamping distance set to 100mm and the tensile speed to 100mm / min. The breaking strength (cN) and elongation at break (%) were tested. Each group was tested 5 times, and outliers were removed and the average value was taken. The test results are shown in Table 2.

[0101] 3. Skin Irritation Test: Referring to GB / T 16886.10-2017 "Biological Evaluation of Medical Devices Part 10: Irritation and Skin Sensitization Tests", a skin patch test was conducted. Fabric samples were cut into 10mm × 10mm pieces and applied to the hairless skin on the rabbit's back. After 24 hours, the samples were removed. After 48 hours, the skin erythema and edema were observed. The irritation level was assessed according to the standard (0 for no irritation, 1 for slight irritation, and 2 or above for irritation). The test results are shown in Table 2.

[0102] Table 2:

[0103]

[0104] Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method of preparing an antibacterial lace fabric, characterized by, The method comprises the following steps: The lower surface of the antibacterial layer is coated with a water-based polyurethane adhesive, then the cotton support layer is stacked below the antibacterial layer, and then hot pressing is performed to combine the layers, and then the nylon 66 lace is laid on both sides of the edges of the antibacterial layer, and hot melt adhesive strips are used for hot pressing to fix the lace, thereby obtaining the antibacterial lace fabric. The preparation method of the antibacterial layer comprises the following steps: S1, dispersing silver-loaded zirconium phosphate and graphene quantum dots in deionized water, adding a treatment solution prepared from KH-560 silane coupling agent and KH-550 silane coupling agent for surface treatment, and then performing reaction and post-treatment to obtain activated composite antibacterial powder; S2, mixing PET chips with the activated composite antibacterial powder after preheating, and then performing melt granulation to obtain core layer raw materials; performing ultrasonic dispersion pretreatment on nano-silver, and then melt-mixing the nano-silver with PBAT resin to obtain skin layer raw materials; feeding the core layer raw materials and the skin layer raw materials into a composite spinning machine respectively, and then extruding the raw materials through a composite spinneret to form a skin-core structure antibacterial fiber precursor after sequentially performing cooling, hot drawing and heat setting; S3, performing plasma treatment on the skin-core structure antibacterial fiber precursor, then immersing the skin-core structure antibacterial fiber precursor in a 3-sulfopropyl methacrylate potassium salt aqueous solution, adding a photoinitiator Irgacure 2959, and then performing reaction under ultraviolet light irradiation, and then performing washing and drying to obtain a modified skin-core structure antibacterial fiber precursor, and then performing KH-570 silane coupling agent grafting treatment on the modified skin-core structure antibacterial fiber precursor to obtain a methacryloyloxy functionalized fiber; S4, dissolving antibacterial peptide LL-37 and polyethylene glycol diglycidyl ether in a mixed solution of ethanol and deionized water to prepare a modification liquid; immersing the methacryloyloxy functionalized fiber in the modification liquid, and then performing constant-temperature oscillation reaction in an inert atmosphere, and then performing washing and drying after the reaction is completed to obtain an antibacterial fiber; S5, spinning the antibacterial fiber to obtain yarn, and then weaving the yarn into a fabric to obtain an antibacterial layer.

2. A method of preparing an antibacterial lace fabric according to claim 1, characterized in that, In the step S1, the mass ratio of the silver-loaded zirconium phosphate to the graphene quantum dots is 7:(1-3).

3. A method of preparing an antibacterial lace fabric according to claim 1, characterized in that, In the step S1, the mass ratio of the KH-560 silane coupling agent to the KH-550 silane coupling agent is 3:(1-2).

4. A process for preparing an anti-bacterial lace fabric according to claim 1, characterized in that, In the step S2, the mass ratio of the PET chips to the activated composite antibacterial powder is 25:(2-5).

5. A process for preparing an anti-bacterial lace fabric according to claim 1, characterized in that, In the step S2, the mass ratio of the PBAT resin to the nano-silver is 108:(10-15).

6. A process for preparing an anti-bacterial lace trim fabric as claimed in claim 1, wherein, The mass concentration of the 3-sulfopropyl methacrylate potassium salt aqueous solution is 5-8%.

7. A process for preparing an anti-bacterial lace fabric according to claim 1, characterized in that, In the step S4, the mass ratio of the antibacterial peptide LL-37 to the polyethylene glycol diglycidyl ether is 5:(2-3).

8. A process for preparing an anti-bacterial lace fabric according to claim 1, characterized in that, In the step S4, the reaction temperature is 40-45℃, and the reaction time is 4-6h.

9. An antibacterial lace fabric, characterized by, The method is prepared by any one of claims 1-8.

Images