Antibacterial lace fabric and preparation method thereof

Abstract

The invention discloses an antibacterial lace fabric and a preparation method thereof, and relates to the technical field of functional fiber fabrics. The preparation method comprises the following steps: firstly, coating the lower surface of the antibacterial layer with a waterborne polyurethane adhesive, then stacking the cotton support layer below the antibacterial layer, carrying out hot-pressing compounding, then laying the chinlon 66 lace on the edges of the two sides of the antibacterial layer, and carrying out hot-pressing fixation by using a hot melt adhesive tape to obtain the antibacterial lace fabric. The lace fabric prepared by the preparation method disclosed by the invention has excellent antibacterial property and antibacterial durability.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of functional fiber fabrics, in particular to an antibacterial lace fabric and a preparation method thereof. BACKGROUND

[0002] The lace fabric occupies an irreplaceable position in the fields of clothing, home textiles, underwear, wedding dresses, etc. due to its exquisite three-dimensional pattern, light and ethereal texture and good decorative properties. In particular, the penetration rate of lace fabric in the category of women's underwear has reached a high level, and it has become a core material for improving the fashion sense and added value of products. With the overall improvement of consumption upgrading and health awareness, the demand for lace fabric has shifted from pure aesthetics to functionality and comfort. The antibacterial property has become a core requirement for products that directly contact the skin, such as underwear, home clothes and baby home textiles. In such scenarios, the fabric is in contact with skin secretions and sweat for a long time, which is easy to breed pathogenic bacteria such as Escherichia coli and Staphylococcus aureus, not only producing odor, but also causing skin itching, inflammation and other health problems, seriously affecting the wearing experience and product competitiveness. SUMMARY

[0003] The purpose of the present application is to provide an antibacterial lace fabric and a preparation method thereof to solve the technical problems raised in the background.

[0004] To achieve the above-mentioned purpose, the present application provides the following technical solutions:

[0005] A preparation method of an antibacterial lace fabric, comprising the following steps:

[0006] 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 them, and then the nylon 66 lace is laid on both sides of the antibacterial layer, and hot melt adhesive strips are used for hot pressing to fix the lace, thereby obtaining the antibacterial lace fabric.

[0007] The preparation method of the antibacterial layer comprises the following steps:

[0008] S1, dispersing silver-loaded zirconium phosphate and graphene quantum dots in deionized water, adding a treatment liquid prepared from KH-560 silane coupling agent and KH-550 silane coupling agent for surface treatment, and then obtaining activated composite antibacterial powder through reaction and post-treatment;

[0009] S2, after mixing and preheating the PET chip and the activated composite antibacterial powder, melt granulation is performed to obtain a core layer raw material; after ultrasonic dispersion pretreatment of the nano-silver, melt mixing is performed with the PBAT resin to obtain a skin layer raw material; the core layer raw material and the skin layer raw material are respectively sent into a composite spinning machine, extruded into a shape through a composite spinneret, and then sequentially subjected to cooling, hot drawing and heat setting to obtain a skin-core structure antibacterial fiber precursor.

[0010] S3, the skin-core structure antibacterial fiber precursor is sequentially subjected to plasma treatment and KH-570 silane coupling agent grafting treatment to obtain a methacryloxy functionalized fiber;

[0011] S4, antibacterial peptide LL-37 and polyethylene glycol diglycidyl ether are dissolved in a mixed solution of ethanol and deionized water to prepare a modification solution; the methacryloxy functionalized fiber is immersed in the modification solution, and a constant temperature oscillation reaction is carried out in an inert atmosphere; after the reaction is completed, washing and drying are carried out to obtain an antibacterial fiber;

[0012] S5, the antibacterial fiber is spun into a yarn, and then woven into a fabric to obtain an antibacterial layer.

[0013] In the technical scheme of the present application, the antibacterial performance of the antibacterial lace fabric is achieved from two aspects. On the one hand, the antibacterial layer fiber core layer is loaded with activated composite antibacterial powder of silver-loaded zirconium phosphate and graphene quantum dots based on PET as the matrix, wherein the silver-loaded zirconium phosphate can release silver ions for a long time, achieve persistent sterilization by destroying bacterial DNA and enzyme activity, the graphene quantum dots can quickly kill bacteria and inhibit the growth of fungi by virtue of their physical puncture effect and active oxygen generated by photocatalysis, and the two synergistically broaden the antibacterial spectrum; the skin layer uses PBAT copolyester to load nano-silver, the nano-silver has small particle size and large specific surface area, can quickly release silver ions to play an instant sterilization role, and makes up for the short board of the core layer antibacterial agent which takes effect slowly. At the same time, the antibacterial powder dispersed by ultrasonic dispersion and modified by coupling agent is uniformly dispersed in the fiber, avoiding the loss of antibacterial sites caused by aggregation, and the skin-core structure realizes the time sequence synergy of rapid sterilization of the skin layer and long-acting antibacterial of the core layer, ensuring that the antibacterial layer can maintain high-efficiency antibacterial effect in different use stages, and the antibacterial agent is coated by the fiber matrix, reducing the loss caused by direct exposure.

[0014] On the other hand, first, plasma treatment etches micro-nano grooves on the surface of the fiber by bombarding the surface with active particles, significantly increasing the specific surface area of the fiber, and introducing a large number of active groups, providing sufficient sites for subsequent functionalization modification and antibacterial peptide grafting; after KH-570 functionalization treatment and polyethylene glycol diglycidyl ether treatment, the fiber can stably combine with the antibacterial peptide LL-37, ensuring that the antibacterial peptide is firmly grafted and uniformly distributed. As a broad-spectrum biological antibacterial agent, the antibacterial peptide LL-37 can be adsorbed on the surface of the bacterial cell membrane through cationic affinity, and then form pores to destroy the integrity of the cell membrane, complementing the mechanism of the first aspect inorganic antibacterial agent in destroying the internal structure of the bacteria, and can achieve high-efficiency killing of pathogenic bacteria such as Escherichia coli, Staphylococcus aureus, and Candida albicans, especially having a significant inhibitory effect on some drug-resistant bacteria resistant to inorganic antibacterial agents. In addition, the grafted antibacterial peptide forms a cross-linked network through polyethylene glycol diglycidyl ether, which is not easy to fall off due to water washing, friction and other external forces, and the biocompatible antibacterial peptide also avoids the skin irritation risk that may be caused by inorganic antibacterial 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 chips 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, after the plasma treatment of the skin-core structure antibacterial fiber precursor, the following modification treatment is performed:

[0020] The plasma-treated fiber is immersed in an aqueous solution of 3-sulfopropyl methacrylate potassium salt, a photoinitiator Irgacure 2959 is added, and the reaction is carried out under ultraviolet light irradiation. After washing and drying, it is obtained.

[0021] In the technical scheme of the present application, it is found through research that there are cationic silver ions in the skin layer of the skin-core structure antibacterial fiber precursor, and the antibacterial peptide LL-37 used for subsequent modification is a cationic polypeptide. Due to the same charge attribute, the two produce obvious electrostatic repulsion on the fiber surface, making it difficult for the antibacterial peptide to effectively bind to the fiber surface, which seriously restricts the synergistic antibacterial effect of the double modification. To further solve this technical problem, the fiber is functionally modified with the zwitterionic 3-sulfopropyl methacrylate potassium salt. The 3-sulfopropyl methacrylate potassium salt molecule has both cationic groups (methacryloyloxy) and anionic groups (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 skin layer, thereby eliminating the electrostatic repulsion between cationic silver ions and cationic antibacterial peptide LL-37, removing the charge barrier for the binding of antibacterial peptide to the fiber surface, and significantly improving the grafting density and distribution uniformity of the antibacterial peptide, further improving the antibacterial performance of the fabric.

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

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

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

[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 preparation method of the antibacterial layer comprises the following steps:

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

[0038] 6 g of KH-560 silane coupling agent and 3.5 g of KH-550 silane coupling agent were weighed, slowly added into 200 mL of an ethanol-deionized water mixed solution, dissolved by stirring, and then a 1 mol / L acetic acid solution was used to adjust the pH to 5.0 to prepare a treatment solution; the treatment solution was uniformly sprayed into the above-mentioned suspension by using a high-pressure sprayer at a rate of 6 mL / min, stirring was maintained at 300 r / min during the spraying process, and after the spraying was completed, it was transferred to a constant-temperature water bath, reacted at 50°C for 3.5 h, after the reaction was completed, a vacuum filter was used for filtration, the filter cake was washed with deionized water until the pH of the washing liquid was 7.0, then dried in a vacuum drying oven at 108°C until the weight was constant, crushed by using a supermicro pulverizer, and then passed through a 300-mesh standard sieve to obtain an activated composite antibacterial powder.

[0039] Step 2: 250 g of PET chips (intrinsic viscosity 0.68 dL / g) and 40 g of the activated composite antibacterial powder were weighed, preheated and mixed in a high-speed mixer at 120°C for 20 min (rotation speed 2500 r / min), then added into a twin-screw extruder (region 1 240°C, region 2 255°C, region 3 265°C, region 4 260°C, region 5 255°C, screw rotation speed 180 r / min) to melt and granulate to obtain core layer raw materials (total mass of the core layer 280 g); 108 g of PBAT (number average molecular weight 25000) and 14 g of nano-silver (particle size 20 nm) were weighed, the nano-silver was added into 10 mL of deionized water, pretreated by ultrasonic dispersion for 20 min by using a 900 W ultrasonic device, and then added into a single-screw extruder together with the PBAT to melt and mix at 215°C (screw rotation speed 150 r / min) to obtain skin layer raw materials (total mass of the skin layer 120 g, skin / core mass ratio 30:70); the core layer and the skin layer raw materials were respectively sent into a composite spinning machine, extruded through a 260°C composite spinneret, cooled by using side-blowing air (air speed 1.0 m / s, temperature 23°C, air distance 15 cm), then subjected to 4.0 times hot drawing on a 90°C hot roller, and finally heat-set in a 115°C heat-setting oven for 35 s to obtain a skin-core structure antibacterial fiber precursor.

[0040] Step 3: The core-sheath structure antibacterial fiber precursor was uniformly wound on a quartz holder and placed in a plasma treatment device. After closing the door, the device was vacuumed to 18 Pa, argon-oxygen mixed gas (volume ratio 2:1) was introduced, the gas inlet valve was adjusted to maintain the pressure in the device at 50 Pa, the radio frequency power was set to 200 W, the treatment was stopped after 5 min, and the plasma-activated fiber was obtained after natural cooling to room temperature.

[0041] The plasma-activated fiber was immersed in a 7% mass concentration aqueous solution of 3-sulfopropyl methacrylate potassium salt, 0.5wt% photoinitiator Irgacure 2959 was added, and the solution was irradiated with 365 nm ultraviolet light at 30°C for 15 min (light intensity 10 mW / cm 2 ). After washing with deionized water until the conductivity was stable, the modified fiber was vacuum dried at 65°C for 1 h.

[0042] A 5% mass concentration KH-570 ethanol solution was prepared, 1 mol / L acetic acid solution was added to adjust the pH to 3.5, the modified fiber was completely immersed in the solution, and the solution was placed in a constant temperature water bath shaker, and the temperature was set to 40°C and the shaking speed was set to 150 r / min for 2.5 h. After the reaction was completed, the fiber was taken out, washed with anhydrous ethanol for 3 times, and dried in a vacuum drying oven at 65°C for 1.5 h to obtain a methacryloyloxy functionalized fiber.

[0043] Step 4: 5 g of antibacterial peptide LL-37 (purity 96%, molecular weight 4500 Da) and 2.8 g of polyethylene glycol diglycidyl ether (molecular weight 400 Da) were dissolved in 1000 mL of an ethanol-deionized water mixed solution (volume ratio 1:1), and 1 mol / L sodium hydroxide solution was added to adjust the pH to 8.0. The methacryloyloxy functionalized fiber was completely immersed in the solution, and the system was replaced with nitrogen three times. After sealing, the solution was placed in a constant temperature water bath shaker, and the temperature was set to 43°C and the shaking speed was set to 180 r / min for 5 h. After the reaction was completed, the fiber was taken out, washed with PBS buffer solution (pH=7.4) for 4 times, and then washed with deionized water until the pH of the washing solution was 7.0. The fiber was dried in a vacuum drying oven at 50°C until the weight was constant to obtain an antibacterial fiber.

[0044] Step 5: The antibacterial fiber was sent to a ring spinning machine, and the spinning speed was set to 120 m / min and the twist was set to 800 twists / m. Thirty yarns were prepared, and then a plain weave was woven on an air-jet loom. The fabric weight was controlled to be 90 g / m 2 , and an antibacterial lace fabric was obtained.

[0045] Example 2

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

[0047] The fabric weight of the antibacterial layer was 60 g / m2 The waterborne polyurethane adhesive was coated in an amount of 130 g / m 2 The cotton support layer was placed on the bottom and hot-pressed at 105℃ and 0.3 MPa for 50 s; the 60 g / m 2 The nylon 66 lace was laid on both sides of the antibacterial layer, and a hot melt adhesive strip was placed, and hot-pressed at 95℃ and 0.1 MPa for 20 s to fix, obtaining the antibacterial lace fabric.

[0048] The preparation method of the antibacterial layer comprises the following steps:

[0049] Step 1: 140 g of silver-loaded zirconium phosphate and 30 g of graphene quantum dots (particle size 8 nm) were weighed, stirred uniformly at room temperature by using a high-speed mixer (rotating speed 3000 r / min) for 15 min, directly added with 900 mL of deionized water, dispersed by using a 900 W ultrasonic cell disruptor for 50 min, and then an antibacterial powder suspension uniformly dispersed was obtained.

[0050] 6 g of KH-560 silane coupling agent and 2.5 g of KH-550 silane coupling agent were weighed, slowly added into 200 mL of an ethanol-deionized water mixed solution, dissolved by stirring, and then a treatment solution was prepared by adjusting the pH to 5.0 by using a 1 mol / L acetic acid solution; the treatment solution was uniformly sprayed into the above-mentioned suspension by using a high-pressure sprayer at a rate of 6 mL / min, stirring was kept at 300 r / min during the spraying process, and after the spraying was completed, it was transferred to a constant-temperature water bath, reacted at 50℃ for 3.5 h, after the reaction was completed, it was filtered by using a vacuum filter, the filter cake was washed by using deionized water until the pH of the washing liquid was 7.0, then dried in a vacuum drying oven at 108℃ until the weight was constant, crushed by using an ultramicro pulverizer, and then passed through a 300-mesh standard sieve, and an activated composite antibacterial powder was obtained.

[0051] Step 2: 250 g of PET chips (intrinsic viscosity 0.68 dL / g) and 30 g of activated composite antibacterial powder were weighed and put into a high-speed mixer for preheating and mixing at 120 ℃ for 20 min (rotation speed 2500 r / min), then added into a twin-screw extruder (zone 1 240 ℃, zone 2 255 ℃, zone 3 265 ℃, zone 4 260 ℃, zone 5 255 ℃, screw rotation speed 180 r / min) for melt granulation to obtain the core layer raw material (total mass of the core layer 280 g); 108 g of PBAT (number average molecular weight 25000) and 12 g of nano-silver (particle size 20 nm) were weighed, the nano-silver was pretreated by ultrasonic dispersion in 10 mL of deionized water for 20 min at 900 W, and then added into a single-screw extruder together with the PBAT for melt mixing at 215 ℃ (screw rotation speed 150 r / min) to obtain the skin layer raw material (total mass of the skin layer 120 g, skin / core mass ratio 30:70); the core layer and the skin layer raw materials were respectively sent into a composite spinning machine, extruded through a 260 ℃ composite spinneret, and cooled by side blowing (wind speed 1.0 m / s, temperature 23 ℃, wind distance 15 cm), then subjected to 4.0 times hot drawing on a 90 ℃ hot roller, and finally heat set in a 115 ℃ heat setting oven for 35 s to obtain a skin-core structure antibacterial fiber precursor.

[0052] Step 3: The skin-core structure antibacterial fiber precursor was evenly wound on a quartz support, and then put into a plasma treatment device. After the door was closed, the device was vacuumized to 18 Pa, argon-oxygen mixed gas (volume ratio 2:1) was introduced, the gas inlet valve was adjusted to maintain the gas pressure in the device at 50 Pa, the radio frequency power was set to 200 W, the gas supply was stopped after 5 min of treatment, and the device was naturally cooled to room temperature. The plasma-activated fiber was obtained.

[0053] The plasma-activated fiber was immersed in a 6% mass concentration 3-sulfopropyl methacrylate potassium salt aqueous solution, 0.5 wt% of a photoinitiator Irgacure 2959 was added, and the mixture was irradiated with 365 nm ultraviolet light at 30 ℃ for 15 min (light intensity 10 mW / cm 2 ), washed with deionized water until the conductivity was stable, and vacuum dried at 65 ℃ for 1 h to obtain a modified fiber.

[0054] A 5% mass concentration KH-570 ethanol solution was prepared, 1 mol / L acetic acid solution was added to adjust the pH to 3.5, the modified fiber was completely immersed in the solution, and the mixture was put into a constant temperature water bath shaker, and reacted at 40 ℃ and 150 r / min for 2.5 h. After the reaction was completed, the fiber was taken out, washed with anhydrous ethanol for 3 times, and dried in a 65 ℃ vacuum drying oven for 1.5 h to obtain a methacryloyloxy functionalized fiber.

[0055] Step 4: 5 g of antibacterial peptide LL-37 (purity 96%, molecular weight 4500 Da), 2.3 g of polyethylene glycol diglycidyl ether (molecular weight 400 Da) were weighed and dissolved in 1000 mL of an ethanol-deionized water mixed solution (volume ratio 1:1). After stirring and dissolving, 1 mol / L sodium hydroxide solution was added to adjust the pH to 8.0. The methyl methacryloyloxy functionalized fiber was completely immersed in the solution, nitrogen was introduced to replace the air in the system for 3 times, and then sealed and placed in a constant temperature water bath oscillator. The constant temperature reaction was carried out at 43°C and 180r / min for 5h. After the reaction was completed, the fiber was taken out, washed with PBS buffer solution (pH=7.4) for 4 times, then washed with deionized water until the pH of the washing liquid was 7.0, and then placed in a 50°C vacuum drying oven for drying until the weight was constant. The antibacterial fiber was obtained.

[0056] Step 5: The antibacterial fiber was sent to a ring spinning machine, and the spinning speed was set to 120 m / min and the twist was set to 800 twists / m. Thirty yarns were prepared, and then a plain weave was woven using an air-jet loom. The fabric weight was controlled to be 90 g / m 2 , and the antibacterial layer fabric was obtained.

[0057] Example 3

[0058] A preparation method of an antibacterial lace fabric, comprising the following steps:

[0059] An aqueous polyurethane adhesive was coated on the lower surface of the antibacterial layer at a coating amount of 60 g / m 2 , and a cotton support layer was placed below at 130 g / m 2 . Hot pressing was performed at 105°C and 0.3 MPa for 50s. A nylon 66 lace was laid on both sides of the antibacterial layer at 60 g / m 2 , a hot melt adhesive strip was placed, and hot pressing was performed at 95°C and 0.1 MPa for 20s to fix, and the antibacterial lace fabric was obtained.

[0060] The preparation method of the antibacterial layer comprises the following steps:

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

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

[0063] Step 2: Take 250g PET chips (intrinsic viscosity 0.68dL / g) and 35g activated composite antibacterial powder, put them into a high-speed mixer, preheat and mix at 120℃ for 20min (rotation speed 2500r / min), then add them into a twin-screw extruder (zone 1 240℃, zone 2 255℃, zone 3 265℃, zone 4 260℃, zone 5 255℃, screw rotation speed 180r / min) for melt granulation to obtain the core layer raw material (total mass of core layer 280g); take 108g PBAT (number average molecular weight 25000) and 13g nano-silver (particle size 20nm), pretreat the nano-silver by dispersing it in 10mL deionized water for 20min with a 900W ultrasonic, then add it into a single-screw extruder together with PBAT for melt mixing at 215℃ (screw rotation speed 150r / min) to obtain the skin layer raw material (total mass of skin layer 120g, skin / core mass ratio 30:70); send the core layer and skin layer raw materials into a composite spinning machine respectively, extrude through a 260℃ composite spinneret, cool by side blowing (wind speed 1.0m / s, temperature 23℃, wind distance 15cm), then perform 4.0 times hot drawing on a 90℃ hot roller, and finally heat set in a 115℃ heat setting oven for 35s to obtain the skin-core structure antibacterial fiber precursor.

[0064] Step 3: evenly wind the skin-core structure antibacterial fiber precursor on a quartz support, put it into a plasma treatment device, vacuumize to 18Pa after closing the door, introduce argon-oxygen mixed gas (volume ratio 2:1), adjust the gas inlet valve to maintain the gas pressure in the device at 50Pa, set the radio frequency power to 200W, stop the gas introduction after 5min of treatment, and naturally cool to room temperature to obtain the plasma-activated fiber.

[0065] Immerse the plasma-activated fiber in a 6.5% mass concentration 3-sulfopropyl methacrylate potassium salt aqueous solution, add 0.5wt% photoinitiator Irgacure2959, irradiate under 365nm ultraviolet light at 30℃ for 15min (light intensity 10mW / cm 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: Take 140 g of silver-loaded zirconium phosphate and 60 g of graphene quantum dots (particle size 8 nm), and stir them uniformly at room temperature using a high-speed mixer (speed 3000 r / min) for 15 min. Then add 900 mL of deionized water, and disperse for 50 min using a 900 W ultrasonic cell disruptor to obtain a uniformly dispersed antibacterial powder suspension.

[0074] Take 6 g of KH-560 silane coupling agent and 4 g of KH-550 silane coupling agent, and slowly add them to a 200 mL ethanol-deionized water mixed solution. After stirring and dissolving, adjust the pH to 5.0 with a 1 mol / L acetic acid solution to prepare a treatment solution. Uniformly spray the treatment solution into the above suspension at a rate of 6 mL / min using a high-pressure sprayer, and maintain stirring at 300 r / min during the spraying process. After spraying is complete, transfer to a constant-temperature water bath and react at 50°C for 3.5 h. After the reaction is complete, 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 in a vacuum drying oven at 108°C until the weight is constant. After crushing using an ultramicro pulverizer and passing through a 300-mesh standard sieve, an activated composite antibacterial powder is obtained.

[0075] Step 2: Take 250 g of PET chips (intrinsic viscosity 0.68 dL / g) and 50 g of activated composite antibacterial powder, and preheat and mix in a high-speed mixer at 120°C for 20 min (speed 2500 r / min). Then melt and granulate in a twin-screw extruder (zone 1 240°C, zone 2 255°C, zone 3 265°C, zone 4 260°C, zone 5 255°C, screw speed 180 r / min) to obtain core layer raw materials (total core layer mass 280 g). Take 108 g of PBAT (number average molecular weight 25000) and 15 g of nano-silver (particle size 20 nm), and pretreat the nano-silver by dispersing in 10 mL of deionized water for 20 min using a 900 W ultrasonic device. Then add the PBAT and the pretreated nano-silver to a single-screw extruder and melt mix at 215°C (screw speed 150 r / min) to obtain skin layer raw materials (total skin layer mass 120 g, skin / core mass ratio 30:70). Feed the core layer and skin layer raw materials into a composite spinning machine, respectively, extrude through a 260°C composite spinneret, cool using side blowing (air speed 1.0 m / s, temperature 23°C, air distance 15 cm), then perform 4.0 times hot drawing on a 90°C hot roller, and finally heat set in a 115°C heat setting oven for 35 s to obtain a skin-core structure antibacterial fiber precursor.

[0076] Step 3: Uniformly wind the skin-core structure antibacterial fiber precursor on a quartz support, and place it in a plasma treatment device. After closing the door and evacuating to 18 Pa, introduce argon-oxygen mixed gas (volume ratio 2:1), adjust the gas inlet valve to maintain the gas pressure in the device at 50 Pa, set the radio frequency power to 200 W, and treat for 5 min. Then stop the gas flow and naturally cool to room temperature. The plasma-activated fiber is obtained.

[0077] The plasma-activated fiber was immersed in an aqueous solution of 3-sulfopropyl methacrylate potassium salt with a mass concentration of 8%, 0.5wt% of a photoinitiator Irgacure 2959 was added, and the solution was irradiated with 365nm ultraviolet light at 30℃ for 15min (light intensity 10mW / cm 2 ), washed with deionized water until the conductivity was stable, and vacuum dried at 65℃ for 1h to obtain the modified fiber.

[0078] An ethanol solution of KH-570 was prepared with a mass concentration of 5%, 1mol / L acetic acid solution was added to adjust the pH to 3.5, the modified fiber was completely immersed in the solution, and the solution was placed in a constant-temperature water bath shaker and oscillated at 40℃ and 150r / min for 2.5h. After the reaction was completed, the fiber was washed with anhydrous ethanol for 3 times, and was dried in a vacuum drying oven at 65℃ for 1.5h to obtain the methacryloyloxy functionalized fiber.

[0079] Step 4: 5g of antibacterial peptide LL-37 (purity 96%, molecular weight 4500Da) and 3g of polyethylene glycol diglycidyl ether (molecular weight 400Da) were dissolved in 1000mL of an ethanol-deionized water mixed solution (volume ratio 1:1), 1mol / L sodium hydroxide solution was added to adjust the pH to 8.0 after stirring and dissolving; the methacryloyloxy functionalized fiber was completely immersed in the solution, nitrogen was introduced to replace the air in the system for 3 times, and then the system was sealed and placed in a constant-temperature water bath shaker, and reacted at 45℃ and 180r / min for 6h; after the reaction was completed, the fiber was taken out, washed with PBS buffer solution (pH=7.4) for 4 times, then washed with deionized water until the pH of the washing liquid was 7.0, and dried in a vacuum drying oven at 50℃ until the weight was constant to obtain the antibacterial fiber.

[0080] Step 5: the antibacterial fiber was sent to a ring spinning machine, the spinning speed was set to 120m / min, and the twist was set to 800 twists / m, 30 yarns were prepared, and then a plain weave was woven by using an air-jet loom, the fabric weight was controlled to be 90g / m 2 , and the antibacterial layer fabric was obtained.

[0081] Example 5

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

[0083] An aqueous polyurethane adhesive was coated on the lower surface of the antibacterial layer at a coating amount of 60g / m 2 , a cotton support layer was placed below at 130g / m 2 , hot pressing was performed at 105℃ and 0.3MPa for 50s, a polyamide 66 lace was laid on both sides of the antibacterial layer at 60g / m 2 , a hot melt adhesive strip was placed, hot pressing was performed at 95℃ and 0.1MPa for 20s to fix, and an antibacterial lace fabric was obtained.

[0084] The preparation method of the antibacterial layer comprises the following steps:

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

[0086] Take 6 g of KH-560 silane coupling agent and 2 g of KH-550 silane coupling agent, and slowly add them to 200 mL of an ethanol-deionized water mixed solution. After stirring and dissolving, adjust the pH to 5.0 with a 1 mol / L acetic acid solution to prepare a treatment solution. Uniformly spray the treatment solution into the above-mentioned suspension at a rate of 6 mL / min using a high-pressure sprayer, and maintain stirring at 300 r / min during the spraying process. After the spraying process is completed, transfer the mixture to a constant-temperature water bath, and react at 50°C for 3.5 h. After the reaction is completed, filter the mixture 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 in a vacuum drying oven at 108°C until the weight is constant. After being crushed by a supermicro pulverizer, pass it through a 300-mesh standard sieve to obtain an activated composite antibacterial powder.

[0087] Step 2: Take 250 g of PET chips (intrinsic viscosity 0.68 dL / g) and 20 g of the activated composite antibacterial powder, and preheat and mix them in a high-speed mixer at 120°C for 20 min (rotation speed 2500 r / min). Then, melt and granulate them in a twin-screw extruder (zone 1 240°C, zone 2 255°C, zone 3 265°C, zone 4 260°C, zone 5 255°C, screw rotation speed 180 r / min) to obtain core layer raw materials (total mass of the core layer 280 g). Take 108 g of PBAT (number average molecular weight 25000) and 10 g of nano-silver (particle size 20 nm), and pretreat the nano-silver by dispersing it in 10 mL of deionized water for 20 min using a 900 W ultrasonic device. Then, melt and mix the PBAT and the pretreated nano-silver in a single-screw extruder at 215°C (screw rotation speed 150 r / min) to obtain skin layer raw materials (total mass of the skin layer 120 g, skin / core mass ratio 30:70). Feed the core layer and skin layer raw materials into a composite spinning machine respectively, extrude them through a 260°C composite spinneret, cool them using side-blowing air (air speed 1.0 m / s, temperature 23°C, air distance 15 cm), then perform 4.0 times hot drawing on a 90°C hot roller, and finally heat-set them in a 115°C heat-setting oven for 35 s to obtain a skin-core structure antibacterial fiber precursor.

[0088] Step 3: The core-sheath structure antibacterial fiber precursor was uniformly wound on a quartz holder, and then was put into a plasma treatment device. After the door was closed, the device was vacuumized to 18 Pa, and then argon-oxygen mixed gas (volume ratio 2:1) was introduced. The gas pressure in the device was maintained at 50 Pa by adjusting the inlet valve. The radio frequency power was set to 200 W, and the treatment was stopped after 5 min. The plasma-activated fiber was obtained after natural cooling to room temperature.

[0089] The plasma-activated fiber was immersed in a 5% mass concentration aqueous solution of 3-sulfopropyl methacrylate potassium salt, and 0.5 wt% of a photoinitiator Irgacure 2959 was added. The solution was irradiated with 365 nm ultraviolet light at 30°C for 15 min (light intensity 10 mW / cm 2 ). The solution was washed with deionized water until the conductivity was stable, and then the modified fiber was vacuum dried at 65°C for 1 h.

[0090] A 5% mass concentration KH-570 ethanol solution was prepared, and 1 mol / L acetic acid solution was added to adjust the pH to 3.5. The modified fiber was completely immersed in the solution, and then was put into a constant-temperature water bath shaker. The constant-temperature oscillation reaction was carried out at 40°C and 150 r / min for 2.5 h. After the reaction was completed, the fiber was washed with anhydrous ethanol for 3 times, and then was dried in a vacuum drying oven at 65°C for 1.5 h to obtain a methacryloyloxy functionalized fiber.

[0091] Step 4: 5 g of antibacterial peptide LL-37 (purity 96%, molecular weight 4500 Da) and 2 g of polyethylene glycol diglycidyl ether (molecular weight 400 Da) were dissolved in 1000 mL of an ethanol-deionized water mixed solution (volume ratio 1:1). After stirring and dissolving, 1 mol / L sodium hydroxide solution was added to adjust the pH to 8.0. The methacryloyloxy functionalized fiber was completely immersed in the solution, and then was replaced with nitrogen gas for 3 times. After being sealed, the solution was put into a constant-temperature water bath shaker, and the constant-temperature reaction was carried out at 40°C and 180 r / min for 4 h. After the reaction was completed, the fiber was taken out, washed with PBS buffer solution (pH=7.4) for 4 times, and then washed with deionized water until the pH of the washing solution was 7.0. The fiber was dried in a vacuum drying oven at 50°C until the weight was constant to obtain an antibacterial fiber.

[0092] Step 5: The antibacterial fiber was sent to a ring spinning machine, and the spinning speed was set to 120 m / min and the twist was set to 800 twists / m. Thirty yarns were prepared, and then were woven into plain weave using an air-jet loom. The fabric weight was controlled to be 90 g / m 2 to obtain an antibacterial layer fabric.

[0093] Comparative Example 1: The difference between Comparative Example 1 and Example 1 is that Step 1 is omitted, and no activated composite antibacterial powder is added in Step 2.

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

[0095] Comparative Example 3: Comparative Example 3 differs from Example 1 in that the plasma-activated fiber in step 3 is not modified with 3-sulfopropyl methacrylate potassium salt.

[0096] Performance test:

[0097] 1. Antibacterial rate test: According 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, and the fabric of the examples and comparative examples was cut into 25mm x 25mm samples. After sterilization at 121°C for 20min, 1x10 6 CFU / mL of bacterial suspension was added, and the samples were incubated at 37°C with shaking at 150r / min for 18h. The antibacterial rate was calculated by plate counting method. At the same time, according to GB / T 8629-2017 “Textiles Household washing and drying procedures for testing”, the samples were washed with water for 50 times, and the antibacterial rate was tested by the same method. Each group of samples was tested 3 times, and the average value was taken. The test results are shown in Table 1:

[0098] Table 1:

[0099]

[0100] 2. Mechanical property test: According to GB / T 3923.1-2013 “Textiles Fabric tensile properties Part 1: determination of breaking force and elongation at break (strip method)”, the fabric was cut into 50mm x 200mm strips (length direction consistent with the warp direction) from the main part of the antibacterial layer without lace. A universal material testing machine was used with a clamping distance of 100mm and a tensile speed of 100mm / min to test the breaking strength (cN) and elongation at break (%). Each group was tested 5 times, and the average value was taken after removing outliers. The test results are shown in Table 2.

[0101] 3. Skin irritation test: According to GB / T 16886.10-2017 “Biological evaluation of medical devices Part 10: tests for irritation and skin sensitization”, a skin patch test was performed. The fabric sample was cut into 10mm x 10mm and applied to the depilated skin on the back of a rabbit for 24h. After removing the sample, the skin was observed for redness and edema after 48h. The irritation level was evaluated according to the standard (0 level: no irritation, 1 level: mild irritation, 2 level and above: irritation). The test results are shown in Table 2.

[0102] Table 2:

[0103]

[0104] Although the present application has been described in detail with reference to the foregoing embodiments, the technical solutions recorded in the foregoing embodiments can be modified, or some of the technical features can be replaced by equivalent features, by those skilled in the art, any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

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 hot pressing is performed to combine the layers, then 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 an 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 obtaining activated composite antibacterial powder after reaction and post-treatment; 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 them into a shape through a composite spinneret, and sequentially performing cooling, hot drawing and heat setting to obtain a skin-core structure antibacterial fiber precursor; S3, sequentially performing plasma treatment and KH-570 silane coupling agent grafting treatment on the skin-core structure antibacterial fiber precursor to obtain a methacryloxy 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 solution; immersing the methacryloxy functionalized fiber in the modification solution, and performing constant temperature oscillation reaction in an inert atmosphere; and after the reaction is completed, performing washing and drying to obtain an antibacterial fiber; S5, spinning the antibacterial fiber into a 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, In the step S3, after the plasma treatment, the following modification treatment is performed on the skin-core structure antibacterial fiber precursor: immersing the plasma-treated fiber in a 3-sulfopropyl methacrylate potassium salt aqueous solution, adding a photoinitiator Irgacure 2959, and performing reaction under ultraviolet light irradiation; and after washing and drying, the modified fiber is obtained.

7. A method of making an antimicrobial lace trim fabric according to claim 6, wherein, The mass concentration of the 3-sulfopropyl methacrylate potassium salt aqueous solution is 5-8%.

8. 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).

9. 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.

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

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