Antibacterial polyester fabric and preparation method thereof

Abstract

This invention discloses an antibacterial polyester fabric and its preparation method, belonging to the field of functional textile technology. Graphene oxide is modified with phytic acid and then combined with Zn... 2+ Coordination, hydrolysis and deposition of TiO2 with L-lysine assistance, followed by hydrothermal treatment, freeze drying, and Ag... + Composite antibacterial particles are prepared by in-situ photoreduction, nitrogen heat treatment, and pulverization. These particles are then combined with PET to form a functional masterbatch, which is melt-spun to obtain antibacterial polyester filament. This filament is used as warp and weft yarns, with seaweed fiber / cotton blended yarn as the primary weft yarn to weave a grey fabric. After desizing, softening, and pre-shrinking finishing, an antibacterial polyester fabric is obtained. The composite antibacterial particles are embedded within the PET fibers, which helps improve the thermal processing stability and wash resistance of the antibacterial components.

Description

Technical Field

[0001] This invention belongs to the field of functional textile technology, specifically relating to an antibacterial polyester fabric and its preparation method. Background Technology

[0002] Antibacterial textiles are in high demand in medical protective equipment, sportswear, and home textiles. Polyester (PET) is the preferred substrate for antibacterial textiles due to its excellent mechanical properties and processability. Current antibacterial polyester is mainly achieved through the following approaches: Silver-based antibacterial agents are the most widely used due to their broad-spectrum and high efficiency; however, nano-silver (Ag NPs) have a large specific surface area and high surface energy, making them prone to aggregation during spinning, resulting in poor fiber spinnability and reduced antibacterial efficiency. Simultaneously, Ag NPs lack effective anchoring with the PET matrix, resulting in insufficient wash resistance and significant attenuation of antibacterial activity after repeated washing. Graphene oxide (GO) can serve as an antibacterial agent carrier due to its large specific surface area and abundant oxygen-containing functional groups; however, its compatibility with the PET matrix is ​​poor, and the chelating ability of its surface functional groups for metal ions is limited, leading to low loading when used alone. Titanium dioxide, as a photocatalytic antibacterial material, can generate electron-hole pairs under ultraviolet light excitation to achieve photocatalytic antibacterial effects. However, TiO2 nanoparticles also face aggregation problems, and conventional TiO2 does not readily support Ag... + The photoreduction efficiency is limited by specific surface area and the number of active sites. To address these issues, existing technologies attempt to combine GO, TiO2, and Ag NPs for synergistic effects. However, the following key drawbacks remain in the composite process: First, there is a lack of effective interfacial chemical bonding between the components, resulting in uneven loading and easy detachment of Ag NPs; second, there is a lack of systematic design for the functional groups on the GO surface to achieve high-density chelation of metal ions and uniform deposition of TiO2; and third, Ag NPs are only loaded onto the carrier surface through physical adsorption, resulting in insufficient stability during melt spinning at high temperatures (≥285℃) and subsequent washing processes. Summary of the Invention

[0003] The purpose of this invention is to provide an antibacterial polyester fabric and its preparation method, so as to improve the agglomeration problem of composite antibacterial particles in PET melt and improve the retention of antibacterial components after high-temperature spinning and multiple washing.

[0004] The objective of this invention can be achieved through the following technical solutions:

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

[0006] S1. Graphene oxide is modified with phytic acid and then reacted with Zn. 2+Coordination was performed to obtain phytic acid-modified graphene oxide zinc-supported material; tetrabutyl titanate was hydrolyzed in the presence of L-lysine and TiO2 was deposited on the surface of the phytic acid-modified graphene oxide zinc-supported material, followed by hydrothermal treatment to obtain a photoreduction carrier; the photoreduction carrier was dispersed in silver nitrate alcohol solution and subjected to ultraviolet irradiation to induce Ag... + The particles are reduced in situ and loaded onto the surface of the photoreduction carrier, then subjected to heat treatment and pulverization in a nitrogen atmosphere to obtain composite antibacterial particles.

[0007] S2. The composite antibacterial particles are blended and granulated with PET chips to obtain a functional masterbatch. The functional masterbatch is then mixed with PET chips and melt-spun to obtain antibacterial polyester filament.

[0008] S3. Using the antibacterial polyester filament as warp and weft yarn, and seaweed fiber / cotton blended yarn as weft yarn, a greige fabric is woven and then finished to obtain the antibacterial polyester fabric.

[0009] By sequentially constructing phytic acid-modified graphene oxide-supported zinc material, TiO2-loaded photoreduction carrier, and Ag-loaded composite antibacterial particles, these particles were introduced into a PET melt-spinning system via a functional masterbatch. This preparation sequence allows the phosphorus-containing, zinc-containing graphene-based carrier, TiO2, and Ag nanoparticles to be loaded and assembled in a predetermined order, which helps reduce local enrichment and agglomeration that occurs when different inorganic components are directly mixed. Dispersing the composite antibacterial particles within PET filaments in an embedded manner reduces wash-off and frictional losses caused by relying solely on surface finishing of the fabric for antibacterial agent loading, and provides a structural basis for the stable retention of antibacterial components after high-temperature spinning. Further weaving the antibacterial polyester filaments with seaweed fiber / cotton blended yarns helps to balance the fabric's antibacterial durability, moisture absorption, and wearing comfort.

[0010] As a preferred embodiment of the present invention, the preparation of the graphene oxide includes: adding graphite powder, mixed acid solution and sodium nitrate into a reactor, stirring in an ice-water bath for 20-30 minutes, adding potassium permanganate in batches, heating to 25°C and stirring for 1-2 hours, then heating to 35°C and reacting for 2-3 days; cooling to 0-5°C, slowly adding deionized water under controlled temperature conditions, then adding 30wt% hydrogen peroxide to terminate the oxidation reaction, then adding 1mol / L hydrochloric acid solution, allowing to stand, centrifuging, washing until neutral and vacuum drying; the mixed acid solution is obtained by mixing 98wt% concentrated sulfuric acid and 68wt% concentrated nitric acid in a volume ratio of 9:1.

[0011] In the preparation of graphene oxide, adding potassium permanganate first under ice-water bath conditions can control the exothermic rate in the initial stage of the oxidation reaction and reduce the risk of over-oxidation and reaction runaway caused by excessively high local temperatures. Subsequently, the reaction is carried out in stages at 25℃ and 35℃, which facilitates the gradual intercalation and oxidation of graphite layers and introduces oxygen-containing functional groups such as hydroxyl, epoxy, and carboxyl groups onto the graphene matrix surface, facilitating subsequent phytic acid modification and Zn... 2+ Coordination and TiO2 deposition provide reaction or adsorption sites. Terminating the oxidation reaction with hydrogen peroxide, followed by hydrochloric acid treatment and washing, reduces the impact of residual high-valence manganese compounds, metal ions, acids, and soluble salts on subsequent modification processes, thereby improving the consistency of the graphene oxide composition and surface state.

[0012] As a preferred technical solution of the present invention, the phytic acid modification and Zn 2+ The coordination process includes: dispersing graphene oxide in deionized water, ultrasonically dispersing for 2-3 hours, adding 50 wt% phytic acid aqueous solution, continuing ultrasonic stirring for 30-40 minutes, stirring and refluxing at 100°C for 10-15 hours, filtering and washing until neutral; redispersing the obtained solid in 50 vol% ethanol aqueous solution, adding zinc nitrate hexahydrate, stirring at 40-50°C for 5-7 hours, centrifuging and washing; the ratio of graphene oxide, deionized water, 50 wt% phytic acid aqueous solution, 50 vol% ethanol aqueous solution and zinc nitrate hexahydrate is 0.14-0.18 g: 120-180 g: 2-3 mL: 100-150 mL: 0.5-0.8 g.

[0013] Phytic acid molecules contain multiple phosphate groups, which can form hydrogen bonds, electrostatic interactions, or other interfacial interactions with oxygen-containing functional groups on the surface of graphene oxide, and can also affect Zn. 2+ Coordination was performed. This was achieved through ultrasonic dispersion, reflux treatment at 100°C, and subsequent Zn... 2+ Coordination between phytic acid and Zn 2+ The phosphorus and zinc are relatively well distributed on the surface of the graphene oxide matrix, which is beneficial for the formation of phosphorus- and zinc-containing interfacial layers and anchoring sites for subsequent inorganic components. Using a 50 vol% ethanol aqueous solution as the coordination medium can balance the dispersion state of the modified graphene oxide and the Zn content. 2+ The mass transfer process is optimized; centrifugation and washing after coordination can remove uncoordinated zinc salts and free phytic acid, reducing the adverse effects of residual soluble substances on TiO2 deposition and PET melt processing. The resulting phytic acid-modified graphene oxide zinc-supported material is beneficial for improving the loading uniformity of TiO2 and Ag components and reducing the disordered nucleation and agglomeration of inorganic particles.

[0014] As a preferred embodiment of the present invention, the method for preparing the photoreduction carrier is as follows: phytic acid-modified graphene oxide zinc-supported material is dispersed in anhydrous ethanol, 1 wt% L-lysine aqueous solution is added, and the mixture is stirred for 1-2 hours. Tetrabutyl titanate, glacial acetic acid, and 68 wt% concentrated nitric acid are added, and the mixture is stirred at room temperature for 48 hours and centrifuged. The solid phase is redispersed in deionized water and hydrothermally treated at 160-180°C for 3-4 hours. The hydrothermally treated product is pre-frozen at -20 to -40°C for 4-6 hours and then freeze-dried under vacuum at 10-100 Pa absolute pressure for 8-10 hours.

[0015] During TiO2 deposition, the amino and carboxyl groups in L-lysine molecules can regulate the hydrolysis and condensation behavior of tetrabutyl titanate at the graphene-based support interface; glacial acetic acid and nitric acid help control the hydrolysis rate of tetrabutyl titanate, reducing its rapid hydrolysis in solution to form independent TiO2 aggregates. Through the combined regulation of these components, the interfacial nucleation and deposition of titanium precursors on the surface of phytic acid-modified graphene oxide zinc-supported material can be promoted. Subsequent hydrothermal treatment helps improve the bonding stability between the TiO2 deposition layer and the graphene-based support, and promotes the formation of TiO2 structures. Pre-freezing the hydrothermal products and then vacuum freeze-drying them under 10–100 Pa absolute pressure can reduce particle shrinkage and secondary agglomeration caused by liquid-phase capillary action during atmospheric pressure or heating drying, which helps maintain the dispersion state and effective surface area of ​​the photoreduction support, providing a suitable environment for Ag. + In-situ photoreduction on the carrier surface provides more loading sites.

[0016] In a preferred embodiment of the present invention, the concentration of the silver nitrate alcohol solution is 0.005 mol / L, and the ratio of the silver nitrate alcohol solution to the photoreduction carrier is 10–20 mL: 50–60 mg; the dominant wavelength of the ultraviolet light is 365 nm, and the irradiation intensity is 50–100 mW / cm². 2 The irradiation time is 2–4 min; the nitrogen atmosphere heat treatment temperature is 300–380℃, the time is 40–80 min, the heating rate is 1.5–2.5℃ / min; the pulverizing pressure is 0.7–0.9 MPa, the feeding speed is 3–6 g / min, and the classifying wheel speed is 7000–8000 rpm.

[0017] The photoreduction support was dispersed in a low-concentration silver nitrate alcohol solution and irradiated under 365 nm ultraviolet light. Photogenerated electrons generated by TiO2 upon photoexcitation promoted the reduction of Ag. + In-situ reduction at the carrier interface facilitates the preferential formation and loading of Ag nanoparticles onto the surfaces of TiO2 and graphene-based carriers. By controlling the concentration of the silver nitrate alcohol solution, the solution-to-carrier ratio, the irradiation intensity, and the irradiation time, the Ag content can be reduced. +Excessive use of Ag raises concerns about the formation of free silver particles and the risk of excessive Ag nanoparticle growth. Subsequently, controlled heat treatment in a nitrogen atmosphere pre-devours and thermally stabilizes the Ag / TiO2 / graphene-based composite antibacterial particles, adapting them for high-temperature melt spinning in PET and improving the structural retention of the antibacterial components during processing and washing. Air jet milling reduces soft agglomerates formed during heat treatment, improves the particle size distribution and dispersibility of the composite antibacterial particles in PET, thereby reducing the risks of abnormal melt filtration pressure, spinneret blockage, and filament breakage.

[0018] In a preferred embodiment of the present invention, in step S2, the PET chips are dried at 160–180°C and an absolute pressure not exceeding 5 kPa for 6–8 hours to reduce their moisture content to not exceeding 50 mg / kg; the composite antibacterial particles are blended with the PET chips at a mass ratio of 1:4 to obtain a functional masterbatch; the functional masterbatch is then mixed with the PET chips at a mass ratio of 5–8:95–92 and melt-spun; the mass content of the composite antibacterial particles in the melt-spun mixture is 1.0%–1.6%.

[0019] Drying PET chips to a moisture content of no more than 50 mg / kg helps reduce the degree of hydrolysis of PET during blending, granulation, and melt spinning, thus maintaining melt rheological properties and spinning stability. First, preparing a functional masterbatch by mixing the composite antibacterial particles with PET at a mass ratio of 1:4 allows the composite antibacterial particles to be pre-dispersed and fixed in the PET carrier, reducing dust generation, metering fluctuations, and localized agglomeration that occur when the powder is directly added to the spinning system. Then, mixing the functional masterbatch with PET chips at a mass ratio of 5–8:95–92 ensures that the final mass content of the composite antibacterial particles is controlled at 1.0%–1.6%. This helps to achieve antibacterial function while controlling the impact of inorganic particles on PET melt viscosity, filtration performance, and fiber mechanical properties.

[0020] As a preferred embodiment of the present invention, the temperatures of the screw zones in the melt spinning process are 240–260°C, 260–270°C, 270–280°C, 270–280°C, and 268–272°C, respectively; the temperature of the spinning box is 285–295°C; and the spinneret has 36 holes / 0.30 mm. The filaments are cooled by side blowing, oiled, and stretched and shaped by multi-stage hot rollers. The side blowing temperature is 20–25°C, the wind speed is 0.4–0.6 m / s, the oiling rate is 0.6%–1.0%, the total stretching ratio is 3.0–3.5 times, the setting temperature is 140–150°C, and the winding speed is 2800–3100 m / min.

[0021] The melt spinning process employs a gradually increasing screw temperature zone with appropriate adjustments at the end. This facilitates the sequential conveying, melting, mixing, and homogenization of PET chips, preventing adhesion caused by excessively high temperatures in the feeding section and reducing the risk of PET thermal degradation due to excessively high temperatures in the later stages. Maintaining the spinning box temperature at 285–295℃ ensures that the PET melt containing composite antibacterial particles maintains suitable fluidity and metering stability. Side-blowing cooling promotes uniform filament solidification, while oiling reduces friction between the filaments and the equipment and improves bundle bonding. Multi-stage hot roller stretching promotes PET molecular chain orientation, and heat setting helps stabilize fiber orientation structure and dimensions. By coordinating the control of side-blowing temperature, wind speed, oiling rate, total stretching ratio, setting temperature, and winding speed, the linear density uniformity, breaking performance, and winding stability of the antibacterial polyester filaments can be balanced.

[0022] As a preferred technical solution of the present invention, in step S3, both the warp and weft yarns are antibacterial polyester filaments with a linear density of 18.2 tex, and the weft yarn is a seaweed fiber / cotton blended yarn with a linear density of 18.2 tex and a seaweed fiber content of 50%. An 8-end 5-fly weft satin weave is adopted, the reed specification is 170 teeth / 10cm, the number of insertions per reed tooth is 2, and the weft yarns A and B are alternately inserted at a ratio of 1:4, with a weft density of 320 weft threads / 10cm.

[0023] The warp, weft (A), and weft (B) yarns are all 18.2 tex, which helps reduce the linear density difference between different yarns and facilitates control of weaving tension and fabric smoothness. The use of an 8-end, 5-fly weft satin weave creates longer weft floats, resulting in a larger continuous distribution area of ​​the weft yarns on the fabric surface. The alternating 1:4 ratio of A and B weft yarns ensures that the antibacterial polyester B weft containing composite antibacterial particles constitutes the majority, improving the continuity of antibacterial polyester distribution on the fabric surface. The use of antibacterial polyester filaments in the warp further forms an antibacterial yarn network running through the warp direction. The seaweed fiber / cotton blended A weft yarn improves the fabric's moisture absorption, softness, and skin-friendly comfort. The specifications of the reed, the number of teeth inserted per reed, and the weft density help stabilize the fabric tightness and structure, achieving a balance between antibacterial yarn coverage, breathability, and a soft hand feel.

[0024] As a preferred embodiment of the present invention, the post-processing sequentially includes neutral enzyme desizing, softening and setting, and pre-shrinking finishing; the desizing solution includes 2 g / L of neutral amylase, 0.5 g / L of pectinase, and 1 g / L of penetrant JFC, with a pH of 6.5-7.0, a bath ratio of 1:15, a temperature of 55°C, and a time of 45 min; the softening and setting process uses 20 g / L of amino silicone oil softener and 3 g / L of antistatic agent, with two dips and two nips, a nip-out rate of 65%-70%, a setting temperature of 155°C, and a setting time of 45 s; the pre-shrinking finishing process involves a rubber blanket temperature of 110°C and a pressure of 3 bar.

[0025] The finishing process employs neutral amylase and pectinase for desizing, which removes starch-based sizing agents and some pectin impurities from the cotton fiber surface under near-neutral conditions. Compared to strong alkaline desizing, this method reduces damage to seaweed fibers, cotton fibers, and antibacterial polyester. The penetrant JFC improves the wetting and penetration of the desizing solution onto the yarn and fabric structure, allowing the enzyme preparation to act more evenly on the greige fabric. A two-dip, two-nip treatment using amino silicone softener and antistatic agent improves the fabric's softness, drape, and antistatic properties. Controlling the amount of softener and the nip-off rate reduces excessive film formation by the finishing agent, which can obscure the effective interface of the antibacterial components. Subsequent heat setting and pre-shrinking finishing help release internal stresses formed during weaving and pretreatment, stabilize fabric width and dimensions, and reduce shrinkage and deformation of the finished product during subsequent use and washing.

[0026] Another objective of this invention is to provide an antibacterial polyester fabric, comprising warp yarns, weft yarns (either type A or type B), wherein the warp yarns and weft yarns (either type A or type B) are PET filaments containing composite antibacterial particles, and the weft yarns (either type A or type B) are seaweed fiber / cotton blended yarns; the composite antibacterial particles comprise a graphene-based carrier containing phosphorus and zinc, and TiO2 and Ag nanoparticles loaded on the graphene-based carrier; the mass content of the composite antibacterial particles in the PET filaments is 1.0% to 1.6%; the fabric is an 8-end 5-fly satin weave, with the ratio of weft yarns (either type A or type B) being 1:4.

[0027] In the antibacterial polyester fabric obtained by this invention, composite antibacterial particles are embedded within the PET filaments, which reduces the direct shedding of surface-loaded antibacterial agents during friction and washing, providing a structural basis for the fabric's antibacterial properties and wash resistance. The composite antibacterial particles use phosphorus- and zinc-containing graphene-based materials as carriers, with TiO2 and Ag nanoparticles loaded on their surface. This increases the dispersion interface of the antibacterial components, reduces the local enrichment of Ag nanoparticles, and provides carrier conditions for the zinc-containing components, TiO2, and Ag components to work together to exert their antibacterial effects. The antibacterial polyester warp and weft constitute the main antibacterial yarn system of the fabric, while the seaweed fiber / cotton blended weft is used to improve moisture absorption and wearing comfort, thus giving the resulting fabric antibacterial function, wash resistance, and textile performance.

[0028] The beneficial effects of this invention are:

[0029] (1) The present invention adopts the order of first constructing a phosphorus-containing and zinc-containing graphene-based support, then depositing TiO2 and loading Ag in situ, which is beneficial to reduce the local enrichment and agglomeration caused by direct physical mixing of different inorganic components.

[0030] (2) The composite antibacterial particles obtained by hydrothermal treatment, controlled freeze drying, nitrogen atmosphere heat treatment and pulverization can be added to PET in the form of functional masterbatch, avoiding the need to rely solely on fabric finishing to achieve antibacterial properties, thereby improving the wash resistance of antibacterial components.

[0031] (3) By controlling the PET moisture content, the amount of composite antibacterial particles added and the spinning temperature, the risk of PET hydrolysis, abnormal melt pressure and spinneret blockage can be reduced while obtaining antibacterial function.

[0032] (4) Antibacterial polyester filament is used as the warp and weft yarn to form the main body of the fabric, and seaweed fiber / cotton blended yarn is used as the weft yarn, which is conducive to taking into account the antibacterial durability, moisture absorption and wearing comfort of the fabric. Detailed Implementation

[0033] The following examples are for illustrative purposes only and are not intended to limit the scope of protection of the invention. Unless otherwise stated, the phytic acid used is a 50wt% aqueous solution of phytic acid, and all vacuum pressures are absolute pressures; the PET slices are dried to a moisture content of no more than 50 mg / kg before use.

[0034] Example 1

[0035] Add 3g of graphite powder, 100mL of a mixed acid solution prepared by mixing 98wt% concentrated sulfuric acid and 68wt% concentrated nitric acid in a volume ratio of 9:1, and 1g of sodium nitrate to a reactor. Stir at 0℃ for 20min, then add 8g of potassium permanganate in batches. Raise the temperature to 25℃ and stir for 1h, then raise the temperature to 35℃ and react for 2d. Cool the reaction system to 0℃, and slowly add 800mL of deionized water under continuous cooling to keep the system temperature below 20℃. Add 20mL of 30wt% hydrogen peroxide to terminate the oxidation reaction, then add 200mL of 1mol / L hydrochloric acid solution. Let stand for 12h, centrifuge, collect the solid phase, wash with deionized water until neutral, and vacuum dry to obtain graphene oxide. 0.14 g of graphene oxide was added to 120 g of deionized water and ultrasonically dispersed for 2 h. 2 mL of 50 wt% phytic acid aqueous solution was added, and ultrasonic stirring continued for 30 min. The mixture was then stirred and refluxed at 100 °C for 10 h. The mixture was filtered and washed until neutral. The solid was redispersed in 100 mL of 50 vol% ethanol aqueous solution, and 0.5 g of zinc nitrate hexahydrate was added. The mixture was stirred at 40 °C for 5 h, centrifuged, and washed to obtain phytic acid-modified graphene oxide zinc-supported material. 30 mg of the phytic acid-modified graphene oxide zinc-supported material was dispersed in 20 mL of anhydrous ethanol, and 0.10 mL of 1 wt% L-lysine aqueous solution was added. The mixture was stirred for 1 h, and then 0.20 mL of tetrabutyl titanate, 3 mL of glacial acetic acid, and 0.05 mL of 68 wt% concentrated nitric acid were added. The mixture was stirred at room temperature for 48 h. After centrifugation, the solid phase was dispersed in 10 mL of deionized water and hydrothermally treated at 160 °C for 3 h. The obtained product was pre-frozen at -30℃ for 4 h, and then freeze-dried under vacuum at 50 Pa absolute pressure for 8 h to obtain the photoreduction support. 50 mg of the photoreduction support was added to 10 mL of 0.005 mol / L silver nitrate ethanol solution, ultrasonically dispersed for 2 min, and then dried at 365 nm and 50 mW / cm². 2 Irradiate for 2 min under the specified conditions; after centrifugation, washing and drying, heat to 300℃ at 1.5℃ / min and hold for 80 min in a nitrogen atmosphere. Repeat the preparation and combine batches until the dried material is no less than 100g, then perform air jet pulverization under the conditions of pulverizing pressure 0.7MPa, feeding rate 3g / min and classifying wheel speed 7000rpm to obtain composite antibacterial particles.

[0036] PET chips were dried at 160℃ and 5kPa absolute pressure for 6 hours. Composite antibacterial particles were mixed with PET chips at a mass ratio of 1:4 and granulated at 265℃ to obtain a functional masterbatch. The functional masterbatch was then mixed with PET chips at a mass ratio of 5:95 and dried at 170℃ and 5kPa absolute pressure for 6 hours before melt spinning. The screw temperatures in each zone were 240℃, 260℃, 270℃, 270℃, and 268℃, the spinning box temperature was 285℃, the spinneret specification was 36 holes / 0.30mm, the side-blowing temperature was 20℃, the air velocity was 0.4m / s, the oiling rate was 0.6%, the total draw ratio was 3.0, the setting temperature was 140℃, and the winding speed was 2800m / min, resulting in 18.2tex antibacterial polyester filament. Using the aforementioned antibacterial polyester filament as warp and weft, and a 18.2 tex seaweed fiber / cotton blended yarn with a seaweed fiber content of 50% as weft, an 8-end 5-fly weft satin weave is used. The reed specification is 170 teeth / 10cm, with 2 insertions per reed tooth. The wefts A and B are alternately inserted at a ratio of 1:4, with a weft density of 320 weft threads / 10cm. After weaving the fabric, it undergoes neutral enzyme desizing, softening setting, and pre-shrinking finishing to obtain the antibacterial polyester fabric.

[0037] Example 2

[0038] Graphene oxide was prepared according to the method in Example 1, wherein the amounts of graphite powder, mixed acid solution, sodium nitrate, potassium permanganate, deionized water, 30 wt% hydrogen peroxide, and 1 mol / L hydrochloric acid solution were 3.5 g, 120 mL, 1.5 g, 9 g, 900 mL, 22 mL, and 250 mL, respectively; the initial temperature was 2 °C, the reaction was carried out at 25 °C for 1.5 h, and at 35 °C for 2.5 d. 0.16 g of graphene oxide, 150 g of deionized water, 2.5 mL of 50 wt% phytic acid aqueous solution, 130 mL of 50 vol% ethanol aqueous solution, and 0.65 g of zinc nitrate hexahydrate were sequentially subjected to ultrasonic dispersion for 2.5 h, phytic acid treatment for 35 min, reflux at 100 °C for 12 h, and coordination reaction at 45 °C for 6 h to obtain phytic acid modified graphene oxide zinc-supported material. Take 35 mg of the phytic acid-modified graphene oxide zinc-supported material, 25 mL of anhydrous ethanol, 0.15 mL of 1 wt% L-lysine aqueous solution, 0.25 mL of tetrabutyl titanate, 4.5 mL of glacial acetic acid, 0.05 mL of 68 wt% concentrated nitric acid, and 15 mL of deionized water, and process them according to the method in Example 1, wherein the L-lysine pretreatment is 1.5 h, the hydrothermal temperature is 170 °C, and the time is 3.5 h; the hydrothermal product is pre-frozen at -35 °C for 5 h, and then freeze-dried at 40 Pa absolute pressure for 9 h. Add 55 mg of the photoreduction carrier to 15 mL of 0.005 mol / L silver nitrate ethanol solution, and heat at 365 nm and 70 mW / cm 2Irradiation was performed for 3 minutes under the following conditions: washing and drying; then heating to 350℃ at a nitrogen atmosphere at a rate of 2.0℃ / min and holding for 60 minutes. Batches of at least 100g were then pulverized using an airflow system at a pulverizing pressure of 0.8MPa, a feeding rate of 4g / min, and a classifying wheel speed of 7500rpm. The composite antibacterial particles were blended with pre-dried PET chips at a mass ratio of 1:4 at 275℃ and granulated. The functional masterbatch was mixed with PET chips at a mass ratio of 6.5:93.5 and dried at 175℃ and 5kPa absolute pressure for 7 hours before melt spinning. The screw temperatures in each zone were 250℃, 265℃, 275℃, 275℃, and 270℃, respectively; the spinning box temperature was 290℃; the side-blowing air temperature was 22℃ with a wind speed of 0.5m / s; the oiling rate was 0.8%; the total draw ratio was 3.3 times; the setting temperature was 145℃; and the winding speed was 3000m / min. The weaving and finishing methods are the same as in Example 1, with a desizing solution pH of 6.8 and a pick-up rate of 68%.

[0039] Example 3

[0040] Graphene oxide was prepared according to the method in Example 1, wherein the amounts of graphite powder, mixed acid solution, sodium nitrate, potassium permanganate, deionized water, 30wt% hydrogen peroxide, and 1mol / L hydrochloric acid solution were 4g, 150mL, 2g, 10g, 1000mL, 25mL, and 300mL, respectively; the initial temperature was 5℃, the reaction was carried out at 25℃ for 2h, and the reaction was carried out at 35℃ for 3d. 0.18g of graphene oxide, 180g of deionized water, 3mL of 50wt% phytic acid aqueous solution, 150mL of 50vol% ethanol aqueous solution, and 0.8g of zinc nitrate hexahydrate were sequentially subjected to ultrasonic dispersion for 3h, phytic acid treatment for 40min, reflux at 100℃ for 15h, and coordination reaction at 50℃ for 7h to obtain phytic acid-modified graphene oxide zinc-supported material. Take 40 mg of the phytic acid-modified graphene oxide zinc-supported material, 30 mL of anhydrous ethanol, 0.20 mL of 1 wt% L-lysine aqueous solution, 0.30 mL of tetrabutyl titanate, 6 mL of glacial acetic acid, 0.05 mL of 68 wt% concentrated nitric acid, and 20 mL of deionized water, and process them according to the method in Example 1, wherein the L-lysine pretreatment is performed for 2 h at a hydrothermal temperature of 180 °C for 4 h; the hydrothermal product is pre-frozen at -40 °C for 6 h, and then freeze-dried at 30 Pa absolute pressure for 10 h. Add 60 mg of the photoreduction carrier to 20 mL of 0.005 mol / L silver nitrate ethanol solution, and perform photoreduction at 365 nm and 100 mW / cm². 2Irradiation was performed for 4 minutes under the following conditions: washing and drying; then heating to 380℃ at a nitrogen atmosphere at a rate of 2.5℃ / min and holding for 40 minutes. Batches of at least 100g were then pulverized using an airflow system at a pulverizing pressure of 0.9MPa, a feeding rate of 6g / min, and a classifying wheel speed of 8000rpm. The composite antibacterial particles were blended with pre-dried PET chips at a mass ratio of 1:4 at 285℃ and granulated. The functional masterbatch was mixed with PET chips at a mass ratio of 8:92 and dried at 180℃ under an absolute pressure not exceeding 5kPa for 8 hours before melt spinning. The screw temperatures in each zone were 260℃, 270℃, 280℃, 280℃, and 272℃, respectively; the spinning box temperature was 295℃; the side-blowing air temperature was 25℃ with a wind speed of 0.6m / s; the oiling rate was 1.0%; the total draw ratio was 3.5 times; the setting temperature was 150℃; and the winding speed was 3100m / min. The weaving and finishing methods are the same as in Example 1, with a desizing solution pH of 7.0 and a pick-up rate of 70%.

[0041] Comparative Example 1

[0042] Except for omitting the zinc nitrate hexahydrate coordination step, the other raw materials, dosages, and process conditions are the same as in Example 2.

[0043] Comparative Example 2

[0044] Except for the absence of 1wt% L-lysine aqueous solution during TiO2 deposition, the raw materials, dosages, and process conditions were the same as in Example 2.

[0045] Comparative Example 3

[0046] After photoreduction, centrifugation, washing, and drying, no heat treatment at 350°C in a nitrogen atmosphere is performed. The resulting material is batched to a minimum of 100g and then pulverized under the same airflow pulverization conditions as in Example 2. The remaining steps are the same as in Example 2.

[0047] Comparative Example 4

[0048] Unmodified graphene oxide was directly dispersed in a 50 vol% ethanol aqueous solution and treated under the same zinc nitrate hexahydrate dosage, temperature, and time conditions as in Example 2; subsequently, L-lysine-assisted TiO2 deposition and Ag were performed. + The photoreduction, nitrogen heat treatment, air jet milling, masterbatch preparation, spinning, weaving and finishing are the same as in Example 2.

[0049] Comparative Example 5

[0050] Without adding composite antibacterial particles, blank fabrics were prepared using the same PET chips melt spinning method as in Example 2, and following the same warp and weft yarn density, seaweed fiber / cotton blended primary and secondary weft, fabric structure, and finishing process as in Example 2.

[0051] Performance testing

[0052] The polyester fabrics prepared in Examples 1-3 and Comparative Examples 1-5 were subjected to the following performance tests:

[0053] 1. Antibacterial performance test

[0054] The prepared polyester fabric was sterilized at 121℃ for 15 minutes. Then, a 0.75g sample was taken and cut into 0.2cm pieces. The antibacterial rate of the fabric sample against Escherichia coli (ATCC25922), Candida albicans (ATCC10231), and Staphylococcus aureus (ATCC6538) was tested according to GB / T 20944.3-2008 "Evaluation of antibacterial properties of textiles - Part 3: Shaking method".

[0055] 2. Washability test

[0056] According to ISO 105-C10:2006 "Textiles - Tests for color fastness - C10 part: Color fastness to washing with soap or washing with soap and soda", the fabric was immersed in a detergent solution (detergent concentration 5 g / L, temperature 40°C, time 15 min, liquor ratio 1:50), and then rinsed thoroughly with tap water. The antibacterial properties were tested after repeating the above washing steps 80 times.

[0057] The test results are shown in Table 1 below:

[0058] Table 1

[0059] Table 1 shows that the polyester fabrics prepared in Examples 1-3 of this invention have good antibacterial properties and long-lasting antibacterial activity. Comparative Examples 1, 2, 3, and 4 all showed varying degrees of decrease in antibacterial rate after washing, with Comparative Example 4 showing the largest decrease. These results indicate that under the experimental conditions, phytic acid modification and Zn... 2+ Coordination, L-lysine-assisted TiO2 deposition, and nitrogen atmosphere heat treatment are related to the antibacterial properties and post-wash retention of the composite antibacterial particles. These steps together constitute the preparation and stabilization process of the composite antibacterial particles.

[0060] The embodiments of the present invention have been described in detail above. However, the present invention is not limited to the above embodiments. Within the scope of knowledge possessed by those skilled in the art, various changes can be made without departing from the spirit of the present invention. Furthermore, features in the embodiments of the present invention can be combined with each other unless otherwise specified.

Claims

1. A method for preparing an antibacterial polyester fabric, characterized in that, Includes the following steps: S1. Graphene oxide is modified with phytic acid and then reacted with Zn. 2+ Coordination was performed to obtain phytic acid-modified graphene oxide zinc-supported material; tetrabutyl titanate was hydrolyzed in the presence of L-lysine and TiO2 was deposited on the surface of the phytic acid-modified graphene oxide zinc-supported material; after hydrothermal treatment, the hydrothermal treatment product was pre-frozen and vacuum freeze-dried to obtain a photoreduction carrier; the photoreduction carrier was dispersed in silver nitrate alcohol solution and subjected to ultraviolet irradiation to induce Ag... + The particles are reduced in situ and loaded onto the surface of the photoreduction carrier, then subjected to nitrogen atmosphere heat treatment and pulverization to obtain composite antibacterial particles; the nitrogen atmosphere heat treatment temperature is 300-380℃ and the time is 40-80min. S2. The composite antibacterial particles are blended and granulated with PET chips to obtain a functional masterbatch. The functional masterbatch is then mixed with PET chips and melt-spun to obtain antibacterial polyester filament. The PET chips are dried at 160-180°C and under an absolute pressure not exceeding 5 kPa for 6-8 hours to ensure that their moisture content is not higher than 50 mg / kg. The mass content of the composite antibacterial particles in the melt-spun mixture is 1.0%-1.6%. The spinning box temperature for melt spinning is 285-295°C. S3. Using the antibacterial polyester filament as warp and weft yarn, and seaweed fiber / cotton blended yarn as weft yarn, a greige fabric is woven and then finished to obtain the antibacterial polyester fabric.

2. The method for preparing an antibacterial polyester fabric according to claim 1, characterized in that, The preparation of the graphene oxide includes: adding graphite powder, mixed acid solution and sodium nitrate into a reactor, stirring in an ice-water bath for 20-30 min, adding potassium permanganate in batches, heating to 25℃ and stirring for 1-2 h, then heating to 35℃ and reacting for 2-3 days; cooling to 0-5℃, slowly adding deionized water under temperature control, then adding 30wt% hydrogen peroxide to terminate the oxidation reaction, then adding 1mol / L hydrochloric acid solution, allowing to stand, centrifuging, washing until neutral and vacuum drying; the mixed acid solution is obtained by mixing 98wt% concentrated sulfuric acid and 68wt% concentrated nitric acid at a volume ratio of 9:

1.

3. The method for preparing an antibacterial polyester fabric according to claim 1, characterized in that, The phytic acid modification and Zn 2+ The coordination process includes: dispersing graphene oxide in deionized water, ultrasonically dispersing for 2-3 hours, adding 50 wt% phytic acid aqueous solution, continuing ultrasonic stirring for 30-40 minutes, stirring and refluxing at 100°C for 10-15 hours, filtering and washing until neutral; redispersing the obtained solid in 50 vol% ethanol aqueous solution, adding zinc nitrate hexahydrate, stirring at 40-50°C for 5-7 hours, centrifuging and washing; the ratio of graphene oxide, deionized water, 50 wt% phytic acid aqueous solution, 50 vol% ethanol aqueous solution and zinc nitrate hexahydrate is 0.14-0.18 g: 120-180 g: 2-3 mL: 100-150 mL: 0.5-0.8 g.

4. The method for preparing an antibacterial polyester fabric according to claim 1, characterized in that, The method for preparing the photoreduction carrier is as follows: phytic acid-modified graphene oxide zinc-supported material is dispersed in anhydrous ethanol, 1 wt% L-lysine aqueous solution is added, and the mixture is stirred for 1-2 h. Tetrabutyl titanate, glacial acetic acid and 68 wt% concentrated nitric acid are added, and the mixture is stirred at room temperature for 48 h and centrifuged. The solid phase is redispersed in deionized water and hydrothermally treated at 160-180℃ for 3-4 h.

5. The method for preparing an antibacterial polyester fabric according to claim 1, characterized in that, The concentration of the silver nitrate alcohol solution is 0.005 mol / L, and the ratio of the silver nitrate alcohol solution to the photoreduction carrier is 10–20 mL: 50–60 mg; the dominant wavelength of the ultraviolet light is 365 nm, and the irradiance is 50–100 mW / cm². 2 The irradiation time is 2–4 min; the heating rate of nitrogen atmosphere heat treatment is 1.5–2.5 °C / min; the crushing pressure is 0.7–0.9 MPa; the feeding speed is 3–6 g / min; and the classifying wheel speed is 7000–8000 rpm.

6. The method for preparing an antibacterial polyester fabric according to claim 1, characterized in that, In step S2, the composite antibacterial particles and PET chips are blended and granulated at a mass ratio of 1:4 to obtain a functional masterbatch. Then, the functional masterbatch and PET chips are mixed at a mass ratio of 5-8:95-92 and melt-spun.

7. The method for preparing an antibacterial polyester fabric according to claim 6, characterized in that, The temperatures of the screw zones in the melt spinning process are 240–260℃, 260–270℃, 270–280℃, 270–280℃, and 268–272℃, respectively. The spinneret has 36 holes / 0.30mm. The filaments are cooled by side blowing, oiled, and stretched and shaped by multi-stage hot rollers. The side blowing temperature is 20–25℃, the wind speed is 0.4–0.6m / s, the oiling rate is 0.6%–1.0%, the total stretch ratio is 3.0–3.5 times, the setting temperature is 140–150℃, and the winding speed is 2800–3100m / min.

8. The method for preparing an antibacterial polyester fabric according to claim 1, characterized in that, In step S3, both the warp and weft yarns are antibacterial polyester filaments with a linear density of 18.2 tex, and the weft yarn is a seaweed / cotton blended yarn with a linear density of 18.2 tex and a seaweed fiber content of 50%. An 8-end 5-fly weft satin weave is used, with a reed specification of 170 teeth / 10cm and 2 insertions per reed tooth. The weft yarns A and B are alternately inserted at a ratio of 1:4, and the weft density is 320 weft threads / 10cm.

9. The method for preparing an antibacterial polyester fabric according to claim 1, characterized in that, The finishing process includes neutral enzyme desizing, softening and setting, and pre-shrinking finishing. The desizing solution contains 2 g / L neutral amylase, 0.5 g / L pectinase, and 1 g / L penetrant JFC, with a pH of 6.5–7.0, a liquor ratio of 1:15, a temperature of 55°C, and a time of 45 min. The softening and setting process uses 20 g / L amino silicone oil softener and 3 g / L antistatic agent, with two dips and two nips, a nip-out rate of 65%–70%, a setting temperature of 155°C, and a setting time of 45 s. The pre-shrinking finishing process involves a rubber blanket temperature of 110°C and a pressure of 3 bar.

10. An antibacterial polyester fabric, prepared by the method according to any one of claims 1-9, comprising warp yarns, weft yarns (A and B), characterized in that, The warp and weft yarns are PET filaments containing composite antibacterial particles, and the weft yarn is a seaweed fiber / cotton blended yarn. The composite antibacterial particles include a graphene-based carrier containing phosphorus and zinc, as well as TiO2 and Ag nanoparticles loaded on the graphene-based carrier. The mass content of the composite antibacterial particles in the PET filament is 1.0% to 1.6%. The fabric is an 8-end 5-fly satin weave, with the ratio of weft yarn to weft yarn being 1:4.

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