Light heat storage antibacterial polyester fiber as well as preparation method and application thereof

Abstract

The invention discloses a light heat storage antibacterial polyester fiber as well as a preparation method and application thereof, and belongs to the technical field of composite fibers. The invention relates to a PET (Polyethylene Terephthalate) composite material which comprises the following components in parts by weight: 90-96 parts of PET slices, 2-4 parts of modified tourmaline, 1-2 parts of modified tea saponin-montmorillonite and 0.1-0.2 part of glycerol monostearate. During preparation, tourmaline is modified by a titanate coupling agent NDZ-101, metal ion agglomeration is reduced, epichlorohydrin is used for mediating covalent grafting of tea saponin and montmorillonite, antibacterial components are fixed, washing resistance is improved, supercritical CO2 is combined for assisting dispersion melt blending, and a finished product is obtained through spinning, stretching and shaping. The invention aims to solve the problems of metal ion migration, poor antibacterial washability and functional powder agglomeration of the existing fiber. Tests show that the light heat storage performance is excellent, the antibacterial effect is long-acting, the mechanical property reaches the standard, and the light heat storage material is suitable for the fields of outdoor warm-keeping clothes, medical protection fabrics and the like and has high performance and industrialization suitability.

Description

Technical Field

[0001] This invention belongs to the field of composite fiber technology, specifically relating to a light-heat-storing antibacterial polyester fiber, its preparation method, and its application. Background Technology

[0002] The mainstream technologies for photothermal heat storage and antibacterial polyester fibers mainly include metal-based inorganic particle composites, bio-based and plant extract composites, and aerogel nanoporous structures. While metal-based technologies (such as nano-zirconia and silver-loaded apatite) offer high photothermal conversion efficiency and significant antibacterial effects, they suffer from problems such as inorganic particle agglomeration affecting spinnability, potential metal ion migration and dissolution, and impact on fiber color. For example, patent application CN113293544A reduces nano-agglomeration through a dispersing needle puncture and pulsed stirring system, improving the uniformity of antibacterial agent adhesion by 30%. However, nano-zirconia and silver-loaded apatite particles still require more than 5% dispersant.

[0003] Bio-based technologies utilize plant extracts, which are environmentally friendly and safe, but their active ingredients face challenges in terms of heat resistance, efficacy stability, and durability. For example, patent application CN119593094A loads Polygonum cuspidatum extract onto cellulose aerogel to achieve a synergistic effect of antibacterial and cooling sensations, but the retention rate of active ingredients is only 68% after spinning at 280°C; CN115961376A uses hydrophilic modification to encapsulate thyme extract, but the antibacterial rate drops from 97% to 81% after 20 washes, highlighting the dual challenges of heat resistance and washability of natural ingredients.

[0004] Aerogel technology achieves lightweight warmth thanks to its excellent heat insulation and heat retention properties, but its nanoporous structure is difficult to maintain during processing, and the dispersion process is complex and costly. Patent application CN116949592A maintains 80%–90% porosity through photoreversible crosslinking, but requires ultraviolet irradiation curing equipment, significantly increasing modification costs. In summary, existing technologies have made some progress in the field of photothermal heat-storing and antibacterial polyester fibers, but there is still room for improvement in functional durability, processing costs, and environmental friendliness. Summary of the Invention

[0005] One of the objectives of this invention is to provide a photothermal heat storage and antibacterial polyester fiber to improve the fiber's high photothermal conversion efficiency, antibacterial properties and mechanical properties, while avoiding the risk of metal ion migration and improving environmental friendliness.

[0006] The second objective of this invention is to provide a method for preparing photothermal heat-storing and antibacterial polyester fiber, which is used to prepare the above-mentioned photothermal heat-storing and antibacterial polyester fiber.

[0007] The third objective of this invention is to provide an application of light-retaining and heat-storing antibacterial polyester fiber in the field of warm and antibacterial textiles.

[0008] The objective of this invention can be achieved through the following technical solutions: A light-retaining, heat-storing, antibacterial polyester fiber, by weight, comprises 90-96 parts PET chips, 2-4 parts modified tourmaline, 1-2 parts modified tea saponin-montmorillonite, and 0.1-0.2 parts glyceryl monostearate.

[0009] Furthermore, the modified tourmaline is prepared by the following steps: Step 1: Take tourmaline powder, add isopropanol solution, and disperse by ultrasonication to form a suspension; Step 2: Add titanate coupling agent NDZ-101 dropwise, heat and stir; centrifuge, vacuum dry to obtain modified tourmaline.

[0010] Furthermore, the tourmaline powder has a particle size between 60-80 nm.

[0011] Furthermore, the weight ratio of the tourmaline powder, isopropanol, and titanate coupling agent is (2.5-3.5):(40-45):(0.1-0.2).

[0012] Furthermore, the ultrasonic dispersion time is 40-50 min, the power is 350-400 W, and the frequency is 28-30 kHz.

[0013] Furthermore, the heating and stirring are carried out at 70-75℃ for 120-150 min; the centrifugation is carried out at 9000-10000 rpm for 15-20 min.

[0014] Furthermore, the modified tea saponin-montmorillonite is prepared by the following steps: Step 1: Take sodium-based montmorillonite, add it to deionized water, stir well to make a montmorillonite suspension; Step 2: Add tea saponin and epichlorohydrin, adjust the pH to 8.8-9.0, heat to react; filter to collect the product, vacuum dry, and pulverize to 100-150 nm to obtain modified tea saponin-montmorillonite.

[0015] Furthermore, the particle size of the sodium-based montmorillonite is between 100-150 nm.

[0016] Furthermore, the weight ratio of sodium montmorillonite, deionized water, tea saponin and epichlorohydrin is (1-1.5):(75-100):(0.7-1):(0.25-0.35).

[0017] Furthermore, the heating reaction is carried out by heating to 65-70°C and stirring for 5-6 hours.

[0018] Furthermore, the vacuum drying is performed under vacuum at 75-80°C for 4-6 hours.

[0019] Furthermore, the PET chips have a viscosity of 0.6-0.7 dL / g and a melting point of 255-260℃.

[0020] A method for preparing a light-storing, heat-retaining, antibacterial polyester fiber includes the following steps: S1. PET chips, modified tourmaline, modified tea saponin-montmorillonite, and glyceryl monostearate are added to the hopper of a twin-screw extruder; supercritical CO2 is introduced into the screw section for melt blending; the mixture is then filtered through a 25μm filter to obtain a polyester composite melt. S2. The polyester composite melt is spun to obtain nascent fibers; after cooling, the nascent fibers are stretched, shaped, and wound to obtain light-retaining and heat-retaining antibacterial polyester fibers.

[0021] Furthermore, the supercritical CO2 has a temperature of 38-39℃, a pressure of 12.8-13MPa, and a flow rate of 6.5-6.8L / kgPET.

[0022] Furthermore, the melt blending parameters are: zone 1 235-240℃, zone 2 245-250℃, zone 3 260-265℃, zone 4 255-260℃, screw speed 280-300rpm, and melt residence time 2.5-3min.

[0023] Furthermore, the spinning temperature is 260-262℃, the spinneret orifice diameter is 0.22mm, and the number of orifices is 48.

[0024] Furthermore, the stretching ratio is 3.2-3.3 times, the temperature is 88-90℃; the setting conditions are 110-115℃, 25-28s; and the winding speed is 3500-3600m / min.

[0025] The application of a light-heat-storing antibacterial polyester fiber in the field of warm and antibacterial textiles involves weaving the light-heat-storing antibacterial polyester fiber into a greige fabric, washing it at 40-45℃ for 15-20 minutes, pre-shrinking it at 100-105℃ for 20-25 seconds, and setting it at 120-125℃ for 35-40 seconds to obtain a light-heat-storing antibacterial knitted fabric.

[0026] The beneficial effects of this invention are: (1) In this invention, by weight, 90-96 parts of PET chips ensure the core mechanical properties of the fiber matrix; 2-4 parts of modified tourmaline achieve efficient photothermal storage performance; 1-2 parts of modified tea saponin-montmorillonite have long-lasting antibacterial and auxiliary dispersion functions; and 0.1-0.2 parts of glyceryl monostearate play an auxiliary lubricating role, which improves the high photothermal conversion efficiency, antibacterial performance and mechanical properties of the fiber, while avoiding the risk of metal ion migration and improving environmental friendliness.

[0027] (2) The modified tourmaline provided by the present invention uses tourmaline rich in Fe.3+ Ti 4+ Metal ions, while the pyrophosphate groups in NDZ-101 can react with Fe on the surface of tourmaline. 3+ Ti 4+ The formation of stable coordination bonds can significantly reduce the agglomeration of tourmaline powder caused by the electrostatic attraction of metal ions; the long-chain alkyl group at the other end of the NDZ-101 molecule can form van der Waals forces with the ester group of the PET molecular chain, which can effectively reduce interfacial tension, avoid the "interfacial slippage" phenomenon during melt flow, and reduce the spinning breakage rate.

[0028] (3) The modified tea saponin-montmorillonite provided by the present invention grafts tea saponin (natural glycoside antibacterial agent) onto the interlayer of sodium-based montmorillonite through epichlorohydrin. The layered structure of montmorillonite can fix tea saponin, solving the problem of easy washing and loss of bio-based antibacterial agents. At the same time, its layers can block the aggregation of tourmaline particles, achieving dual functions of antibacterial and dispersion.

[0029] (4) Since the tourmaline modified by NDZ-101 has a weak positive charge on its surface, it can form an electrostatic attraction with the modified tea saponin-montmorillonite, so that the montmorillonite sheets are uniformly adsorbed on the tourmaline surface, which improves the dispersibility of the components and reduces agglomeration. Combined with the supercritical CO2-assisted dispersion and the electrostatic synergy of modified tea saponin-montmorillonite, the dispersion uniformity of functional particles in PET is improved, and no additional large amount of dispersant is required, which takes into account both dispersion effect and economy. Detailed Implementation

[0030] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, specific embodiments of the present invention will be described in detail below.

[0031] In some embodiments, a light-retaining, heat-storing, antibacterial polyester fiber comprises, by weight, 90-96 parts PET chips, 2-4 parts modified tourmaline, 1-2 parts modified tea saponin-montmorillonite, and 0.1-0.2 parts glyceryl monostearate.

[0032] When the PET chip content is below 90 parts, the high proportion of functional components disrupts the continuous PET phase, making the fibers brittle and unable to meet the mechanical requirements for textile weaving and use. When the content is above 96 parts, the functional component content is insufficient, leading to decreased light-heat storage efficiency and antibacterial rate. When the modified tourmaline content is below 2 parts, the metal ion concentration is insufficient, resulting in low light absorption efficiency and weak heat storage effect. When the content is above 4 parts, tourmaline tends to agglomerate, causing uneven melt viscosity during spinning, increased breakage rate, and a rough fiber feel. When the modified tea saponin-montmorillonite content is below 1 part, the tea saponin content is insufficient, resulting in a low antibacterial rate and fewer montmorillonite flakes, increasing the risk of tourmaline agglomeration. When the content is above 2 parts, excessive montmorillonite flakes tend to accumulate, increasing fiber rigidity, worsening the feel, and making tea saponin prone to precipitation. When the amount of glyceryl monostearate is less than 0.1 parts, the lubricating effect is insufficient; when it is more than 0.2 parts, the excess lubricant is prone to migrate to the fiber surface, resulting in a decrease in fiber cohesion, easy yarn breakage during weaving, and affecting the skin-friendliness of the fabric.

[0033] In some embodiments, the modified tourmaline is prepared by the following steps: Step 1: Take tourmaline powder, add isopropanol solution, and disperse by ultrasonication to form a suspension; Step 2: Add titanate coupling agent NDZ-101 dropwise, heat and stir; centrifuge, vacuum dry to obtain modified tourmaline.

[0034] In some embodiments, the tourmaline powder has a particle size between 60-80 nm. Using 60-80 nm tourmaline powder can balance specific surface area and dispersibility, ensuring photothermal energy storage efficiency.

[0035] In some embodiments, the weight ratio of the tourmaline powder, isopropanol, and titanate coupling agent is (2.5-3.5):(40-45):(0.1-0.2). This ratio achieves a balance between uniform tourmaline modification and cost.

[0036] In some embodiments, the ultrasonic dispersion time is 40-50 minutes, the power is 350-400W, and the frequency is 28-30kHz, so as to achieve uniform suspension of tourmaline.

[0037] In some embodiments, the heating and stirring are performed at 70-75°C for 120-150 min; the centrifugation is performed at 9000-10000 rpm for 15-20 min.

[0038] In some embodiments, the modified tea saponin-montmorillonite is prepared by the following steps: Step 1: Take sodium-based montmorillonite, add it to deionized water, stir well to make a montmorillonite suspension; Step 2: Add tea saponin and epichlorohydrin, adjust the pH to 8.8-9.0, heat to react; filter to collect the product, vacuum dry, and pulverize to 100-150 nm to obtain modified tea saponin-montmorillonite.

[0039] In some embodiments, the sodium-based montmorillonite has a particle size between 100-150 nm. Montmorillonite with a particle size of 100-150 nm can balance the dispersibility of the lamellar structure with the grafting efficiency of the antibacterial agent.

[0040] In some embodiments, the weight ratio of sodium montmorillonite, deionized water, tea saponin, and epichlorohydrin is (1-1.5):(75-100):(0.7-1):(0.25-0.35). This ratio ensures grafting efficiency and functional stability.

[0041] In some embodiments, the heating reaction is carried out by heating to 65-70°C and stirring for 5-6 hours. Suitable experimental conditions can ensure sufficient grafting and stability of the antibacterial agent.

[0042] In some embodiments, the vacuum drying is performed under vacuum at 75-80°C for 4-6 hours. This avoids the generation of air bubbles during subsequent spinning and ensures the quality of the spinning process.

[0043] In some embodiments, the PET chips have a viscosity of 0.6-0.7 dL / g and a melting point of 255-260℃. When the viscosity is <0.6 dL / g, the PET molecular weight is low, resulting in insufficient fiber tensile strength; when the viscosity is >0.7 dL / g, the melt viscosity is high, making spinning difficult. When the melting point is not between 255-260℃, it is mismatched with the melt blending temperature, easily leading to PET degradation or incomplete melting, affecting fiber properties.

[0044] A method for preparing a light-storing, heat-retaining, antibacterial polyester fiber includes the following steps: S1. PET chips, modified tourmaline, modified tea saponin-montmorillonite, and glyceryl monostearate are added to the hopper of a twin-screw extruder; supercritical CO2 is introduced into the screw section for melt blending; the mixture is then filtered through a 25μm filter to obtain a polyester composite melt. S2. The polyester composite melt is spun to obtain nascent fibers; after cooling, the nascent fibers are stretched, shaped, and wound to obtain light-retaining and heat-retaining antibacterial polyester fibers.

[0045] Supercritical CO2 is used to assist dispersion, which reduces melt viscosity and promotes uniform distribution of functional particles.

[0046] In some embodiments, the supercritical CO2 has a temperature of 38-39°C, a pressure of 12.8-13 MPa, and a flow rate of 6.5-6.8 L / kg PET.

[0047] In some embodiments, the melt blending parameters are: zone 1 235-240℃, zone 2 245-250℃, zone 3 260-265℃, and zone 4 255-260℃; screw speed 280-300 rpm; and melt residence time 2.5-3 min. When the temperature is below this range, PE melts insufficiently, resulting in uneven mixing; when the temperature is above this range, PET degrades, the fibers yellow, and mechanical properties decrease.

[0048] In some embodiments, the spinning temperature is 260-262°C, the spinneret orifice diameter is 0.22 mm, and the number of orifices is 48. By limiting the number of orifices, spinning efficiency and fiber uniformity can be balanced to meet the needs of textile weaving.

[0049] In some embodiments, the stretch ratio is 3.2-3.3 times, the temperature is 88-90℃; the setting conditions are 110-115℃, 25-28s; and the winding rate is 3500-3600m / min. If the stretch ratio is too low, the fiber crystallinity is low and the strength is insufficient; if the stretch ratio is too high, the fiber is prone to breakage. At low temperatures, stretching is difficult and stress concentration is likely; at high temperatures, the fiber thermal shrinkage rate is high, and setting is difficult.

[0050] In some embodiments, the application of a light-retaining and antibacterial polyester fiber in the field of thermal insulation and antibacterial textiles involves weaving the light-retaining and antibacterial polyester fiber into a greige fabric, followed by washing at 40-45℃ for 15-20 minutes, pre-shrinking at 100-105℃ for 20-25 seconds, and setting at 120-125℃ for 35-40 seconds to obtain a light-retaining and antibacterial knitted fabric. By limiting the weaving parameters, the cleanliness, dimensional stability, and functional retention of the fabric are ensured.

[0051] The specific embodiments of the present invention will be described in detail below, but it should be understood that the scope of protection of the present invention is not limited to the specific embodiments.

[0052] Example 1: This embodiment provides a photothermal heat-storing antibacterial polyester fiber, its preparation method, and its application, including the following steps: S1. Take 3.0 parts by weight of natural orange tourmaline powder, add 40 parts by weight of isopropanol solution, and ultrasonically disperse for 40 minutes (power 350W, frequency 28kHz) to form a suspension; Add 0.15 parts by weight of titanate coupling agent NDZ-101, stir at 70°C for 120 min (350 rpm), centrifuge (9000 rpm, 18 min), and vacuum dry at 80°C for 4 h to obtain modified tourmaline; S2. Take 1.2 parts by weight of sodium montmorillonite, add 80 parts by weight of deionized water, stir for 30 minutes (250 rpm) to prepare a montmorillonite suspension; Add 0.8 parts by weight of tea saponin and 0.3 parts by weight of epichlorohydrin, adjust the pH to 9.0, and react at 65°C for 5 hours; filter and collect the product, vacuum dry at 75°C for 4 hours, and pulverize to 100-150 nm to obtain modified tea saponin-montmorillonite. S3. Add 94 parts by weight of PET chips, 3.0 parts by weight of modified tourmaline, 1.5 parts by weight of modified tea saponin-montmorillonite, and 0.15 parts by weight of glycerol monostearate to the hopper of a twin-screw extruder; introduce supercritical CO2 (temperature 38℃, pressure 13MPa, flow rate 6.5L / kgPET) into the screw section; melt blending parameters: zone 1 235℃, zone 2 250℃, zone 3 260℃, zone 4 255℃, screw speed 280rpm, melt residence time 2.8min; filter through a 25μm filter to obtain a non-agglomerated polyester composite melt; S4. The melt is conveyed to the spinning box, the spinning temperature is 260℃, the spinneret orifice diameter is 0.22mm and the number of orifices is 48; the cooling air is 23℃ and the wind speed is 0.7m / s. The nascent fiber is stretched (3.3 times, temperature 88℃), shaped (115℃, 25s), and wound (3600m / min) to obtain light-retaining heat-storing antibacterial polyester fiber. The light-heat-storing and antibacterial polyester fiber is woven into a greige fabric on a circular knitting machine, and then washed at 45℃ for 15 minutes, pre-shrinked at 105℃ for 20 seconds, and set at 125℃ for 35 seconds to obtain the light-heat-storing and antibacterial knitted fabric.

[0053] Example 2: The difference between this embodiment and Embodiment 1 is that the proportions of each component of the light-heat-storing antibacterial polyester fiber are adjusted. The specific implementation steps of S3 are as follows: S3. Add 96 parts by weight of PET chips, 2 parts by weight of modified tourmaline, 1 part by weight of modified tea saponin-montmorillonite, and 0.1 parts by weight of glyceryl monostearate to the hopper of a twin-screw extruder; introduce supercritical CO2 (temperature 39℃, pressure 13MPa, flow rate 6.6L / kgPET) into the screw section; melt blending parameters: zone 1 235℃, zone 2 250℃, zone 3 265℃, zone 4 258℃, screw speed 280rpm, melt residence time 2.8min; filter through a 25μm filter screen to obtain a non-agglomerated polyester composite melt; The remaining raw materials and preparation process are the same as in Example 1.

[0054] Example 3: The difference between this embodiment and Embodiment 1 is that the proportions of each component of the light-heat-storing antibacterial polyester fiber are adjusted. The specific implementation steps of S3 are as follows: S3. Add 90 parts by weight of PET chips, 4 parts by weight of modified tourmaline, 2 parts by weight of modified tea saponin-montmorillonite, and 0.2 parts by weight of glycerol monostearate to the hopper of a twin-screw extruder; introduce supercritical CO2 (temperature 38℃, pressure 13MPa, flow rate 6.7L / kgPET) into the screw section; melt blending parameters: zone 1 238℃, zone 2 248℃, zone 3 262℃, zone 4 255℃, screw speed 290rpm, melt residence time 3min; filter through a 25μm filter screen to obtain a non-agglomerated polyester composite melt; The remaining raw materials and preparation process are the same as in Example 1.

[0055] Example 4: The difference between this embodiment and Example 1 is that the weight ratio of tourmaline powder, isopropanol, and titanate coupling agent is adjusted. The specific implementation steps of S1 are as follows: S1. Take 3.5 parts by weight of natural orange tourmaline powder, add 45 parts by weight of isopropanol solution, and ultrasonically disperse for 40 minutes (power 350W, frequency 28kHz) to form a suspension. Add 0.1 parts by weight of titanate coupling agent NDZ-101, stir at 75°C for 150 min (350 rpm), centrifuge (9000 rpm, 18 min), and vacuum dry at 80°C for 4 h to obtain modified tourmaline; The remaining raw materials and preparation process are the same as in Example 1.

[0056] Example 5: The difference between this embodiment and Example 1 is that the weight ratio of tourmaline powder, isopropanol, and titanate coupling agent is adjusted. The specific implementation steps of S1 are as follows: S1. Take 2.5 parts by weight of natural orange tourmaline powder, add 40 parts by weight of isopropanol solution, and ultrasonically disperse for 45 minutes (power 380W, frequency 30kHz) to form a suspension; Add 0.2 parts by weight of titanate coupling agent NDZ-101, stir at 70°C for 120 min (350 rpm), centrifuge (10000 rpm, 15 min), and vacuum dry at 80°C for 4 h to obtain modified tourmaline; The remaining raw materials and preparation process are the same as in Example 1.

[0057] Example 6: The difference between this embodiment and Example 1 is that the weight ratio of sodium montmorillonite, deionized water, tea saponin, and epichlorohydrin is adjusted. The specific implementation steps of S2 are as follows: S2. Take 1.5 parts by weight of sodium montmorillonite, add 90 parts by weight of deionized water, stir for 30 minutes (250 rpm) to prepare a montmorillonite suspension; Add 0.7 parts by weight of tea saponin and 0.35 parts by weight of epichlorohydrin, adjust the pH to 8.8, react at 65°C for 6 hours; filter and collect the product, vacuum dry at 75°C for 4 hours, and pulverize to 100-150 nm to obtain modified tea saponin-montmorillonite. The remaining raw materials and preparation process are the same as in Example 1.

[0058] Example 7: The difference between this embodiment and Example 1 is that the weight ratio of sodium montmorillonite, deionized water, tea saponin, and epichlorohydrin is adjusted. The specific implementation steps of S2 are as follows: S2. Take 1 part by weight of sodium montmorillonite, add 85 parts by weight of deionized water, stir for 30 minutes (250 rpm) to prepare a montmorillonite suspension. Add 1 part by weight of tea saponin and 0.35 parts by weight of epichlorohydrin, adjust the pH to 9.0, react at 68℃ for 5 h; filter and collect the product, vacuum dry at 80℃ for 4 h, and pulverize to 100-150 nm to obtain modified tea saponin-montmorillonite. The remaining raw materials and preparation process are the same as in Example 1.

[0059] Comparative Example 1: The difference between this comparative example and Example 1 is that the coupling agent for the tourmaline is different (KH-550). The specific implementation steps of S1 are as follows: S1. Take 3.0 parts by weight of natural orange tourmaline powder, add 40 parts by weight of isopropanol solution, and ultrasonically disperse for 40 minutes (power 350W, frequency 28kHz) to form a suspension; Add 0.15 parts by weight of KH-550 dropwise, stir at 70℃ for 120 min (350 rpm), centrifuge (9000 rpm, 18 min), and vacuum dry at 80℃ for 4 h to obtain modified tourmaline; The remaining raw materials and preparation process are the same as in Example 1.

[0060] Comparative Example 2: The difference between this comparative example and Example 1 is that the tourmaline is not modified with a coupling agent. The specific implementation steps are as follows: S1. Take 1.2 parts by weight of sodium montmorillonite, add 80 parts by weight of deionized water, stir for 30 minutes (250 rpm) to prepare a montmorillonite suspension; Add 0.8 parts by weight of tea saponin and 0.3 parts by weight of epichlorohydrin, adjust the pH to 9.0, and react at 65°C for 5 hours; filter and collect the product, vacuum dry at 75°C for 4 hours, and pulverize to 100-150 nm to obtain modified tea saponin-montmorillonite. S2. Add 94 parts by weight of PET chips, 3.0 parts by weight of tourmaline, 1.5 parts by weight of modified tea saponin-montmorillonite, and 0.15 parts by weight of glycerol monostearate to the hopper of a twin-screw extruder; introduce supercritical CO2 (temperature 38℃, pressure 13MPa, flow rate 6.5L / kgPET) into the screw section; melt blending parameters: zone 1 235℃, zone 2 250℃, zone 3 260℃, zone 4 255℃, screw speed 280rpm, melt residence time 2.8min; filter through a 25μm filter to obtain a non-agglomerated polyester composite melt; S3. The melt is conveyed to the spinning box, the spinning temperature is 260℃, the spinneret orifice diameter is 0.22mm and the number of orifices is 48; the cooling air is 23℃ and the wind speed is 0.7m / s. The nascent fiber is stretched (3.3 times, temperature 88℃), shaped (115℃, 25s), and wound (3600m / min) to obtain light-heat-storing antibacterial polyester fiber. The light-heat-storing and antibacterial polyester fiber is woven into a greige fabric on a circular knitting machine, and then washed at 45℃ for 15 minutes, pre-shrinked at 105℃ for 20 seconds, and set at 125℃ for 35 seconds to obtain the light-heat-storing and antibacterial knitted fabric.

[0061] The remaining raw materials and preparation process are the same as in Example 1.

[0062] Comparative Example 3: The difference between this comparative example and Example 1 is that the modified tea saponin-montmorillonite is replaced with conventional chitosan. The specific implementation steps are as follows: S1. Take 3.0 parts by weight of natural orange tourmaline powder, add 40 parts by weight of isopropanol solution, and ultrasonically disperse for 40 minutes (power 350W, frequency 28kHz) to form a suspension; Add 0.15 parts by weight of titanate coupling agent NDZ-101, stir at 70°C for 120 min (350 rpm), centrifuge (9000 rpm, 18 min), and vacuum dry at 80°C for 4 h to obtain modified tourmaline; S2. Add 94 parts by weight of PET chips, 3.0 parts by weight of modified tourmaline, 1.5 parts by weight of chitosan, and 0.15 parts by weight of glycerol monostearate to the hopper of a twin-screw extruder; introduce supercritical CO2 (temperature 38℃, pressure 13MPa, flow rate 6.5L / kgPET) into the screw section; melt blending parameters: zone 1 235℃, zone 2 250℃, zone 3 260℃, zone 4 255℃, screw speed 280rpm, melt residence time 2.8min; filter through a 25μm filter to obtain a non-agglomerated polyester composite melt; S3. The melt is conveyed to the spinning box, the spinning temperature is 260℃, the spinneret orifice diameter is 0.22mm and the number of orifices is 48; the cooling air is 23℃ and the wind speed is 0.7m / s. The nascent fiber is stretched (3.3 times, temperature 88℃), shaped (115℃, 25s), and wound (3600m / min) to obtain light-heat-storing antibacterial polyester fiber. The light-heat-storing and antibacterial polyester fiber is woven into a greige fabric on a circular knitting machine, and then washed at 45℃ for 15 minutes, pre-shrinked at 105℃ for 20 seconds, and set at 125℃ for 35 seconds to obtain the light-heat-storing and antibacterial knitted fabric.

[0063] The remaining raw materials and preparation process are the same as in Example 1.

[0064] Comparative Example 4: The difference between this comparative example and Example 1 is that epichlorohydrin is not added. The specific implementation steps of S2 are as follows: S2. Take 1.5 parts by weight of sodium montmorillonite, add 80 parts by weight of deionized water, stir for 30 minutes (250 rpm) to prepare a montmorillonite suspension; Add 1 part by weight of tea saponin, adjust the pH to 9.0, react at 65℃ for 5 h; filter and collect the product, vacuum dry at 75℃ for 4 h, and pulverize to 100-150 nm to obtain modified tea saponin-montmorillonite. The remaining raw materials and preparation process are the same as in Example 1.

[0065] Comparative Example 5: The difference between this comparative example and Example 1 is that modified tea saponin-montmorillonite is not added. The specific implementation steps are as follows: S1. Take 3.0 parts by weight of natural orange tourmaline powder, add 40 parts by weight of isopropanol solution, and ultrasonically disperse for 40 minutes (power 350W, frequency 28kHz) to form a suspension; Add 0.15 parts by weight of titanate coupling agent NDZ-101, stir at 70°C for 120 min (350 rpm), centrifuge (9000 rpm, 18 min), and vacuum dry at 80°C for 4 h to obtain modified tourmaline; S2. Add 95 parts by weight of PET chips, 3.5 parts by weight of modified tourmaline, and 0.2 parts by weight of glycerol monostearate to the hopper of a twin-screw extruder; introduce supercritical CO2 (temperature 38℃, pressure 13MPa, flow rate 6.5L / kgPET) into the screw section; melt blending parameters: zone 1 235℃, zone 2 250℃, zone 3 260℃, zone 4 255℃, screw speed 280rpm, melt residence time 2.8min; filter through a 25μm filter to obtain a non-agglomerated polyester composite melt; S3. The melt is conveyed to the spinning box, the spinning temperature is 260℃, the spinneret orifice diameter is 0.22mm and the number of orifices is 48; the cooling air is 23℃ and the wind speed is 0.7m / s. The nascent fiber is stretched (3.3 times, temperature 88℃), shaped (115℃, 25s), and wound (3600m / min) to obtain light-heat-storing antibacterial polyester fiber. The light-heat-storing and antibacterial polyester fiber is woven into a greige fabric on a circular knitting machine, and then washed at 45℃ for 15 minutes, pre-shrinked at 105℃ for 20 seconds, and set at 125℃ for 35 seconds to obtain the light-heat-storing and antibacterial knitted fabric.

[0066] The remaining raw materials and preparation process are the same as in Example 1.

[0067] Comparative Example 6: The difference between this comparative example and Example 1 is that, while the tourmaline is not modified with a coupling agent, the modified tea saponin-montmorillonite is replaced with conventional chitosan. The specific implementation steps are as follows: S1. Take 1.2 parts by weight of sodium montmorillonite, add 80 parts by weight of deionized water, stir for 30 minutes (250 rpm) to prepare a montmorillonite suspension; Add 0.8 parts by weight of tea saponin and 0.3 parts by weight of epichlorohydrin, adjust the pH to 9.0, and react at 65°C for 5 hours; filter and collect the product, vacuum dry at 75°C for 4 hours, and pulverize to 100-150 nm to obtain modified tea saponin-montmorillonite. S2. Add 94 parts by weight of PET chips, 3.0 parts by weight of tourmaline, 1.5 parts by weight of chitosan, and 0.15 parts by weight of glyceryl monostearate to the hopper of a twin-screw extruder; introduce supercritical CO2 (temperature 38℃, pressure 13MPa, flow rate 6.5L / kgPET) into the screw section; melt blending parameters: zone 1 235℃, zone 2 250℃, zone 3 260℃, zone 4 255℃, screw speed 280rpm, melt residence time 2.8min; filter through a 25μm filter to obtain a non-agglomerated polyester composite melt; S3. The melt is conveyed to the spinning box, the spinning temperature is 260℃, the spinneret orifice diameter is 0.22mm and the number of orifices is 48; the cooling air is 23℃ and the wind speed is 0.7m / s. The nascent fiber is stretched (3.3 times, temperature 88℃), shaped (115℃, 25s), and wound (3600m / min) to obtain light-heat-storing antibacterial polyester fiber. The light-heat-storing and antibacterial polyester fiber is woven into a greige fabric on a circular knitting machine, and then washed at 45℃ for 15 minutes, pre-shrinked at 105℃ for 20 seconds, and set at 125℃ for 35 seconds to obtain the light-heat-storing and antibacterial knitted fabric.

[0068] The remaining raw materials and preparation process are the same as in Example 1.

[0069] Performance testing 1. Photothermal storage performance (400W / m²) 2 According to GB / T 18319-2019 "Test Methods for Photothermal Storage Performance of Textiles", the photothermal storage performance of the photothermal storage antibacterial polyester fibers obtained in the various embodiments and comparative examples of this application was tested. 2. Antibacterial properties: The antibacterial properties (Escherichia coli / Staphylococcus aureus) of the light-heat-storing antibacterial polyester fibers obtained in the various embodiments and comparative examples of this application were tested according to GB / T 20944.3-2008 "Evaluation of antibacterial properties of textiles - Part 3: Vibration method". 3. Tensile strength: The tensile strength of the light-heat-storing antibacterial polyester fibers obtained in the various embodiments and comparative examples of this application was tested according to GB / T 14344-2022 "Test Method for Tensile Properties of Chemical Fiber Filaments". 4. Wash resistance: The wash resistance of the light-heat-storing antibacterial polyester fibers obtained in the various embodiments and comparative examples of this application was tested according to GB / T 8629-2017 "Home washing and drying procedures for textile testing". The results are shown in Table 1: Table 1

[0070] As can be seen from Table 1, the examples exhibit excellent photothermal storage performance, with an average temperature rise of 5.6-6.2℃. This is due to the Fe content in the tourmaline. 3+ / Fe 2+ Ti 4+ The energy level transitions allow for efficient absorption of light energy in the 400-1100nm wavelength range, while the pyrophosphate groups of NDZ-101 form stable coordination bonds with metal ions on the tourmaline surface, ensuring stable photothermal conversion performance. After 50 washes, the antibacterial rate remains above 90%. This is because the epichlorohydrin in the modified tea saponin-montmorillonite forms an ether bond with the hydroxyl group of tea saponin at one end and a covalent bond with the Si-OH group of montmorillonite at the other end, resulting in low tea saponin loss during washing. PET chips ensure the continuous phase structure of the matrix, and the lubricating effect of glyceryl monostearate prevents melt fracture caused by excessive functional components. Furthermore, the layered support of the modified tea saponin-montmorillonite supplements some of the mechanical strength, meeting the requirements of textile weaving. In Example 1, after 50 washes, the average temperature rise of photothermal storage was still 5.8℃, which was much higher than the 4.1℃ of Comparative Example 3. This is because the coordination bond structure of the modified tourmaline and the interlayer fixation of the modified tea saponin-montmorillonite jointly improve the wash resistance. Specifically, the modification of NDZ-101 makes the tourmaline firmly anchored in the PET matrix, making it less likely to fall off during the washing process; the layered barrier structure of montmorillonite protects the tea saponin from water erosion.

[0071] In Comparative Example 1, KH-550 can only form hydrogen bonds with the hydroxyl groups on the tourmaline surface, unlike NDZ-101 which can form strong coordination bonds with metal ions. Furthermore, KH-550 lacks the compatibility of long-chain alkyl groups with PET, resulting in a sharp drop in photothermal storage and mechanical properties. Comparative Example 2, using unmodified tourmaline, showed a decrease in light absorption efficiency, with an average temperature rise of only 4.5℃; and particle agglomeration led to a decrease in fiber breaking strength to 3.1 cN / dtex. In Comparative Example 3, modified tea saponin-montmorillonite was replaced with chitosan. Conventional chitosan lacks an interlayer fixation structure and is easily dissolved and lost during washing. After 50 washes, the antibacterial rate against E. coli plummeted from 98.5% to 76.3%. Simultaneously, the poor interfacial compatibility between chitosan and PET significantly reduced the retention rate of photothermal storage and wash resistance. In Comparative Example 4, due to the lack of covalent grafting with epichlorohydrin, tea saponin only adhered to the montmorillonite layers through physical adsorption. After 50 washes, the high loss rate led to a decrease in antibacterial rate. Furthermore, without the effect of epichlorohydrin, the interlayer spacing of the montmorillonite could not be expanded, resulting in a decrease in tourmaline embedding effect and a reduction in the retention rate of light-heat storage and wash resistance. Comparative Example 5, lacking modified tea saponin-montmorillonite, suffered from a loss of dispersibility and antibacterial function. This was because the absence of physical barriers from the montmorillonite layers increased the tourmaline aggregation rate, reducing the average light-heat storage temperature rise to 5.2℃. The absence of antibacterial components resulted in the fiber having no antibacterial properties, and the dispersing aid effect of montmorillonite disappeared. In Comparative Example 6, due to the unmodified tourmaline and the use of chitosan as a substitute, the average temperature rise from light-induced heat storage was only 4.3°C, and the antibacterial rate dropped to 74.6% after 50 washes, while the fiber breaking strength dropped to 3.0 cN / dtex. This demonstrates the necessity of using modified tourmaline and the modified tea saponin-montmorillonite system in this invention.

[0072] The above-disclosed embodiments are merely a few specific examples of the present invention. However, the embodiments of the present invention are not limited thereto, and any variations that can be conceived by those skilled in the art should fall within the protection scope of the present invention.

Claims

1. A light-retaining, heat-storing, antibacterial polyester fiber, characterized in that, By weight, it includes 90-96 parts PET chips, 2-4 parts modified tourmaline, 1-2 parts modified tea saponin-montmorillonite, and 0.1-0.2 parts glyceryl monostearate.

2. The photothermal heat-storing and antibacterial polyester fiber according to claim 1, characterized in that, The modified tourmaline is prepared by the following steps: Step 1: Take tourmaline powder, add isopropanol solution, and disperse by ultrasonication to form a suspension; Step 2: Add titanate coupling agent NDZ-101 dropwise, heat and stir; centrifuge, vacuum dry to obtain modified tourmaline; The tourmaline powder has a particle size between 60-80 nm; The ultrasonic dispersion time is 40-50 min, the power is 350-400 W, and the frequency is 28-30 kHz; The heating and stirring are carried out at 70-75℃ for 120-150 min; the centrifugation is carried out at 9000-10000 rpm for 15-20 min. The vacuum drying is performed under vacuum at 75-80℃ for 4-6 hours.

3. The photothermal heat-storing and antibacterial polyester fiber according to claim 2, characterized in that, The weight ratio of the tourmaline powder, isopropanol, and titanate coupling agent is (2.5-3.5):(40-45):(0.1-0.2).

4. The photothermal heat-storing and antibacterial polyester fiber according to claim 1, characterized in that, The modified tea saponin-montmorillonite is prepared by the following steps: Step 1: Take sodium-based montmorillonite, add it to deionized water, stir well to make a montmorillonite suspension; Step 2: Add tea saponin and epichlorohydrin, adjust the pH to 8.8-9.0, heat the reaction; filter and collect the product, vacuum dry, and pulverize to 100-150 nm to obtain modified tea saponin-montmorillonite; The particle size of the sodium-based montmorillonite is between 100-150 nm; The heating reaction is carried out by heating to 65-70℃ and stirring for 5-6 hours. The vacuum drying is performed under vacuum at 75-80℃ for 4-6 hours.

5. The photothermal heat-storing and antibacterial polyester fiber according to claim 4, characterized in that, The weight ratio of sodium montmorillonite, deionized water, tea saponin and epichlorohydrin is (1-1.5):(75-100):(0.7-1):(0.25-0.35).

6. The photothermal heat-storing and antibacterial polyester fiber according to claim 1, characterized in that, The PET chips have a viscosity of 0.6-0.7 dL / g and a melting point of 255-260℃.

7. A method for preparing a light-storing, heat-retaining, antibacterial polyester fiber, characterized in that, The method for preparing the light-storing, heat-retaining, antibacterial polyester fiber according to any one of claims 1-6 comprises the following steps: S1. PET chips, modified tourmaline, modified tea saponin-montmorillonite, and glyceryl monostearate are added to the hopper of a twin-screw extruder; supercritical CO2 is introduced into the screw section for melt blending; the mixture is then filtered through a 25μm filter to obtain a polyester composite melt. S2. The polyester composite melt is spun to obtain nascent fibers; after cooling, the nascent fibers are stretched, shaped, and wound to obtain light-retaining and heat-storing antibacterial polyester fibers.

8. The method for preparing a photothermal heat-storing antibacterial polyester fiber according to claim 7, characterized in that, The supercritical CO2 has a temperature of 38-39℃, a pressure of 12.8-13MPa, and a flow rate of 6.5-6.8L / kg PET. The melt blending parameters are: zone 1 235-240℃, zone 2 245-250℃, zone 3 260-265℃, zone 4 255-260℃, screw speed 280-300rpm, and melt residence time 2.5-3min.

9. The method for preparing a photothermal heat-storing antibacterial polyester fiber according to claim 7, characterized in that, The spinning temperature is 260-262℃, the spinneret orifice diameter is 0.22mm, and the number of orifices is 48. The stretching ratio is 3.2-3.3 times, and the temperature is 88-90℃; the setting conditions are 110-115℃, 25-28s; and the winding speed is 3500-3600m / min.

10. The application of a light-retaining, heat-storing, antibacterial polyester fiber in the field of warm-keeping and antibacterial textiles, characterized in that, The photothermal heat-storing and antibacterial polyester fiber used is prepared by the preparation method according to any one of claims 7-9; The application steps include: weaving light-heat-storing and antibacterial polyester fibers into a greige fabric, washing it with water at 40-45℃ for 15-20 minutes, pre-shrinking it at 100-105℃ for 20-25 seconds, and setting it at 120-125℃ for 35-40 seconds to obtain a light-heat-storing and antibacterial knitted fabric.

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