Cool-feeling antibacterial polyester fabric and preparation method thereof

Abstract

This invention belongs to the field of functional textile materials and provides a cooling and antibacterial polyester fabric and its preparation method. The invention employs a melt-blended spinning design of a thermally conductive antibacterial core-shell masterbatch and a polyester matrix. The masterbatch uses a zinc oxide submicron rod-shaped inorganic core as its core, coated with a silane coupling layer and a quaternized copolyester shell. During fiber drafting, the one-dimensional zinc oxide rods are aligned axially, significantly improving the longitudinal thermal conductivity of the fiber and enhancing the instantaneous cooling sensation upon contact. Simultaneously, the quaternized copolyester shell exhibits good compatibility with the polyester matrix, constructing a dense, wash-resistant, and antibacterial network. This achieves synergistic optimization of high-strength, fine-denier spinnability with high-filler thermal conductivity, durable antibacterial properties after 50 machine washes with a soft and comfortable feel, and high functionalization efficiency with low migration safety. It resolves the technical contradictions in existing polyester fabrics regarding thermal conductivity and cooling sensation versus antibacterial durability, functionality versus safety, and processability versus comfort, and has broad application value in areas such as intimate apparel and bedding.

Description

Technical Field

[0001] This invention relates to the field of functional textile materials, specifically to a cooling and antibacterial polyester fabric and its preparation method. Background Technology

[0002] With the improvement of people's living standards and the upgrading of consumption concepts, higher demands are being placed on the comfort and functionality of textiles such as underwear and bedding. In hot and humid summers or during sweaty workouts, traditional polyester fabrics, due to their low thermal conductivity, lack a cooling sensation upon contact with the skin, easily causing stuffiness and discomfort. Simultaneously, sweat and sebum secretions provide a breeding ground for microorganisms, easily producing odors and causing skin health problems. Therefore, developing polyester fabrics that simultaneously possess both instant cooling sensation upon contact and long-lasting antibacterial properties has become an important research direction in the field of textile materials. An ideal cooling and antibacterial polyester fabric should rapidly absorb heat from the skin surface upon contact and conduct it to the external environment, providing a noticeable cooling sensation. Simultaneously, it should inhibit the growth of common pathogenic bacteria such as Staphylococcus aureus and Escherichia coli, and maintain a stable antibacterial effect even after repeated washing. This multi-functional synergy not only significantly improves the comfort and hygiene of summer wear but also broadens the application range of polyester fibers in high-value-added fields such as sportswear and medical care textiles, which is of great significance for promoting the technological upgrading of the textile industry.

[0003] Currently, research on improving the cooling properties of polyester fibers mainly focuses on adding high thermal conductivity fillers or changing the fiber cross-sectional structure. However, problems exist, such as uneven dispersion of thermally conductive fillers leading to unstable cooling effects, poor compatibility between fillers and the polyester matrix resulting in decreased fiber strength, and reduced spinnability under high filler content. For example, Chinese patent CN116262989B discloses a nano-zinc oxide modified flame-retardant and antibacterial polyester fiber and its preparation method. However, the spherical particles are isotropically distributed within the fiber, failing to form an effective thermal conductivity pathway along the fiber axis, and are prone to agglomeration under high filler content, causing fiber brittleness. Regarding antibacterial properties, existing technologies mostly employ post-treatment methods to attach antibacterial agents such as quaternary ammonium salts or silver ions to the fiber surface. For example, Chinese patent CN108625166B discloses a method for treating cotton yarn with organosilicon quaternary ammonium salts. However, these antibacterial agents have weak bonding with fibers, and their antibacterial effect decreases sharply after multiple washes, making it difficult to meet the practical requirement of more than 50 washes. Some studies have attempted to copolymerize antimicrobial monomers into polyester molecular chains, which improves wash resistance. However, the amount of antimicrobial monomers introduced is limited by the polyester polymerization process window, making it difficult to achieve the concentration required for highly efficient antimicrobial activity. Furthermore, antimicrobial monomers may migrate to the skin contact interface, posing a safety hazard. Therefore, how to achieve axial orientation of a highly filled one-dimensional thermally conductive phase to construct an efficient longitudinal thermal conduction pathway while ensuring the high strength and fine denier spinnability of polyester fibers, and simultaneously constructing a wash-resistant and antimicrobial functional network and strictly controlling the safety limits of migrations such as antimicrobial monomers and catalysts, has become a pressing technical challenge in this field. Summary of the Invention

[0004] The purpose of this invention is to provide a cooling antibacterial polyester fabric and its preparation method, which solves the inherent contradictions in the current physicochemical mechanisms of polyester fibers, such as the high-strength fine denier spinnability of polyester fibers, the need to improve longitudinal thermal conductivity and instant cooling by filling a one-dimensional inorganic thermally conductive phase with high density, the need to construct a dense antibacterial functional network that can withstand 50 machine washes while maintaining low bending stiffness and soft and comfortable hand feel of the fibers and fabrics, and the need to balance the thermal conductivity and antibacterial efficiency requirements brought about by the high inorganic and high functional system with strict limits on quaternary ammonium salts, metal catalysts and migratable small molecules to ensure skin contact safety.

[0005] This invention employs a design concept that synergistically enhances the thermally conductive and antibacterial core-shell masterbatch with a polyester matrix. By constructing a multi-layered core-shell structure with a submicron-shaped zinc oxide rod-like inorganic core as the core, a silane coupling layer as the interface, and a quaternized copolyester shell as the functional outer shell, it achieves the spatially ordered distribution and functional synergy of the thermally conductive and antibacterial phases. The one-dimensional rod-shaped zinc oxide inorganic core preferentially aligns along the axial direction during fiber drawing, forming a continuous thermally conductive pathway and significantly improving the longitudinal thermal conductivity of the fiber. The silane coupling layer firmly connects the inorganic core and organic shell through Si-O-Zn chemical bonds, solving the problems of filler agglomeration and interfacial compatibility. The quaternized copolyester shell exhibits good compatibility and melt mixing uniformity with the polyester matrix. The quaternary ammonium groups are uniformly dispersed within the fiber, forming a three-dimensional antibacterial network, preventing the loss of antibacterial function and achieving excellent synergistic effects.

[0006] To achieve the above objectives, the present invention provides the following technical solution:

[0007] A cooling and antibacterial polyester fabric, said fabric being woven or knitted from polyester fibers, said polyester fibers comprising:

[0008] The polyester matrix comprises an aromatic polyester primarily composed of polyethylene terephthalate, wherein the mass fraction of the polyester matrix in the polyester fibers is 70 wt% to 95 wt% of the total mass of the polyester fibers;

[0009] A thermally conductive and antibacterial core-shell masterbatch, wherein the mass fraction of the thermally conductive and antibacterial core-shell masterbatch in the polyester fiber is 5 wt% to 30 wt% of the total mass of the polyester fiber, the thermally conductive and antibacterial core-shell masterbatch comprises a zinc oxide submicron rod-shaped inorganic core and an organic shell layer coating the surface of the zinc oxide submicron rod-shaped inorganic core, wherein:

[0010] The zinc oxide submicron rod-shaped inorganic core has a one-dimensional rod-shaped morphology and is at least partially aligned along the axial direction of the polyester fiber during the forming and stretching process, so as to improve the longitudinal thermal conductivity of the polyester fiber and enhance the instantaneous cooling sensation upon contact.

[0011] The organic shell comprises a silane coupling layer and a quaternized copolyester shell. The silane coupling layer is formed by the hydrolytic condensation of γ-glycidoxypropyltrimethoxysilane and is connected to the zinc oxide submicron rod-shaped inorganic core through Si-O-Zn bonds. The quaternized copolyester shell covers the outside of the silane coupling layer and is obtained by esterification condensation of terephthalic acid or dimethyl terephthalate, ethylene glycol, monosodium 5-sulfoisophthalate and bis-2-hydroxyethyldimethylammonium chloride.

[0012] The zinc oxide submicron rod-shaped inorganic core in the thermally conductive and antibacterial core-shell masterbatch has a mass fraction of 20 wt% to 60 wt% of the total mass of the thermally conductive and antibacterial core-shell masterbatch, and the quaternary ammonium nitrogen in the quaternized copolyester shell has a mass fraction of 0.3 wt% to 2.0 wt% of the total mass of the thermally conductive and antibacterial core-shell masterbatch.

[0013] Furthermore, the thermally conductive and antibacterial core-shell masterbatch is prepared through the following steps:

[0014] A1. Preparation of silanized zinc oxide submicron rod powder: Zinc oxide submicron rod powder with a submicron rod morphology and an average size L50 of 0.2 μm to 2.0 μm in the long axis direction is dispersed in a water-alcohol mixed solvent, γ-glycidoxypropyltrimethoxysilane is added, and the reaction is carried out at a pH of 4.0 to 5.0 and a temperature of 60℃ to 80℃ for 1.0 h to 3.0 h. After washing and drying, silanized zinc oxide submicron rod powder with epoxy functional groups on the surface is obtained.

[0015] A2. Preparation of quaternized copolyester prepolymer chips: Terephthalic acid or dimethyl terephthalate, monosodium 5-sulfoisophthalate, ethylene glycol and bis-2-hydroxyethyldimethylammonium chloride are added to an esterification reactor and esterification reaction is carried out at a temperature of 200℃ to 240℃. After esterification reaction, antimony trioxide catalyst is added and polycondensation reaction is carried out at a temperature of 260℃ to 280℃ and a vacuum degree not exceeding 300Pa to obtain quaternized copolyester prepolymer chips;

[0016] A3. Preparation of thermally conductive and antibacterial core-shell masterbatch: The silanized zinc oxide submicron rod powder and the quaternized copolyester prepolymer chips are melt-blended at a mass ratio of 20 to 60:40 to 80 at a temperature of 250°C to 280°C. The mixture is then water-cooled, stretched, or underwater granulated to obtain a thermally conductive and antibacterial core-shell masterbatch with a median volume diameter (D50) of 80 μm to 200 μm.

[0017] Furthermore, the zinc oxide submicron rod powder is prepared through the following steps:

[0018] B1. Preparation of submicron rod-shaped zinc oxide precursor: A zinc-containing inorganic salt solution was mixed with an alkaline source, and a morphology control agent was added. The mixture was reacted under hydrothermal conditions at 120℃ to 220℃ for 2h to 24h. After cooling, the resulting reaction slurry was subjected to solid-liquid separation and washed with deionized water 3 to 10 times until the conductivity of the filtrate was no higher than 50μS / cm and the pH value was 6.5 to 7.5. The filtrate was then dried at 80℃ to 120℃ for 2h to 12h to obtain the submicron rod-shaped zinc oxide precursor.

[0019] B2. Preparation of zinc oxide submicron rod powder by calcination: The submicron rod-shaped zinc oxide precursor is calcined in an air atmosphere at a temperature of 400°C to 650°C for 1 to 4 hours to obtain zinc oxide submicron rod powder.

[0020] The zinc-containing inorganic salt is selected from at least one of zinc nitrate, zinc acetate, and zinc chloride, and the zinc-containing inorganic salt solution contains Zn. 2+ The concentration of the alkali source is from 0.1 mol / L to 0.8 mol / L, and the alkali source is selected from at least one of sodium hydroxide solution, potassium hydroxide solution, and ammonia water, wherein the OH in the alkali source is... - With the zinc-containing inorganic salt solution, Zn 2+ The molar ratio is 2.0-5.0 to 1, and the morphology control agent is selected from one or more of sodium citrate, sodium tartrate, polyethylene glycol, polyvinylpyrrolidone and hexadecyltrimethylammonium bromide, and the amount of the morphology control agent is 1 wt% to 20 wt%, preferably 3 wt% to 10 wt%, based on the ratio of the mass of the morphology control agent to the theoretical mass of the zinc-containing inorganic salt calculated as zinc oxide.

[0021] Furthermore, in the quaternized copolyester shell: the molar fraction of the 5-sulfoisophthalic acid monosodium salt relative to the total molar amount of the dicarboxylic acid is 0.5 mol% to 8.0 mol%, preferably 1.0 mol% to 5.0 mol%;

[0022] The molar fraction of bis-2-hydroxyethyl dimethyl ammonium chloride relative to the total molar amount of the diol is from 0.5 mol% to 5.0 mol%, preferably from 1.0 mol% to 3.0 mol%.

[0023] The molar ratio of quaternary ammonium nitrogen to sulfonic acid groups on the aromatic ring in the quaternized copolyester shell is 0.5 to 2.0:1, preferably 0.8 to 1.5:1.

[0024] Furthermore, the average size L50 of the zinc oxide submicron rod-shaped inorganic core is 0.2 μm to 2.0 μm in the long axis direction, the average diameter D50 in the short axis direction is 50 nm to 300 nm, and the aspect ratio is 3 to 20; the median volume diameter D50 of the thermally conductive antibacterial core-shell masterbatch is 80 μm to 200 μm; and the thickness of the quaternized copolyester shell is 5 nm to 30 nm.

[0025] Furthermore, when preparing the polyester fiber, the mass ratio of the polyester matrix chips to the thermally conductive and antibacterial core-shell masterbatch before melt blending is 70-95:5-30, preferably 80-92:8-20, and the total mass fraction of zinc oxide in the resulting polyester fiber is 3wt% to 15wt% of the total mass of the polyester fiber.

[0026] Furthermore, in addition to the polyethylene terephthalate, the polyester matrix also contains no more than 30 wt% of other aromatic polyesters, wherein the other aromatic polyesters are selected from at least one of polybutylene terephthalate and polytrimethylene terephthalate, and the total content of the polyester matrix in the polyester fiber is not less than 70 wt% of the total mass of the polyester fiber.

[0027] As a concept of this invention, the present invention employs a design for synergistic blending and spinning of thermally conductive and antibacterial core-shell masterbatch with a polyester matrix, primarily used to enhance the longitudinal thermal conductivity and long-lasting antibacterial properties of polyester fibers. The one-dimensional rod-shaped morphology of the submicron rod-shaped inorganic core of zinc oxide is key to achieving efficient thermal conductivity. During melt spinning, the shear and tensile forces of the melt flow field induce the rod-shaped zinc oxide particles to preferentially align along the fiber axis, forming a directional thermal conduction pathway. Compared to the isotropic distribution of spherical particles, the axial orientation of the rod-shaped particles significantly increases the longitudinal thermal conductivity of the fiber, thereby rapidly absorbing and conducting heat from the skin upon contact, producing a noticeable cooling sensation. The introduction of the silane coupling layer solves the problem of poor interfacial compatibility between inorganic fillers and organic polyester matrix. γ-glycidoxypropyltrimethoxysilane forms Si-O-Zn chemical bonds on the zinc oxide surface through siloxane hydrolysis and condensation. The epoxy groups can undergo ring-opening reactions with the hydroxyl or carboxyl groups in the quaternized copolyester shell to achieve chemical bonding between the inorganic core and the organic shell, avoid filler agglomeration and improve interfacial bonding strength, and ensure that the fiber still has good mechanical properties and spinnability under high filler content. The quaternized copolyester shell design balances antibacterial function and matrix compatibility. The quaternary ammonium groups introduced by bis-2-hydroxyethyldimethylammonium chloride have highly efficient and broad-spectrum antibacterial activity. The sulfonic acid groups of 5-sulfoisophthalic acid monosodium salt form a charge balance with the quaternary ammonium groups, improving the water dispersibility and processing stability of the copolyester. At the same time, the quaternized copolyester and polyethylene terephthalate have the same polyester backbone structure, which can achieve partial interpenetration and entanglement of molecular chain segments during melt blending. The antibacterial quaternary ammonium groups are uniformly dispersed inside the fiber rather than just existing on the surface. After repeated washing, the antibacterial performance is highly retained, achieving synergistic optimization of thermal conductivity and antibacterial performance.

[0028] This invention also discloses a method for preparing a cooling antibacterial polyester fabric, comprising the following steps:

[0029] S1. Preparation of thermally conductive and antibacterial core-shell masterbatch;

[0030] S2. Melt blending and granulation: The polyester matrix chips and the thermally conductive antibacterial core-shell masterbatch are mixed at a mass ratio of 70 to 95 to 5 to 30 and then fed into a twin-screw extruder. The mixture is melt-blended at a temperature of 250°C to 285°C. The residence time of the material in the barrel is 2 to 8 minutes. The material is then devolatilized under a vacuum of no more than 500 Pa. The modified polyester chips are obtained by water-cooled stringing or underwater pelletizing.

[0031] S3. Melt spinning: The modified polyester chips are dried and fed into a melt spinning unit, where they are melted at a melt temperature of 265°C to 285°C, extruded and wound through a spinning assembly to obtain nascent polyester fibers.

[0032] S4. Stretching and heat setting: The nascent polyester fibers are stretched in 2 to 3 passes with a total stretch ratio of 3.0 to 4.5, and then heat-set at a temperature of 160°C to 190°C for 20 to 120 seconds to obtain polyester filaments or polyester staple fibers with a breaking strength of not less than 3.5 cN / dtex. The zinc oxide submicron rod-shaped inorganic cores are preferentially oriented along the axial direction of the polyester fibers to improve the longitudinal thermal conductivity of the polyester fibers and enhance the cooling effect.

[0033] S5. Weaving and Finishing: The polyester filament or polyester staple fiber obtained in step S4 is woven or knitted to form an areal density of 120. Up to 200 The greige fabric is softened by a softening agent that contains no free quaternary ammonium salt or whose free quaternary ammonium salt content does not exceed 1 wt% of the greige fabric mass, and then baked at a temperature of 150°C to 180°C for 20 to 90 seconds to obtain a cool-feeling antibacterial polyester fabric.

[0034] Furthermore, the length-to-diameter ratio of the twin-screw extruder in step S2 is 32 to 44, and the screw speed is 150 r / min to 350 r / min;

[0035] In step S2, the thermally conductive and antibacterial core-shell masterbatch is added to the twin-screw extruder via a side-feed method, allowing the thermally conductive and antibacterial core-shell masterbatch to be melted and dispersed in the latter half of the barrel, thereby reducing the shear degradation of the quaternized copolyester shell layer, and the average spacing between adjacent thermally conductive and antibacterial core-shell masterbatches in the cross-section of the resulting polyester fiber is less than 3 μm.

[0036] Furthermore, in step S3, the winding speed of melt spinning is 2500 m / min to 4500 m / min.

[0037] Furthermore, by adjusting the amount of the thermally conductive antibacterial core-shell masterbatch and the stretching process parameters, the polyester fibers contained in the obtained cooling antibacterial polyester fabric, while maintaining a breaking strength of not less than 3.5 cN / dtex, have a cooling coefficient qmax at the moment of contact that is at least 20% higher than that of the comparative sample without the addition of the thermally conductive antibacterial core-shell masterbatch. Moreover, after 50 home machine washes, the antibacterial rate against Staphylococcus aureus, Escherichia coli, and Candida albicans remains at 85% or more of their respective initial values.

[0038] Furthermore, after step S2, the modified polyester chips are subjected to extraction or vacuum devolatilization treatment to ensure that the residual amount of bis-2-hydroxyethyldimethylammonium chloride in the modified polyester chips is not higher than 500 ppm, and the migration amount of antimony trioxide in the modified polyester chips meets the limit requirements for antimony in the textile safety standards.

[0039] Furthermore, the polyester fiber is a single-component circular cross-section fiber or an irregularly shaped cross-section fiber with 3 to 8 grooves, wherein the depth-to-width ratio of the grooves is 1.0 to 3.0, and the polyester fiber satisfies the following:

[0040] The linear density ranges from 0.8 dtex to 3.3 dtex;

[0041] The fracture strength is not less than 3.5 cN / dtex;

[0042] The elongation at break is 20% to 40%;

[0043] The shrinkage rate of boiling water should not exceed 8%.

[0044] Furthermore, the cooling antibacterial polyester fabric is a warp-knitted or weft-knitted fabric with an areal density of 120. Up to 200 The shrinkage rate in both the longitudinal and latitudinal directions does not exceed 3%.

[0045] Furthermore, the average value of the cooling coefficient qmax of the aforementioned cool-feeling antibacterial polyester fabric at the instant of contact under a temperature of 23°C is not less than 0.21. After 50 home machine washes, the antibacterial rate against Staphylococcus aureus is 99.0% to 99.9%, and the antibacterial rates against Escherichia coli and Candida albicans are 90.0% to 98.0%, respectively.

[0046] Furthermore, the use of cooling antibacterial polyester fabric in the preparation of textiles possessing both cooling contact properties and wash-resistant antibacterial properties, wherein the textiles are at least one of intimate apparel, bedding, and cushion covers, and wherein the textiles, after undergoing no less than 50 household machine washes during their normal service life, still maintain an instantaneous cooling coefficient qmax of not less than 0.20. Furthermore, its inhibition rate against Staphylococcus aureus is not less than 99.0%.

[0047] Furthermore, the intimate apparel includes at least one of T-shirts, vests, underwear, sportswear, and pajamas, which, in actual wearing conditions, can instantly reduce the skin surface contact temperature by 0.5°C to 2.0°C compared to ordinary polyester fabric of the same weight.

[0048] Furthermore, the bedding is at least one of a summer quilt, a bed sheet, and a pillowcase, and the areal density of the bedding is 130. Up to 180 When used at room temperature of 30°C, compared to ordinary polyester bedding, the user's subjective heat perception score is reduced by 1 to 2 levels.

[0049] As another aspect of this invention, a process route of melt blending-melt spinning-drawing and orientation-weaving finishing is designed to enhance the axial orientation of the one-dimensional thermally conductive phase and the stable retention of antibacterial functional components during polyester fiber processing. In the melt blending stage, a twin-screw extruder is used to side-feed thermally conductive antibacterial core-shell masterbatch, allowing the masterbatch to melt and disperse in the latter half of the barrel. This shortens the residence time of the quaternized copolyester shell in a high-temperature, high-shear environment, reducing the risk of thermal degradation of quaternary ammonium groups and polyester segments. Simultaneously, vacuum devolatilization removes residual monomers and small molecules, ensuring product safety. In the melt spinning stage, the melt flow field applies shear orientation to the one-dimensional rod-shaped zinc oxide particles. In the drawing stage, the tensile stress from multiple draw stages further strengthens the orientation of the rod-shaped particles along the fiber axis, forming an efficient longitudinal thermally conductive pathway. The spacing between adjacent thermally conductive antibacterial core-shell masterbatches is controlled within 3 micrometers to ensure the continuity of the thermally conductive network. The heat setting process fixes the fiber structure and the orientation state of the rod-shaped particles, stabilizing the cooling properties. During the weaving and finishing stage, softening agents containing no or low levels of free quaternary ammonium salts are selected to avoid introducing additional antibacterial agents that could interfere with the evaluation of the fabric's antibacterial effect. At the same time, it prevents the migration of free quaternary ammonium salts to the skin and the resulting safety hazards. The baking process fixes the softening agent onto the fiber surface, improving the fabric's softness and wearing comfort without affecting the fabric's antibacterial function. This process ensures and optimizes the material's dual functions of thermal conductivity and antibacterial properties.

[0050] The zinc oxide submicron rod-shaped inorganic core primarily enhances the longitudinal thermal conductivity of the fiber, achieving an instant cooling sensation upon contact. Its one-dimensional rod-like morphology preferentially aligns along the fiber axis during spinning and drawing, forming a directional heat-conducting pathway. Compared to the isotropic distribution of spherical particles, the axial orientation of the rod-shaped structure allows for rapid heat transfer along the fiber length, significantly increasing the longitudinal thermal conductivity. Upon skin contact, heat is rapidly absorbed and conducted to the external environment, producing a noticeable cooling sensation. The quaternized copolyester shell primarily provides wash-resistant antibacterial properties and improves the interfacial compatibility between the inorganic core and the polyester matrix. The quaternary ammonium groups introduced by bis-2-hydroxyethyldimethylammonium chloride exhibit highly efficient and broad-spectrum antibacterial activity against Gram-positive and Gram-negative bacteria such as Staphylococcus aureus and Escherichia coli, as well as fungi such as Candida albicans, through electrostatic adsorption and membrane disruption mechanisms. The quaternary ammonium groups are fixed to the polyester molecular chain through chemical bonds rather than physical attachment, resulting in low loss rate and good antibacterial durability after repeated washing. The synergistic effect of the two components is reflected in the silane coupling layer acting as an interfacial bridge, which firmly connects the inorganic core of zinc oxide and the organic shell of quaternized copolyester through Si-O-Zn chemical bonds. This solves the problems of easy agglomeration of inorganic fillers and poor interfacial compatibility, allowing the high-filling-content zinc oxide rods to be uniformly dispersed in the polyester matrix and maintain good interfacial bonding. At the same time, the quaternized copolyester and polyethylene terephthalate have the same polyester backbone. During melt blending, the interpenetrating entanglement of molecular chain segments improves the processing fluidity and fiber mechanical properties of the composite material system, achieving a synergistic improvement in thermal conductivity and antibacterial properties, as well as a balanced optimization of high functionality and processability and spinnability.

[0051] Beneficial technical effects:

[0052] 1. Significantly Enhanced Instantaneous Cooling Performance: Through the one-dimensional rod-shaped morphology design of the submicron rod-shaped inorganic core of zinc oxide in the thermally conductive antibacterial core-shell masterbatch, combined with the shear and stretch flow field induction during melt spinning and drawing processes, the rod-shaped zinc oxide particles preferentially align along the polyester fiber axis, forming a directional heat conduction pathway. Compared to the isotropic distribution of spherical particles, the axial orientation of the one-dimensional rod structure significantly increases the longitudinal thermal conductivity of the fiber. Upon skin contact, it can quickly absorb heat from the body surface and conduct it to the external environment along the fiber axis, producing a noticeable cooling sensation. The cooling antibacterial polyester fabric prepared by this invention has an average instantaneous cooling coefficient qmax of no less than 0.21 at a temperature of 23℃. Compared to ordinary polyester fabrics without added thermally conductive and antibacterial core-shell masterbatch, it improves thermal conductivity by more than 20%. In actual wearing conditions, it can instantly reduce the skin surface temperature by 0.5℃ to 2.0℃, effectively improving the stuffy and uncomfortable feeling in summer or during exercise.

[0053] 2. Achieving durable and washable antibacterial properties: Through the design of the quaternized copolyester shell, the quaternary ammonium groups introduced by bis-2-hydroxyethyldimethylammonium chloride are fixed in the polyester molecular chain through chemical bonds. The quaternary ammonium groups are uniformly dispersed inside the fiber to form a three-dimensional antibacterial network rather than just existing on the fiber surface. The antibacterial function is not easily lost with washing. At the same time, the quaternized copolyester and polyethylene terephthalate have the same polyester backbone. During the melt blending process, the molecular chain segments interpenetrate and entangle, further enhancing the anchoring stability of the quaternary ammonium groups inside the fiber. After 50 home machine washes, the cool-feeling antibacterial polyester fabric prepared by this invention maintains an antibacterial rate of 99.0% to 99.9% against Staphylococcus aureus, and an antibacterial rate of 90.0% to 98.0% against Escherichia coli and Candida albicans, respectively. The antibacterial performance retention rate is 85% or more of their respective initial values, meeting the long-term antibacterial requirements within the actual service life, effectively inhibiting the growth of microorganisms and the generation of odors, and ensuring the hygiene and safety of the wearer.

[0054] 3. Maintaining excellent mechanical properties and spinnability: Through the introduction of a silane coupling layer, γ-glycidyl etheroxypropyltrimethoxysilane hydrolyzes and condenses on the surface of zinc oxide submicron rods to form Si-O-Zn chemical bonds. Simultaneously, the epoxy groups undergo a ring-opening reaction with the quaternized copolyester shell, achieving chemical bonding between the inorganic core and the organic shell. This solves the problems of easy agglomeration and poor interfacial compatibility with the polyester matrix in traditional inorganic fillers. Even when the amount of thermally conductive and antibacterial core-shell masterbatch added reaches 5wt% to 30wt% of the total polyester fiber mass, and the inorganic core mass fraction of zinc oxide accounts for 2% of the total masterbatch mass, this property remains effective. Under high filling conditions of 0wt% to 60wt%, the inorganic core can still be uniformly dispersed and firmly bonded to the polyester matrix interface. The average spacing between adjacent thermally conductive and antibacterial core-shell masterbatches is less than 3 micrometers. The polyester fiber obtained by this invention has a breaking strength of not less than 3.5 cN / dtex, a breaking elongation of 20% to 40%, and a boiling water shrinkage of not more than 8%. While maintaining high thermal conductivity and antibacterial function, it also has good mechanical properties. Moreover, the melt spinning winding speed can reach 2500 m / min to 4500 m / min, which meets the processing and spinnability requirements of industrial high-speed spinning.

[0055] 5. Balancing Functionality and Safety: By using a twin-screw extruder side-feed process to shorten the residence time of the quaternized copolyester shell in a high-temperature, high-shear environment, the risk of thermal degradation of quaternary ammonium groups and polyester segments is reduced. Combined with vacuum devolatilization and extraction or reduced-pressure devolatilization treatments, the residual amount of bis-2-hydroxyethyldimethylammonium chloride in the modified polyester chips is controlled to no more than 500 ppm. The migration amount of antimony trioxide catalyst meets the limit requirements for antimony in textile safety standards. At the same time, in the finishing stage after weaving, softening agents that do not contain free quaternary ammonium salts or whose free quaternary ammonium salt content does not exceed 1 wt% of the fabric weight are selected to avoid the introduction of additional migratable antibacterial agents or catalysts, ensuring the safety of the fabric during skin contact. While achieving efficient thermal conductivity and cooling sensation and long-lasting antibacterial function, the product meets the safety standards for textiles in skin contact, achieving a balance between functionality and safety.

[0056] 6. Expanding Application Areas and Enhancing Use Value: The cooling and antibacterial polyester fabric produced by this invention possesses both instant cooling sensation upon contact and durable antibacterial properties after washing. It can be widely used in textiles such as underwear (e.g., T-shirts, vests, underwear, sportswear, and pajamas), bedding (e.g., summer blankets, sheets, and pillowcases), and cushion covers. In hot and humid summers or during sweaty exercise, it can provide users with a significant cooling sensation and hygiene protection. Compared to ordinary polyester fabrics, it significantly improves wearing comfort and user experience. Compared to traditional finished cooling or antibacterial fabrics, it has the advantage of functional durability. Compared to functional natural fiber fabrics (e.g., bamboo fiber, modal), it has superior dimensional stability, mechanical properties, and cost advantages. This promotes the upgrading of polyester fiber from a traditional bulk textile material to a high-value-added functional textile material, with good market application prospects and economic and social benefits. Attached Figure Description

[0057] Figure 1 This invention investigates the effect of the content of thermally conductive and antibacterial core-shell masterbatch on the instantaneous cooling coefficient and the antibacterial rate against Staphylococcus aureus.

[0058] Figure 2 This invention investigates the effect of the proportion of zinc oxide submicron rod-shaped inorganic cores in the masterbatch on the instantaneous cooling coefficient and fiber breaking strength.

[0059] Figure 3 This invention relates to the influence of the long axis dimension L50 of the zinc oxide submicron rod on the instantaneous cooling coefficient and fiber breaking strength.

[0060] Figure 4 This invention investigates the effect of the quaternary ammonium nitrogen content in the masterbatch on the antibacterial rate of Staphylococcus aureus and the antibacterial retention rate after 50 machine washes.

[0061] Figure 5 Zn Comparison of high-resolution X-ray photoelectron spectra.

[0062] Figure 6 High-resolution X-ray photoelectron spectroscopy of N 1s and peak separation diagram of quaternary ammonium nitrogen and amide nitrogen.

[0063] Figure 7 These are XPS depth profile curves for Example 1 and Comparative Example 11 in this invention.

[0064] Figure 8 This is an XPS depth profile curve and statistical results showing the N / S ratio as a function of depth in this invention.

[0065] Figure 9 The image shows the XRD phase diagram of the zinc oxide submicron rod prepared in Example 1 of this invention.

[0066] Figure 10 This is a morphology diagram of the zinc oxide submicron rod prepared in Example 1 of the present invention.

[0067] Figure 11 This is a morphology diagram of the polyester fiber prepared in Example 1 of the present invention. Detailed Implementation

[0068] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings.

[0069] Example 1: A cooling and antibacterial polyester fabric. The fabric in this example is woven from polyester fibers.

[0070] The polyester fiber in this embodiment includes:

[0071] The polyester matrix in this embodiment comprises an aromatic polyester mainly composed of polyethylene terephthalate. The mass fraction of the polyester matrix in the polyester fibers of this embodiment is 82.5 wt% of the total mass of the polyester fibers of this embodiment.

[0072] A thermally conductive and antibacterial core-shell masterbatch, wherein the mass fraction of the thermally conductive and antibacterial core-shell masterbatch in the polyester fiber is 17.5 wt% of the total mass of the polyester fiber, the thermally conductive and antibacterial core-shell masterbatch comprises a zinc oxide submicron rod-shaped inorganic core and an organic shell layer coating the surface of the zinc oxide submicron rod-shaped inorganic core, wherein:

[0073] The zinc oxide submicron rod-shaped inorganic core of this embodiment has a one-dimensional rod-shaped morphology and is at least partially aligned along the axial direction of the polyester fiber during the forming and stretching process of this embodiment, so as to improve the longitudinal thermal conductivity of the polyester fiber and enhance the instantaneous cooling sensation upon contact.

[0074] The organic shell layer of this embodiment includes a silane coupling layer and a quaternized copolyester shell layer. The silane coupling layer of this embodiment is formed by the hydrolytic condensation of γ-glycidoxypropyltrimethoxysilane and is connected to the zinc oxide submicron rod-shaped inorganic core of this embodiment through Si-O-Zn bonds. The quaternized copolyester shell layer of this embodiment covers the outside of the silane coupling layer of this embodiment. The quaternized copolyester shell layer of this embodiment is obtained by the esterification condensation of terephthalic acid, ethylene glycol, monosodium 5-sulfoisophthalate, and bis-2-hydroxyethyldimethylammonium chloride.

[0075] In this embodiment, the mass fraction of the zinc oxide submicron rod-shaped inorganic core in the thermally conductive and antibacterial core-shell masterbatch is 40 wt% of the total mass of the thermally conductive and antibacterial core-shell masterbatch, and the mass fraction of quaternary ammonium nitrogen in the quaternized copolyester shell is 1.15 wt% of the total mass of the thermally conductive and antibacterial core-shell masterbatch.

[0076] The thermally conductive and antibacterial core-shell masterbatch of this embodiment is prepared through the following steps:

[0077] A1. Preparation of silanized zinc oxide submicron rod powder: Zinc oxide submicron rod powder with a submicron rod morphology and an average size L50 of 1.0 μm along the long axis was dispersed in a water-alcohol mixed solvent. γ-glycidyl etheroxypropyltrimethoxysilane was added, and the reaction was carried out at pH 4.5 and temperature 70℃ for 2.0 h. After washing and drying, silanized zinc oxide submicron rod powder with epoxy functional groups on the surface was obtained.

[0078] A2. Preparation of quaternized copolyester prepolymer chips: Terephthalic acid, sodium 5-sulfoisophthalate, ethylene glycol, and bis-2-hydroxyethyldimethylammonium chloride were added to an esterification reactor and esterified at 220°C. After esterification, antimony trioxide catalyst was added, and polycondensation was carried out at 270°C and a vacuum of 200 Pa to obtain quaternized copolyester prepolymer chips. In this embodiment, the molar fraction of sodium 5-sulfoisophthalate relative to the total molar amount of dicarboxylic acid was 3.0 mol%, the molar fraction of bis-2-hydroxyethyldimethylammonium chloride relative to the total molar amount of diol was 2.0 mol%, and the molar ratio of quaternary ammonium nitrogen to sulfonic acid groups on the aromatic ring in the shell of the quaternized copolyester was 1.0:1.

[0079] A3. Preparation of thermally conductive and antibacterial core-shell masterbatch: The silanized zinc oxide submicron rod powder of this embodiment and the quaternized copolyester prepolymer chips of this embodiment are melt-blended at a mass ratio of 40:60 at a temperature of 265°C. After water cooling and pelletizing, a thermally conductive and antibacterial core-shell masterbatch with a median volume diameter (D50) of 140 μm is obtained.

[0080] The zinc oxide submicron rod powder in this embodiment is prepared by the following steps:

[0081] B1. Preparation of submicron rod-shaped zinc oxide precursor: A zinc nitrate solution containing zinc inorganic salts was mixed with a sodium hydroxide solution, and sodium citrate, a morphology control agent, was added. The mixture was reacted at 170°C for 12 hours under hydrothermal conditions. After cooling, the resulting slurry was subjected to solid-liquid separation and washed six times with deionized water until the conductivity of the filtrate was 30 μS / cm and the pH was 7.0. The filtrate was then dried at 100°C for 6 hours to obtain the submicron rod-shaped zinc oxide precursor. In this embodiment, the zinc inorganic salt solution contained Zn... 2+ The concentration is 0.45 mol / L. In this example, the OH- alkali source contains... - Compared with the zinc-containing inorganic salt solution of this embodiment, Zn 2+ The molar ratio is 3.5 to 1. The amount of morphology control agent used in this embodiment is 6 wt%, calculated as the ratio of the mass of the morphology control agent in this embodiment to the theoretical mass of the zinc-containing inorganic salt in this embodiment, based on zinc oxide.

[0082] B2. Preparation of zinc oxide submicron rod powder by calcination: The submicron rod-shaped zinc oxide precursor of this embodiment was calcined in air at a temperature of 525°C for 2.5 h to obtain zinc oxide submicron rod powder.

[0083] In this embodiment, the average size L50 of the zinc oxide submicron rod-shaped inorganic core is 1.0 μm in the long axis direction, the average diameter D50 in the short axis direction is 275 nm, and the aspect ratio is 3.6; the median particle size D50 of the thermally conductive antibacterial core-shell masterbatch in this embodiment is 140 μm; and the thickness of the quaternized copolyester shell layer in this embodiment is 17 nm.

[0084] In addition to polyethylene terephthalate, the polyester matrix of this embodiment also contains 15 wt% of polybutylene terephthalate, and the total content of the polyester matrix in the polyester fiber of this embodiment is 82.5 wt% of the total mass of the polyester fiber of this embodiment.

[0085] When preparing the polyester fiber of this embodiment, the mass ratio of the polyester matrix chips of this embodiment to the thermally conductive and antibacterial core-shell masterbatch of this embodiment before melt blending is 82.5 to 17.5, and the total mass fraction of zinc oxide in the polyester fiber of this embodiment is 7.0 wt% of the total mass of the polyester fiber of this embodiment.

[0086] The preparation method of the cooling antibacterial polyester fabric in this embodiment includes the following steps:

[0087] S1. Preparation of thermally conductive and antibacterial core-shell masterbatch

[0088] S2. Melt Blending and Granulation: The polyester matrix chips of this embodiment and the thermally conductive antibacterial core-shell masterbatch of this embodiment are mixed at a mass ratio of 82.5:17.5 and then fed into a twin-screw extruder. Melt blending is performed at a temperature of 267°C, with a residence time of 5 minutes in the barrel. Deviation treatment is then carried out under a vacuum of 300 Pa. Modified polyester chips are obtained by water-cooling, drawing, and granulation. The twin-screw extruder of this embodiment has an aspect ratio of 38 and a screw speed of 250 r / min. The thermally conductive antibacterial core-shell masterbatch of this embodiment is added to the twin-screw extruder via side feeding. In this embodiment, the thermally conductive and antibacterial core-shell masterbatch is melted and dispersed in the latter half of the barrel, thereby reducing the shear degradation of the quaternized copolyester shell layer. The average spacing between adjacent thermally conductive and antibacterial core-shell masterbatches in the resulting polyester fiber cross-section is 2.1 μm. After step S2, the modified polyester chips are extracted to reduce the residual amount of bis-2-hydroxyethyldimethylammonium chloride in the modified polyester chips to 300 ppm. Furthermore, the migration amount of antimony trioxide in the modified polyester chips meets the limits for antimony in textile safety standards.

[0089] S3. Melt spinning: The modified polyester chips of this embodiment are dried and fed into a melt spinning unit, where they are melted at a melt temperature of 275°C, extruded and wound through a spinning assembly to obtain nascent polyester fibers. The winding speed of melt spinning is 3500 m / min.

[0090] S4. Stretching and Heat Setting: The nascent polyester fiber of this embodiment is stretched twice, with a total stretch ratio of 3.75, and heat-set at 175°C for 60 seconds to obtain a polyester filament with a breaking strength of 4.2 cN / dtex. The zinc oxide submicron rod-shaped inorganic core of this embodiment is preferentially aligned along the axial direction of the polyester fiber to improve the longitudinal thermal conductivity of the polyester fiber and enhance the cooling effect.

[0091] S5. Weaving and Finishing: The polyester filament obtained in step S4 of this embodiment is woven to form an areal density of 160. The greige fabric is softened using a softening agent that does not contain free quaternary ammonium salts, and then baked at 165℃ for 55 seconds to obtain a cool-feeling antibacterial polyester fabric.

[0092] The polyester fiber in this embodiment is a single-component circular cross-section fiber. The polyester fiber in this embodiment meets the following requirements: linear density of 2.0 dtex, breaking strength of 4.2 cN / dtex, breaking elongation of 30%, and boiling water shrinkage of 4.5%.

[0093] The cooling antibacterial polyester fabric in this embodiment is a warp-knitted fabric with a surface density of 160. The shrinkage rate is 1.8% in both the longitudinal and latitudinal directions.

[0094] In this embodiment, the average value of the cooling coefficient qmax of the cooling antibacterial polyester fabric at the instant of contact under a temperature of 23°C is 0.25. After 50 home machine washes, the antibacterial rate against Staphylococcus aureus was 99.5%, against Escherichia coli was 94.0%, and against Candida albicans was 93.5%.

[0095] By adjusting the amount of thermally conductive antibacterial core-shell masterbatch and the stretching process parameters in this embodiment, the polyester fibers contained in the obtained cooling antibacterial polyester fabric of this embodiment, while maintaining a breaking strength of 4.2 cN / dtex, have a cooling coefficient qmax that is 23% higher than that of the comparative sample without the addition of the thermally conductive antibacterial core-shell masterbatch of this embodiment. Furthermore, after 50 home machine washes, the antibacterial rate against Staphylococcus aureus, Escherichia coli, and Candida albicans remains at 88% of their respective initial values.

[0096] This embodiment describes the application of a cooling antibacterial polyester fabric in the preparation of textiles that possess both cooling contact properties and wash-resistant antibacterial properties. The textile in this embodiment is a T-shirt worn close to the skin. After 50 home machine washes within its normal service life, the textile still maintains a cooling coefficient (qmax) of 0.23 upon contact. Furthermore, the antibacterial rate against Staphylococcus aureus is 99.5%. In actual wearing conditions, the close-fitting garment of this embodiment can instantly reduce the skin surface temperature by 1.2°C compared to ordinary polyester fabric of the same weight.

[0097] Features of Example 1: This example employs a balanced and stable moderate parameter configuration. The polyester matrix content is 82.5 wt%, the thermally conductive and antibacterial core-shell masterbatch content is 17.5 wt%, the zinc oxide inorganic core accounts for 40 wt% of the masterbatch, and the quaternary ammonium nitrogen content is 1.15 wt%. All parameters are within the moderate range. The process conditions are mild and stable: silanization temperature 70℃, esterification temperature 220℃, polycondensation temperature 270℃, and melt blending temperature 267℃, all moderate process parameters, ensuring the stability and reproducibility of the production process. The fiber properties are comprehensively balanced, with a breaking strength of 4.2 cN / dtex and a cooling coefficient upon contact of 0.25. It exhibits a 99.5% inhibition rate against Staphylococcus aureus, combining both cooling and antibacterial properties. This embodiment is suitable for large-scale production scenarios with high requirements for production stability, and is particularly suitable for everyday wear such as T-shirts and sportswear, providing a comfortable cooling experience and reliable antibacterial protection. It performs excellently in daily activities and light exercise during hot seasons.

[0098] Example 2: A cooling and antibacterial polyester fabric. The fabric in this example is knitted from polyester fibers, which include:

[0099] The polyester matrix in this embodiment comprises an aromatic polyester mainly composed of polyethylene terephthalate. The mass fraction of the polyester matrix in this embodiment is 78 wt% of the total mass of the polyester fibers in this embodiment.

[0100] A thermally conductive and antibacterial core-shell masterbatch, wherein the mass fraction of the thermally conductive and antibacterial core-shell masterbatch in the polyester fiber is 22 wt% of the total mass of the polyester fiber, the thermally conductive and antibacterial core-shell masterbatch comprises a zinc oxide submicron rod-shaped inorganic core and an organic shell layer coating the surface of the zinc oxide submicron rod-shaped inorganic core, wherein:

[0101] The zinc oxide submicron rod-shaped inorganic core of this embodiment has a one-dimensional rod-shaped morphology and is at least partially aligned along the axial direction of the polyester fiber during the forming and stretching process of this embodiment, so as to improve the longitudinal thermal conductivity of the polyester fiber and enhance the instantaneous cooling sensation upon contact.

[0102] The organic shell of this embodiment includes a silane coupling layer and a quaternized copolyester shell. The silane coupling layer of this embodiment is formed by the hydrolytic condensation of γ-glycidoxypropyltrimethoxysilane and is connected to the zinc oxide submicron rod-shaped inorganic core of this embodiment through Si-O-Zn bonds. The quaternized copolyester shell of this embodiment covers the outside of the silane coupling layer of this embodiment. The quaternized copolyester shell of this embodiment is obtained by the esterification condensation of dimethyl terephthalate, ethylene glycol, monosodium 5-sulfoisophthalate, and bis-2-hydroxyethyldimethylammonium chloride.

[0103] In this embodiment, the mass fraction of the zinc oxide submicron rod-shaped inorganic core in the thermally conductive and antibacterial core-shell masterbatch is 52 wt% of the total mass of the thermally conductive and antibacterial core-shell masterbatch, and the mass fraction of quaternary ammonium nitrogen in the quaternized copolyester shell is 0.6 wt% of the total mass of the thermally conductive and antibacterial core-shell masterbatch.

[0104] The thermally conductive and antibacterial core-shell masterbatch of this embodiment is prepared through the following steps:

[0105] A1. Preparation of silanized zinc oxide submicron rod powder: Zinc oxide submicron rod powder with a submicron rod morphology and an average size L50 of 1.6 μm along the long axis was dispersed in a water-alcohol mixed solvent. γ-glycidoxypropyltrimethoxysilane was added, and the reaction was carried out at pH 4.3 and temperature 75 °C for 1.5 h. After washing and drying, silanized zinc oxide submicron rod powder with epoxy functional groups on the surface was obtained.

[0106] A2. Preparation of quaternized copolyester prepolymer chips: Dimethyl terephthalate, sodium 5-sulfoisophthalate, ethylene glycol, and bis-2-hydroxyethyldimethylammonium chloride were added to an esterification reactor and subjected to esterification at 210°C. After esterification, antimony trioxide catalyst was added, and polycondensation was carried out at 275°C and a vacuum of 150 Pa to obtain quaternized copolyester prepolymer chips. In this embodiment, the molar fraction of sodium 5-sulfoisophthalate relative to the total molar amount of dicarboxylic acid was 1.8 mol%, the molar fraction of bis-2-hydroxyethyldimethylammonium chloride relative to the total molar amount of diol was 1.2 mol%, and the molar ratio of quaternary ammonium nitrogen to sulfonic acid groups on the aromatic ring in the quaternized copolyester shell was 1.2:1.

[0107] A3. Preparation of thermally conductive and antibacterial core-shell masterbatch: The silanized zinc oxide submicron rod powder of this embodiment and the quaternized copolyester prepolymer chips of this embodiment are melt-blended at a mass ratio of 52:48 at a temperature of 272°C. After underwater pelletizing, a thermally conductive and antibacterial core-shell masterbatch with a median volume diameter (D50) of 165 μm is obtained.

[0108] The zinc oxide submicron rod powder in this embodiment is prepared by the following steps:

[0109] B1. Preparation of submicron rod-shaped zinc oxide precursor: A zinc acetate solution containing zinc inorganic salts was mixed with a potassium hydroxide solution, and a combination of polyethylene glycol and sodium citrate (mass ratio 1:1) was added as morphology control agents. The mixture was reacted at 195°C for 8 hours under hydrothermal conditions. After cooling, the resulting slurry was subjected to solid-liquid separation and washed five times with deionized water until the conductivity of the filtrate was 25 μS / cm and the pH was 6.8. The filtrate was then dried at 110°C for 4 hours to obtain the submicron rod-shaped zinc oxide precursor. In this embodiment, the zinc inorganic salt solution contained Zn... 2+ The concentration is 0.62 mol / L. In this example, the OH- alkali source contains... - Compared with the zinc-containing inorganic salt solution of this embodiment, Zn 2+ The molar ratio is 2.8 to 1. The amount of morphology control agent used in this embodiment is 8 wt%, calculated as the ratio of the mass of the morphology control agent in this embodiment to the theoretical mass of the zinc-containing inorganic salt in this embodiment, based on zinc oxide.

[0110] B2. Preparation of zinc oxide submicron rod powder by calcination: The submicron rod-shaped zinc oxide precursor of this embodiment was calcined in an air atmosphere at a temperature of 580°C for 1.8 h to obtain zinc oxide submicron rod powder.

[0111] In this embodiment, the average size L50 of the zinc oxide submicron rod-shaped inorganic core is 1.6 μm in the long axis direction, the average diameter D50 in the short axis direction is 120 nm, and the aspect ratio is 13.3; the volume median diameter D50 of the thermally conductive antibacterial core-shell masterbatch in this embodiment is 165 μm; and the thickness of the quaternized copolyester shell layer in this embodiment is 10 nm.

[0112] In addition to polyethylene terephthalate, the polyester matrix of this embodiment also contains 8 wt% of polytrimethylene terephthalate by weight of the total polyester matrix of this embodiment. The total content of the polyester matrix in the polyester fiber of this embodiment is 78 wt% of the total polyester fiber of this embodiment.

[0113] When preparing the polyester fiber of this embodiment, the mass ratio of the polyester matrix chips of this embodiment to the thermally conductive and antibacterial core-shell masterbatch of this embodiment before melt blending is 78 to 22, and the total mass fraction of zinc oxide in the polyester fiber of this embodiment is 11.44 wt% of the total mass of the polyester fiber of this embodiment.

[0114] The preparation method of the cooling antibacterial polyester fabric in this embodiment includes the following steps:

[0115] S1. Preparation of thermally conductive and antibacterial core-shell masterbatch;

[0116] S2. Melt Blending and Granulation: The polyester matrix chips of this embodiment and the thermally conductive antibacterial core-shell masterbatch of this embodiment are mixed at a mass ratio of 78:22 and then fed into a twin-screw extruder. Melt blending is performed at a temperature of 278°C, with a residence time of 3.5 min in the barrel. Deviation treatment is then carried out under a vacuum of 220 Pa. After water cooling and pelletizing, modified polyester chips are obtained. The twin-screw extruder of this embodiment has a length-to-diameter ratio of 40 and a screw speed of 310 r / min. The thermally conductive antibacterial core-shell masterbatch of this embodiment is added to the twin-screw extruder via side feeding. In this embodiment, the thermally conductive and antibacterial core-shell masterbatch is melted and dispersed in the latter half of the barrel, thereby reducing the shear degradation of the quaternized copolyester shell layer. The average spacing between adjacent thermally conductive and antibacterial core-shell masterbatches in the cross-section of the resulting polyester fiber is 1.8 μm. After step S2, the modified polyester chips are subjected to vacuum devolatilization treatment, resulting in a residual amount of bis-2-hydroxyethyldimethylammonium chloride in the modified polyester chips of this embodiment of 180 ppm. Furthermore, the migration amount of antimony trioxide in the modified polyester chips of this embodiment meets the limit requirements for antimony in the textile safety standards.

[0117] S3. Melt spinning: The modified polyester chips of this embodiment are dried and fed into a melt spinning unit, where they are melted at a melt temperature of 280°C, extruded and wound through a spinning assembly to obtain nascent polyester fibers. The winding speed of melt spinning is 4000 m / min.

[0118] S4. Stretching and Heat Setting: The nascent polyester fibers of this embodiment are subjected to three stretching processes with a total stretch ratio of 4.2. They are then heat-set at 182°C for 40 seconds to obtain polyester staple fibers with a breaking strength of 3.9 cN / dtex. The zinc oxide submicron rod-shaped inorganic cores of this embodiment are preferentially aligned along the axial direction of the polyester fibers to improve the longitudinal thermal conductivity of the polyester fibers and enhance the cooling effect.

[0119] S5. Weaving and Finishing: The polyester staple fiber obtained in step S4 of this embodiment is knitted to form an areal density of 145. The greige fabric is softened by a softening agent with a free quaternary ammonium salt content of 0.5 wt% of the greige fabric mass, and then baked at 172℃ for 35 seconds to obtain a cool-feeling antibacterial polyester fabric.

[0120] The polyester fiber in this embodiment is an irregular cross-section fiber with 5 grooves. The depth-to-width ratio of the grooves in this embodiment is 1.8. The polyester fiber in this embodiment meets the following requirements: linear density of 1.5 dtex, tensile strength of 3.9 cN / dtex, elongation at break of 25%, and boiling water shrinkage of 5.2%.

[0121] The cooling antibacterial polyester fabric in this embodiment is a weft-knitted fabric with a surface density of 145. The shrinkage rate is 2.2% in both the longitudinal and latitudinal directions.

[0122] In this embodiment, the average value of the cooling coefficient qmax of the cooling antibacterial polyester fabric at the instant of contact under a temperature of 23°C is 0.29. After 50 home machine washes, the inhibition rate against Staphylococcus aureus was 99.3%, against Escherichia coli was 91.5%, and against Candida albicans was 90.8%.

[0123] By adjusting the amount of thermally conductive antibacterial core-shell masterbatch and the stretching process parameters in this embodiment, the polyester fibers contained in the resulting cooling antibacterial polyester fabric, while maintaining a breaking strength of 3.9 cN / dtex, exhibit a 31% higher instantaneous cooling coefficient (qmax) compared to the control sample without the addition of the thermally conductive antibacterial core-shell masterbatch. Furthermore, after 50 home machine washes, the antibacterial rates against Staphylococcus aureus, Escherichia coli, and Candida albicans all remain at 86% of their initial values.

[0124] This embodiment describes the application of a cooling antibacterial polyester fabric in the preparation of textiles that possess both cooling contact properties and wash-resistant antibacterial properties. The textile in this embodiment is a summer bedding blanket. After undergoing 50 machine washes within its normal service life, the textile still maintains a cooling coefficient (qmax) of 0.27 upon contact. Furthermore, the antibacterial rate against Staphylococcus aureus is 99.3%, and the surface density of the bedding in this embodiment is 145. When used at room temperature of 30°C, the user's subjective thermal sensation rating is 2 levels lower than that of ordinary polyester bedding.

[0125] Example 2 Features: This example employs a high thermal conductivity optimized configuration, reducing the polyester matrix content to 78wt% and increasing the content of thermally conductive and antibacterial core-shell masterbatch to 22wt%. The proportion of zinc oxide inorganic core in the masterbatch reaches as high as 52wt%, significantly enhancing thermal conductivity. The zinc oxide submicron rods achieve an aspect ratio of 13.3 and a long axis dimension of 1.6μm, which is beneficial for axial orientation along the fiber, greatly improving the longitudinal thermal conductivity. The quaternary ammonium nitrogen content is controlled at a low 0.6wt%, maximizing cooling performance while ensuring basic antibacterial effects. The process parameters favor high temperature and high speed: melt blending temperature 278℃, winding speed 4000m / min, total draw ratio 4.2, and heat setting temperature 182℃, which is beneficial for the orientation of zinc oxide rod-shaped particles. The fiber adopts a 5-groove irregular cross-section design with a depth-to-width ratio of 1.8, further increasing the contact area and thermal conductivity, achieving a cooling coefficient of 0.29 upon contact. This represents a 31% improvement over the control sample. This embodiment is particularly suitable for summer bedding products that require a strong cooling effect, such as summer quilts and cooling mat covers. It can provide a significant instantaneous cooling sensation in high-temperature environments, and the user's subjective heat perception score can be reduced by 2 levels. It is suitable for use during hot summer nights and provides a high-quality option for consumers who seek the ultimate cooling experience.

[0126] Example 3: A cooling and antibacterial polyester fabric. The fabric in this example is woven from polyester fibers, which include:

[0127] The polyester matrix in this embodiment comprises an aromatic polyester mainly composed of polyethylene terephthalate. The mass fraction of the polyester matrix in this embodiment is 88 wt% of the total mass of the polyester fibers in this embodiment.

[0128] A thermally conductive and antibacterial core-shell masterbatch, wherein the mass fraction of the thermally conductive and antibacterial core-shell masterbatch in the polyester fiber is 12 wt% of the total mass of the polyester fiber, the thermally conductive and antibacterial core-shell masterbatch comprises a zinc oxide submicron rod-shaped inorganic core and an organic shell layer coating the surface of the zinc oxide submicron rod-shaped inorganic core, wherein:

[0129] The zinc oxide submicron rod-shaped inorganic core of this embodiment has a one-dimensional rod-shaped morphology and is at least partially aligned along the axial direction of the polyester fiber during the forming and stretching process of this embodiment, so as to improve the longitudinal thermal conductivity of the polyester fiber and enhance the instantaneous cooling sensation upon contact.

[0130] The organic shell layer of this embodiment includes a silane coupling layer and a quaternized copolyester shell layer. The silane coupling layer of this embodiment is formed by the hydrolytic condensation of γ-glycidoxypropyltrimethoxysilane and is connected to the zinc oxide submicron rod-shaped inorganic core of this embodiment through Si-O-Zn bonds. The quaternized copolyester shell layer of this embodiment covers the outside of the silane coupling layer of this embodiment. The quaternized copolyester shell layer of this embodiment is obtained by the esterification condensation of terephthalic acid, ethylene glycol, monosodium 5-sulfoisophthalate, and bis-2-hydroxyethyldimethylammonium chloride.

[0131] In this embodiment, the mass fraction of the zinc oxide submicron rod-shaped inorganic core in the thermally conductive and antibacterial core-shell masterbatch is 28 wt% of the total mass of the thermally conductive and antibacterial core-shell masterbatch, and the mass fraction of quaternary ammonium nitrogen in the quaternized copolyester shell is 1.7 wt% of the total mass of the thermally conductive and antibacterial core-shell masterbatch.

[0132] The thermally conductive and antibacterial core-shell masterbatch of this embodiment is prepared through the following steps:

[0133] A1. Preparation of silanized zinc oxide submicron rod powder: Zinc oxide submicron rod powder with a submicron rod morphology and an average size L50 of 0.5 μm along the long axis was dispersed in a water-alcohol mixed solvent. γ-glycidoxypropyltrimethoxysilane was added, and the reaction was carried out at pH 4.7 and temperature 65℃ for 2.5 h. After washing and drying, silanized zinc oxide submicron rod powder with epoxy functional groups on the surface was obtained.

[0134] A2. Preparation of quaternized copolyester prepolymer chips: Terephthalic acid, sodium 5-sulfoisophthalate, ethylene glycol, and bis-2-hydroxyethyldimethylammonium chloride were added to an esterification reactor and esterified at 230°C. After esterification, antimony trioxide catalyst was added, and polycondensation was carried out at 265°C and a vacuum of 250 Pa to obtain quaternized copolyester prepolymer chips. In this embodiment, the molar fraction of sodium 5-sulfoisophthalate relative to the total molar amount of dicarboxylic acid was 4.5 mol%, the molar fraction of bis-2-hydroxyethyldimethylammonium chloride relative to the total molar amount of diol was 2.7 mol%, and the molar ratio of quaternary ammonium nitrogen to sulfonic acid groups on the aromatic ring in the shell of the quaternized copolyester was 0.9:1.

[0135] A3. Preparation of thermally conductive and antibacterial core-shell masterbatch: The silanized zinc oxide submicron rod powder of this embodiment and the quaternized copolyester prepolymer chips of this embodiment are melt-blended at a mass ratio of 28:72 at a temperature of 258°C. After water cooling and pelletizing, a thermally conductive and antibacterial core-shell masterbatch with a median volume diameter (D50) of 115 μm is obtained.

[0136] The zinc oxide submicron rod powder in this embodiment is prepared by the following steps:

[0137] B1. Preparation of submicron rod-shaped zinc oxide precursor: A zinc chloride solution containing zinc inorganic salt was mixed with ammonia water, and a combination of sodium tartrate and polyvinylpyrrolidone (mass ratio 2:1) was added as morphology control agents. The mixture was reacted at 145°C for 18 hours under hydrothermal conditions. After cooling, the resulting slurry was subjected to solid-liquid separation and washed 8 times with deionized water until the conductivity of the filtrate was 20 μS / cm and the pH was 7.2. The filtrate was then dried at 90°C for 8 hours to obtain the submicron rod-shaped zinc oxide precursor. In this embodiment, the zinc inorganic salt solution contained Zn 2+ The concentration is 0.28 mol / L. In this example, the OH- alkali source contains... - Compared with the zinc-containing inorganic salt solution of this embodiment, Zn 2+ The molar ratio of ⁺ is 4.2 to 1. The amount of morphology control agent used in this embodiment is 4 wt%, calculated as the ratio of the mass of the morphology control agent in this embodiment to the theoretical mass of the zinc-containing inorganic salt in this embodiment, based on zinc oxide.

[0138] B2. Preparation of zinc oxide submicron rod powder by calcination: The submicron rod-shaped zinc oxide precursor of this embodiment was calcined in air at a temperature of 470°C for 3.2 h to obtain zinc oxide submicron rod powder.

[0139] In this embodiment, the average size L50 of the zinc oxide submicron rod-shaped inorganic core is 0.5 μm in the long axis direction, the average diameter D50 in the short axis direction is 150 nm, and the aspect ratio is 3.3; the volume median diameter D50 of the thermally conductive antibacterial core-shell masterbatch in this embodiment is 115 μm; and the thickness of the quaternized copolyester shell layer in this embodiment is 25 nm.

[0140] In addition to polyethylene terephthalate, the polyester matrix of this embodiment also contains 22 wt% of polybutylene terephthalate, which is the total mass of the polyester matrix of this embodiment. The total content of the polyester matrix in the polyester fiber of this embodiment is 88 wt% of the total mass of the polyester fiber of this embodiment.

[0141] When preparing the polyester fiber of this embodiment, the mass ratio of the polyester matrix chips of this embodiment to the thermally conductive and antibacterial core-shell masterbatch of this embodiment before melt blending is 88 to 12, and the total mass fraction of zinc oxide in the polyester fiber of this embodiment is 3.36 wt% of the total mass of the polyester fiber of this embodiment.

[0142] The preparation method of the cooling antibacterial polyester fabric in this embodiment includes the following steps:

[0143] S1. Preparation of thermally conductive and antibacterial core-shell masterbatch;

[0144] S2. Melt Blending and Granulation: The polyester matrix chips of this embodiment and the thermally conductive antibacterial core-shell masterbatch of this embodiment are mixed at a mass ratio of 88:12 and then fed into a twin-screw extruder. Melt blending is performed at 260°C, with a residence time of 6.5 min in the barrel. Deviation is then carried out under a vacuum of 400 Pa. Modified polyester chips are obtained by underwater pelletizing. The twin-screw extruder of this embodiment has an aspect ratio of 36 and a screw speed of 190 r / min. The thermally conductive antibacterial core-shell masterbatch of this embodiment is added to the twin-screw extruder via side feeding. In this embodiment, the thermally conductive and antibacterial core-shell masterbatch is melted and dispersed in the latter half of the barrel, thereby reducing the shear degradation of the quaternized copolyester shell layer. The average spacing between adjacent thermally conductive and antibacterial core-shell masterbatches in the cross-section of the resulting polyester fiber is 2.7 μm. After step S2, the modified polyester chips are extracted to reduce the residual amount of bis-2-hydroxyethyldimethylammonium chloride in the modified polyester chips to 420 ppm. The migration amount of antimony trioxide in the modified polyester chips meets the limit requirements for antimony in the textile safety standards.

[0145] S3. Melt spinning: The modified polyester chips of this embodiment are dried and fed into a melt spinning unit, where they are melted at a melt temperature of 270°C, extruded and wound through a spinning assembly to obtain nascent polyester fibers. The winding speed of melt spinning is 2800 m / min.

[0146] S4. Stretching and Heat Setting: The nascent polyester fibers of this embodiment are subjected to two stretching processes with a total stretch ratio of 3.2, and then heat-set at 168°C for 85 seconds to obtain polyester filaments with a breaking strength of 4.5 cN / dtex. The zinc oxide submicron rod-shaped inorganic core of this embodiment is preferentially aligned along the axial direction of the polyester fibers.

[0147] The orientation is arranged to improve the longitudinal thermal conductivity of the polyester fibers in this embodiment and enhance the cooling effect;

[0148] S5. Weaving and Finishing: The polyester filament obtained in step S4 of this embodiment is woven to form an areal density of 175. The greige fabric is softened by a softening agent with a free quaternary ammonium salt content of 0.8 wt% of the greige fabric mass, and then baked at 158℃ for 70 seconds to obtain a cool-feeling antibacterial polyester fabric.

[0149] The polyester fiber in this embodiment is a non-circular cross-section fiber with 6 grooves. The depth-to-width ratio of the grooves in this embodiment is 2.5. The polyester fiber in this embodiment meets the following requirements: linear density of 2.8 dtex, tensile strength of 4.5 cN / dtex, elongation at break of 35%, and boiling water shrinkage of 3.2%.

[0150] The cooling antibacterial polyester fabric in this embodiment is a warp-knitted fabric with a areal density of 175. The shrinkage rate is 1.5% in both the longitudinal and latitudinal directions.

[0151] In this embodiment, the average value of the cooling coefficient qmax of the cooling antibacterial polyester fabric at the instant of contact under a temperature of 23°C is 0.22. After 50 home machine washes, the antibacterial rate against Staphylococcus aureus was 99.8%, against Escherichia coli was 97.5%, and against Candida albicans was 96.8%.

[0152] By adjusting the amount of thermally conductive antibacterial core-shell masterbatch and the stretching process parameters in this embodiment, the polyester fibers contained in the obtained cooling antibacterial polyester fabric of this embodiment, while maintaining a breaking strength of 4.5 cN / dtex, have a cooling coefficient qmax that is 21% higher than that of the comparative sample without the addition of the thermally conductive antibacterial core-shell masterbatch of this embodiment. Furthermore, after 50 home machine washes, the antibacterial rate against Staphylococcus aureus, Escherichia coli, and Candida albicans remains at 93% of their respective initial values.

[0153] This embodiment describes the application of a cooling antibacterial polyester fabric in the preparation of textiles that possess both cooling contact properties and wash-resistant antibacterial properties. The textiles in this embodiment are underwear and bedding pillowcases. After undergoing 50 home machine washes within their normal service life, the textiles in this embodiment still maintain a cooling coefficient (qmax) of 0.21 upon contact. Furthermore, the antibacterial rate against Staphylococcus aureus is 99.8%. In actual wearing conditions, the close-fitting clothing of this embodiment can instantly reduce the skin surface temperature by 0.8°C compared to ordinary polyester fabric of the same weight. The bedding of this embodiment has a surface density of 175g / m². When used at room temperature of 30°C, the user's subjective thermal sensation score is reduced by 1 level compared to ordinary polyester bedding.

[0154] Features of Example 3: This example employs a highly optimized antibacterial configuration, increasing the polyester matrix content to 88 wt%, reducing the thermally conductive antibacterial core-shell masterbatch content to 12 wt%, and achieving a zinc oxide inorganic core ratio of 28 wt% in the masterbatch. The quaternary ammonium nitrogen content is as high as 1.7 wt%, significantly enhancing antibacterial performance. The quaternized copolyester shell thickness reaches 25 nm, with a 4.5 mol% molar fraction of 5-sulfoisophthalic acid monosodium salt and a 2.7 mol% molar fraction of bis-2-hydroxyethyldimethylammonium chloride, both at high levels, ensuring sufficient antibacterial active sites. Process parameters are moderate and stable, with a melt blending temperature of 260℃, a winding speed of 2800 m / min, a total draw ratio of 3.2, and a heat setting temperature of 168℃ with an extended time of 85 s, facilitating the full expansion and stable fixation of the quaternary ammonium salt groups. The fiber exhibits excellent properties, with a breaking strength of 4.5 cN / dtex, a boiling water shrinkage rate of only 3.2%, and good dimensional stability. It exhibits outstanding antibacterial properties, achieving a 99.8% inhibition rate against Staphylococcus aureus, and 97.5% and 96.8% inhibition rates against Escherichia coli and Candida albicans, respectively. Even after 50 machine washes, it retains 93% of its initial value. This product is particularly suitable for intimate apparel textiles requiring high hygiene and antibacterial properties, such as underwear, pajamas, and pillowcases. It is especially suitable for sensitive skin, infant products, and medical care applications, providing long-lasting inhibition of bacterial and fungal growth. While maintaining a basic cooling effect, it offers excellent antibacterial protection, making it suitable for all seasons. Its antibacterial advantages are even more pronounced in humid environments.

[0155] Example 4: A cooling and antibacterial polyester fabric. The fabric in this example is knitted from polyester fibers, which include:

[0156] The polyester matrix in this embodiment comprises an aromatic polyester mainly composed of polyethylene terephthalate. The mass fraction of the polyester matrix in this embodiment is 72 wt% of the total mass of the polyester fibers in this embodiment.

[0157] A thermally conductive and antibacterial core-shell masterbatch, wherein the mass fraction of the thermally conductive and antibacterial core-shell masterbatch in the polyester fiber is 28 wt% of the total mass of the polyester fiber, the thermally conductive and antibacterial core-shell masterbatch comprises a zinc oxide submicron rod-shaped inorganic core and an organic shell layer coating the surface of the zinc oxide submicron rod-shaped inorganic core, wherein:

[0158] The zinc oxide submicron rod-shaped inorganic core of this embodiment has a one-dimensional rod-shaped morphology and is at least partially aligned along the axial direction of the polyester fiber during the forming and drawing process of this embodiment, so as to improve the longitudinal thermal conductivity of the polyester fiber and enhance the instantaneous cooling sensation upon contact.

[0159] The organic shell of this embodiment includes a silane coupling layer and a quaternized copolyester shell. The silane coupling layer of this embodiment is formed by the hydrolytic condensation of γ-glycidoxypropyltrimethoxysilane and is connected to the zinc oxide submicron rod-shaped inorganic core of this embodiment through Si-O-Zn bonds. The quaternized copolyester shell of this embodiment covers the outside of the silane coupling layer of this embodiment. The quaternized copolyester shell of this embodiment is obtained by the esterification condensation of dimethyl terephthalate, ethylene glycol, monosodium 5-sulfoisophthalate, and bis-2-hydroxyethyldimethylammonium chloride.

[0160] In this embodiment, the mass fraction of the zinc oxide submicron rod-shaped inorganic core in the thermally conductive and antibacterial core-shell masterbatch is 22 wt% of the total mass of the thermally conductive and antibacterial core-shell masterbatch, and the mass fraction of quaternary ammonium nitrogen in the quaternized copolyester shell is 1.9 wt% of the total mass of the thermally conductive and antibacterial core-shell masterbatch.

[0161] The thermally conductive and antibacterial core-shell masterbatch of this embodiment is prepared through the following steps:

[0162] A1. Preparation of silanized zinc oxide submicron rod powder: Zinc oxide submicron rod powder with a submicron rod morphology and an average size L50 of 0.25 μm along the long axis was dispersed in a water-alcohol mixed solvent. γ-glycidoxypropyltrimethoxysilane was added, and the reaction was carried out at pH 4.1 and temperature 77℃ for 1.2 h. After washing and drying, silanized zinc oxide submicron rod powder with epoxy functional groups on the surface was obtained.

[0163] A2. Preparation of quaternized copolyester prepolymer chips: Dimethyl terephthalate, sodium 5-sulfoisophthalate, ethylene glycol, and bis-2-hydroxyethyldimethylammonium chloride were added to an esterification reactor and subjected to esterification at 235°C. After esterification, antimony trioxide catalyst was added, and polycondensation was carried out at 263°C and a vacuum of 280 Pa to obtain quaternized copolyester prepolymer chips. In this embodiment, the molar fraction of sodium 5-sulfoisophthalate relative to the total molar amount of dicarboxylic acid was 7.0 mol%, the molar fraction of bis-2-hydroxyethyldimethylammonium chloride relative to the total molar amount of diol was 4.3 mol%, and the molar ratio of quaternary ammonium nitrogen to sulfonic acid groups on the aromatic ring in the quaternized copolyester shell was 0.55:1.

[0164] A3. Preparation of thermally conductive and antibacterial core-shell masterbatch: The silanized zinc oxide submicron rod powder of this embodiment and the quaternized copolyester prepolymer chips of this embodiment are melt-blended at a mass ratio of 22:78 at a temperature of 254°C. After underwater pelletizing, a thermally conductive and antibacterial core-shell masterbatch with a median volume diameter (D50) of 185 μm is obtained.

[0165] The zinc oxide submicron rod powder in this embodiment is prepared by the following steps:

[0166] B1. Preparation of submicron rod-shaped zinc oxide precursor: A mixed solution of zinc nitrate and zinc acetate (mass ratio 1:1) containing zinc inorganic salts was mixed with sodium hydroxide solution, and hexadecyltrimethylammonium bromide, a morphology control agent, was added. The mixture was reacted at 202°C for 4 hours under hydrothermal conditions. After cooling, the resulting slurry was subjected to solid-liquid separation and washed four times with deionized water until the conductivity of the filtrate was 45 μS / cm and the pH was 6.7. The filtrate was then dried at 115°C for 3 hours to obtain the submicron rod-shaped zinc oxide precursor. In this embodiment, the zinc-containing inorganic salt solution contained Zn 2+ The concentration is 0.72 mol / L. In this example, the OH- alkali source contains... - Compared with the zinc-containing inorganic salt solution of this embodiment, Zn 2+ The molar ratio is 2.3 to 1. The amount of morphology control agent used in this embodiment is 17 wt%, calculated as the ratio of the mass of the morphology control agent in this embodiment to the theoretical mass of the zinc-containing inorganic salt in this embodiment, based on zinc oxide.

[0167] B2. Preparation of zinc oxide submicron rod powder by calcination: The submicron rod-shaped zinc oxide precursor of this embodiment was calcined in an air atmosphere at a temperature of 620°C for 1.2 h to obtain zinc oxide submicron rod powder.

[0168] In this embodiment, the average size L50 of the zinc oxide submicron rod-shaped inorganic core is 0.25 μm in the long axis direction, the average diameter D50 in the short axis direction is 65 nm, and the aspect ratio is 3.8; the median particle size D50 of the thermally conductive antibacterial core-shell masterbatch in this embodiment is 185 μm; and the thickness of the quaternized copolyester shell layer in this embodiment is 28 nm.

[0169] In addition to the polyethylene terephthalate of this embodiment, the polyester matrix of this embodiment also contains 27 wt% of a mixture of polybutylene terephthalate and polytrimethylene terephthalate (mass ratio 1:1) of the total mass of the polyester matrix of this embodiment. The total content of the polyester matrix of this embodiment in the polyester fiber of this embodiment is 72 wt% of the total mass of the polyester fiber of this embodiment.

[0170] When preparing the polyester fiber of this embodiment, the mass ratio of the polyester matrix chips of this embodiment to the thermally conductive and antibacterial core-shell masterbatch of this embodiment before melt blending is 72 to 28, and the total mass fraction of zinc oxide in the polyester fiber of this embodiment is 6.16 wt% of the total mass of the polyester fiber of this embodiment.

[0171] The preparation method of the cooling antibacterial polyester fabric in this embodiment includes the following steps:

[0172] S1. Preparation of thermally conductive and antibacterial core-shell masterbatch;

[0173] S2. Melt Blending and Granulation: The polyester matrix chips of this embodiment and the thermally conductive antibacterial core-shell masterbatch of this embodiment are mixed at a mass ratio of 72:28 and then fed into a twin-screw extruder. Melt blending is performed at a temperature of 283°C, with a residence time of 2.5 min in the barrel. Deviation treatment is then carried out under a vacuum of 150 Pa. After water cooling and pelletizing, modified polyester chips are obtained. The twin-screw extruder of this embodiment has an aspect ratio of 42 and a screw speed of 330 r / min. The thermally conductive antibacterial core-shell masterbatch of this embodiment is added to the twin-screw extruder via side feeding. In this embodiment, the thermally conductive and antibacterial core-shell masterbatch is melted and dispersed in the latter half of the barrel, thereby reducing the shear degradation of the quaternized copolyester shell layer. The average spacing between adjacent thermally conductive and antibacterial core-shell masterbatches in the cross-section of the resulting polyester fiber is 1.4 μm. After step S2, the modified polyester chips are subjected to vacuum devolatilization treatment, resulting in a residual amount of bis-2-hydroxyethyldimethylammonium chloride of 95 ppm in the modified polyester chips. Furthermore, the migration amount of antimony trioxide in the modified polyester chips meets the limit requirements for antimony in the textile safety standards.

[0174] S3. Melt spinning: The modified polyester chips of this embodiment are dried and fed into a melt spinning unit, where they are melted at a melt temperature of 283°C, extruded and wound through a spinning assembly to obtain nascent polyester fibers. The winding speed of melt spinning is 4300 m / min.

[0175] S4. Stretching and Heat Setting: The nascent polyester fibers of this embodiment are subjected to three stretching processes with a total stretch ratio of 4.35. They are then heat-set at 186°C for 25 seconds to obtain polyester staple fibers with a breaking strength of 3.7 cN / dtex. The zinc oxide submicron rod-shaped inorganic cores of this embodiment are preferentially aligned along the axial direction of the polyester fibers to improve the longitudinal thermal conductivity of the polyester fibers and enhance the cooling effect.

[0176] S5. Weaving and finishing: The polyester staple fiber obtained in step S4 is knitted into a greige fabric with an areal density of 128 g / m², and then softened with a softening agent containing 0.2 wt% of the greige fabric mass of free quaternary ammonium salt. The fabric is then baked at 177°C for 25 seconds to obtain a cool-feeling antibacterial polyester fabric.

[0177] The polyester fiber in this embodiment is a non-circular cross-section fiber with 7 grooves. The depth-to-width ratio of the grooves in this embodiment is 1.2. The polyester fiber in this embodiment meets the following requirements: linear density of 1.0 dtex, tensile strength of 3.7 cN / dtex, elongation at break of 22%, and boiling water shrinkage of 7.2%.

[0178] The cooling antibacterial polyester fabric in this embodiment is a weft-knitted fabric with a surface density of 128 g / m² and a shrinkage rate of 2.8% in both the warp and weft directions.

[0179] In this embodiment, the average value of the cooling coefficient qmax of the cooling antibacterial polyester fabric at the instant of contact under a temperature of 23°C is 0.24. After 50 home machine washes, the inhibition rate against Staphylococcus aureus was 99.7%, against Escherichia coli was 95.5%, and against Candida albicans was 94.2%.

[0180] By adjusting the amount of thermally conductive antibacterial core-shell masterbatch and the stretching process parameters in this embodiment, the polyester fibers contained in the cool-feeling antibacterial polyester fabric of this embodiment, while maintaining a breaking strength of 3.7 cN / dtex, have a cooling coefficient qmax that is 26% higher than that of the comparative sample without the addition of the thermally conductive antibacterial core-shell masterbatch of this embodiment. Furthermore, after 50 home machine washes, the antibacterial rate against Staphylococcus aureus, Escherichia coli, and Candida albicans remains at 90% of their respective initial values.

[0181] This embodiment describes the application of a cooling antibacterial polyester fabric in the preparation of textiles that possess both cooling contact properties and wash-resistant antibacterial properties. The textiles in this embodiment are vests and cushion covers designed for close-fitting use. After undergoing 50 home machine washes within their normal service life, the textiles in this embodiment still maintain a cooling coefficient (qmax) of 0.22 upon contact. Furthermore, the antibacterial rate against Staphylococcus aureus is 99.7%. In actual wearing conditions, the close-fitting garment of this embodiment can instantly reduce the skin surface temperature by 1.5°C compared to ordinary polyester fabric of the same weight.

[0182] Example 4 Features: This example employs a boundary verification configuration, focusing on verifying the feasibility of the scope boundaries. The polyester matrix content is selected as 72 wt% in the lower boundary region (8% of the scope), the thermally conductive and antibacterial core-shell masterbatch content is selected as 28 wt% in the upper boundary region (92% of the scope), the zinc oxide inorganic core accounts for 22 wt% of the masterbatch (5% of the scope), and the quaternary ammonium nitrogen content is 1.9 wt% (94% of the scope). Several key parameters are close to but do not reach the absolute boundaries, verifying the complete scope of the claims. The process parameters also reflect the boundary characteristics: the zinc oxide rod L50 is 0.25 μm (close to the lower limit), the calcination temperature is 620℃ (close to the upper limit), the melt blending temperature is 283℃ (close to the upper limit), the winding speed is 4300 m / min (close to the upper limit), the total draw ratio is 4.35 (close to the upper limit), the heat setting temperature is 186℃ (close to the upper limit) but the time is only 25 s (close to the lower limit), and the twin-screw length-to-diameter ratio is 42 (close to the upper limit). These boundary parameters are carefully designed to ensure mutual coordination. Despite the use of boundary parameters, this embodiment still maintains good performance, with a breaking strength of 3.7 cN / dtex and a contact instantaneous cooling coefficient of 0.24. The 99.7% inhibition rate against Staphylococcus aureus fully demonstrates the scientific rationality and technological feasibility of the claims. This embodiment is suitable for verifying the feasibility of the technical solution's boundaries, providing strong support for the scope of patent protection. It is also suitable for summer clothing with special requirements for lightness and coolness, such as vests and tank tops, as well as home furnishings requiring cooling and antibacterial functions, such as cushion covers and sofa covers. It has good application prospects in indoor and outdoor leisure scenarios during hot seasons.

[0183] Comparative Example 1: It is basically the same as Example 1, except that the mass fraction of the polyester matrix is ​​65 wt% of the total mass of polyester fibers, the mass fraction of the thermally conductive and antibacterial core-shell masterbatch is 35 wt%, and the amounts of other components and preparation conditions remain unchanged.

[0184] Comparative Example 2: It is basically the same as Example 1, except that the mass fraction of the polyester matrix is ​​96 wt% of the total mass of polyester fibers, the mass fraction of the thermally conductive and antibacterial core-shell masterbatch is 4 wt%, and the amounts of other components and preparation conditions remain unchanged.

[0185] Comparative Example 3: It is basically the same as Example 1, except that the mass fraction of zinc oxide submicron rod-shaped inorganic core in the thermally conductive antibacterial core-shell masterbatch is 15 wt% of the total mass of the thermally conductive antibacterial core-shell masterbatch, the proportion of quaternized copolyester shell is increased to 85 wt% accordingly, and the amount of other components and preparation conditions remain unchanged.

[0186] Comparative Example 4: It is basically the same as Example 1, except that the mass fraction of zinc oxide submicron rod-shaped inorganic core in the thermally conductive antibacterial core-shell masterbatch is 68 wt% of the total mass of the thermally conductive antibacterial core-shell masterbatch, and the proportion of quaternized copolyester shell is reduced to 32 wt% accordingly. The amount of other components and preparation conditions remain unchanged.

[0187] Comparative Example 5: It is basically the same as Example 1, except that the mass fraction of quaternary ammonium nitrogen in the quaternized copolyester shell is 0.15 wt% of the total mass of the thermally conductive and antibacterial core-shell masterbatch, the amount of 5-sulfoisophthalic acid monosodium salt and bis-2-hydroxyethyldimethylammonium chloride are adjusted accordingly, and the amount of other components and preparation conditions remain unchanged.

[0188] Comparative Example 6: It is basically the same as Example 1, except that the mass fraction of quaternary ammonium nitrogen in the quaternized copolyester shell is 2.5 wt% of the total mass of the thermally conductive and antibacterial core-shell masterbatch, the amount of 5-sulfoisophthalic acid monosodium salt and bis-2-hydroxyethyldimethylammonium chloride is adjusted accordingly, and the amount of other components and preparation conditions remain unchanged.

[0189] Comparative Example 7: It is basically the same as Example 1, except that the average size L50 of the zinc oxide submicron rod powder in the long axis direction is 0.08 μm, which is obtained by adjusting the hydrothermal reaction temperature to 100°C and the time to 4 h. The amount of other components and the preparation conditions remain unchanged.

[0190] Comparative Example 8: It is basically the same as Example 1, except that the average size L50 of the zinc oxide submicron rod powder in the long axis direction is 2.8 μm, which is obtained by adjusting the hydrothermal reaction temperature to 240°C and the time to 30 h. The amount of other components and preparation conditions remain unchanged.

[0191] Comparative Example 9: It is basically the same as Example 1, except that the average diameter D50 of the zinc oxide submicron rod powder in the short axis direction is 35 nm and the aspect ratio is 28. It is obtained by adjusting the amount of morphology control agent to 0.3 wt% of the theoretical mass of zinc-containing inorganic salt based on zinc oxide. The amounts of other components and preparation conditions remain unchanged.

[0192] Comparative Example 10: It is basically the same as Example 1, except that the average diameter D50 of the zinc oxide submicron rod powder in the short axis direction is 380 nm and the aspect ratio is 2.6. It is obtained by adjusting the amount of morphology control agent to 25 wt% of the theoretical mass of zinc-containing inorganic salt based on zinc oxide. The amounts of other components and preparation conditions remain unchanged.

[0193] Comparative Example 11: Basically the same as Example 1, except that the silanization reaction temperature was 50°C, the pH value was 3.5, the reaction time was 0.5 h, and the amounts of other components and preparation conditions remained unchanged.

[0194] Comparative Example 12: It is basically the same as Example 1, except that the temperature of the silanization reaction is 92 °C, the pH value is 5.8, and the reaction time is 4.5 h. The dosages of other components and the preparation conditions remain unchanged.

[0195] Comparative Example 13: It is basically the same as Example 1, except that the temperature of the quaternization copolyester esterification reaction is 185 °C, the temperature of the polycondensation reaction is 245 °C, and the vacuum degree is 450 Pa. The dosages of other components and the preparation conditions remain unchanged.

[0196] Comparative Example 14: It is basically the same as Example 1, except that the melt blending temperature is 240 °C, the melt spinning temperature is 255 °C, and the residence time of the material in the barrel of the twin-screw extruder is 9 min. The dosages of other components and the preparation conditions remain unchanged.

[0197] Performance Test:

[0198] Instantaneous cool feeling coefficient test: The test object is the finished cool feeling antibacterial polyester fabric of the present invention, and the test purpose is to evaluate the heat conduction performance and cool feeling intensity when the fabric contacts the skin instantaneously. The test principle is based on the heat flow method. When the fabric contacts the constant temperature hot plate instantaneously, the heat is transferred from the hot plate to the fabric, and the instantaneous cool feeling intensity is characterized by measuring the maximum heat flow per unit area per unit time. The experimental method is to cut the fabric sample into a square of 10 cm × 10 cm, balance it for 24 h in a standard environment of 23 ± 1 °C and relative humidity of 50 ± 5%, use an instantaneous cool feeling tester (Alambeta instrument or similar equipment), contact the test head preheated to 35 °C with the fabric sample under a pressure of 0.2 kPa, and record the instantaneous heat flow qmax at 0.1 s, with the unit of 。The standard is based on GB / T 35263-2017 "Textiles - Detection and Evaluation of Instantaneous Cool Feeling Performance" or ISO 16840 "Textiles - Physiological Comfort Testing". The key parameters include the test head temperature of 35 ± 0.5 °C, the contact pressure of 0.2 ± 0.02 kPa, the ambient temperature of 23 ± 1 °C, and the relative humidity of 50 ± 5%. The data processing is to test 5 different parts of each sample, take the arithmetic mean ± standard deviation, and qmax ≥ 0.20 is judged as qualified.

[0199] Antibacterial performance test and evaluation of wash resistance: The test objects are the finished cool feeling antibacterial polyester fabric of the present invention and the samples after being treated with different washing times. The test purpose is to evaluate the antibacterial rates of the fabric against Staphylococcus aureus, Escherichia coli, and Candida albicans and the wash resistance performance. The test principle adopts the shake flask method. A certain amount of bacterial suspension is shaken and contacted with the fabric sample under specified conditions, and the antibacterial rate is calculated by comparing the change in the number of viable bacteria before and after inoculation. The experimental method is to cut the fabric sample into a specimen of 0.4 g ± 0.01 g, and inoculate them with a concentration of 1×10 5Staphylococcus aureus, Escherichia coli or Candida albicans suspension at CFU / mL was incubated at 37±1°C with an oscillation frequency of 100 rpm for 18 h. The viable bacteria count was determined by the plate counting method, and the antibacterial rate was calculated as (viable bacteria count of the control sample - viable bacteria count of the test sample) / viable bacteria count of the control sample × 100%. The wash durability evaluation was carried out by repeating the antibacterial test after washing 0, 10, 20, 30, 50 times using the domestic machine washing program of GB / T 8629-2017. The standard basis is GB / T20944.3-2008 "Textiles - Evaluation of antibacterial properties - Part 3: Oscillation method". The key parameters include an inoculation concentration of 1×10 5 CFU / mL, an action time of 18 h, and an oscillation frequency of 100 rpm. Data processing: For each group, 3 parallel samples were set, and the average value ± standard deviation was taken. An antibacterial rate of ≥90% was determined as effective antibacterial.

[0200] Testing of fiber breaking strength and elongation at break: The test object was the polyester fiber monofilament or multifilament of the present invention, and the test purpose was to evaluate the tensile mechanical properties of the fiber, including breaking strength and elongation at break. The test principle was based on the constant rate of elongation method. The fiber specimen was fixed between the upper and lower holders of the tensile tester and stretched at a constant speed until it broke, and the maximum force and elongation at break were recorded. The experimental method was to condition for 24 h in a standard environment of 20±2°C and a relative humidity of 65±2%. An electronic single yarn strength tester was used, with a clamping distance of 500 mm and a stretching speed of 500 mm / min. 20 monofilaments of each sample were tested. The breaking strength was expressed in cN / dtex, and the calculation formula was the breaking force F (cN) divided by the fiber linear density (dtex); the elongation at break was expressed as a percentage, and the calculation formula was (elongation at break / original length) × 100%. The standard basis was GB / T 14344-2008 "Test method for tensile properties of chemical fiber filaments" or ASTM D3822-14 "Standard test method for tensile properties of single textile fibers". The key parameters included a clamping distance of 500 mm, a stretching speed of 500 mm / min, an environmental temperature of 20±2°C, and a relative humidity of 65±2%. Data processing: After excluding outliers, the arithmetic mean ± standard deviation was taken. A breaking strength of ≥3.5 cN / dtex was determined as qualified.

[0201] Testing of boiling water shrinkage rate of fibers and fabrics: The test objects are the finished polyester fibers and cool-sensing antibacterial polyester fabrics of the present invention, and the test purpose is to evaluate the thermal dimensional stability of the fibers and fabrics. The test principle is to measure the change rate of length or size after treating the specimen in boiling water for a specified time. The experimental method is to mark a 500-mm length on the fiber specimen in a naturally straight state, cut the fabric specimen into 30 cm × 30 cm and mark a 25-cm distance on both the warp and weft directions, immerse it in a boiling water bath for 30 min, take it out and cool it in room-temperature water for 10 min, lay it flat and dry it to a constant weight, and measure the change in the distance between the marks. The calculation formula for the boiling water shrinkage rate is (length before treatment - length after treatment) / length before treatment × 100%. The standard basis is GB / T 6505-2017 "Test Method for Heat Shrinkage Rate of Chemical Fiber Filaments - Boiling Water Shrinkage Method" or FZ / T 01034-2008 "Textiles - Test Method for Boiling Water Shrinkage Rate". The key parameters include a boiling water temperature of 100 ± 2 °C, a treatment time of 30 min, and a cooling water temperature of 20 ± 5 °C. For data processing, 10 fiber specimens are tested and the average value ± standard deviation is taken, 5 fabric samples are tested and the average value ± standard deviation is taken. When the boiling water shrinkage rate of the fibers ≤ 8% and the fabric shrinkage rate ≤ 3%, it is judged as qualified.

[0202] Testing of boiling water shrinkage rate of fibers and fabrics: The test objects are the finished polyester fibers and cool-sensing antibacterial polyester fabrics of the present invention, and the test purpose is to evaluate the thermal dimensional stability of the fibers and fabrics. The test principle is to measure the change rate of length or size after treating the specimen in boiling water for a specified time. The experimental method is to mark a 500-mm length on the fiber specimen in a naturally straight state, cut the fabric specimen into 30 cm × 30 cm and mark a 25-cm distance on both the warp and weft directions, immerse it in a boiling water bath for 30 min, take it out and cool it in room-temperature water for 10 min, lay it flat and dry it to a constant weight, and measure the change in the distance between the marks. The calculation formula for the boiling water shrinkage rate is (length before treatment - length after treatment) / length before treatment × 100%. The standard basis is GB / T 6,505-2017 "Test Method for Heat Shrinkage Rate of Chemical Fiber Filaments - Boiling Water Shrinkage Method" or FZ / T 01034-2008 "Textiles - Test Method for Boiling Water Shrinkage Rate". The key parameters include a boiling water temperature of 100 ± 2 °C, a treatment time of 30 min, and a cooling water temperature of 20 ± 5 °C. For data processing, 10 fiber specimens are tested and the average value ± standard deviation is taken, 5 fabric samples are tested and the average value ± standard deviation is taken. When the boiling water shrinkage rate of the fibers ≤ 8% and the fabric shrinkage rate ≤ 3%, it is judged as qualified.

[0203] X-ray diffraction structural characterization: The test object was the zinc oxide submicron rod powder of this invention, and the purpose of the test was to analyze the crystal phase composition and lattice parameters. The test principle is based on Bragg diffraction of X-rays in crystals. Different crystal planes produce characteristic diffraction peaks, and crystal structure information is obtained by the position, intensity, and width of the diffraction peaks. The experimental method was to press the powder sample into a pellet, use an X-ray diffractometer, and use a Cu Kα radiation source (λ=0.15406 nm), with a scanning range of 10-80° (2θ), a step size of 0.02°, and a scanning speed of 4° / min. Phase search and Rietveld refinement were performed using Jade or HighScore software to calculate the lattice parameters a, c, and grain size of the zinc oxide wurtzite structure. Key parameters included the X-ray source Cu Kα, the scanning range of 10-80°, the step size of 0.02°, and the scanning speed of 4° / min.

[0204] X-ray photoelectron spectroscopy surface chemical state analysis: The test objects were the silanized zinc oxide submicron rod powder and the thermally conductive and antibacterial core-shell masterbatch of this invention. The purpose of the test was to analyze the surface elemental composition, chemical valence state, and the coating of the silane coupling layer and the quaternized copolyester shell. The test principle is based on the photoelectric effect; X-rays excite the emission of inner-shell electrons from the atoms on the sample surface, and the element types and chemical states are determined by analyzing the photoelectron binding energy. The experimental method involved uniformly dispersing the powder sample on a conductive adhesive and using an X-ray photoelectron spectrometer with an Al Kα ray source (hν = 1486.6 eV). The vacuum level in the analysis chamber was ≤ Pa, full-scan binding energy range 0-1200 eV, high-resolution scanning of Zn 2p, Si 2p, N 1s, and C 1s regions, energy resolution ≤0.5 eV. Peak fitting and semi-quantitative analysis were performed using CasaXPS software to calculate the atomic percentages of Zn, Si, and N on the surface. The formation of Si-O-Zn bonds was verified by the peak shift of the Zn 2p spectrum, and quaternary ammonium nitrogen was distinguished by the N 1s spectrum. And amide nitrogen. Key parameters are AlKα source, vacuum degree ≤ Pa, energy resolution ≤0.5 eV. Data is exported in CSV format, including BE(eV), Intensity, Element, and Chemical_State columns, which facilitates Origin in plotting high-resolution spectra and performing peak area statistics.

[0205] Figure 1To investigate the effect of the thermally conductive and antibacterial core-shell masterbatch content on the instantaneous cooling coefficient and the antibacterial rate against Staphylococcus aureus in this invention, the following parameters were fixed: zinc oxide submicron rod-shaped inorganic core accounting for 40 wt% of the masterbatch mass fraction, quaternary ammonium nitrogen accounting for 1.15 wt% of the masterbatch mass fraction, average zinc oxide rod size L50 of 1.0 μm, average diameter D50 of 175 nm, silanization reaction temperature of 70℃, pH value of 4.5, reaction time of 2.0 h, esterification reaction temperature of 220℃, polycondensation reaction temperature of 270℃, vacuum degree of 200 Pa, melt blending temperature of 267℃, melt spinning temperature of 275℃, winding speed of 3500 m / min, total draw ratio of 3.75, heat setting temperature of 175℃, and time of 60 s. The variable parameters were the mass fraction of the thermally conductive and antibacterial core-shell masterbatch in the polyester fiber, ranging from 3 wt% to 35 wt%. When the masterbatch mass fraction is between 17.5 and 28 wt%, the instantaneous cooling coefficient and the Staphylococcus aureus inhibition rate simultaneously reach their peak range. When the masterbatch mass fraction is below 5 wt%, the insufficient density of the zinc oxide rod and the discontinuous heat conduction path cause the cooling coefficient to drop to 0.18 J·(cm²·s). -1 Furthermore, the antibacterial active sites are sparse, resulting in an antibacterial rate of only 87.5%. Although the cooling coefficient increases to 0.29 J·(cm²·s) when the concentration is above 30 wt%, the antibacterial activity is still limited. -1 However, excessive masterbatch disrupts the continuity of the polyester matrix, resulting in a fiber breaking strength below 3.5 cN·dtex. -1 The minimum requirements and significantly increased processing difficulty demonstrate that an appropriate masterbatch content can simultaneously ensure thermal conductivity, antibacterial effect, and mechanical strength.

[0206] Figure 2 To investigate the effect of the proportion of submicron zinc oxide rod-shaped inorganic core in the masterbatch on the instantaneous cooling coefficient and fiber breaking strength, the following parameters were fixed: polyester matrix mass fraction 82.5 wt%, thermally conductive and antibacterial core-shell masterbatch mass fraction 17.5 wt%, quaternary ammonium nitrogen in the masterbatch mass fraction 1.15 wt%, average zinc oxide rod size L50 of 1.0 μm, and the same silanization reaction conditions, esterification polycondensation conditions, and spinning drawing conditions. Figure 1 With fixed parameters, the mass fraction of zinc oxide submicron rod-shaped inorganic cores in the thermally conductive and antibacterial core-shell masterbatch ranged from 15 wt% to 68 wt%. When the inorganic core proportion in the masterbatch was 35 to 52 wt%, the optimal balance between the instantaneous cooling coefficient and fiber breaking strength was achieved. Below 20 wt%, insufficient inorganic cores limited thermal conductivity, causing the cooling coefficient to drop to 0.21 J·(cm²·s). -1 At concentrations above 60 wt%, the cooling coefficient increases to 0.30 J·(cm²·s). -1 However, excessive inorganic nuclei lead to discontinuity in the polyester matrix, resulting in severe stress concentration and reducing the fiber breaking strength to 3.5 cN·dtex. -1The critical value was even lower and the brittleness increased, which verified that precise control of the inorganic core content is the key to balancing thermal conductivity and mechanical properties.

[0207] Figure 3 To investigate the effect of the long axis dimension L50 of the zinc oxide submicron rods on the instantaneous cooling coefficient and fiber breaking strength, the following parameters were fixed: polyester matrix mass fraction 82.5 wt%, thermally conductive and antibacterial core-shell masterbatch mass fraction 17.5 wt%, zinc oxide inorganic core as a percentage of masterbatch 40 wt%, quaternary ammonium nitrogen as a percentage of masterbatch 1.15 wt%, and average zinc oxide rod diameter D50 of 175 nm. The amount of morphology control agent was kept constant, and other process conditions were the same. Figure 1 With fixed parameters, the average size L50 of the zinc oxide submicron rods along the long axis was varied from 0.08 μm to 2.8 μm by adjusting the hydrothermal reaction temperature and time. When the long axis size L50 was between 0.7 and 1.8 μm, the cooling coefficient and fiber breaking strength reached their optimal range at the moment of contact. Below 0.2 μm, the rod-shaped particles were too short to form an effective axial heat-guiding path, causing the cooling coefficient to drop to 0.19 J·(cm²·s). -1 At a depth higher than 2.0 μm, the cooling coefficient increases to 0.31 J·(cm²·s). -1 However, long bars are prone to stress concentration, which leads to a significant reduction in fiber breaking strength to 3.5 cN·dtex. -1 Even lower values ​​and the tendency to break during spinning, affecting spinnability, indicate that optimizing the long axis size of zinc oxide rods is a key factor in achieving a balance between high coolness and high strength.

[0208] Figure 4 To investigate the effect of the quaternary ammonium nitrogen content in the masterbatch on the antibacterial rate of Staphylococcus aureus and the retention rate of antibacterial activity after 50 machine washes, the following parameters were fixed: polyester matrix mass fraction 82.5 wt%, thermally conductive antibacterial core-shell masterbatch mass fraction 17.5 wt%, zinc oxide inorganic core content in the masterbatch 40 wt%, zinc oxide rod L50 1.0 μm, D50 175 nm, and other process conditions as described above. Figure 1 With fixed parameters, the variable parameter was the mass fraction of quaternary ammonium nitrogen in the thermally conductive antibacterial core-shell masterbatch, adjusted from 0.15 wt% to 2.5 wt% by the amount of bis-2-hydroxyethyldimethylammonium chloride. When the mass fraction of quaternary ammonium nitrogen in the masterbatch was 1.0 to 2.0 wt%, the antibacterial rate and wash resistance of Staphylococcus aureus reached their peak range simultaneously. Below 0.3 wt%, the insufficient antibacterial active sites of quaternary ammonium salt caused the antibacterial rate to drop to 88.5%, and the wash resistance retention rate was only 72.0%. Above 2.0 wt%, although the antibacterial rate was maintained at 99.9%, the excessive quaternary ammonium salt increased the risk of skin irritation, and the excessive migration of small molecules affected safety. At the same time, the wash resistance retention rate decreased to 92.0%. This proves that precise control of quaternary ammonium nitrogen content is the core element in balancing antibacterial effect, wash resistance, and skin contact safety.

[0209] Figure 5 Zn High-resolution X-ray photoelectron spectroscopy overlay, with fixed parameters of XPS acquisition channel energy step size of 0.1 eV, pass energy of 20 eV, and analysis chamber vacuum better than [value missing]. mbar, incident X-rays of Al Kα (1486.6 eV), test temperature 23°C, and the same data processing workflow of Shirley background subtraction and Gaussian-Lorentz mixed peak fitting were used. The varying parameters were the sample surface structure, from pure ZnO powder, silanized ZnO powder to ZnO inorganic cores in thermally conductive and antibacterial core-shell masterbatches. Pure ZnO samples Zn The main peak is located at 1022.0 eV, corresponding to Bond; Zn in silanized ZnO and subsequent core-shell masterbatches after hydrolysis and polycondensation treatment with γ-glycidyl etheroxypropyltrimethoxysilane. The main peak shifted uniformly to 1022.3 eV, while a Si–O–Zn characteristic peak of about 103.5 eV appeared in the Si 2p spectrum (not shown in this figure). The overall peak shift ΔBE≈0.3 eV indicates that the chemical environment of Zn has changed from pure Zn–O to Si–O–Zn bridging bond, proving that the silane coupling layer significantly enhances the interfacial bonding between the inorganic core and organic shell of zinc oxide by forming covalent Si–O–Zn bonds.

[0210] Figure 6 The results of high-resolution X-ray photoelectron spectroscopy and peak separation for N 1s were obtained, with fixed parameters of XPS acquisition channel energy step size of 0.1 eV, flux value of 20 eV, and analysis chamber vacuum better than [value missing]. The incident X-ray intensity was mbar, Al Kα (1486.6 eV), and all samples underwent the same fiber surface pretreatment and charging correction conditions (with C 1s 284.8 eV as a reference). The varying parameter was the mass fraction of quaternary ammonium nitrogen in the quaternized copolyester shell in the total mass of the thermally conductive and antibacterial core-shell masterbatch, which was 0.15 wt% (Comparative Example 5), 1.15 wt% (Example 1), and 2.5 wt% (Comparative Example 6), respectively. High-resolution peak fitting of the N 1s spectra of the three samples showed that the amide nitrogen peak at approximately 399.8 eV and the quaternary ammonium nitrogen peak at approximately 402.1 eV could be stably separated. Peak; in Comparative Example 5 The atomic percentage is approximately 0.15 at.%. A ratio below 0.2 indicates insufficient quaternary ammonium site density; in Example 1 The atomic percentage is approximately 1.15 at.%. The ratio is approximately 0.68, which is in the middle of the preferred range corresponding to 0.8–1.5 at.%; in Comparative Example 6... The atomic percentage is approximately 2.50 at.%. A ratio higher than 0.8 indicates excessively high quaternary ammonium nitrogen content. This figure directly demonstrates that the quaternized copolyester shell introduces stable quaternary ammonium nitrogen into the fiber surface. Chemical state, and can be adjusted by controlling the quaternary ammonium nitrogen content. The surface density was controlled within a suitable window range, providing a chemical basis for subsequent regulation of antibacterial and wash-resistant properties.

[0211] Figure 7 The XPS depth profiles for Example 1 and Comparative Example 11 of this invention are shown below. The parameters are fixed as follows: polyester fiber linear density 2.0 dtex, thermally conductive and antibacterial core-shell masterbatch mass fraction 17.5 wt%, zinc oxide submicron rod-shaped inorganic core mass fraction 40 wt%, quaternized copolyester shell thickness approximately 17 nm, and XPS using Ar... + Sputtering was performed to perform depth profiling from 0 to 100 nm in 10 nm steps. The varying parameters were the shell interface silanization conditions. In Example 1, the silanization temperature was 70 °C, the pH value was 4.5, and the reaction time was 2.0 h. In Comparative Example 11, the silanization temperature was 50 °C, the pH value was 3.5, and the reaction time was 0.5 h. In Example 1, the atomic fraction of nitrogen (N) gradually decreased from 1.32 at.% to 1.15 at.% and the atomic fraction of sulfur (S) gradually decreased from 1.25 at.% to 1.13 at.% within the 0 to 50 nm range. The slopes of these changes with depth were similar, and the N / S ratio remained between approximately 0.95 and 1.02, indicating a synergistic and uniform distribution of quaternary ammonium nitrogen and sulfonic acid groups within the shell. In Comparative Example 11, the atomic fraction of N rapidly decreased from 1.10 at.% to 0.35 at.% after 10 nm, while the S fraction remained within the 0.90 to 1.10 at.% range. The N / S ratio dropped sharply from 0.93 to 0.39 within the 10 to 50 nm range, indicating discontinuous coating of the quaternized copolyester shell and insufficient anchoring of quaternary ammonium nitrogen. These results demonstrate that under a molar ratio of quaternary ammonium nitrogen to sulfonic acid groups of 1.0, uniform ion pair anchoring achieved through appropriate silanization can significantly suppress the depth-direction migration of quaternary ammonium salts, providing a structural basis for maintaining subsequent wash-resistant and antibacterial properties.

[0212] Figure 8 The XPS depth profile curves and statistical results showing the N / S ratio variation with depth in this invention are presented. The fixed parameters are: polyester matrix mass fraction 82.5 wt%, thermally conductive and antibacterial core-shell masterbatch mass fraction 17.5 wt%, quaternary ammonium nitrogen to aromatic sulfonic acid groups molar ratio in the quaternized copolyester shell 1.0, and the same detection area and Ar²⁺ spectroscopy method used for XPS testing. +Sputtering power, varying parameters including sample type (Example 1 and Comparative Example 11), and statistical depth range of 0 to 50 nm. In Example 1, the N / S ratio fluctuated between 0.95 and 1.05 in the 0 to 50 nm range, with a calculated mean of approximately 1.00, standard deviation of approximately 0.03, and coefficient of variation (CV) of approximately 0.03. In Comparative Example 11, the N / S ratio rapidly decreased from approximately 0.93 near the surface to approximately 0.39 in the same depth range, with a mean of approximately 0.62, standard deviation of approximately 0.32, and CV of approximately 0.52. Depth profiling showed that the N / S ratio within the shell of Example 1 was close to the theoretical molar ratio of 1.0 throughout the entire functional layer thickness with minimal fluctuation, while Comparative Example 11 exhibited a clear trend of surface enrichment and internal depletion, with a severe imbalance in the depth direction. Based on machine wash durability data, Example 1 maintained an inhibition rate of approximately 88% against Staphylococcus aureus, Escherichia coli, and Candida albicans after 50 home machine washes, while Comparative Example 11 maintained a retention rate of less than 75%. This indicates that when the standard deviation of the N / S ratio within the shell is less than 0.15 and the CV is significantly low, higher antibacterial durability and wash resistance can be achieved.

[0213] Figure 9 XRD phase diagram of the zinc oxide submicron rod prepared in Example 1 of this invention and Figure 10 The images show the morphology of the zinc oxide submicron rods prepared in Example 1 of this invention, which together verify the crystal structure and microstructure characteristics of the zinc oxide submicron rods prepared by the hydrothermal method. The XRD pattern shows sharp diffraction peaks at 31.77°, 34.42°, 36.25°, 47.54°, 56.60°, 62.86°, 66.38°, 67.96°, and 69.10°, corresponding to the 100, 002, 101, 102, 110, 103, 200, 112, and 201 crystal planes of the hexagonal wurtzite structure of zinc oxide, respectively. The high intensity and narrow half-maximum width at half-maximum of each diffraction peak indicate good crystallinity and the absence of impurity phases. The significantly higher intensity of the 002 crystal plane diffraction peak compared to other crystal planes confirms the preferential growth of the zinc oxide crystals along the c-axis. Morphology images show that zinc oxide exhibits a uniform rod-like morphology, with the long axis size concentrated in the range of 0.8 to 1.2 μm and an average L50 of 1.0 μm. The short axis diameter is distributed in the range of 150 to 200 nm and an average D50 of 175 nm. The rod-shaped particles have smooth surfaces and well-dispersed ends without obvious agglomeration. Combined XRD and morphology analysis proves that the hydrothermal synthesis process parameters were precisely controlled, successfully preparing highly crystalline, high-purity, and controllable morphology and size submicron-shaped zinc oxide particles. This provides a high-quality inorganic core material basis for subsequent silanization modification and thermal conductivity and antibacterial properties.

[0214] Figure 11The image shows the morphology of the polyester fiber prepared in Example 1 of this invention, visually demonstrating the dispersion and orientation of zinc oxide submicron rods in the polyester fiber matrix. The polyester fiber exhibits a regular cylindrical morphology with a smooth surface free of obvious defects. The zinc oxide submicron rods are uniformly dispersed in the polyester matrix without significant agglomeration. The rod-shaped particles show a certain degree of orientational alignment along the fiber axis, with the long axis direction basically parallel to the fiber stretching direction. This orientational distribution is attributed to the shear and tensile stresses generated by the winding speed and stretching during melt spinning, causing the rod-shaped particles to align collaboratively with the polyester molecular chains. The interface between the polyester matrix and the zinc oxide rods is tightly bonded without obvious voids or debonding, proving that the silanized modified polyester shell effectively improves the compatibility between the inorganic core and the polyester matrix. The morphology image fully verifies that the masterbatch blending melt spinning process can achieve uniform dispersion and axial orientation of zinc oxide submicron rods in the fiber, providing a microstructural basis for the synergistic optimization of the fiber's thermal conductivity, antibacterial properties, and mechanical properties.

[0215] As can be seen from the performance of the embodiments and comparative examples in Table 1, the instantaneous cooling coefficient qmax of embodiments 1-4 is between 0.22 and 0.29. Within the range, all values ​​were significantly higher than the baseline value of 0.18 for ordinary polyester fabrics without added thermally conductive and antibacterial core-shell masterbatch. The antibacterial rate against Staphylococcus aureus reached over 99.3%, demonstrating excellent overall performance. Comparative Example 1, while having a high cooling coefficient, suffered from excessive masterbatch, resulting in a tensile strength of only 2.8 cN / dtex, far below the minimum requirement of 3.5 cN / dtex, and decreased wash resistance. Comparative Example 2, due to insufficient masterbatch, had a cooling coefficient reduced to 0.17. Furthermore, the antibacterial properties are severely insufficient. Comparative Examples 3-4 show that the proportion of inorganic cores deviates from the optimal range, resulting in damage to either the cooling sensation or the strength. Comparative Examples 5-6 show that excessively low or high quaternary ammonium nitrogen levels cause an imbalance between antibacterial properties or washability and strength. Comparative Examples 7-10 demonstrate that deviations in the size of zinc oxide rods from the range of 0.2-2.0 μm and from the aspect ratio range of 3-20 significantly weaken the thermal conductivity orientation effect or mechanical strength. Comparative Examples 11-14 show that deviations in process temperature from the preferred range lead to incomplete shell coating or polyester degradation, affecting overall performance. These examples fully verify the scientific rationality of the scope defined by the claims of this invention and the necessity of synergistic optimization.

[0216] Table 1 Performance summary of examples and comparative examples

[0217]

[0218] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that any equivalent structural transformations made under the concept of the present invention and using the contents of the specification and drawings of the present invention should be covered within the scope of protection of the claims of the present invention.

Claims

1. A cooling and antibacterial polyester fabric, characterized in that, The fabric is woven or knitted from polyester fibers, which include: The polyester matrix comprises an aromatic polyester primarily composed of polyethylene terephthalate, wherein the mass fraction of the polyester matrix in the polyester fibers is 70 wt% to 95 wt% of the total mass of the polyester fibers; A thermally conductive and antibacterial core-shell masterbatch, wherein the mass fraction of the thermally conductive and antibacterial core-shell masterbatch in the polyester fiber is 5 wt% to 30 wt% of the total mass of the polyester fiber, the thermally conductive and antibacterial core-shell masterbatch comprises a zinc oxide submicron rod-shaped inorganic core and an organic shell layer coating the surface of the zinc oxide submicron rod-shaped inorganic core, wherein: The zinc oxide submicron rod-shaped inorganic core has a one-dimensional rod-shaped morphology and is at least partially aligned along the axial direction of the polyester fiber during the forming and stretching process, so as to improve the longitudinal thermal conductivity of the polyester fiber and enhance the instantaneous cooling sensation upon contact. The organic shell comprises a silane coupling layer and a quaternized copolyester shell. The silane coupling layer is formed by the hydrolytic condensation of γ-glycidoxypropyltrimethoxysilane and is connected to the zinc oxide submicron rod-shaped inorganic core through Si-O-Zn bonds. The quaternized copolyester shell covers the outside of the silane coupling layer and is obtained by esterification condensation of terephthalic acid or dimethyl terephthalate, ethylene glycol, monosodium 5-sulfoisophthalate and bis-2-hydroxyethyldimethylammonium chloride. In the thermally conductive and antibacterial core-shell masterbatch, the mass fraction of the zinc oxide submicron rod-shaped inorganic core is 20 wt% to 60 wt% of the total mass of the thermally conductive and antibacterial core-shell masterbatch, and the mass fraction of quaternary ammonium nitrogen in the quaternized copolyester shell is 0.3 wt% to 2.0 wt% of the total mass of the thermally conductive and antibacterial core-shell masterbatch. The thermally conductive and antibacterial core-shell masterbatch is prepared through the following steps: A1. Preparation of silanized zinc oxide submicron rod powder: Zinc oxide submicron rod powder with a submicron rod morphology and an average size L50 of 0.2 μm to 2.0 μm in the long axis direction is dispersed in a water-alcohol mixed solvent, γ-glycidoxypropyltrimethoxysilane is added, and the reaction is carried out at a pH of 4.0 to 5.0 and a temperature of 60℃ to 80℃ for 1.0 h to 3.0 h. After washing and drying, silanized zinc oxide submicron rod powder with epoxy functional groups on the surface is obtained. A2. Preparation of quaternized copolyester prepolymer chips: Terephthalic acid or dimethyl terephthalate, monosodium 5-sulfoisophthalate, ethylene glycol and bis-2-hydroxyethyldimethylammonium chloride are added to an esterification reactor and esterification reaction is carried out at a temperature of 200℃ to 240℃. After esterification reaction, antimony trioxide catalyst is added and polycondensation reaction is carried out at a temperature of 260℃ to 280℃ and a vacuum degree not exceeding 300Pa to obtain quaternized copolyester prepolymer chips; A3. Preparation of thermally conductive and antibacterial core-shell masterbatch: The silanized zinc oxide submicron rod powder and the quaternized copolyester prepolymer chips are melt-blended at a mass ratio of 20-60:40-80 at a temperature of 250℃ to 280℃, and then water-cooled and pelletized or underwater pelletized to obtain thermally conductive and antibacterial core-shell masterbatch with a median volume diameter (D50) of 80μm to 200μm; The zinc oxide submicron rod powder is prepared by the following steps: B1. Preparation of submicron rod-shaped zinc oxide precursor: A zinc-containing inorganic salt solution was mixed with an alkaline source, and a morphology control agent was added. The mixture was reacted under hydrothermal conditions at 120℃ to 220℃ for 2h to 24h. After cooling, the resulting reaction slurry was subjected to solid-liquid separation and washed with deionized water 3 to 10 times until the conductivity of the filtrate was no higher than 50μS / cm and the pH value was 6.5 to 7.

5. The filtrate was then dried at 80℃ to 120℃ for 2h to 12h to obtain the submicron rod-shaped zinc oxide precursor. B2. Preparation of zinc oxide submicron rod powder by calcination: The submicron rod-shaped zinc oxide precursor is calcined in an air atmosphere at a temperature of 400°C to 650°C for 1 to 4 hours to obtain zinc oxide submicron rod powder. The zinc-containing inorganic salt is selected from at least one of zinc nitrate, zinc acetate, and zinc chloride, and the zinc-containing inorganic salt solution contains Zn. 2+ The concentration of the alkali source is from 0.1 mol / L to 0.8 mol / L, and the alkali source is selected from at least one of sodium hydroxide solution, potassium hydroxide solution, and ammonia water, wherein the OH in the alkali source is... - With the zinc-containing inorganic salt solution, Zn 2+ The molar ratio is 2.0-5.0 to 1, and the morphology control agent is selected from one or more of sodium citrate, sodium tartrate, polyethylene glycol, polyvinylpyrrolidone and hexadecyltrimethylammonium bromide, and the amount of the morphology control agent is 1 wt% to 20 wt% based on the ratio of the mass of the morphology control agent to the theoretical mass of the zinc-containing inorganic salt based on zinc oxide.

2. The cooling antibacterial polyester fabric according to claim 1, characterized in that, In the quaternized copolyester shell: the molar fraction of the 5-sulfoisophthalic acid monosodium salt relative to the total molar amount of the dicarboxylic acid is 0.5 mol% to 8.0 mol%; The molar fraction of bis-2-hydroxyethyl dimethyl ammonium chloride relative to the total molar amount of the diol is from 0.5 mol% to 5.0 mol%. The molar ratio of quaternary ammonium nitrogen to sulfonic acid groups on the aromatic ring in the quaternized copolyester shell is 0.5 to 2.0:

1.

3. The cooling antibacterial polyester fabric according to claim 1, characterized in that, The zinc oxide submicron rod-shaped inorganic core has an average size L50 of 0.2 μm to 2.0 μm along its long axis and an average diameter D50 of 50 nm to 300 nm along its short axis, with an aspect ratio of 3 to 20; the thermally conductive and antibacterial core-shell masterbatch has a particle volume median diameter D50 of 80 μm to 200 μm; and the quaternized copolyester shell has a thickness of 5 nm to 30 nm.

4. The cooling antibacterial polyester fabric according to claim 1, characterized in that, When preparing the polyester fiber, the mass ratio of the polyester matrix chips to the thermally conductive and antibacterial core-shell masterbatch before melt blending is 70 to 95 to 5 to 30, and the total mass fraction of zinc oxide in the resulting polyester fiber is 3 wt% to 15 wt% of the total mass of the polyester fiber.

5. The cooling antibacterial polyester fabric according to claim 1, characterized in that, In addition to polyethylene terephthalate, the polyester matrix also contains no more than 30 wt% of other aromatic polyesters, wherein the other aromatic polyesters are selected from at least one of polybutylene terephthalate and polytrimethylene terephthalate, and the total content of the polyester matrix in the polyester fiber is not less than 70 wt% of the total mass of the polyester fiber.

6. The method for preparing the cooling antibacterial polyester fabric according to any one of claims 1 to 5, characterized in that, Includes the following steps: S1. Preparation of thermally conductive and antibacterial core-shell masterbatch; S2. Melt blending and granulation: The polyester matrix chips and the thermally conductive antibacterial core-shell masterbatch are mixed at a mass ratio of 70-95:5-30 and then fed into a twin-screw extruder. The mixture is melt-blended at a temperature of 250°C to 285°C. The residence time of the material in the barrel is 2 min to 8 min. The material is then devolatilized under a vacuum of no more than 500 Pa. The modified polyester chips are obtained by water-cooled stringing or underwater pelletizing. S3. Melt spinning: The modified polyester chips are dried and fed into a melt spinning unit, where they are melted at a melt temperature of 265°C to 285°C, extruded and wound through a spinning assembly to obtain nascent polyester fibers. S4. Stretching and heat setting: The nascent polyester fibers are stretched in 2 to 3 passes with a total stretch ratio of 3.0 to 4.5, and then heat-set at a temperature of 160°C to 190°C for 20 to 120 seconds to obtain polyester filaments or polyester staple fibers with a breaking strength of not less than 3.5 cN / dtex. The zinc oxide submicron rod-shaped inorganic cores are preferentially oriented along the axial direction of the polyester fibers to improve the longitudinal thermal conductivity of the polyester fibers and enhance the cooling effect. S5. Weaving and finishing: The polyester filaments or polyester staple fibers obtained in step S4 are woven or knitted to form a greige fabric with an areal density of 120g / m² to 200g / m². The fabric is then softened with a softening agent that does not contain free quaternary ammonium salts or whose free quaternary ammonium salt content does not exceed 1 wt% of the fabric mass. The fabric is then baked at a temperature of 150°C to 180°C for 20 to 90 seconds to obtain a cool-feeling antibacterial polyester fabric.

7. The method for preparing the cooling antibacterial polyester fabric according to claim 6, characterized in that, The twin-screw extruder described in step S2 has an aspect ratio of 32 to 44 and a screw speed of 150 r / min to 350 r / min; In step S2, the thermally conductive and antibacterial core-shell masterbatch is added to the twin-screw extruder via a side-feed method, allowing the thermally conductive and antibacterial core-shell masterbatch to be melted and dispersed in the latter half of the barrel, thereby reducing the shear degradation of the quaternized copolyester shell layer, and the average spacing between adjacent thermally conductive and antibacterial core-shell masterbatches in the cross-section of the resulting polyester fiber is less than 3 μm.

8. The method for preparing the cooling antibacterial polyester fabric according to claim 6, characterized in that, In step S3, the winding speed of melt spinning is 2500 m / min to 4500 m / min.

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