Oleophobic stain-repellent textile fabric and preparation method thereof

Abstract

The invention discloses an oleophobic dirt-repellent textile fabric and a preparation method thereof, and relates to the technical field of textile fabrics, the textile fabric is prepared by blending modified polyester fibers and modified bamboo fibers, the polyester fibers and the bamboo fibers are modified respectively, and after the modified polyester fibers and the modified bamboo fibers are mixed, the oleophobic dirt-repellent textile fabric is prepared. And carrying out high-temperature curing and emulsion soaking treatment, spinning, weaving and dyeing to obtain the textile fabric. By designing the fluorine-free modified polyester fiber, the green and environment-friendly functions are realized, the problems of environmental pollution, high energy consumption and long process period caused by fluorine-containing compounds are solved, the environmental pollution caused by the modification process can be avoided, the heat resistance and the size stability of the polyester fiber are improved, and the processing period is shortened.

Description

Technical Field

[0001] The present invention relates to the technical field of textile fabrics, and specifically to an oil-repellent and stain-resistant textile fabric and a preparation method thereof. Background Art

[0002] Traditional textiles use natural fibers and chemical fibers as raw materials, and go through processes such as yarn production, weaving, dyeing and finishing, and printing to form basic structures such as woven fabrics, knitted fabrics, and non-woven fabrics. With the development of modern technology, bio-based fibers, environmentally friendly synthetic fibers, and functional fibers have been developed, and the performance of fabrics has been improved through nanotechnology and intelligent materials; Traditional processes generally rely on fluorocarbons to reduce the surface energy of fabrics. However, these substances are difficult to degrade and easily accumulate in the environment for a long time, causing water and soil pollution. In addition, the lack of long-term durability of the prepared textile fabrics leads to waste of resources.

[0003] Patent CN105506989B discloses a three-proof and easy-to-decontaminate textile fabric and a preparation method thereof. The above patent realizes that the textile fabric has a whitening aesthetic effect, and at the same time has the properties of three-proof and easy-to-decontaminate and antistatic.

[0004] The above patent makes the textile fabric have a whitening aesthetic effect and the properties of three-proof and easy-to-decontaminate and antistatic through whitening treatment, three-proof and easy-to-decontaminate treatment, and antistatic treatment. There is room for optimization in the environmental protection of textile fabric preparation.

[0005] Therefore, this application proposes a green and environmentally friendly oil-repellent and stain-resistant textile fabric and a preparation method thereof. Summary of the Invention

[0006] The purpose of the present invention is to provide an oil-repellent and stain-resistant textile fabric and a preparation method thereof, so as to solve the technical problem of using fluorine-containing compounds for treatment to have hydrophobicity proposed in the above background art.

[0007] To achieve the above purpose, the present invention provides the following technical solution: A preparation method of an oil-repellent and stain-resistant textile fabric, the textile fabric is made by mixing and weaving modified polyester fibers and modified bamboo fibers; The preparation method of the modified polyester fiber is as follows: S1: Immerse the polyester fiber in a 10% sodium hydroxide solution at a temperature of 95°C, treat for 30 minutes, after neutralization and washing, use hot air at 80°C to dry for 10 minutes, and then use low-temperature plasma to treat the polyester fiber at a power of 200W - 300W for 2 minutes - 3 minutes; S2: In an environment with a pH of 5 - 6, keep the temperature constant at 80°C for 30 minutes with a non-fluorinated silicone emulsion with a concentration of 80g / L - 100g / L, polyester fiber, and 2% - 3% isocyanate cross-linking agent; S3: Immerse the fiber in an ethyl acetate solution with a concentration of 5%, and react at 50 °C for 0.5 h to 1 h; S4: Mix hydrophobic silica nanoparticles with a size of 20 nm to 50 nm and polyurethane resin at a weight ratio of 1:4, add cetyltriethoxysilane as a coupling agent, ultrasonically disperse for 30 min at 40 kHz, and then add 2% polyether-modified silicone oil to obtain mixture A; S5: Put mixture A into a twin-screw extruder, add 3% to 5% polydimethylsiloxane and 2% maleic anhydride graft compatibilizer, and extrude in an environment of 240 °C to 250 °C to obtain modified polyester fiber.

[0008] Preferably, the preparation method of the modified bamboo fiber is as follows: S1: Crush the bamboo slices and wash them with water to remove surface impurities, and add a plasticizer and a heat stabilizer in an environment of 105 °C and dry for 8 h to 12 h; S2: Add 1-ethyl-3-methylimidazolium chloride ionic liquid to the dried bamboo fiber, add a 0.05 wt% sodium borohydride solution, and ultrasonically treat for 30 min in an environment of 50 °C to 60 °C; S3: Add a maleic acid solution with a concentration of 5 wt%, and react at 60 °C for 1 h to 2 h; S4: After the reaction is completed, wash with a phosphate buffer solution with a pH of 5; S5: Adjust the pH to 8 to 9, then add an amphoteric crosslinking agent, and stir at 75 °C for 2 h; S6: Add a modification liquid and a surfactant, cool down to 60 °C, magnetically stir for 1 h to 3 h, and obtain modified bamboo fiber by centrifugal separation.

[0009] Preferably, the preparation method of the textile fabric is as follows: S1: Uniformly mix the modified polyester fiber and the modified bamboo fiber at a weight ratio of 50:50 to 70:30; S2: Place the mixed fiber in an environment of 80 °C to 120 °C for preheating and then enter an environment of 180 °C to 200 °C, and carry out high-temperature curing under a pressure of 0.5 MPa to 1.2 MPa; S3: Immerse the cured mixed fiber in an emulsion, add a coupling agent, impregnate at 60 °C for 1 h and ultrasonically disperse at 40 kHz for 30 min, and then raise the temperature to 80 °C and impregnate for 2 h; S4: Wash with a phosphate buffer solution with a pH of 6.5; S5: Dry at 50 °C for 10 min and then dry at 120 °C; S6: The dried mixed fiber is made into a textile fabric after spinning, weaving and dyeing treatments.

[0010] Preferably, the fluorine-free organosilicon emulsion is prepared by premixing fluorine-free organosilicon and polyether-modified polysiloxane at 60°C to 70°C, adding deionized water and shearing at high speed, and adding acetic acid to adjust the pH to 5 to 6.

[0011] Preferably, the plasticizer is a 0.5 wt% glycerol solution, and the heat stabilizer is a 0.2 wt% citric acid solution.

[0012] Preferably, the amphoteric crosslinking agent is an epoxy-octadecyl quaternary ammonium salt amphoteric crosslinking agent with a concentration of 0.8 wt%.

[0013] Preferably, the modified liquid is prepared by dissolving stearyl primary amine in an ethanol-water mixed solution with a volume ratio of 3:1 to prepare a 10 wt% stearyl primary amine ethanol-aqueous solution, and the surfactant is a 0.1 wt% sodium dodecyl sulfonate solution.

[0014] Preferably, the emulsion is prepared by compounding 40% solids content polyurethane resin and hydrophobic silica nanoparticles at a weight ratio of 1:4.

[0015] Preferably, the coupling agent is a 3% γ-aminopropyltriethoxysilane solution.

[0016] Preferably, the textile fabric is prepared by the above preparation method.

[0017] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. By designing fluorine-free modified polyester fibers, the present invention realizes the function of environmental protection, solves the problems of environmental pollution, high energy consumption and long process cycle caused by fluorine-containing compounds, can avoid environmental pollution during the modification process, improves the heat resistance and dimensional stability of polyester fibers, and shortens the processing cycle. 2. By designing the process of crosslinking first and then hydrophobic modification in the preparation of modified bamboo fibers, the present invention realizes the function of synergistically improving the mechanical properties and hydrophobicity of modified bamboo fibers, solves the problems of low crosslinking efficiency, hindrance of the hydrophobic layer to the penetration and grafting of crosslinking agents, and decrease in material toughness, can improve the penetration efficiency and grafting rate of crosslinking agents, enhances the mechanical properties and interfacial stability of modified bamboo fibers, avoids the appearance of surface microcracks, and shortens the processing time. 3. By designing the preparation of textile fabrics by mixing modified polyester fibers and modified bamboo fibers, the present invention realizes the function of shortening the natural degradation cycle of textile fabrics, solves the problems of weak antibacterial performance and environmental pollution, can make the properties of polyester fibers and bamboo fibers complementary, improves the antibacterial performance of textile fabrics, and reduces the irritation of textile fabrics to the skin. 4. The present invention realizes the function of improving the properties of hybrid fibers by designing the treatment of modified polyester fibers and modified bamboo fibers after mixing during the preparation process of textile fabrics, solves the performance conflicts in the modification stage, the problems of selective coverage and secondary acid-base corrosion, can reduce resource consumption, shortens the degradation and collection of textile fabrics, and reduces the manual processing pressure. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 It is a schematic flow chart of the preparation of modified polyester fibers of the present invention; Figure 2 It is a schematic flow chart of the preparation of modified bamboo fibers of the present invention; Figure 3 It is a schematic flow chart of the preparation of textile fabrics of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0019] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0020] Example 1: Please refer to Figure 1 、 Figure 2 and Figure 3 , a method for preparing an oil-repellent and stain-resistant textile fabric, the textile fabric is made by mixing and weaving modified polyester fibers and modified bamboo fibers; The preparation method of the modified polyester fibers is as follows: S1: Immerse the polyester fibers in a 10% sodium hydroxide solution at a temperature of 95°C for 30 minutes, after neutralization and cleaning, use hot air drying at 80°C for 10 minutes, and then use low-temperature plasma to treat the polyester fibers at a power of 200W for 3 minutes; S2: In an environment with a pH of 5, keep the temperature constant at 80°C for 30 minutes with a fluorine-free silicone emulsion with a concentration of 80 g / L, polyester fibers, and a 2% isocyanate crosslinking agent; S3: Immerse the fibers in an ethyl acetate solution with a concentration of 5% and react at 50°C for 0.5 h; S4: Mix 30 nm hydrophobic silica nanoparticles and polyurethane resin in a weight ratio of 1:4, add cetyltriethoxysilane as a coupling agent, after ultrasonic dispersion at 40 kHz for 30 minutes, add 2% polyether-modified silicone oil to obtain mixture A; S5: Put mixture A into a twin-screw extruder, add 5% polydimethylsiloxane and 2% maleic anhydride graft compatibilizer, and extrude in an environment of 240°C to obtain modified polyester fibers; The preparation method of the modified bamboo fiber is as follows: S1: Crush the bamboo slices, wash them with water to remove surface impurities, and add a plasticizer and a heat stabilizer in an environment of 105°C, then dry for 8 h; S2: Add 1-ethyl-3-methylimidazolium chloride ionic liquid to the dried bamboo fiber, add a 0.05 wt% sodium borohydride solution, and perform ultrasonic treatment for 30 min in an environment of 50°C; S3: Add a maleic acid solution with a concentration of 5 wt%, and react at 60°C for 1 h; S4: After the reaction is completed, wash with a phosphate buffer solution with pH = 5; S5: Adjust the pH to 8.5, then add an amphoteric crosslinking agent, and stir at 75°C for 2 h; S6: Add a modification solution and a surfactant, cool down to 60°C, stir magnetically for 2 h, and obtain the modified bamboo fiber through centrifugal separation; The preparation method of the textile fabric is as follows: S1: Uniformly mix the modified polyester fiber and the modified bamboo fiber according to a weight ratio of 65:35; S2: Place the mixed fiber in an environment of 80°C for preheating and then enter an environment of 180°C, and perform high-temperature curing under a pressure of 1 MPa; S3: Immerse the cured mixed fiber in an emulsion, add a coupling agent, impregnate at a temperature of 60°C for 1 h and disperse with 40 kHz ultrasonic waves for 30 min, and then raise the temperature to 80°C and impregnate for 2 h; S4: Wash with a phosphate buffer solution with pH = 6.5; S5: Dry at 50°C for 10 min and then dry at 120°C; S6: The dried mixed fiber is made into a textile fabric after spinning, weaving and dyeing treatments; The fluorine-free silicone emulsion is prepared by premixing fluorine-free silicone and polyether-modified polysiloxane at 60°C, adding deionized water and performing high-speed shearing, and adding acetic acid to adjust the pH to 5; The plasticizer is a 0.5 wt% glycerol solution, and the heat stabilizer is a 0.2 wt% citric acid solution; The amphoteric crosslinking agent is a 0.8 wt% epoxy-octadecyl quaternary ammonium salt amphoteric crosslinking agent; The preparation method of the modification solution is to dissolve stearyl primary amine in an ethanol-water mixed solution with a volume ratio of 3:1 to prepare a 10 wt% stearyl primary amine ethanol-aqueous solution, and the surfactant is a 0.1 wt% sodium dodecyl sulfonate solution; The emulsion is prepared by compounding a 40% solids content polyurethane resin and hydrophobic silica nanoparticles according to a weight ratio of 1:4; The coupling agent is a 3% γ-aminopropyltriethoxysilane solution; Further, immerse the polyester fiber in a 10% sodium hydroxide solution at 95°C for 30 min. After neutralization and washing, dry it with hot air at 80°C for 10 min. Then, treat the polyester fiber with low-temperature plasma at a power of 200 W for 3 min. Immerse the fiber in a fluorine-free organosilicon emulsion with a concentration of 80 g / L, polyester fiber, and 2% isocyanate crosslinking agent in an environment with pH = 5, and perform a constant-temperature treatment at 80°C for 30 min. Immerse the fiber in an ethyl acetate solution with a concentration of 5% and react at 50°C for 0.5 h. Mix 30 nm hydrophobic silica nanoparticles and polyurethane resin in a weight ratio of 1:4, add cetyltriethoxysilane as a coupling agent, perform ultrasonic dispersion at 40 kHz for 30 min, and then add 2% polyether-modified silicone oil to obtain mixture A. Put mixture A into a twin-screw extruder, add 5% polydimethylsiloxane and 2% maleic anhydride graft compatibilizer, and extrude in an environment at 240°C to obtain modified polyester fiber. Crush the bamboo slices, wash them with water to remove surface impurities, add a plasticizer and a heat stabilizer, and dry them at 105°C for 8 h. Add 1-ethyl-3-methylimidazolium chloride ionic liquid to the dried bamboo fiber, add a 0.05 wt% sodium borohydride solution, perform ultrasonic treatment at 50°C for 30 min, add a maleic acid solution with a concentration of 5 wt%, react at 60°C for 1 h, wash with a phosphate buffer solution with pH = 5 after the reaction is completed, adjust the pH to 8.5, add an amphoteric crosslinking agent, stir at 75°C for 2 h, add a modification solution and a surfactant, cool down to 60°C, and perform magnetic stirring for 2 h. Obtain modified bamboo fiber by centrifugal separation. Uniformly mix the modified polyester fiber and the modified bamboo fiber in a weight ratio of 65:35. Preheat the mixed fiber at 80°C and then enter an environment at 180°C, and perform high-temperature curing under a pressure of 1 MPa. Immerse the cured mixed fiber in an emulsion, add a coupling agent, impregnate at 60°C for 1 h and perform ultrasonic dispersion at 40 kHz for 30 min, then raise the temperature to 80°C and impregnate for 2 h. Wash with a phosphate buffer solution with pH = 6.5, dry at 50°C for 10 min and then dry at 120°C. The dried mixed fiber is made into a textile fabric after spinning, weaving, and dyeing treatments; Control group 1: Do not modify the polyester fiber, keep other conditions unchanged, and prepare the textile fabric; Control group 2: Do not modify the bamboo fiber, keep other conditions unchanged, and prepare the textile fabric; Control group 3: When preparing the modified bamboo fiber, perform crosslinking first and then hydrophobic modification, keep other conditions unchanged, and prepare the textile fabric Control group 4: When performing the mixed preparation, do not perform high-temperature curing, keep other conditions unchanged, and prepare the textile fabric; Control group 5: When performing the mixing preparation, emulsion impregnation is not carried out, and other conditions remain unchanged for the preparation of the textile fabric.

[0021] Example 2: Please refer to Figure 1 , a method for preparing an oil-repellent and stain-resistant textile fabric, the textile fabric is made by mixing and weaving modified polyester fibers and modified bamboo fibers; The preparation method of the modified polyester fiber is as follows: S1: Immerse the polyester fiber in a 10% sodium hydroxide solution at 95 °C, treat for 30 min, wash and neutralize, then dry with hot air at 80 °C for 10 min, and then treat the polyester fiber with low-temperature plasma at a power of 200 W for 3 min; S2: Immerse the non-fluorinated silicone emulsion with a concentration of 80 g / L, polyester fiber and 2% isocyanate cross-linking agent in an environment with pH = 5 and treat at a constant temperature of 80 °C for 30 min; S3: Immerse the fiber in an ethyl acetate solution with a concentration of 5% and react at 50 °C for 0.5 h; S4: Mix 30 nm hydrophobic silica nanoparticles and polyurethane resin in a weight ratio of 1:4, add cetyltriethoxysilane as a coupling agent, disperse by ultrasonic wave at 40 kHz for 30 min, and then add 2% polyether-modified silicone oil to obtain mixture A; S5: Put mixture A into a twin-screw extruder, add 5% polydimethylsiloxane and 2% maleic anhydride graft compatibilizer, and extrude in an environment of 240 °C to obtain modified polyester fibers; The non-fluorinated silicone emulsion is prepared by premixing non-fluorinated silicone and polyether-modified polysiloxane at 60 °C - 70 °C, adding deionized water and high-speed shearing, and adjusting the pH to 5 -6 with acetic acid; Further, during the preparation of modified polyester fibers, after the polyester fibers are immersed in a 10% sodium hydroxide solution at 95°C for etching treatment, low-temperature plasma is used to bombard the fiber surface through high-energy particles to further enhance the subsequent coating adhesion, forming a dual surface modification effect. Subsequently, an 80 g / L fluorine-free silicone emulsion and a 2% isocyanate crosslinking agent are mixed with the polyester fibers, and the mixture is subjected to a constant-temperature treatment at 80°C for 30 min in an environment with a pH of 5. Compared with the existing process that uses fluorine-containing compounds for treatment to achieve hydrophobicity, not only is the pollution of fluorine-containing compounds avoided, and the wastewater discharge is reduced, but also a stable three-dimensional network structure is formed through crosslinking reaction. Subsequently, the residual siloxane oligomers are removed by a 5% ethyl acetate solution, avoiding the problem of residues in water washing and reducing the use of cleaning resources at the same time. 30 nm hydrophobic silica nanoparticles and polyurethane resin are mixed at a weight ratio of 1:4, cetyltriethoxysilane is added as a coupling agent, and after ultrasonic dispersion at 40 kHz for 30 min, 2% polyether-modified silicone oil is added to obtain mixture A. After extrusion by a twin-screw extruder, modified polyester fibers are obtained, enabling the nanoparticles to improve the mechanical strength of the fibers through the pinning effect. At the same time, polydimethylsiloxane is added during the extrusion process to enhance the wear resistance and flexibility of the fibers. After modification, the feel of the polyester fibers is improved, and the hydrophobicity, wear resistance, high-temperature resistance, and structural stability are also enhanced.

[0022] Example 3: Please refer to Figure 2 , a preparation method of an oil-repellent and stain-resistant textile fabric, and the preparation method of the modified bamboo fibers is as follows: S1: Crush the bamboo slices and then wash them with water to remove surface impurities, and add a plasticizer and a heat stabilizer and dry them at 105°C for 8 h; S2: Add 1-ethyl-3-methylimidazolium chloride ionic liquid to the dried bamboo fibers, add a 0.05 wt% sodium borohydride solution, and ultrasonically treat them at 50°C for 30 min; S3: Add a maleic acid solution with a concentration of 5 wt%, and react at 60°C for 1 h; S4: After the reaction is completed, wash with a phosphate buffer solution with a pH of 5; S5: Adjust the pH to 8.5 and then add an amphoteric crosslinking agent, and stir at 75°C for 2 h; S6: Add a modification solution and a surfactant, cool down to 60°C, stir magnetically for 2 h, and obtain modified bamboo fibers by centrifugal separation; The plasticizer is a 0.5 wt% glycerol solution, and the heat stabilizer is a 0.2 wt% citric acid solution; The amphoteric crosslinking agent is a 0.8 wt% epoxy-octadecyl quaternary ammonium salt amphoteric crosslinking agent; The method for preparing the modification liquid is to dissolve stearyl primary amine in an ethanol-water mixed solution with a volume ratio of 3:1 to prepare a 10wt% stearyl primary amine ethanol-aqueous solution, and the surfactant is a 0.1wt% sodium dodecyl sulfonate solution; Furthermore, after the bamboo slices are crushed and washed with water, adding a 0.5wt% glycerol solution as a plasticizer weakens the hydrogen bond effect and improves the flexibility of the bamboo fibers. Adding a 0.2wt% citric acid solution as a heat stabilizer reduces the decomposition of the bamboo fibers at high temperatures. When adding a 0.8wt% epoxy-octadecyl quaternary ammonium salt amphoteric crosslinking agent to carry out the crosslinking reaction, a three-dimensional network is formed in the bamboo fibers, improving the tensile strength and wear resistance of the bamboo fibers, making the bamboo fibers more resistant to high temperatures during processing and use. The quaternary ammonium salt group can also destroy the bacterial cell membrane and combine with the antibacterial properties carried by the bamboo fibers themselves to further enhance the antibacterial properties of the modified bamboo fibers. During the hydrophobic modification, by introducing stearyl primary amine to cover the surface of the bamboo fibers, a hydrophobic layer is formed to reduce the absorption rate and improve the stain resistance of the bamboo fibers. During the crosslinking and hydrophobic modification, after adjusting the pH to 8.5, adding a 0.8wt% epoxy-octadecyl quaternary ammonium salt amphoteric crosslinking agent, stirring in a 75°C environment for 2h, then cooling to 60°C, adding a 10wt% stearyl primary amine ethanol-aqueous solution prepared by dissolving stearyl primary amine in an ethanol-water mixed solution with a volume ratio of 3:1 as the modification liquid and a 0.1wt% sodium dodecyl sulfonate solution as the surfactant. After the crosslinking network is constructed, an open pore structure is formed inside the material, allowing the modification liquid to penetrate into the fiber interior through diffusion, avoiding the hydrophobic layer from prematurely hindering the crosslinking agent from contacting the active sites. When immersing from the crosslinking stage into the hydrophobic modification stage, the temperature is lowered to avoid reaction condition conflicts, improve the reaction rate, and avoid surface microcracks caused by local acid-base imbalance.

[0023] Example 4: Please refer to Figure 3 , a preparation method of an oil-repellent and stain-resistant textile fabric, and the preparation method of the textile fabric is as follows: S1: Uniformly mix the modified polyester fibers and the modified bamboo fibers according to a weight ratio of 65:35; S2: Place the mixed fibers in an 80°C environment for preheating and then enter a 180°C environment, and carry out high-temperature curing under a pressure of 1MPa; S3: Immerse the cured mixed fibers in the emulsion, add a coupling agent, impregnate at 60°C for 1h and disperse with 40kHz ultrasonic waves for 30min, and then raise the temperature to 80°C and impregnate for 2h; S4: Wash with a phosphate buffer solution with a pH of 6.5; S5: Dry at 50°C for 10min and then dry at 120°C; S6: The dried mixed fibers are processed through spinning, weaving, and dyeing to obtain the textile fabric; The emulsion is prepared by compounding 40% solids content polyurethane resin and hydrophobic silica nanoparticles in a weight ratio of 1:4; The coupling agent is a 3% γ-aminopropyltriethoxysilane solution; Furthermore, during the preparation of the textile fabric, the modified polyester fiber and the modified bamboo fiber are uniformly mixed in a weight ratio of 65:35. Then, the mixed fibers are placed in a hot air circulation oven and gradually heated to 80°C for 20 minutes of preheating, causing the polyurethane resin on the polyester side to start softening and flowing, while the modified layer of the bamboo fiber remains stable. Subsequently, the temperature is raised to 180°C and maintained for 10 minutes, enabling the maleic anhydride compatibilizer on the surface of the modified polyester fiber to undergo a ring-opening reaction with the epoxy-octadecyl quaternary ammonium salt cross-linking agent of the bamboo fiber, forming an ester bond cross-linked network. The temperature is raised again to 200°C to completely melt the polydimethylsiloxane, which penetrates into the fiber gaps to form a hydrophobic barrier. At the same time, the stearyl primary amine groups of the modified bamboo fiber physically entangle with the siloxane bonds of the polydimethylsiloxane. Under the action of a pressure roller at 1 MPa, the silica nanoparticles in the modified polyester fiber are mechanically interlocked with the micropores on the surface of the bamboo fiber, thereby enhancing the interfacial shear strength. Subsequently, the mixed fibers are placed in an emulsion prepared by compounding 40% solids content polyurethane resin and hydrophobic silica nanoparticles in a weight ratio of 1:4, and a 3% γ-aminopropyltriethoxysilane solution is added as a coupling agent. At a temperature of 60°C, the thermophoretic effect is utilized to drive the nanoparticles to enrich at the fiber interface. Subsequently, the temperature is raised to 80°C to crosslink and cure the emulsion, forming an interpenetrating network structure. During this process, ultrasonic waves are used for auxiliary dispersion to enable the emulsion to effectively fill the micropores of the modified bamboo fiber and the groove structure of the modified polyester fiber. After neutralization, segmented drying is also adopted in the drying stage to avoid coating cracking caused by phase separation. By performing high-temperature curing and emulsion impregnation during the process of mixing the modified polyester fiber and the modified bamboo fiber to prepare the textile fabric, rather than during their respective modification processes, the performance conflicts during the modification stage are avoided. The modified polyester needs to be extruded in a high-temperature environment, while the bamboo fiber is prone to thermal degradation at high temperatures. Uniform curing after mixing can not only ensure the plasticization of the polyester resin and protect the modified structure of the bamboo fiber, but also avoid secondary acid-base corrosion. At the same time, the mixed preparation of the modified polyester fiber and the modified bamboo fiber shortens the degradation cycle of the textile fabric and further improves the environmental performance of the textile fabric.

[0024] Example 5: Please refer to Figure 3 , a preparation method of an oil-repellent and stain-resistant textile fabric, and the preparation method of the textile fabric is as follows: S1: Uniformly mix the modified polyester fiber and the modified bamboo fiber in a weight ratio of 65:35; S2: Place the mixed fibers in an 80°C environment for preheating and then enter an environment of 180°C for high-temperature curing under a pressure of 1 MPa; S3: Immerse the solidified hybrid fibers in the emulsion, add the coupling agent, impregnate at 60 °C for 1 h and disperse with 40 kHz ultrasonic waves for 30 min, and then raise the temperature to 80 °C and impregnate for 2 h; S4: Wash with phosphate buffer solution with pH = 6.5; S5: Dry at 50 °C for 10 min and then at 120 °C; S6: The dried hybrid fibers are processed by spinning, weaving and dyeing to obtain a textile fabric; The emulsion is prepared by compounding 40% solids content polyurethane resin and hydrophobic silica nanoparticles in a weight ratio of 1:4; The coupling agent is a 3% γ-aminopropyltriethoxysilane solution; Furthermore, when preparing the textile fabric, polyester fibers and bamboo fibers are selected as raw materials. After being modified separately, they are mixed and prepared. Bamboo fibers have a porous structure and bamboo quinone components. When used alone, their hourly drying performance is poor, while the moisture absorption ability of polyester fibers is weak. Through mixing and preparation, the textile fabric can quickly absorb moisture through bamboo fibers, and polyester fibers accelerate the diffusion of moisture through capillary action, improving the dynamic moisture absorption rate of the textile fabric. Although natural bamboo quinone has strong antibacterial properties, the breaking strength of bamboo fibers is low, and they are prone to wear and fuzzing. After the polyester fibers are reinforced with silica nanoparticles, the breaking strength is increased, but their antibacterial properties rely on chemical modifiers. When used in combination with bamboo fibers, the use of chemical antibacterial agents is reduced, lowering the production cost. The extraction process of bamboo fibers is complex. When mixed with polyester fibers for weaving, the production cost is also reduced. In addition, polyester belongs to non-degradable synthetic fibers and takes more than 500 years to completely degrade under natural conditions. Although it can be decomposed by high-temperature incineration, harmful gases will be generated, causing secondary pollution to the environment. While bamboo fibers, as natural cellulose fibers, can degrade more than 90% within 180 days in the natural environment. After the textile fabric prepared by mixing the two is subjected to reform treatment, the degradation period is 3 to 5 years, improving the environmental protection performance of the textile fabric and reducing the pressure of manual treatment.

[0025] Performance Test Test 1: Prepare 5 pieces each of the textile fabrics with smooth surfaces, no wrinkles and no contaminants prepared in Example 1 and Control Groups 1 - 5. The size of the textile fabric is 40 * 40 cm. Place the textile fabrics in a thermostatic and humidified chamber, and use an automatic titration device to slowly drop 2 μL - 5 μL of standard mineral oil onto the surface of the textile fabric. After the liquid drop is stable, use a high-definition microscope and a high-speed camera to capture the liquid drop morphology, extract the edge contour line of the liquid drop through professional contact angle analysis software to generate a digital image, calculate the contact angle based on the Young-Laplace equation or the spherical cap model, and confirm the oil repellency grade of the textile fabric with reference to Standard AATCC118 - 2002. The test results are shown in the following table:

[0026] Test 2: Replace the standard mineral oil dropped by the automatic titration device in Test 1 with distilled water. The volume of the liquid drops dropped by the automatic titration device becomes 3 μL - 6 μL. Keep other conditions unchanged and conduct the contact angle test of the textile fabric with water. The test results are shown in the following table:

[0027] Test 3: Prepare 5 pieces of textile fabrics with flat surfaces, no wrinkles and no contaminants prepared in Example 1 and Control Groups 1 - 5 respectively. The size of the textile fabric is 40 * 40 cm. Adjust the test environment temperature to 18°C - 22°C and the humidity to 60% - 70%. Place the samples horizontally on 2 layers of filter paper. Use a micropipette to drop 0.05 ml of first-pressed refined oil at 3 different positions on the surface of the sample from a height of 10 mm above the sample surface. After standing for 30 s, observe the liquid form at a 45° light source and rate according to GB / T30159.1 - 2013. Grade 1 is the worst and Grade 5 is the best. The test results are shown in the following table:

[0028] Test 4: Prepare 5 pieces of textile fabrics with flat surfaces, no wrinkles and no contaminants prepared in Example 1 and Control Groups 1 - 5 respectively. The size of the textile fabric is 40 * 40 cm. Adjust the test environment temperature to 18°C - 22°C and the humidity to 60% - 70%. Fix the solid-state group samples flat on the inner wall of the test cylinder. Place 10 g of solid contaminants evenly mixed with a mass ratio of 10:1 of mixed dust with a particle size of 75 μm and high pigment carbon black at the bottom of the cylinder. Place the test cylinder in a tumbling box and roll it 200 times at a speed of 20 r / min. Then take out the specimen, use a hair dryer to blow off the floating dust on the surface at a wind speed of 1 m / s, compare the color difference between the contaminated area and the non-contaminated area with a gray scale, and rate the color difference according to GB / T250. The color difference deviation decreases from Grade 1 to Grade 5 in turn. The test results are shown in the following table:

[0029] Working principle: Immerse polyester fibers in a 10% sodium hydroxide solution at 95°C for 30 minutes. After neutralization and washing, perform hot air drying at 80°C for 10 minutes. Subsequently, treat the polyester fibers with low-temperature plasma at a power of 200 W to 300 W for 2 minutes to 3 minutes. Add a fluorine-free silicone emulsion prepared by premixing fluorine-free organosilicon and polyether-modified polysiloxane at a concentration of 80 g / L to 100 g / L in deionized water at 60°C to 70°C, followed by high-speed shearing and then adjusting the pH to 5 to 6 with acetic acid, polyester fibers, and a 2% to 3% isocyanate crosslinking agent in an environment with pH = 5 to 6, and perform a constant temperature treatment at 80°C for 30 minutes. Immerse the fibers in an ethyl acetate solution with a concentration of 5%, and react at 50°C for 0.5 h to 1 h. Mix hydrophobic silica nanoparticles with a size of 20 nm to 50 nm and polyurethane resin in a weight ratio of 1:4, add cetyltriethoxysilane as a coupling agent, perform ultrasonic dispersion for 30 minutes at 40 kHz, and then add 2% polyether-modified silicone oil to obtain mixture A. Put mixture A into a twin-screw extruder, add 3% to 5% polydimethylsiloxane and 2% maleic anhydride graft compatibilizer, and extrude in an environment at 240°C to 250°C to obtain modified polyester fibers; Crush bamboo slices and perform water washing to remove surface impurities. Add a 0.5 wt% glycerol solution as a plasticizer and a 0.2 wt% citric acid solution as a heat stabilizer in an environment at 105°C and dry for 8 h to 12 h. Add 1-ethyl-3-methylimidazolium chloride ionic liquid to the dried bamboo fibers, add a 0.05 wt% sodium borohydride solution, perform ultrasonic treatment for 30 minutes in an environment at 50°C to 60°C, add a maleic acid solution with a concentration of 5 wt%, and react at 60°C for 1 h to 2 h. After the reaction is completed, wash with a phosphate buffer solution with pH = 5, adjust the pH to 8 to 9, and then add a 0.8 wt% epoxy-octadecyl quaternary ammonium salt amphoteric crosslinking agent, stir at 75°C for 2 h, add a 10 wt% stearylamine ethanol-aqueous solution prepared by dissolving stearylamine in an ethanol-water mixed solution with a volume ratio of 3:1 and a 0.1 wt% sodium dodecylsulfonate solution, cool to 60°C, and perform magnetic stirring for 1 h to 3 h. Obtain modified bamboo fibers by centrifugal separation; The modified polyester fiber and the modified bamboo fiber are uniformly mixed at a weight ratio of 50:50 to 70:30. The mixed fibers are preheated in an environment of 80°C to 120°C and then enter an environment of 180°C to 200°C, and are subjected to high-temperature curing under a pressure of 0.5 MPa to 1.2 MPa. The cured mixed fibers are immersed in an emulsion prepared by compounding a polyurethane resin with a solid content of 40% and hydrophobic silica nanoparticles at a weight ratio of 1:4, and 3% γ-aminopropyltriethoxysilane solution is added as a coupling agent. It is impregnated at a temperature of 60°C for 1 h and dispersed by 40 kHz ultrasonic waves for 30 min, then the temperature is raised to 80°C and impregnated for 2 h, washed with a phosphate buffer solution with pH = 6.5, dried at 50°C for 10 min and then dried at 120°C; The dried mixed fibers are made into a textile fabric after spinning, weaving and dyeing treatments.

[0030] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and the present invention can be implemented in other specific forms without departing from the spirit or basic characteristics of the present invention. Therefore, from any point of view, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be embraced within the present invention. Any reference signs in the claims should not be regarded as limiting the claimed rights.

Claims

1. A preparation method of an oil-repellent and stain-resistant textile fabric, characterized in that: The textile fabric is made by mixing modified polyester fibers and modified bamboo fibers; The preparation method of the modified polyester fibers is as follows: S1: Immerse the polyester fibers in a 10% sodium hydroxide solution at 95°C for 30 minutes, wash and neutralize, then dry with hot air at 80°C for 10 minutes. Subsequently, treat the polyester fibers with low-temperature plasma at a power of 200W - 300W for 2 - 3 minutes; S2: In an environment with a pH of 5 - 6, keep the temperature at 80°C for 30 minutes with a fluorine-free silicone emulsion with a concentration of 80g / L - 100g / L, polyester fibers, and 2% - 3% isocyanate crosslinking agent; S3: Immerse the fibers in an ethyl acetate solution with a concentration of 5% and react at 50°C for 0.5 - 1 hour; S4: Mix hydrophobic silica nanoparticles with a size of 20nm - 50nm and polyurethane resin in a weight ratio of 1:4, add cetyltriethoxysilane as a coupling agent, disperse by ultrasonic wave at 40kHz for 30 minutes, and then add 2% polyether-modified silicone oil to obtain mixture A; S5: Put mixture A into a twin-screw extruder, add 3% - 5% polydimethylsiloxane and 2% maleic anhydride graft compatibilizer, and extrude in an environment of 240°C - 250°C to obtain modified polyester fibers.

2. The preparation method of an oil-repellent and stain-resistant textile fabric according to claim 1, wherein: The preparation method of the modified bamboo fibers is as follows: S1: Crush the bamboo slices and wash them with water to remove surface impurities, and add a plasticizer and a heat stabilizer and dry at 105°C for 8 - 12 hours; S2: Add 1-ethyl-3-methylimidazolium chloride ionic liquid to the dried bamboo fibers, add a 0.05wt% sodium borohydride solution, and perform ultrasonic treatment at 50°C - 60°C for 30 minutes; S3: Add a maleic acid solution with a concentration of 5wt% and react at 60°C for 1 - 2 hours; S4: After the reaction, wash with a phosphate buffer solution with a pH of 5; S5: Adjust the pH to 8 - 9 and then add an amphoteric crosslinking agent, and stir at 75°C for 2 hours; S6: Add a modification liquid and a surfactant, cool down to 60°C, stir magnetically for 1 - 3 hours, and obtain modified bamboo fibers by centrifugal separation.

3. The preparation method of an oil-repellent and stain-resistant textile fabric according to claim 1, wherein: The preparation method of the textile fabric is as follows: S1: Uniformly mix the modified polyester fibers and the modified bamboo fibers in a weight ratio of 50:50 - 70:30; S2: Preheat the mixed fibers in an environment of 80°C - 120°C and then enter an environment of 180°C - 200°C, and perform high-temperature curing under a pressure of 0.5MPa - 1.2MPa; S3: Immerse the cured mixed fibers in an emulsion, add a coupling agent, impregnate at 60°C for 1 hour and disperse by ultrasonic wave at 40kHz for 30 minutes, and then raise the temperature to 80°C and impregnate for 2 hours; S4: Wash with a phosphate buffer solution with a pH of 6.5; S5: Dry at 50°C for 10 minutes and then dry at 120°C; S6: The dried mixed fibers are made into a textile fabric after spinning, weaving, and dyeing treatments.

4. The preparation method of an oil-repellent and stain-resistant textile fabric according to claim 1, wherein: The fluorine-free silicone emulsion is prepared by premixing fluorine-free silicone and polyether-modified polysiloxane at 60°C - 70°C, adding deionized water and performing high-speed shearing, and adjusting the pH to 5 - 6 by adding acetic acid.

5. The preparation method of an oil-repellent and stain-repellent textile fabric according to claim 2, characterized in that: The plasticizer is a 0.5 wt% glycerol solution, and the heat stabilizer is a 0.2 wt% citric acid solution.

6. The preparation method of an oil-repellent and stain-resistant textile fabric according to claim 2, characterized in that: The amphoteric crosslinking agent is an epoxy-octadecyl quaternary ammonium salt amphoteric crosslinking agent with a concentration of 0.8 wt%.

7. The preparation method of an oil-repellent and stain-resistant textile fabric according to claim 2, characterized in that: The method for preparing the modification liquid is to dissolve stearyl primary amine in an ethanol-water mixed solution with a volume ratio of 3:1 to prepare a 10 wt% stearyl primary amine ethanol-aqueous solution, and the surfactant is a 0.1 wt% sodium dodecyl sulfonate solution.

8. The preparation method of an oil-repellent and stain-resistant textile fabric according to claim 3, wherein: The emulsion is prepared by compounding 40% solids content polyurethane resin and hydrophobic silica nanoparticles at a weight ratio of 1:

4.

9. The preparation method of an oil-repellent and stain-resistant textile fabric according to claim 3, characterized in that: The coupling agent is a 3% γ-aminopropyltriethoxysilane solution.

10. An oil-repellent and stain-resistant textile fabric, applicable to the preparation method of an oil-repellent and stain-resistant textile fabric according to any one of claims 1-9, characterized in that: The textile fabric is prepared by the said preparation method.

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