Plant extract-antibacterial fabric

Abstract

The application discloses a plant-extracted antibacterial fabric, and relates to the technical field of fabrics, which is prepared from the following raw materials in parts by weight: 60 parts of polypropylene resin, 15 parts of plant extract, 5 parts of activator and 7.4 parts of antibacterial agent; the activator is lactic acid; the plant extract is ginger polyphenol, and the content of 6-gingerol is not less than 80%; and the antibacterial agent comprises 3 parts of carbon nanohorn, 1.2 parts of lanthanide-doped up-conversion particle, 1 part of octadecyl glucoside and 2.2 parts of zinc oxide nanorod. The antibacterial fabric can realize longer antibacterial effect and stronger antibacterial capacity, and even has high antibacterial capacity under several times of water washing and sweat stain pH value change.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of fabric, in particular to a plant-extracted antibacterial fabric. BACKGROUND

[0002] Polypropylene fiber, commonly known as polypropylene fiber, is a fiber made of polypropylene as raw material through polymerization and melt spinning. Because of its abundant raw material sources, low price and simple production process, it is widely used in clothing, decoration and industrial products, especially easy to be blended with natural fibers or chemical fibers to make fabric, which is very suitable for manufacturing underwear, T-shirts, bed sheets and other textiles directly contacting with human skin.

[0003] However, the above-mentioned fabric does not have antibacterial and skin care functions, and is easy to be contaminated by various human secretions and environmental pollutants when in contact with human skin, and bacteria or microorganisms are easy to breed, which often causes great harm to human body and affects people's health.

[0004] In the prior art, antibacterial particles such as metal particles containing silver, iron and zinc are often used to increase antibacterial ability, but the interface bonding degree of metal particles in the fabric is poor, the position in the fabric is difficult to fix, and the metal particles are easy to fall off in repeated washing when on the surface of the fabric, and it is difficult to play a bacteriostatic role when wrapped inside the fabric. And because it is often used in fabric directly contacting with human skin, it is easy to contact with sweat stains, and in an acid-base environment, metal ions are easy to oxidize and migrate, resulting in antibacterial failure. SUMMARY

[0005] The plant-extracted antibacterial fabric provided by the embodiments of the present application solves the problem that metal ion antibacterial is easy to cause metal particle failure in abnormal environment in actual use in the prior art, and realizes long-acting and stable antibacterial effect.

[0006] The plant-extracted antibacterial fabric provided by the embodiments of the present application includes polypropylene resin 60 parts, plant extract 15 parts, activator 5 parts and antibacterial agent 7.4 parts by weight.

[0007] The antibacterial agent includes carbon nanohorn 3 parts, lanthanide-doped upconversion particle 1.2 parts, octadecyl glucoside 1 part and zinc oxide nanorod 2.2 parts.

[0008] Further, the carbon nanohorn includes carbon nanohorn quantum emitter and carbon nanohorn photon trap, the particle size of the carbon nanohorn photon trap is 20 nm, the particle size of the carbon nanohorn quantum emitter is 2 nm, and the mass of the carbon nanohorn photon trap is 2 times the mass of the carbon nanohorn quantum emitter.

[0009] Further, the pre-treatment method of the carbon nanohorn quantum emitter is as follows: carbon nanohorn quantum emitters, ZnO nanorods and 90% ethanol as a solvent are added into a sealed reaction kettle under nitrogen protection; the reaction is carried out at 180°C and 3MPa for 6 hours to obtain a quantum anchoring unit.

[0010] Further, the pre-treatment method of the carbon nanohorn photon trap is as follows: carbon nanohorn photon traps are dispersed in DMF solvent, and 0.5 parts of octadecyl glucoside is added as a hydrophobic template; the mixture is ultrasonically treated at 45°C for 30 minutes at 300W to obtain a photon trapping unit.

[0011] Further, the pre-treatment method of the lanthanide-doped upconversion particle is as follows: the lanthanide-doped upconversion particle is dispersed in 50% ethanol, and 0.1M 4-mercaptobenzoic acid ligand is added; the mixture is oscillated at 120rpm for 24 hours at 25°C (pH=6.5±0.2) to obtain an activated lanthanide-doped upconversion particle.

[0012] Further, the preparation method of the antibacterial fabric is as follows:

[0013] The quantum anchoring unit and polypropylene resin are melt blended at 230±1°C, and 5000s -1 High shear rate dispersion, 0.1wt% tripropyl borate anti-agglomerating agent is added to prepare a sheath spinning solution;

[0014] Under nitrogen protection, ginger polyphenol and 3-mercaptopropionic acid are mixed in a molar ratio of 1:2 (based on 6-gingerol) and added into EDC / NHS catalyst (0.1M); the mixture is reacted at 25°C for 12h to generate a gingerol thiol derivative; then the gingerol thiol derivative is reacted with 0.5 parts of octadecyl glucoside in a pH=7.4 phosphate buffer solution at 50°C for 6h to form a ginger polyphenol complex; then the ginger polyphenol complex is melt blended with the photon trapping unit and the activated NaYF4 and polypropylene at 210±1°C at a shear rate of 1000s -1 to prepare a core spinning solution;

[0015] By melt coaxial spinning, a double-channel spinning is adopted, the sheath spinning solution is extruded through the outer channel, and the core spinning solution is extruded through the inner channel at a flow ratio of sheath:core=2:1; the draw ratio is 1:50; the temperature of the spinneret is controlled in sections: the core layer is at 210±1°C, and the sheath layer is at 230±1°C; the drawing speed is 3000m / min; then the fiber is rapidly cooled and solidified at 200°C / s; then the fiber is irradiated with a 475nm LED array (5000lux intensity) in a hot air environment at 120°C to perform energy level calibration;

[0016] Then the plant-extracted antibacterial fabric is prepared through spinning, weaving, bleaching and dyeing, and setting.

[0017] Further, the sizing is attached to the fabric using a working fluid, then immersed in the fluid, and finally baked at 180℃ for 40 minutes. The working fluid is an acrylate polymer (low molecular weight type, 100000-120000 g / mol) and ginger polyphenol additives in a mass ratio of 6:1.

[0018] The one or more technical solutions provided in the embodiments of the present application have at least the following technical effects or advantages:

[0019] The combination of CNHs and NaYF4 covers the UV-NIR full spectrum activation, solving the problem of narrow spectral response of traditional antibacterial agents; the ZnO-CNHs Z-type heterojunction + NaYF4 up-conversion inhibits e - -h + The combination of CNHs and NaYF4 covers the UV-NIR full spectrum activation, solving the problem of narrow spectral response of traditional antibacterial agents; the ZnO-CNHs Z-type heterojunction + NaYF4 up-conversion inhibits e DETAILED DESCRIPTION

[0020] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs; the terminology used in the description herein is for describing particular embodiments only and is not intended to be limiting of the application; the use herein of the terms "and / or" includes a set of one or more associated listed items.

[0021] Embodiment one: a plant extract antibacterial fabric, the raw materials thereof include polypropylene resin 60 parts, plant extract 15 parts, activator 5 parts, and antibacterial agent 7.4 parts; the activator is lactic acid; the plant extract is ginger polyphenol, wherein the 6-gingerol content is not less than 80%;

[0022] The antibacterial agent includes carbon nanohorns (CNHs) 3 parts, lanthanide-doped up-conversion particles (NaYF4:Yb 3+ / Er 3+ ) 1.2 parts, octadecyl glucoside 1 part, and zinc oxide nanorods 2.2 parts (crystal face (002): crystal face (101) total surface area = 3:1);

[0023] The carbon nanohorns include CNHs quantum emitters and CNHs photon traps, the particle size of the CNHs photon traps is 20 nm, the particle size of the CNHs quantum emitters is 2 nm, and the mass of the CNHs photon traps is 2 times the mass of the CNHs quantum emitters;

[0024] The pretreatment method of the antibacterial agent in the above antibacterial fabric is:

[0025] In a sealed reaction kettle under nitrogen protection, CNHs quantum emitter and ZnO nanorod and solvent 90% ethanol were added; under the conditions of 180℃ and 3MPa pressure, reaction was carried out for 6 hours to obtain quantum anchoring unit;

[0026] The CNHs photon trapping body was dispersed in DMF solvent, and octadecyl glucoside 0.5 parts was added as a hydrophobic template, and 300W ultrasonic treatment was carried out at 45℃ for 30 minutes to obtain a photon trapping unit;

[0027] NaYF4:Yb 3+ / Er 3+ was dispersed in 50% ethanol, 0.1M 4-mercaptobenzoic acid (MPA) ligand was added, and oscillation was carried out at 25℃ for 24 hours (pH=6.5±0.2) at 120rpm to obtain activated NaYF4;

[0028] The preparation method of the above antibacterial fabric is:

[0029] The quantum anchoring unit was melt blended with polypropylene resin at 230±1℃, and 5000s -1 high shear rate dispersion was carried out, and 0.1wt% tripropyl borate anti-agglomerating agent was added to prepare a skin layer spinning solution;

[0030] Under nitrogen protection, ginger polyphenol and 3-mercaptopropionic acid were mixed in a molar ratio of 1:2 (based on 6-gingerol) and added to EDC / NHS catalyst (0.1M), and reacted at 25℃ for 12h to generate gingerol thiol derivative; then reacted with octadecyl glucoside 0.5 parts in pH=7.4 phosphate buffer solution, stirred at 50℃ for 6h to form ginger polyphenol complex, and then melt with photon trapping unit and activated NaYF4 and polypropylene at 210±1℃, and shear rate 1000s -1 to prepare a core layer spinning solution;

[0031] By melt coaxial spinning method, double channel spinning was adopted, the skin layer spinning solution was extruded from the outer channel, the core layer spinning solution was extruded from the inner channel, the flow ratio of skin layer:core layer was 2:1, the draw ratio was 1:50, the spinneret temperature partition control was core layer 210±1℃ and skin layer 230±1℃, the drawing speed was 3000 m / min, and then the fiber was rapidly cooled and solidified at 200℃ / s; then the fiber was irradiated in a 120℃ hot air environment with a 475nm LED array (5000lux intensity) to calibrate the energy level;

[0032] Then the plant extracted antibacterial fabric was prepared through spinning, weaving, bleaching and dyeing, and setting;

[0033] Wherein the shaping is to use the working fluid to adhere on the fabric, then dip in the liquid, and finally, at 180℃, bake for 40min, the working fluid is acrylate polymer (low molecular weight type, 100000-120000g / mol) and ginger polyphenol auxiliary agent, according to the mass ratio of 6:1.

[0034] The technical solutions in the embodiments of the application have at least the following technical effects or advantages:

[0035] The benzene ring structure (containing phenolic hydroxyl and β-hydroxy ketone) of 6-gingerol can be combined with the phospholipid of the bacterial membrane through hydrogen bonding or hydrophobic interaction, thereby destroying the membrane integrity; the phenolic hydroxyl group releases protons (H + ), thereby unbalancing the membrane potential and attacking the bacterial proteins and DNA through oxidative stress (generating ROS); the phenolic hydroxyl group acts as an electron donor to quench free radicals (such as ·OH) and improve the antioxidant properties, thereby protecting the fiber matrix;

[0036] The phenolic hydroxyl group of ginger polyphenol can form an interface layer with the MPA ligand (-SH) on the surface of the upconversion particle through hydrogen bonding, thereby enhancing the particle dispersibility; the antioxidant properties of gingerol can inhibit the damage to the fiber caused by the excessive ROS generated by the photocatalysis of the upconversion particle;

[0037] The gingerol thiol derivative (-SH) is anchored on the surface of the ZnO nanorod through a covalent bond (S-Zn), thereby forming a “phenol-nanohybrid” interface and improving the electron transfer efficiency.

[0038] The carbon nanohorns (CNHs) include quantum emitters (2nm) and photon traps (20nm): the small size leads to quantum confinement effect, and the valence band electrons are excited to jump to the conduction band, thereby generating fluorescence resonance energy transfer (FRET), enhancing near-infrared light absorption, and the large particle size provides a high specific surface area (sp 2 carbon network) that can capture a broad spectrum of light energy through plasmonic resonance (LSPR) and convert it into heat energy or transfer it to the quantum emitters;

[0039] The photon trap (20nm) absorbs light energy and transfers the energy to the quantum emitter (2nm) through non-radiative Förster resonance energy transfer (FRET), and the latter injects electrons into the ZnO conduction band (ZnO-CNHs heterojunction) through quantum tunneling effect, thereby promoting the separation of photo-generated electrons and holes and enhancing the antibacterial activity (ZnO+hν→e - +h + , h + oxidizing the bacterial membrane);

[0040] The sp 2 carbon network of the CNHs acts as an electron acceptor to capture the visible light emitted by the upconversion particle, thereby forming a “light energy relay” (NaYF4→CNHs→ZnO) and widening the spectral response range.

[0041] Yb 3+ Absorb 980 nm infrared light, excite Er by energy transfer (ET) 3+ Emit 540 nm (green light) and 660 nm (red light), penetrate bacterial biofilm, 540 nm light excite ZnO valence band electrons, 660 nm light is absorbed by gingerol (π→π* transition), synergistically produce reactive oxygen species (ROS);

[0042] Upconversion particles form Type-II heterojunction with ZnO, photo-generated electrons transfer from NaYF4 to ZnO, holes remain in NaYF4, inhibit e - -h + Recombination, prolong the life of ROS; also with gingerol: Er 3+ 4f electrons and gingerol π electron cloud dipole-dipole interaction, enhance the interface polarizability, improve the utilization of light energy.

[0043] The hydrophobicity of CNHs in the skin layer spinning solution is highly compatible with polypropylene (PP) resin, forming a nanometer barrier in the skin layer to prevent bacterial adhesion and delay the loss of antibacterial agents; 20 nm CNHs / NaYF4 in the core layer spinning solution provides photothermal + photodynamic dual action, penetrates the interior of the fiber to kill latent bacteria, and finally excites by absorbing infrared light through SPR enhancement of upconversion CNHs; gingerol improves antibacterial ability; CNHs combination combined with NaYF4 covers UV-NIR full spectrum activation, solving the problem of narrow spectral response of traditional antibacterial agents; ZnO-CNHs Z-type heterojunction + NaYF4 upconversion inhibits e - -h + Recombination, prolong the life of ROS, solve the problem of short active oxygen life, reduce washing loss through the skin layer (PP / CNHs hydrophobic barrier) and the core layer (slow-release gingerol), solve the problem of poor antibacterial durability, and finally through 20 nm CNHs photothermal softening film and NaYF4 deep penetration light, enhance the efficiency of ROS entering the bacterial membrane, solve the problem of bacterial biofilm penetration.

[0044] And in the sweat environment (pH 4.5-7.5), in the acidic environment, the phenolic hydroxyl group (-OH) of gingerol is protonated to enhance hydrophobicity, making it easier to insert into the bacterial membrane and destroy membrane fluidity (similar to cationic antimicrobial peptides) to improve antibacterial ability; ZnO partially dissolves to release zinc ions for direct antibacterial effect; In an alkaline environment, ·OH generation is inhibited, but ·O2 - production (O2 + e - →·O2 - ) improves the oxidative bactericidal effect, especially for E. coli.

[0045] To verify the effect between components and antibacterial ability, grouping experiments were carried out. The control group was polypropylene resin fabric without adding antibacterial agents and plant extracts. The experimental groups included single component group (ginger polyphenol group, 20 nm CNHs group, NaYF4 group), double component group (ginger polyphenol + CNHs group, ginger polyphenol + NaYF4 group, CNHs + NaYF4 group), and full component group. In order to verify the combination effect of multi-particle size CNHs, single particle size and combined particle size verification were carried out.

[0046] Among them, the single component experiment is only adding a single component, the single component group is only adding one component pretreated component (CNHs photon trapping body, ginger polyphenol complex, activated NaYF4), the double component group is the combination of single components, and the full component is the combination of three components. In the particle size comparison group, the particle size comparison group is the technical solution described in this embodiment, the single particle size group uses CNHs photon trapping body as the full component group, and the skin core layer uses CNHs photon trapping body.

[0047] The experiment includes antibacterial experiment, active oxygen (ROS) experiment and stability experiment. The antibacterial experiment (ISO 20743) is to inoculate E. coli in LB medium (37°C, 24h), dilute with PBS to 10 5 CFU / mL, cut the fabric (5×5cm), ultraviolet sterilize for 30min, add 100μL bacterial solution, cover sterile film, simulate sunlight (xenon lamp, 400-800nm, 1W / cm²) irradiation for 30min; PBS flush the fabric, eluent dilution plate (LB agar), 37°C culture for 24h, count colonies (CFU), and calculate the antibacterial rate. ;

[0048] The active oxygen experiment uses flow cytometry. The fabric is cut into pieces (1×1mm), immersed in 10μM DCFH-DA solution (PBS, pH7.4), incubated in the dark for 30min, irradiated with 980nm laser (0.5W / cm 2 ) for 10min, and assisted with visible light (400-800nm, 0.5W / cm 2 ). The green fluorescence (Ex / Em=488 / 525nm) was detected by flow cytometry, 10,000 particles were analyzed, and the average fluorescence intensity (MFI) was recorded.

[0049] The stability experiment is a water washing experiment. The water washing method is referred to AATCC TM61. The washing liquid is 0.15% soap solution containing 5g steel beads. The temperature is 40°C. Each time is 45 minutes (equivalent to 5 times of home washing). The antibacterial capacity is detected after 100 times of water washing. The antibacterial effect is re-detected. The stability experiment also includes pH stability experiment. The antibacterial effect is detected after soaking in pH 5.5, 7.0 (the pH of other experiments is 7.0) and 7.4 buffer for 1h. The results are shown in Table 1.

[0050] Table 1. Experimental verification results

[0051]

[0052] Example 2: The above example prepares a biologically extracted antibacterial fabric. On this basis, the application method is improved. This example is a cleaning method.

[0053] The fabric is soaked in a citric acid buffer solution with pH=5.0±0.2 (temperature 30°C) for 10 minutes. A protease cleaning agent is used as a detergent. The concentration is 0.5wt%. The water temperature is 20-25°C. The flow rate is less than 1m / s. The time is 8-10 minutes. Then, 20Hz low-frequency mechanical vibration is used for 3 minutes. After dehydration, the fabric is dried in the air. During the drying process, intermittent blue light irradiation (475nm, 500lux, 30s / 2min) is used.

[0054] The technical solutions in the above examples of the present application have at least the following technical effects or advantages:

[0055] The weak acid environment triggers the pH-responsive switch to release zinc ions to combine with the carboxyl groups on the edge of CNHs to form a temporary protective layer (anti-mechanical shear). Mechanical vibration is used. Stress waves are transmitted to 2nm CNHs to generate a piezoelectric electric field. The piezoelectric electric field drives the photo-generated holes of ZnO to migrate and remove the surface organic residues. Blue light excites 20nm CNHs to generate LSPR. Local temperature rises (50-60°C) to accelerate water molecule desorption. Thermal energy simultaneously activates upconversion particles to continuously generate antibacterial free radicals.

[0056] The above only describes the preferred embodiments of the present application and is not used to limit the present application. For those skilled in the art, the present application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A plant-derived antibacterial fabric, characterized in that, The raw materials, by weight, include 60 parts polypropylene resin, 15 parts plant extract, 5 parts activator, and 7.4 parts antibacterial agent; the activator is lactic acid; the plant extract is ginger polyphenol, of which 6-gingerol content is not less than 80%; ginger polyphenol and 3-mercaptopropionic acid are mixed in a 1:2 molar ratio and added to EDC / NHS catalyst, and reacted at 25℃ for 12h to generate gingerol thiol derivative, which is then reacted with 0.5 parts octadecyl glucoside in phosphate buffer at pH=7.4 and stirred at 50℃ for 6h to form ginger polyphenol complex; The antibacterial agent comprises 3 parts carbon nanoparticles, 1.2 parts lanthanide-doped upconversion particles, 1 part octadecyl glucoside, and 2.2 parts zinc oxide nanorods; the lanthanide-doped upconversion particles are NaYF4. The carbon nano-angle includes a carbon nano-angle quantum emitter and a carbon nano-angle photon trap. The particle size of the carbon nano-angle photon trap is 20 nm, the particle size of the carbon nano-angle quantum emitter is 2 nm, and the mass of the carbon nano-angle photon trap is twice the mass of the carbon nano-angle quantum emitter. The pretreatment method for carbon nano-angle quantum emitters is as follows: In a nitrogen-protected sealed reaction vessel, carbon nano-angle quantum emitters, zinc oxide nanorods, and 90% ethanol solvent are added; the reaction is carried out at 180℃ and 3MPa pressure for 6 hours to obtain quantum anchoring units; The pretreatment method of carbon nano-angle photon trap is as follows: disperse carbon nano-angle photon trap in DMF solvent, add 0.5 parts of octadecyl glucoside as a hydrophobic template, and sonicate at 300W at 45℃ for 30 minutes to obtain photon trapping unit; The pretreatment method for lanthanide-doped upconversion particles is as follows: lanthanide-doped upconversion particles are dispersed in 50% ethanol, 0.1M 4-mercaptobenzoic acid ligand is added, and the mixture is shaken at 120 rpm for 24 hours at 25°C to obtain activated lanthanide-doped upconversion particles.

2. The antibacterial fabric extracted from plants as described in claim 1, characterized in that, The preparation method of antibacterial fabric is as follows: The quantum anchoring unit was melt-blended with polypropylene resin at 230±1℃ and applied for 5000 seconds. -1 High shear rate dispersion, with the addition of 0.1 wt% tripropyl borate as an anti-agglomeration agent, yielded a skin spinning solution; The ginger polyphenol complex, along with photon trapping units and activated lanthanide-doped upconversion particles, was melted with polypropylene at 210±1℃ and a shear rate of 1000 s⁻¹. -1 The core spinning solution was prepared. The fiber was produced using a melt coaxial spinning method with a dual-channel spinning process. The outer channel extruded the sheath spinning solution, while the inner channel extruded the core spinning solution. The flow rate ratio of sheath to core was 2:1, the draw ratio was 1:50, and the spinneret temperature was controlled in zones: core 210±1℃ and sheath 230±1℃. The traction speed was 3000 m / min. The fiber was then rapidly cooled and cured at 200℃ / s. Finally, the fiber was irradiated with a 475nm LED array in a 120℃ hot air environment for energy level calibration. Then, through spinning, weaving, dyeing, and setting, plant-derived antibacterial fabrics are produced.

3. The antibacterial fabric extracted from plants as described in claim 2, characterized in that, The shaping process involves applying a working solution to the fabric, followed by immersion and tying, and finally baking at 180°C for 40 minutes. The working solution consists of an acrylate polymer and ginger polyphenols in a mass ratio of 6:1.

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