Antibacterial and easy-to-clean fabric and preparation method thereof

Abstract

This application discloses an antibacterial, easy-to-clean fabric and a preparation method thereof, wherein the antibacterial, easy-to-clean fabric comprises a nylon fabric and an antibacterial layer supported on the nylon fabric, wherein the water contact angle of the antibacterial layer is 20 to 50 degrees; the raw materials of the antibacterial layer comprise an acrylic emulsion and an antibacterial agent, wherein the antibacterial agent is used in an amount of 1 to 3 wt%. The comonomers of the acrylic emulsion comprise: 30 to 50 wt% unsaturated carboxylic acid, 30 to 40 wt% alkyl acrylate, 10 to 20 wt% divinylbenzene, and 10 to 15 wt% allyl polyoxyethylene ether; the number of ethylene oxide units in the allyl polyoxyethylene ether is 7 to 12. The purpose of this application is to solve the problems of decreased softness and weakened cleaning performance of nylon fabric after antibacterial finishing treatment, so that the fabric has excellent long-lasting antibacterial properties, softness, and easy cleaning.

Description

Technical Field

[0001] The present application relates to the field of antibacterial fabrics, and in particular to an antibacterial and easy-to-clean fabric and a preparation method thereof. Background Art

[0002] Antimicrobial nylon fabrics combine moisture absorption, breathability, and antibacterial properties, reducing skin irritation caused by sweat-induced bacteria. They have significant application potential in sportswear, household bedding, and medical protective equipment. Currently, the mainstream manufacturing process relies on post-finishing techniques, which functionalize the fabric by applying an antimicrobial layer to the surface. These layers typically consist of an adhesive and an antimicrobial agent, with the adhesive often using a cross-linked resin. This enhances the adhesion and washability of the antimicrobial agent by increasing the density of the coating.

[0003] For example, patent application CN103774431A demonstrates significant improvement in the mechanical stability of a coating by cross-linking and curing a polyurethane resin with an isocyanate. However, this process has two major drawbacks: First, the cross-linking and curing process increases the hardness of the coating and reduces the softness of the fabric, affecting wearing comfort. This makes it particularly unsuitable for applications requiring a high sense of touch, such as undergarments or medical dressings. Second, the cross-linking reaction consumes the hydrophilic groups in the adhesive, reducing the coating's hydrophilicity and making the surface susceptible to adsorption of dirt such as sebum and dust, which in turn weakens the fabric's cleanability. Summary of the Invention

[0004] In order to solve the problem that the current nylon fabric has reduced softness and weakened cleaning performance after antibacterial finishing treatment, the present application provides an antibacterial and easy-to-clean fabric and a preparation method thereof.

[0005] In a first aspect, the present application provides an antibacterial and easy-to-clean fabric, which includes a nylon fabric and an antibacterial layer loaded on the nylon fabric, wherein the water contact angle of the antibacterial layer is 20 to 50°; the raw materials of the antibacterial layer include an acrylic emulsion and an antibacterial agent, the amount of the antibacterial agent is 1 to 3 wt%, and the comonomer of the acrylic emulsion includes: 30 to 50 wt% unsaturated carboxylic acid, 30 to 40 wt% alkyl acrylate, 10 to 20 wt% divinylbenzene, and 10 to 15 wt% allyl polyoxyethylene ether; the number of ethylene oxide units in the allyl polyoxyethylene ether is 7 to 12.

[0006] In any of the above technical solutions, the acrylic ester emulsion is obtained by polymerization in an emulsifier solution, and the amount of the emulsifier used is 8 to 15 wt % of the mass of the comonomer.

[0007] In any of the above technical solutions, the D50 particle size of the acrylic emulsion is 40 to 80 nm.

[0008] In any of the above technical solutions, the unsaturated carboxylic acid is selected from one or more of acrylic acid, maleic acid, itaconic acid, and fumaric acid.

[0009] In any of the above technical solutions, the alkyl acrylate is selected from one or more of methyl methacrylate, ethyl acrylate, ethyl methacrylate, and butyl acrylate.

[0010] This application utilizes a specific ratio of comonomers to prepare an acrylic emulsion, resulting in an antimicrobial layer that combines crosslinking strength (resistance to water swelling), softness, and easy cleaning. Unsaturated carboxylic acid is a key component in regulating hydrophilicity. Its carboxylic acid groups impart moderate hydrophilicity to the antimicrobial layer, maintaining a water contact angle between 20° and 50°. When the water contact angle is above 50°, insufficient hydrophilicity prevents water from carrying away dirt, resulting in reduced cleanability. When the water contact angle is below 20°, excessive hydrophilic groups can cause the antimicrobial layer to absorb water and swell, disrupting the coating structure and reducing washability and antimicrobial durability. Alkyl acrylates and divinylbenzene work synergistically to provide mechanical strength and swelling resistance: the long alkyl chains of the alkyl acrylates provide a certain degree of water repellency, while the double bonds of divinylbenzene form a three-dimensional crosslinking network, enhancing resistance to water permeation. Because the crosslinking of divinylbenzene occurs solely through free radical polymerization, without consuming hydrophilic groups such as carboxylic acid, the layer maintains hydrophilicity while enhancing water resistance. The introduction of allyl polyoxyethylene ether (10-15wt%) plays a key role. Its polyoxyethylene chain segments are flexible and hydrophilic, enhancing the flexible mobility of the molecular chains, reducing the rigidity of the coating and improving the softness of the fabric. The synergistic effect of the four monomers creates a microscopically balanced rigid-flexible network structure in the antimicrobial layer, ensuring washability, comfort, and easy cleanability.

[0011] It should be noted that the number of repeating units in the polyoxyethylene chain segment should be controlled between 7 and 12 ethylene oxide units. If the number of repeating units is greater than 12, the grafting ability will decrease and the local hydrophilicity will be too high; if the number of repeating units is less than 7, the flexibility and toughness enhancement capabilities will be insufficient.

[0012] In any of the above technical solutions, the nylon fabric is woven from nylon fibers, and the polyamide resin molecules of the nylon fibers contain adipic acid, hexamethylenediamine, and pyridyl dicarboxylic acid segments in a molar ratio of 1:1 to 1.05:0.02 to 0.06, and the pyridyl dicarboxylic acid segments are Zn-containing. 2+ and / or Cu 2+ coordination.

[0013] In any of the above technical solutions, the pyridyl-containing dicarboxylic acid is selected from one or more of 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, and 2,2'-bipyridine-3,3'-dicarboxylic acid.

[0014] The present invention introduces a dicarboxylic acid segment containing a pyridine group into the polyamide resin, and the nitrogen atom on the pyridine ring can react with Zn 2+ or Cu 2+ Forming a stable coordination bond. Metal ions are evenly dispersed inside the fiber through coordination, forming a slow-release antibacterial mechanism: on the one hand, when metal ions come into contact with bacterial cell membranes, they destroy their osmotic pressure balance and interfere with enzyme activity, achieving immediate sterilization; on the other hand, the dynamic balance of the coordination structure allows the metal ions to be slowly released, extending the antibacterial cycle. In addition, Zn 2+ / Cu 2+ The strong coordination with the polyamide molecular chain can resist ion loss during the washing process and ensure long-term antibacterial properties.

[0015] In any of the above technical solutions, the preparation method of the nylon fiber is as follows:

[0016] The polyamide resin is added into a screw extruder, and nylon fiber is obtained through melting, spinning, cooling, oiling, drawing, and heat setting. The cooling adopts side blowing cooling, and the cooling air temperature is set in a gradient, including: the air temperature is 10-15°C in the range of 150-600 mm from the spinneret; the air temperature is 20-25°C in the range of 600-1000 mm from the spinneret.

[0017] In any of the above technical solutions, the coordination is carried out by adding zinc salt and / or copper salt to the oiling agent for oiling, and the content of zinc salt and / or copper salt in the oiling agent is 5-10wt%.

[0018] In any of the above technical solutions, the zinc salt is selected from one or more of zinc chloride, zinc sulfate, zinc acetate, and zinc nitrate.

[0019] In any of the above technical solutions, the copper salt is selected from one or more of copper chloride, copper sulfate, copper acetate, and copper nitrate.

[0020] This application adopts a gradient cooling process: the interval of 0 to 150 mm from the spinneret is a windless zone; the interval of 150 to 600 mm from the spinneret is subjected to rapid cooling at 10 to 15 ° C, so that the fiber surface is rapidly solidified to form a dense crystalline area, while the internal shrinkage stress is generated due to the temperature gradient, resulting in micro cracks on the surface; the interval of 600 to 1000 mm from the spinneret is subjected to room temperature cooling (20 to 25 ° C) to reduce internal stress concentration and avoid fiber breakage. The surface micro cracks have a dual synergistic effect. First, as a metal ion penetration channel, the Zn in the oil agent 2+ / Cu 2+The nanoparticles in the acrylic emulsion penetrate the fibers through microcracks, increasing the coordination density and enhancing antimicrobial efficacy. Secondly, they create a physical anchoring effect. The nanoparticles in the acrylic emulsion penetrate the microcracks, forming a physical connection with the fibers similar to a mortise and tenon joint, increasing the interfacial bonding area between the antimicrobial layer and the fabric fibers. This mechanical interlocking effectively enhances the adhesion of the antimicrobial layer to the fibers, significantly improving washability.

[0021] The above-mentioned side-blowing cooling controls the wind temperature and humidity through the central air-conditioning system to ensure that the wind temperature is constant within the preset range and avoid moderate fluctuations in zone temperature.

[0022] In any of the above technical solutions, the comonomer of the acrylic ester emulsion contains 5 to 10 wt % of vinyl aniline.

[0023] Furthermore, vinylaniline was introduced into the acrylic emulsion, and its amino group (-NH2) and the pyridine group in the fiber could react with the Zn in the fiber. 2+ / Cu 2+ The antimicrobial layer is anchored to the fiber surface through a ternary complex structure of "pyridyl-metal ion-amino group" by forming a coordination bridge. This bridging effect does not rely on chemical crosslinking, avoiding the rigid curing issues of traditional adhesives. Therefore, it does not affect the softness and hydrophilicity of the coating, synergistically enhancing its washability and ease of cleaning.

[0024] In any of the above technical solutions, the preparation method of the polyamide resin is:

[0025] Dissolving the pyridyl dicarboxylic acid in dilute hydrochloric acid at a pH of 3 to 4, mixing with adipic acid and hexamethylenediamine, and adding deionized water to obtain a solution with a solid content of 30 to 40%; stirring and heating to 60 to 80° C. under nitrogen protection, adjusting the pH to 7.5 to 8.5, and performing a salt-forming reaction to obtain a prepolymer;

[0026] The prepolymer is heated to 220-240° C., reduced to 0.5-1.0 MPa, and dehydrated and condensed; the temperature is further raised to 270-280° C., the vacuum degree is increased to <100 Pa, and the reaction is carried out for 5-8 hours to obtain a polyamide resin.

[0027] In a second aspect, the present application provides a method for preparing an antibacterial and easy-to-clean fabric, which comprises: mixing an antibacterial agent and an acrylic emulsion according to any of the above-mentioned raw material ratios of the antibacterial layer to form a finishing liquid; applying the finishing liquid to the surface of a nylon fabric, and drying and curing it to form an antibacterial layer with a thickness of 1 to 5 μm.

[0028] In summary, this application has the following beneficial effects:

[0029] This application achieves a comprehensive improvement in the performance of antibacterial nylon fabrics through molecular design of acrylic polymers. Specifically, the synergistic effect of unsaturated carboxylic acid, allyl polyoxyethylene ether and divinylbenzene in the acrylic emulsion enables the antibacterial layer to have a hydrophilic angle of 20 to 50 degrees (easy to clean), high softness and water washability (long-lasting antibacterial properties). In addition, the introduction of a coordination structure of pyridyl dicarboxylic acid and metal ions into the polyamide resin provides long-lasting antibacterial properties, and the microcracks formed by the gradient cooling process of the nylon fiber promote the penetration of metal ion antibacterial agents and enhance interfacial bonding. The amino-functionalized emulsion further enhances the bonding strength through metal bridging, ultimately obtaining a soft, skin-friendly, long-lasting antibacterial and easy-to-clean composite fabric suitable for high-end sportswear, medical dressings and other fields. DETAILED DESCRIPTION

[0030] Preparation Example 1-1, an acrylic emulsion, was prepared as follows:

[0031] Pre-emulsification: Dissolve 4.0 kg of acrylic acid, 3.5 kg of butyl acrylate, 1.5 kg of divinylbenzene, 1.0 kg of allyl polyoxyethylene ether (APEG-10, EO=10), 0.5 kg of vinylaniline and 1.2 kg of emulsifier (sodium lauryl sulfate: OP-10=4:1) in 8 kg of deionized water, and high-speed shear at 8000 rpm for 30 min to obtain a pre-emulsion.

[0032] Polymerization: Add 1 / 3 of the pre-emulsion to the reactor, replace the atmosphere with nitrogen, raise the temperature to 75°C, and add 0.3 kg of 10 wt% ammonium persulfate aqueous solution dropwise within 30 minutes. Add the remaining pre-emulsion dropwise within 2 hours, and maintain the temperature for 2 hours. Cool to 40°C, adjust the pH to 7.5 with ammonia water, and filter to obtain an acrylic emulsion with a D50 of 60 nm and a PDI of 0.15.

[0033] Preparation Example 1-2, an acrylic emulsion, was prepared as follows:

[0034] Pre-emulsification: Dissolve 3.0 kg of maleic acid, 4.0 kg of methyl methacrylate, 2.0 kg of divinylbenzene, 1.0 kg of allyl polyoxyethylene ether (APEG-7, EO=7), 0.5 kg of vinylaniline and 1.5 kg of emulsifier (sodium lauryl sulfate: OP-10=4:1) in 8 kg of deionized water, and high-speed shear at 5000 rpm for 40 min to obtain a pre-emulsion.

[0035] Polymerization: Add 1 / 3 of the pre-emulsion to the reactor, replace the atmosphere with nitrogen, raise the temperature to 80°C, and add 0.4 kg of a 10 wt% potassium persulfate aqueous solution dropwise over 40 minutes. Add the remaining pre-emulsion dropwise over 3 hours, and maintain the temperature for 3 hours. Cool to 40°C, adjust the pH to 7.0 with ammonia water, and filter to obtain an acrylate emulsion with a D50 of 80 nm and a PDI of 0.25.

[0036] Preparation Example 1-3, an acrylic emulsion, was prepared as follows:

[0037] Pre-emulsification: Dissolve 5.0 kg of itaconic acid, 3.0 kg of ethyl acrylate, 1.0 kg of divinylbenzene, 1.2 kg of allyl polyoxyethylene ether (APEG-12, EO=12), 0.5 kg of vinylaniline and 1.2 kg of emulsifier (sodium lauryl sulfate: OP-10=5:1) in 8 kg of deionized water, and high-speed shear at 6000 rpm for 30 min to obtain a pre-emulsion.

[0038] Polymerization: Add one-third of the pre-emulsion to the reactor, replace the atmosphere with nitrogen, raise the temperature to 70°C, and add 0.2 kg of 10 wt% ammonium persulfate aqueous solution dropwise over 30 minutes. Add the remaining pre-emulsion dropwise over 2.5 hours, and maintain the temperature for 3 hours. Cool to 40°C, adjust the pH to 8.0 with aqueous ammonia, and filter to obtain an acrylic emulsion with a D50 of 40 nm and a PDI of 0.10.

[0039] Preparation Example 1-4 is an acrylic ester emulsion, which differs from Preparation Example 1-1 in that vinyl aniline is replaced by an equal amount of acrylic acid.

[0040] Preparation Example 1-5, an acrylic ester emulsion, differs from Preparation Example 1-1 in that the raw material ratio of the comonomer is: 2.0 kg acrylic acid, 5.5 kg butyl acrylate, 1.5 kg divinylbenzene, 1.0 kg allyl polyoxyethylene ether (APEG-10, EO=10), and 0.5 kg vinylaniline.

[0041] Preparation Example 1-6, an acrylic ester emulsion, differs from Preparation Example 1-1 in that the raw material ratio of the comonomer is: 6.0 kg acrylic acid, 1.5 kg butyl acrylate, 1.5 kg divinylbenzene, 1.0 kg allyl polyoxyethylene ether (APEG-10, EO=10), and 0.5 kg vinylaniline.

[0042] Preparation Example 1-7, an acrylic ester emulsion, differs from Preparation Example 1-1 in that the raw material ratio of the comonomer is: 7.5 kg acrylic acid, 1.5 kg divinylbenzene, 1.0 kg allyl polyoxyethylene ether (APEG-10, EO=10), and 0.5 kg vinylaniline.

[0043] Preparation Example 1-8 is an acrylic emulsion, which differs from Preparation Example 1-1 in that divinylbenzene is replaced by an equal amount of styrene.

[0044] Preparation Example 1-9, an acrylic emulsion, differs from Preparation Example 1-1 in that an equal amount of allyl polyoxyethylene ether (APEG-5, EO=5) is used to replace allyl polyoxyethylene ether (APEG-10, EO=10).

[0045] Preparation Example 1-10, an acrylic emulsion, differs from Preparation Example 1-1 in that an equal amount of allyl polyoxyethylene ether (APEG-15, EO=15) is used to replace allyl polyoxyethylene ether (APEG-10, EO=10).

[0046] Preparation Example 1-11, an acrylic ester emulsion, differs from Preparation Example 1-1 in that allyl polyoxyethylene ether (APEG-10, EO=10) is replaced by an equal amount of acrylic acid.

[0047] Preparation Example 2-1: A nylon fiber was prepared according to the following steps:

[0048] Dissolve 6.68g of 2,6-pyridinedicarboxylic acid (0.04mol) in 200ml of dilute hydrochloric acid (pH=3.5) and stir until completely dissolved. Mix 146.14g of adipic acid (1mol), 119.11g of hexamethylenediamine (1.03mol) and the 2,6-pyridinedicarboxylic acid solution in a reaction kettle. Add deionized water to a total mass of 1.0kg. Under ammonia protection, heat to 70°C, adjust the pH to 8.0, and react at this constant temperature for 2 hours to obtain a prepolymer.

[0049] The prepolymer was heated to 230° C., depressurized to 0.8 MPa, dehydrated for 1 hour, and then heated to 275° C. The vacuum degree was reduced to 50 Pa, and reacted for 4 hours to obtain a polyamide resin.

[0050] 5 kg of polyamide resin pellets were added to a twin-screw extruder, set at 270°C and a screw speed of 50 rpm. Nylon fiber was produced through spinning, cooling, oiling, stretching, and heat setting. The process parameters were set as follows:

[0051] Spinning: spinneret aperture 0.2 mm, spinning speed 300 m / min.

[0052] Cooling: within the range of 150-600mm from the spinneret, the wind temperature is 12±1℃, the humidity is 60±2%, and the wind speed is 0.8m / s; within the range of 600-1000mm from the spinneret, the wind temperature is 22±1℃, the humidity is 60±2%, and the wind speed is 0.8m / s.

[0053] Oiling: The oil contains 40% white oil, 10% lauryl polyoxyethylene ether, 10% PEG-40 stearate, 8% copper acetate, and water as the balance; the oiling rate is 0.8%.

[0054] Drawing: drawing ratio 3.5 times, drawing temperature 80℃.

[0055] Heat setting: 160℃ hot roller setting, winding to obtain nylon fiber.

[0056] Preparation Example 2-2: A nylon fiber was prepared according to the following steps:

[0057] Dissolve 3.34 g of 3,4-pyridinedicarboxylic acid (0.02 mol) in 150 ml of dilute hydrochloric acid (pH 3.0) and stir until completely dissolved. Mix 146.14 g of adipic acid (1 mol) and 122.02 g of hexamethylenediamine (1.05 mol) with the 3,4-pyridinedicarboxylic acid solution in a reaction kettle. Add deionized water to a total mass of 1.2 kg. Heat to 65°C under ammonia protection, adjust the pH to 7.8, and continue the reaction at this constant temperature for 3.5 hours to obtain a prepolymer.

[0058] The prepolymer was heated to 235° C., depressurized to 0.6 MPa, dehydrated for 1.5 hours, and then heated to 270° C. The vacuum degree was reduced to 80 Pa, and reacted for 3.5 hours to obtain a polyamide resin.

[0059] 5 kg of polyamide resin pellets were added to a twin-screw extruder, set at 265°C and a screw speed of 50 rpm. Nylon fiber was produced through spinning, cooling, oiling, drawing, and heat setting. The process parameters were set as follows:

[0060] Spinning and cooling: spinneret aperture 0.2 mm, spinning speed 300 m / min.

[0061] Cooling: within the range of 150-600mm from the spinneret, the wind temperature is 11±1℃, the humidity is 50±2%, and the wind speed is 0.6m / s; within the range of 600-1000mm from the spinneret, the wind temperature is 24±1℃, the humidity is 50±2%, and the wind speed is 0.6m / s.

[0062] Oiling: The oil contains white oil 40%, lauryl polyoxyethylene ether 10%, PEG-40 stearate 10%, zinc chloride 2%, copper chloride 3%, and water as the balance; the oiling rate is 1.0%.

[0063] Drawing: drawing ratio 4 times, drawing temperature 80℃.

[0064] Heat setting: 160℃ hot roller setting, winding to obtain nylon fiber.

[0065] Preparation Example 2-3: A nylon fiber was prepared according to the following steps:

[0066] Dissolve 14.03 g of 2,2'-bipyridine-3,3'-dicarboxylic acid (0.06 mol) in 250 ml of dilute hydrochloric acid (pH = 4.0) and stir until completely dissolved. Mix 146.14 g of adipic acid (1 mol), 116.21 g of hexamethylenediamine (1 mol), and the 2,2'-bipyridine-3,3'-dicarboxylic acid solution in a reaction kettle. Add deionized water to a total mass of 1.0 kg. Under ammonia protection, heat to 80°C, adjust the pH to 8.0, and react at this constant temperature for 1.5 hours to obtain a prepolymer.

[0067] The prepolymer was heated to 225° C., depressurized to 1.0 MPa, dehydrated for 0.8 hours, and then heated to 280° C. The vacuum degree was reduced to 30 Pa, and reacted for 4 hours to obtain a polyamide resin.

[0068] 5 kg of polyamide resin pellets were added to a twin-screw extruder, set at 275°C and a screw speed of 40 rpm. Nylon fiber was produced through spinning, cooling, oiling, drawing, and heat setting. The process parameters were set as follows:

[0069] Spinning and cooling: The spinneret aperture is 0.2 mm, and the spinning speed is 300 m / min. The cooling process has two cooling zones:

[0070] Cooling: within the range of 150-600mm from the spinneret, the wind temperature is 14±1℃, the humidity is 60±2%, and the wind speed is 0.7m / s; within the range of 600-1000mm from the spinneret, the wind temperature is 21±1℃, the humidity is 60±2%, and the wind speed is 0.7m / s.

[0071] Oiling: The oiling agent comprises 40wt% white oil, 10wt% lauryl polyoxyethylene ether, 10wt% PEG-40 stearate, 10wt% copper sulfate, and the balance is water; the oiling rate is 0.6%.

[0072] Drawing: drawing ratio 3.0 times, drawing temperature 85℃.

[0073] Heat setting: 165℃ hot roller setting, winding to obtain nylon fiber.

[0074] Preparation Example 2-4 is a nylon fiber, which differs from Preparation Example 2-1 in that 2,6-pyridinedicarboxylic acid is replaced by an equimolar amount of adipic acid.

[0075] Preparation Example 2-5, a nylon fiber, differs from Preparation Example 2-1 in that copper acetate is replaced by an equal mass of water in the oiling agent.

[0076] Preparation Example 2-6, a nylon fiber, differs from Preparation Example 2-1 in that the cooling process parameters are set as follows: in the range of 150 to 600 mm from the spinneret, the wind temperature is 22±1°C, the humidity is 60±2%, and the wind speed is 0.8 m / s; in the range of 600 to 1000 mm from the spinneret, the wind temperature is 12±1°C, the humidity is 60±2%, and the wind speed is 0.8 m / s.

[0077] Preparation Example 2-7, a nylon fiber, differs from Preparation Example 2-1 in that the cooling process parameters are set as follows: 150 to 1000 mm from the spinneret, wind temperature 12±1°C, humidity 60±2%, and wind speed 0.8 m / s.

[0078] Preparation Example 2-8, a nylon fiber, differs from Preparation Example 2-1 in that the cooling process parameters are set as follows: 150 to 1000 mm from the spinneret, wind temperature 22±1°C, humidity 60±2%, and wind speed 0.8 m / s.

[0079] Example 1: An antibacterial and easy-to-clean fabric, prepared as follows:

[0080] Preparation of nylon fabric: The nylon fibers obtained in Preparation Example 2-1 were used to make plain weave fabric (warp and weft density 80×60 strands / cm 2 ).

[0081] Preparation of finishing liquid: 9.7 kg of acrylic acid ester emulsion (Preparation Example 1-1) and 0.3 kg of polyhexamethylene biguanide were mixed and stirred at 500 rpm for 30 minutes to obtain a uniform finishing liquid.

[0082] Preparation of the antibacterial layer: Using a doctor blade coating method, the finishing liquid was evenly applied to the nylon fabric surface at a coating speed of 2 m / min and a gap thickness of 100 μm (wet film). Pre-drying with hot air at 80°C for 3 minutes removed 90% of the moisture. Curing with a hot roller at 120°C for 2 minutes formed a dry antibacterial layer with a thickness of 3 ± 0.5 μm.

[0083] Example 2: An antibacterial and easy-to-clean fabric, prepared as follows:

[0084] Preparation of nylon fabric: The nylon fiber obtained in Preparation Example 2-2 was used to make a twill fabric (warp and weft density 70×50 strands / cm 2 ).

[0085] Preparation of finishing liquid: 9.5 kg of acrylic emulsion (Preparation Example 1-2) was mixed with 0.5 kg of benzalkonium chloride and stirred at 500 rpm for 30 minutes to obtain a uniform finishing liquid.

[0086] Preparation of the antibacterial layer: Using a doctor blade coating method, evenly apply the finishing liquid to the nylon fabric surface at a coating speed of 2 m / min and a gap thickness of 100 μm (wet film). Pre-dry with hot air at 70°C for 5 minutes to remove 90% of the moisture. Then, heat roller cure at 130°C for 1 minute to form a dry antibacterial layer with a thickness of 1.5 ± 0.5 μm.

[0087] Example 3: An antibacterial and easy-to-clean fabric, prepared as follows:

[0088] Preparation of nylon fabric: The nylon fibers obtained in Preparation Example 2-3 were used to make plain weave fabric (warp and weft density 80×60 strands / cm 2 ).

[0089] Preparation of finishing liquid: 9.8 kg of acrylate emulsion (Preparation Example 1-3) was mixed with 0.2 kg of dodecylguanidine acetate, and stirred at 500 rpm for 30 minutes to obtain a uniform finishing liquid.

[0090] Preparation of the antibacterial layer: Using a doctor blade coating method, evenly apply the finishing liquid to the nylon fabric surface at a coating speed of 2 m / min and a gap thickness of 100 μm (wet film). Pre-dry with hot air at 60°C for 4 minutes to remove 90% of the moisture. Then, use a hot roller to cure at 110°C for 3 minutes to form a dry antibacterial layer with a thickness of 4 ± 0.5 μm.

[0091] Example 4: An antibacterial and easy-to-clean fabric. The difference from Example 1 is that the acrylate emulsion of Preparation Example 1-1 is replaced by an equal amount of the acrylate emulsion of Preparation Example 1-4.

[0092] Example 5: An antibacterial and easy-to-clean fabric, which differs from Example 1 in that the nylon fiber of Preparation Example 2-1 is replaced by an equal amount of nylon fiber of Preparation Example 2-4.

[0093] Example 6: An antibacterial and easy-to-clean fabric, which differs from Example 1 in that the nylon fiber of Preparation Example 2-1 is replaced by an equal amount of nylon fiber of Preparation Example 2-5.

[0094] Example 7: An antibacterial and easy-to-clean fabric, which differs from Example 4 in that the nylon fiber of Preparation Example 2-1 is replaced by an equal amount of nylon fiber of Preparation Example 2-5.

[0095] Example 8: An antibacterial and easy-to-clean fabric, which differs from Example 5 in that the nylon fiber of Preparation Example 2-1 is replaced by an equal amount of the nylon fiber of Preparation Example 2-5.

[0096] Example 9: An antibacterial and easy-to-clean fabric. The difference from Example 8 is that the acrylate emulsion of Preparation Example 1-1 is replaced by an equal amount of the acrylate emulsion of Preparation Example 1-4.

[0097] Example 10: An antibacterial and easy-to-clean fabric, which differs from Example 1 in that the nylon fiber of Preparation Example 2-1 is replaced by an equal amount of nylon fiber of Preparation Example 2-6.

[0098] Example 11: An antibacterial and easy-to-clean fabric, which differs from Example 1 in that the nylon fiber of Preparation Example 2-1 is replaced by an equal amount of nylon fiber of Preparation Example 2-7.

[0099] Example 12: An antibacterial and easy-to-clean fabric, which differs from Example 1 in that the nylon fiber of Preparation Example 2-1 is replaced by an equal amount of nylon fiber of Preparation Example 2-8.

[0100] Example 13: An antibacterial and easy-to-clean fabric, which differs from Example 4 in that the nylon fiber of Preparation Example 2-1 is replaced by an equal amount of nylon fiber of Preparation Example 2-8.

[0101] Example 14: An antibacterial and easy-to-clean fabric, which differs from Example 6 in that the nylon fiber of Preparation Example 2-1 is replaced by an equal amount of nylon fiber of Preparation Example 2-8.

[0102] Comparative Example 1

[0103] An antibacterial and easy-to-clean fabric is disclosed, which differs from Example 1 in that the acrylate emulsion of Preparation Example 1-1 is replaced by an equal amount of the acrylate emulsion of Preparation Example 1-5.

[0104] Comparative Example 2

[0105] An antibacterial and easy-to-clean fabric is disclosed, which differs from Example 1 in that the acrylate emulsion of Preparation Example 1-1 is replaced by an equal amount of the acrylate emulsion of Preparation Example 1-6.

[0106] Comparative Example 3

[0107] An antibacterial and easy-to-clean fabric is disclosed, which differs from Example 1 in that the acrylate emulsion of Preparation Example 1-1 is replaced by an equal amount of the acrylate emulsion of Preparation Example 1-7.

[0108] Comparative Example 4

[0109] An antibacterial and easy-to-clean fabric is disclosed, which differs from Example 1 in that the acrylate emulsion of Preparation Example 1-1 is replaced by an equal amount of the acrylate emulsion of Preparation Example 1-8.

[0110] Comparative Example 5

[0111] An antibacterial and easy-to-clean fabric is disclosed, which differs from Example 1 in that the acrylate emulsion of Preparation Example 1-1 is replaced by an equal amount of the acrylate emulsion of Preparation Example 1-9.

[0112] Comparative Example 6

[0113] An antibacterial and easy-to-clean fabric is disclosed, which differs from Example 1 in that the acrylate emulsion of Preparation Example 1-1 is replaced by an equal amount of the acrylate emulsion of Preparation Example 1-10.

[0114] Comparative Example 7

[0115] An antibacterial and easy-to-clean fabric is disclosed, which differs from Example 1 in that the acrylate emulsion of Preparation Example 1-1 is replaced by an equal amount of the acrylate emulsion of Preparation Example 1-11.

[0116] Test 1: Fabric water contact angle test:

[0117] Sample preparation: Take the fabric samples (10×10 cm) of the embodiment and comparative example and equilibrate them in a standard environment (temperature 25±2°C, humidity 65±5%) for 24 hours.

[0118] Test method: Refer to ASTM D7334-08 and use a contact angle meter (Krüss DSA25). Place the sample flat on the test bench and drop 3 μL of deionized water onto the surface. The contact angle is automatically calculated. Five points are measured per sample, and the average is calculated.

[0119] Test 2: Fabric antibacterial performance test:

[0120] Sample preparation: Cut the sample into 5×5 cm size and sterilize it (high pressure steam 121°C, 20 min).

[0121] Test method: Refer to GB / T 20944.3-2008 "Evaluation of Antimicrobial Properties of Textiles." Test bacteria: Staphylococcus aureus (ATCC 6538) and Escherichia coli (ATCC 25922).

[0122] Steps: Inoculate the bacteria into LB medium, culture at 37℃ for 18h, and dilute to 1×10 6 CFU / mL; soak the sample in bacterial solution (0.2 mL), cover with polyethylene film, and incubate at 37°C for 24 h; elute the bacterial solution, dilute it, spread it on agar plates, incubate at 37°C for 24 h, and count the colonies; antibacterial rate = (number of colonies in the blank group - number of colonies in the sample group) / number of colonies in the blank group × 100%.

[0123] Test 3: Fabric long-term antibacterial property (wash resistance) test:

[0124] Sample preparation: Same as test 2 sample.

[0125] Test method: Wash 50 times according to GB / T 3921-2008 (each wash temperature: 40°C, time: 30 minutes, 1g / standard detergent). After washing, the antibacterial rate of the sample is tested according to the method in Test 2.

[0126] Test 4: Fabric cleanability:

[0127] Sample preparation: Cut the sample to 10 × 10 cm in size and evenly apply artificial sebum dirt (ingredients: olive oil 40%, squalene 30%, cholesterol 20%, stearic acid 10%) on the surface at a coating weight of 0.1 g / cm 2 .

[0128] Test method: The following customized evaluation method is used for evaluation:

[0129] Simulated cleaning: Immerse the contaminated sample in 40°C deionized water (containing 0.1% sodium lauryl sulfate) with magnetic stirring (200 rpm) for 10 minutes. After drying, measure the color difference ΔE between the contaminated and clean areas using a colorimeter (e.g., X-Rite Ci64). Cleaning rate = (initial ΔE - post-cleaning ΔE) / initial ΔE × 100%.

[0130] Test 5: Fabric softness test:

[0131] Sample preparation: Cut the sample to a size of 2.5 × 15 cm without creases.

[0132] Test method: Refer to ASTM D1388-18, "Fabric Bending Length Test," using a fabric softness tester. Place the sample horizontally on a platform and slowly push it out until the front end reaches a 41.5° angle. Record the push-out length, L, and calculate the bending length, C, as L / 2. A smaller value indicates softer fabric.

[0133] Table 1. Test results of antibacterial and easy-to-clean fabric performance

[0134]

[0135] In Example 4 (no amino groups grafted into the acrylic emulsion), the long-term antibacterial rate decreased slightly. In Example 5 (no pyridine dicarboxylic acid segments introduced into the nylon fiber), the antibacterial rate also decreased slightly, with a significant decrease in long-term antibacterial performance, and the rate of decrease was greater than that in Example 4. The results in Example 6 (no metal ions in the fiber oil) were similar to those in Example 5. This indicates that the introduction of amino groups into the emulsion, pyridyl groups into the nylon fiber, or zinc / copper metal ion coordination all contribute to improved washability and long-term antibacterial performance. This may be due to the synergistic interaction between the amino groups in the emulsion, the pyridyl groups in the fiber, and the metal ions, which facilitate the formation of a bridging structure and enhance the adhesion of the antibacterial layer. Furthermore, the decrease in Examples 5 and 6 was more pronounced. This is due to the inability to form a bridging structure, resulting in reduced adhesion and washability of the antibacterial layer. Furthermore, the inability to coordinate with the metal ions weakens the sustained-release antibacterial effect.

[0136] Furthermore, the long-term antibacterial performance of Examples 7 (no amino group grafted into the emulsion, and no metal ions added to the oil), 8 (no dipicolinate segments introduced into the fiber, and no metal ions added to the oil), and 9 (no amino group grafted into the emulsion, no dipicolinate segments introduced into the fiber, and no metal ions added to the oil) decreased, but remained close to the results of Examples 5 and 6. This demonstrates that the three methods have a synergistic effect in achieving long-term antibacterial performance, which cannot be achieved without any of the technical means.

[0137] The long-term antimicrobial performance of Example 10 (fiber spinning cooling process performed initially at room temperature and then rapidly) was significantly reduced. This may be because the spinning temperature was lower due to the initial rapid cooling followed by room temperature cooling, making it difficult to generate large temperature differences and stresses. Consequently, microcracks were less likely to form in the surface layer. This lacked permeation and diffusion channels for metal ions and the nanoparticles of the acrylic emulsion, significantly reducing the bridging effect between the antimicrobial layer and the fiber and the interfacial bonding area. This, in turn, reduced the antimicrobial layer's washability and long-term antimicrobial rate. Example 11 (rapid cooling throughout the entire cooling process) showed improved long-term antimicrobial performance. However, due to the increased crack formation, the crystallinity and orientation were lower, and the fiber's mechanical properties were significantly reduced, failing to meet fabric weaving requirements. Therefore, testing was not performed. Example 12 (room temperature cooling throughout the cooling process) showed a significant decline in long-term antimicrobial performance. This may be because the lack of rapid cooling prevented the formation of microcracks.

[0138] Furthermore, the long-term antibacterial performance of Example 13 (no amino groups grafted into the acrylic emulsion, and only room temperature cooling) and Example 14 (no metal ions added to the oil, and only room temperature cooling) declined significantly, with the rate of decline higher than that of Example 12. This may be because, while microcracks could not form to achieve the mortise and tenon connection between the antibacterial layer and the fiber, the metal ions could not bridge the gap between the two, resulting in a further decline in washability (long-term antibacterial rate).

[0139] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make non-creative modifications to the present embodiment as needed, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. An antibacterial and easy-to-clean fabric, characterized in that: The invention comprises a nylon fabric and an antibacterial layer supported on the nylon fabric, wherein the water contact angle of the antibacterial layer is 20-50°; the raw materials of the antibacterial layer comprise an acrylate emulsion and an antibacterial agent, the amount of the antibacterial agent is 1-3wt%, the comonomers of the acrylate emulsion comprise: 30-50wt% unsaturated carboxylic acid, 30-40wt% alkyl acrylate, 10-20wt% divinylbenzene, and 10-15wt% allyl polyoxyethylene ether; the number of ethylene oxide units in the allyl polyoxyethylene ether is 7-12; the nylon fabric is woven from nylon fibers, and the polyamide resin molecules of the nylon fibers comprise adipic acid, hexamethylenediamine, and pyridyl dicarboxylic acid chain segments in a molar ratio of 1:1-1.05:0.02-0.06, and the pyridyl dicarboxylic acid chain segments are Zn-containing. 2+ and / or Cu 2+ Coordination; the preparation method of the nylon fiber is as follows: adding polyamide resin to a screw extruder, melting, spinning, cooling, oiling, drawing, and heat setting to obtain nylon fiber; the cooling adopts side blowing cooling, and the cooling air temperature is set in a gradient, including: within the range of 150 to 600 mm from the spinneret, the air temperature is 10 to 15°C; within the range of 600 to 1000 mm from the spinneret, the air temperature is 20 to 25°C; the coordination is achieved by adding zinc salt and / or copper salt to the oiling agent for oiling.

2. The antibacterial and easy-to-clean fabric according to claim 1, characterized in that: The unsaturated carboxylic acid is selected from one or more of acrylic acid, maleic acid, itaconic acid and fumaric acid.

3. The antibacterial and easy-to-clean fabric according to claim 1, characterized in that: The alkyl acrylate is selected from one or more of methyl methacrylate, ethyl acrylate, ethyl methacrylate, and butyl acrylate.

4. The antibacterial and easy-to-clean fabric according to claim 1, characterized in that: The pyridyl-containing dicarboxylic acid is selected from one or more of 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, and 2,2'-bipyridine-3,3'-dicarboxylic acid.

5. The antibacterial and easy-to-clean fabric according to claim 1, characterized in that: The content of zinc salt and / or copper salt in the oil is 5-10 wt %.

6. The antibacterial and easy-to-clean fabric according to claim 5, characterized in that: The comonomer of the acrylic ester emulsion contains 5 to 10 wt % of vinyl aniline.

7. The antibacterial and easy-to-clean fabric according to claim 1, characterized in that: The preparation method of the polyamide resin is: Dissolving the pyridyl dicarboxylic acid in dilute hydrochloric acid at a pH of 3 to 4, mixing with adipic acid and hexamethylenediamine, and adding deionized water to obtain a solution with a solid content of 30 to 40%; stirring and heating to 60 to 80° C. under nitrogen protection, adjusting the pH to 7.5 to 8.5, and performing a salt-forming reaction to obtain a prepolymer; The prepolymer is heated to 220-240° C., reduced to 0.5-1.0 MPa, and dehydrated and condensed; the temperature is further raised to 270-280° C., the vacuum degree is increased to <100 Pa, and the reaction is carried out for 5-8 hours to obtain a polyamide resin.

8. A method for preparing an antibacterial and easy-to-clean fabric, characterized in that: According to the composition of the antibacterial and easy-to-clean fabric according to any one of claims 1 to 7, an antibacterial agent and an acrylic ester emulsion are mixed to prepare a finishing liquid; the finishing liquid is applied to the surface of the nylon fabric, and dried and solidified to form an antibacterial layer with a thickness of 1 to 5 μm.

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