Antibacterial easy-to-clean fabric and preparation method thereof

Abstract

The invention discloses an antibacterial easy-to-clean fabric and a preparation method thereof, the antibacterial easy-to-clean fabric comprises a nylon fabric and an antibacterial layer loaded on the nylon fabric, and the water contact angle of the antibacterial layer is 20-50 degrees; the antibacterial layer is prepared from the following raw materials in percentage by weight: 30 to 50 percent of unsaturated carboxylic acid, 30 to 40 percent of alkyl acrylate, 10 to 20 percent of divinyl benzene and 10 to 15 percent of allyl polyoxyethylene ether, and the dosage of the antibacterial agent is 1 to 3 percent by weight, and a comonomer of the acrylate emulsion is prepared from 30 to 50 percent by weight of unsaturated carboxylic acid, 30 to 40 percent by weight of alkyl acrylate, 10 to 20 percent by weight of divinyl benzene and 10 to 15 percent by weight of allyl polyoxyethylene ether; the number of ethylene oxide units in the allyl polyoxyethylene ether is 7 to 12. The invention aims to solve the problems that the softness is reduced and the cleaning performance is weakened after the nylon fabric is subjected to antibacterial after-finishing treatment, so that the nylon fabric has excellent long-acting antibacterial property, softness and easy-to-clean property.

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] Antibacterial nylon fabrics have both moisture absorption, breathability and antibacterial functions, which can reduce the irritation of bacteria grown by sweat on the skin. They have significant application value in sportswear, household bedding and medical protective equipment. At present, the mainstream preparation process mostly adopts post-finishing technology to achieve functionalization by coating the antibacterial layer on the surface of the fabric. Such antibacterial layers are usually composed of adhesives and antibacterial agents, among which the adhesives are mostly cross-linked resins, which aim to enhance the adhesion and washing resistance of the antibacterial agent by improving the density of the coating.

[0003] For example, in the patent application with publication number CN103774431A, the mechanical stability of the coating is significantly improved by cross-linking and curing polyurethane resin and isocyanate. However, this process has two major defects: first, the cross-linking and curing process increases the hardness of the coating and reduces the softness of the fabric, which affects the wearing comfort. It is especially not suitable for scenes with high requirements for touch, such as underwear or medical dressings; second, the cross-linking reaction consumes the hydrophilic groups in the adhesive, resulting in a decrease in the hydrophilicity of the coating, and the surface is easily adsorbed by dirt such as sebum and dust, which weakens the easy cleaning of the fabric. 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, the present application provides an antibacterial and easy-to-clean fabric and a preparation method thereof.

[0005] In the 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 copolymer monomer of the acrylic emulsion includes: 30 to 50 wt% of unsaturated carboxylic acid, 30 to 40 wt% of alkyl acrylate, 10 to 20 wt% of divinyl benzene, and 10 to 15 wt% of 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] The present application prepares an acrylic emulsion by using a specific ratio of comonomers, so that the antibacterial layer has cross-linking strength (anti-swelling of water molecules), softness and easy cleaning. Unsaturated carboxylic acid is a key component for regulating hydrophilicity. Its carboxylic acid group gives the antibacterial layer moderate hydrophilicity, so that the water contact angle is controlled between 20 and 50°. When the water contact angle is higher than 50°, the hydrophilicity is insufficient, the dirt is difficult to be carried away by the water flow, and the easy cleaning performance decreases; when the water contact angle is lower than 20°, too many hydrophilic groups will cause the antibacterial layer to absorb water and swell, destroy the coating structure, and reduce the water wash resistance and antibacterial durability. Alkyl acrylate and divinylbenzene work synergistically to provide mechanical strength and anti-swelling ability: the long alkyl chain of alkyl acrylate provides certain water repellency, while the double bond cross-linking of divinylbenzene forms a three-dimensional network structure, which improves the resistance to water molecule permeability. Since the cross-linking of divinylbenzene is only achieved through free radical polymerization, the hydrophilic groups such as carboxylic acid are not consumed, so the hydrophilicity is maintained while the water resistance is enhanced. The introduction of allyl polyoxyethylene ether (10-15wt%) plays a key role. Its polyoxyethylene chain segment is flexible and hydrophilic. It reduces the rigidity of the coating and improves the softness of the fabric by improving the flexible movement of the molecular chain. The synergistic effect of the four types of monomers enables the antibacterial layer to form a balanced network structure of rigidity and flexibility at the microscopic level, taking into account washability, comfort and easy cleaning.

[0011] It should be noted that the number of repeating units in the polyoxyethylene segment should be controlled within 7 to 12 ethylene oxide units. If the number of repeating units is greater than 12, the grafting ability is reduced and the local hydrophilicity is too high. If the number of repeating units is less than 7, the flexibility and toughness enhancement capabilities are 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 chain segments in a molar ratio of 1:1 to 1.05:0.02 to 0.06, and the pyridyl dicarboxylic acid chain segments are Zn 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 pyridine-containing dicarboxylic acid segment into the polyamide resin, and the nitrogen atom on the pyridine ring can react with Zn 2+ Cu 2+ Form a stable coordination bond. The metal ions are evenly dispersed inside the fiber through coordination, forming a slow-release antibacterial mechanism: on the one hand, when the metal ions come into contact with the bacterial cell membrane, they destroy its 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 the loss of ions 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: Add polyamide resin into a screw extruder, and obtain nylon fiber 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 150-600mm from the spinneret; the air temperature is 20-25°C in the range of 600-1000mm from the spinneret.

[0016] 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%.

[0017] 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.

[0018] 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.

[0019] 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 zone, and 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, Zn in the oil agent 2+ / Cu 2+Penetrate into the fiber through microcracks, increase the coordination density and enhance the antibacterial effect. Secondly, it can form a physical anchoring effect. The nanoparticles in the acrylic emulsion penetrate into the microcracks and form a physical connection structure similar to "mortise and tenon" with the fiber, increasing the interface bonding area between the antibacterial layer and the fabric fiber. This mechanical interlocking effectively improves the adhesion between the antibacterial layer and the fiber, and significantly improves the water-washing resistance.

[0020] 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 a preset range and avoid excessive fluctuations in zone temperature.

[0021] In any of the above technical solutions, the copolymerizable monomer of the acrylic ester emulsion contains 5 to 10 wt % of vinyl aniline.

[0022] Furthermore, vinyl aniline was introduced into the acrylic emulsion, and its amino group (—NH 2 ) and pyridine groups in the fiber can react with Zn 2+ / Cu 2+ The coordination bridge is formed, and the antibacterial layer is anchored on the fiber surface through the "pyridyl-metal ion-amino" ternary complex structure. This bridging effect does not rely on chemical cross-linking, avoiding the rigid curing problem of traditional adhesives, so it does not affect the softness and hydrophilicity of the coating, and its washability and easy cleaning properties are synergistically enhanced.

[0023] In any of the above technical solutions, the preparation method of the polyamide resin is: Dissolve the pyridyl dicarboxylic acid in dilute hydrochloric acid with a pH of 3 to 4, mix with adipic acid and hexamethylenediamine, add deionized water to obtain a solution with a solid content of 30 to 40%; stir and heat to 60 to 80° C. under nitrogen protection, adjust the pH to 7.5 to 8.5, perform salt-forming reaction, and obtain a prepolymer; The prepolymer is heated to 220-240° C., and the pressure is reduced to 0.5-1.0 MPa for dehydration condensation; the temperature is further raised to 270-280° C., the vacuum degree is increased to <100 Pa, and the reaction is performed for 5-8 hours to obtain a polyamide resin.

[0024] 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 to form an antibacterial layer with a thickness of 1 to 5 μm.

[0025] In summary, this application has the following beneficial effects: 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 acids, allyl polyoxyethylene ethers and divinylbenzene in acrylic emulsions enables the antibacterial layer to have a hydrophilic angle of 20 to 50° (easy to clean), high softness and water washability (long-lasting antibacterial properties). In addition, the coordination structure of pyridyl dicarboxylic acid and metal ions introduced into the polyamide resin provides long-lasting antibacterial properties, and the microcracks formed by the gradient cooling process of nylon fibers promote the penetration of metal ion antibacterial agents and enhance interfacial bonding. The amino-functionalized emulsion further enhances the bonding strength through metal bridging, and ultimately obtains a soft, skin-friendly, antibacterial, durable and easy-to-clean composite fabric, which is suitable for high-end sportswear, medical dressings and other fields. DETAILED DESCRIPTION

[0026] Preparation Example 1-1, an acrylic emulsion, is prepared as follows: Pre-emulsification: 4.0 kg acrylic acid, 3.5 kg butyl acrylate, 1.5 kg divinylbenzene, 1.0 kg allyl polyoxyethylene ether (APEG-10, EO=10), 0.5 kg vinylaniline and 1.2 kg emulsifier (sodium dodecyl sulfate: OP-10=4:1) were dissolved in 8 kg deionized water, and the pre-emulsion was obtained by high-speed shearing at 8000 rpm for 30 min.

[0027] Polymerization reaction: Add 1 / 3 of the pre-emulsion into the reactor, replace with nitrogen, heat to 75°C, add 0.3kg of ammonium persulfate aqueous solution (10wt%), and drip it within 30 minutes; add the remaining pre-emulsion within 2 hours, and keep it warm for 2 hours. Cool down to 40°C, adjust the pH to 7.5 with ammonia water, and filter to obtain an acrylic emulsion with a D50 of 60nm and a PDI of 0.15.

[0028] Preparation Example 1-2, an acrylic emulsion, is prepared as follows: Pre-emulsification: 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 dodecyl sulfate: OP-10=4:1) were dissolved in 8 kg of deionized water, and the pre-emulsion was obtained by high-speed shearing at 5000 rpm for 40 min.

[0029] Polymerization reaction: Add 1 / 3 of the pre-emulsion into the reactor, replace with nitrogen, heat to 80°C, add 0.4kg potassium persulfate aqueous solution (10wt%) dropwise, and finish dripping within 40 minutes; add the remaining pre-emulsion dropwise within 3 hours, and keep warm for 3 hours. Cool down to 40°C, adjust the pH to 7.0 with ammonia water, and filter to obtain an acrylic emulsion with a D50 of 80nm and a PDI of 0.25.

[0030] Preparation Example 1-3, an acrylic emulsion, is prepared as follows: Pre-emulsification: 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 dodecyl sulfate: OP-10=5:1) were dissolved in 8 kg of deionized water, and the pre-emulsion was obtained by high-speed shearing at 6000 rpm for 30 min.

[0031] Polymerization reaction: Add 1 / 3 of the pre-emulsion into the reactor, replace with nitrogen, heat to 70°C, add 0.2kg of ammonium persulfate aqueous solution (10wt%), and drip it within 30 minutes; add the remaining pre-emulsion within 2.5 hours, and keep warm for 3 hours. Cool down to 40°C, adjust the pH to 8.0 with ammonia water, and filter to obtain an acrylic emulsion with a D50 of 40nm and a PDI of 0.10.

[0032] 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.

[0033] Preparation Example 1-5, an acrylic emulsion, is different 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.

[0034] Preparation Example 1-6, an acrylic emulsion, is different 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.

[0035] Preparation Example 1-7, an acrylic emulsion, is different 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.

[0036] Preparation Example 1-8, an acrylic emulsion, differs from Preparation Example 1-1 in that divinylbenzene is replaced by an equal amount of styrene.

[0037] Preparation Example 1-9, an acrylic emulsion, is different 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).

[0038] Preparation Example 1-10, an acrylic emulsion, is different 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).

[0039] Preparation Example 1-11, an acrylic emulsion, is different from Preparation Example 1-1 in that allyl polyoxyethylene ether (APEG-10, EO=10) is replaced by an equal amount of acrylic acid.

[0040] Preparation Example 2-1, a nylon fiber is prepared according to the following steps: Dissolve 6.68g 2,6-pyridinedicarboxylic acid (0.04mol) in 200ml dilute hydrochloric acid with pH=3.5 and stir until completely dissolved. Mix 146.14g adipic acid (1mol), 119.11g hexamethylenediamine (1.03mol) and 2,6-pyridinedicarboxylic acid solution in a reactor, add deionized water to a total mass of 1.0kg, heat to 70℃ under ammonia protection, adjust pH to 8.0, and react at constant temperature for 2 hours to obtain a prepolymer.

[0041] 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.

[0042] 5kg of polyamide resin pellets were added to the twin-screw extruder, and the temperature was set at 270°C and the screw speed was 50rpm. After spinning, cooling, oiling, drawing, and heat setting, nylon fibers were obtained. The parameters of each process were set as follows: Spinning: spinneret aperture 0.2mm, spinning speed 300m / min.

[0043] 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.

[0044] Oiling: The oiling agent 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%.

[0045] Drawing: drawing ratio 3.5 times, drawing temperature 80℃.

[0046] Heat setting: 160℃ hot roller setting, winding to get nylon fiber.

[0047] Preparation Example 2-2, a nylon fiber is prepared according to the following steps: Dissolve 3.34g 3,4-pyridinedicarboxylic acid (0.02mol) in 150ml dilute hydrochloric acid with pH=3.0 and stir until completely dissolved. Mix 146.14g adipic acid (1mol), 122.02g hexamethylenediamine (1.05mol) and 3,4-pyridinedicarboxylic acid solution in a reactor, add deionized water to a total mass of 1.2kg, heat to 65°C under ammonia protection, adjust pH to 7.8, and react at constant temperature for 3.5 hours to obtain a prepolymer.

[0048] 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.

[0049] 5kg of polyamide resin pellets were added to the twin-screw extruder, and the temperature was set at 265°C and the screw speed was 50rpm. After spinning, cooling, oiling, drawing, and heat setting, nylon fibers were obtained. The parameters of each process were set as follows: Spinning and cooling: spinneret aperture 0.2 mm, spinning speed 300 m / min.

[0050] 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.

[0051] Oiling: The oiling agent 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%.

[0052] Drawing: drawing ratio 4 times, drawing temperature 80℃.

[0053] Heat setting: 160℃ hot roller setting, winding to get nylon fiber.

[0054] Preparation Example 2-3, a nylon fiber is prepared according to the following steps: Dissolve 14.03g 2,2'-bipyridine-3,3'-dicarboxylic acid (0.06mol) in 250ml dilute hydrochloric acid with pH=4.0 and stir until completely dissolved. Mix 146.14g adipic acid (1mol), 116.21g hexamethylenediamine (1mol) and 2,2'-bipyridine-3,3'-dicarboxylic acid solution in a reactor, add deionized water to a total mass of 1.0kg, heat to 80°C under ammonia protection, adjust pH to 8.0, and react at constant temperature for 1.5 hours to obtain a prepolymer.

[0055] 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.

[0056] Take 5kg of polyamide resin pellets and add them into the twin-screw extruder, set the temperature to 275℃ and the screw speed to 40rpm. After spinning, cooling, oiling, drawing and heat setting, nylon fiber is obtained. The parameters of each process are set as follows: 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: 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.

[0057] Oiling: The oiling agent comprises 40wt% white oil, 10wt% lauryl polyoxyethylene ether, 10wt% PEG-40 stearate, 10wt% copper sulfate, and water as the balance; the oiling rate is 0.6%.

[0058] Drawing: drawing ratio 3.0 times, drawing temperature 85℃.

[0059] Heat setting: 165℃ hot roller setting, winding to get nylon fiber.

[0060] Preparation Example 2-4, a nylon fiber, is different from Preparation Example 2-1 in that 2,6-pyridinedicarboxylic acid is replaced by an equimolar amount of adipic acid.

[0061] Preparation Example 2-5, a nylon fiber, differs from Preparation Example 2-1 in that an equal mass of water is used to replace copper acetate in the oiling agent.

[0062] 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.

[0063] Preparation Example 2-7, a nylon fiber, differs from Preparation Example 2-1 in that the cooling process parameters are set as follows: 150-1000 mm from the spinneret, wind temperature 12±1°C, humidity 60±2%, and wind speed 0.8 m / s.

[0064] Preparation Example 2-8, a nylon fiber, differs from Preparation Example 2-1 in that the cooling process parameters are set as follows: 150-1000 mm from the spinneret, wind temperature 22±1°C, humidity 60±2%, and wind speed 0.8 m / s.

[0065] Example 1: An antibacterial and easy-to-clean fabric, the preparation steps are as follows: Preparation of nylon fabric: The nylon fiber obtained in Preparation Example 2-1 was used to make a plain fabric (warp and weft density 80×60 strands / cm 2 ).

[0066] Preparation of finishing liquid: 9.7 kg of acrylic 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.

[0067] Preparation of antibacterial layer: Use the doctor blade coating method to evenly apply the finishing liquid on the surface of nylon fabric, the coating speed is 2m / min, and the gap thickness is set to 100μm (wet film). Pre-dry with 80℃ hot air for 3 minutes to remove 90% of the moisture; then use 120℃ hot roller curing for 2 minutes to form a dry antibacterial layer with a thickness of 3±0.5um.

[0068] Example 2: An antibacterial and easy-to-clean fabric, the preparation steps are as follows: 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 ).

[0069] 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.

[0070] Preparation of antibacterial layer: Use the doctor blade coating method to evenly apply the finishing liquid on the surface of nylon fabric, the coating speed is 2m / min, and the gap thickness is set to 100μm (wet film). Pre-dry with 70℃ hot air for 5 minutes to remove 90% of the moisture; then heat roller cure at 130℃ for 1 minute to form a dry antibacterial layer with a thickness of 1.5±0.5um.

[0071] Example 3: An antibacterial and easy-to-clean fabric, the preparation steps are as follows: Preparation of nylon fabric: The nylon fibers obtained in Preparation Example 2-3 were used to make plain woven fabric (warp and weft density 80×60 strands / cm 2 ).

[0072] Preparation of finishing liquid: 9.8 kg of acrylic 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.

[0073] Preparation of antibacterial layer: Use the doctor blade coating method to evenly apply the finishing liquid on the surface of nylon fabric, the coating speed is 2m / min, and the gap thickness is set to 100μm (wet film). Pre-dry with hot air at 60℃ for 4 minutes to remove 90% of the moisture; then use a hot roller at 110℃ for 3 minutes to form a dry antibacterial layer with a thickness of 4±0.5um.

[0074] Example 4: An antibacterial and easy-to-clean fabric, 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 1-4.

[0075] 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.

[0076] 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.

[0077] Example 7: An antibacterial and easy-to-clean fabric, which differs from Example 4 in that the nylon fibers of Preparation Example 2-1 are replaced with an equal amount of nylon fibers of Preparation Example 2-5.

[0078] 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 nylon fiber of Preparation Example 2-5.

[0079] Example 9: An antibacterial and easy-to-clean fabric, which differs from Example 8 in that the acrylate emulsion of Preparation Example 1-1 is replaced by an equal amount of the acrylate emulsion of Preparation Example 1-4.

[0080] Example 10: An antibacterial and easy-to-clean fabric, which differs from Example 1 in that the nylon fibers of Preparation Example 2-1 are replaced with an equal amount of nylon fibers of Preparation Example 2-6.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] 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.

[0085] Comparative Example 1 An antibacterial and easy-to-clean fabric, 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.

[0086] Comparative Example 2 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.

[0087] Comparative Example 3 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.

[0088] Comparative Example 4 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.

[0089] Comparative Example 5 An antibacterial and easy-to-clean fabric, 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.

[0090] Comparative Example 6 An antibacterial and easy-to-clean fabric, 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.

[0091] Comparative Example 7 An antibacterial and easy-to-clean fabric, 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.

[0092] Test 1: Fabric water contact angle test: Sample preparation: Take the fabric samples (10×10 cm) of the embodiments and comparative examples and equilibrate them in a standard environment (temperature 25±2° C., humidity 65±5%) for 24 hours.

[0093] Test method: Refer to ASTM D7334-08 and use a contact angle meter (Krüss DSA25). Spread the sample flat on the test bench, drop 3uL of deionized water on the sample surface, and automatically calculate the contact angle. Measure 5 points for each sample and take the average value.

[0094] Test 2: Fabric antibacterial performance test: Sample preparation: Cut the sample into a size of 5×5 cm and sterilize it (high pressure steam 121°C, 20 min).

[0095] Test method: Refer to GB / T 20944.3-2008 "Evaluation of antibacterial properties of textiles". Test bacteria: Staphylococcus aureus (ATCC6538), Escherichia coli (ATCC25922).

[0096] 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 (0.2mL), cover with polyethylene film, and culture at 37℃ for 24h; elute the bacterial solution, spread on agar plate after dilution, culture at 37℃ for 24h, and count the colonies; antibacterial rate = (number of colonies in blank group - number of colonies in sample group) / number of colonies in blank group × 100%.

[0097] Test 3: Long-term antibacterial property (wash resistance) test of fabrics: Sample preparation: Same as test 2 samples.

[0098] Test method: Wash 50 times according to GB / T 3921-2008 standard (each washing temperature is 40℃, time is 30min, 1g / standard detergent). After washing, the antibacterial rate of the sample is tested according to the test 2 method.

[0099] Test 4: Fabric cleanability: Sample preparation: Cut the sample to a size of 10×10 cm and evenly apply artificial sebum dirt (ingredients: 40% olive oil, 30% squalene, 20% cholesterol, 10% stearic acid) on the surface with a coating amount of 0.1 g / cm 2 .

[0100] Test method: The following custom evaluation method is used for evaluation: Simulated cleaning: immerse the contaminated sample in 40℃ deionized water (containing 0.1% sodium dodecyl sulfate) and stir magnetically (200rpm) for 10min. After drying, measure the color difference ΔE between the contaminated area and the clean area using a colorimeter (such as X-Rite Ci64). Cleaning rate = (initial ΔE-ΔE after cleaning) / initial ΔE×100%.

[0101] Test 5: Fabric softness test: Sample preparation: Cut samples with a size of 2.5×15 cm without creases.

[0102] Test method: Refer to ASTM D1388-18 "Fabric Bending Length Test" and use a fabric softness tester. Place the sample horizontally on the platform and slowly push it out until the front end sags and reaches an inclination angle of 41.5°; record the push-out length L and calculate the bending length C=L / 2. The smaller the value, the softer it is.

[0103] Table 1. Test results of antibacterial and easy-to-clean fabric performance

[0104] In Example 4 (no grafted amino groups in the acrylic emulsion), the long-term antibacterial rate decreased slightly. In Example 5 (no pyridine dicarboxylic acid segments were introduced into the nylon fiber), the antibacterial rate decreased slightly, and the long-term antibacterial performance decreased significantly and the decrease rate was greater than that of Example 4; the results of Example 6 (no metal ions in the fiber oil agent) were close to those of Example 5. It shows that the introduction of amino groups in the emulsion, the introduction of pyridine groups in the nylon fiber, or the introduction of zinc / copper metal ion coordination can help improve its water washing resistance and improve the long-term antibacterial performance. The reason may be that the synergistic coordination of amino groups in the emulsion, pyridine groups in the fiber, and metal ions helps to form a bridging structure and improve the adhesion of the antibacterial layer. In addition, the decrease in Examples 5 and 6 is more obvious, because on the one hand, it cannot form a bridging effect, resulting in a decrease in the adhesion of the antibacterial layer and a decrease in water washing resistance, and on the other hand, it cannot coordinate with metal ions, and the sustained-release antibacterial effect is weakened.

[0105] Furthermore, the long-term antibacterial performance of Example 7 (the latex was not grafted with amino groups, and no metal ions were added to the oil), Example 8 (the fiber was not introduced with dipyridine carboxylic acid segments, and no metal ions were added to the oil), and Example 9 (the latex was not grafted with amino groups, the fiber was not introduced with dipyridine carboxylic acid segments, and no metal ions were added to the oil) decreased and was close to the results of Example 5 and Example 6. This shows that the three have a synergistic effect in achieving long-term antibacterial performance, which cannot be achieved without any technical means.

[0106] The long-term antibacterial performance of Example 10 (the fiber spinning cooling process is first cooled at room temperature and then rapidly cooled) is significantly reduced. The reason may be that since the spinning temperature is lowered first and then rapidly cooled, it is difficult to form a large temperature difference and stress, so it is difficult to form microcracks on the surface, and the metal ions and nanoparticles of the acrylic emulsion lack a permeation and diffusion channel, which significantly reduces the bridging effect and interface bonding area between the antibacterial layer and the fiber, and the water washing resistance and long-term antibacterial rate of the antibacterial layer are reduced accordingly. In Example 11 (rapid cooling during the entire cooling process), the long-term antibacterial performance is improved, because it forms more cracks, but the crystallinity and orientation are low, and the mechanical properties of the fiber are significantly reduced, which cannot meet the fabric weaving requirements. Therefore, no detection is performed. In Example 12 (normal temperature cooling during the entire cooling process), the long-term antibacterial performance is significantly reduced. The reason may be that microcracks cannot be formed without rapid cooling.

[0107] Furthermore, the long-term antibacterial performance of Example 13 (no amino group grafted in the acrylic emulsion, and only cooled at room temperature) and Example 14 (no metal ions added to the oil, and only cooled at room temperature) decreased significantly, and the decrease rate was higher than that of Example 12. The reason may be that while microcracks cannot be formed to achieve the mortise and tenon connection between the antibacterial layer and the fiber, the bridging effect between the two cannot be completed by metal ions, resulting in a further decrease in water wash resistance (long-term antibacterial rate).

[0108] 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 modifications to the present embodiment without any creative contribution as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. An antibacterial and easy-to-clean fabric, characterized in that: The invention comprises a nylon fabric and an antibacterial layer loaded 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, wherein the amount of the antibacterial agent is 1-3wt%, and the copolymer monomer of the acrylate emulsion comprises: 30-50wt% of unsaturated carboxylic acid, 30-40wt% of alkyl acrylate, 10-20wt% of divinyl benzene, and 10-15wt% of allyl polyoxyethylene ether; and the number of ethylene oxide units in the allyl polyoxyethylene ether is 7-12.

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 nylon fabric is woven from nylon fibers, wherein the polyamide resin molecules of the nylon fibers contain 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 2+ and / or Cu 2+ Coordination.

5. The antibacterial and easy-to-clean fabric according to claim 4, 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.

6. The antibacterial and easy-to-clean fabric according to claim 4, characterized in that: The preparation method of the nylon fiber is as follows: Add polyamide resin into a screw extruder, and obtain nylon fiber 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 150-600mm from the spinneret; the air temperature is 20-25°C in the range of 600-1000mm from the spinneret.

7. The antibacterial and easy-to-clean fabric according to claim 6, characterized in that: The coordination is carried out by adding zinc salt and / or copper salt to the oil for oiling, and the content of zinc salt and / or copper salt in the oil is 5-10wt%.

8. The antibacterial and easy-to-clean fabric according to claim 7, characterized in that: The copolymer monomer of the acrylic ester emulsion contains 5 to 10 wt % of vinyl aniline.

9. The antibacterial and easy-to-clean fabric according to claim 4, characterized in that: The preparation method of the polyamide resin is: Dissolve the pyridyl dicarboxylic acid in dilute hydrochloric acid with a pH of 3 to 4, mix with adipic acid and hexamethylenediamine, add deionized water to obtain a solution with a solid content of 30 to 40%; stir and heat to 60 to 80° C. under nitrogen protection, adjust the pH to 7.5 to 8.5, perform salt-forming reaction, and obtain a prepolymer; The prepolymer is heated to 220-240° C., and the pressure is reduced to 0.5-1.0 MPa for dehydration condensation; the temperature is further raised to 270-280° C., the vacuum degree is increased to <100 Pa, and the reaction is performed for 5-8 hours to obtain a polyamide resin.

10. 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 9, an antibacterial agent and an acrylic emulsion are mixed to prepare a finishing liquid; the finishing liquid is applied to the surface of the nylon fabric, and after drying and curing, an antibacterial layer with a thickness of 1 to 5 μm is formed.

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