Antibacterial and antifouling fabric and preparation method thereof

Abstract

The application discloses an antibacterial and antifouling fabric and a preparation method thereof, and relates to the technical field of textile processing, and comprises the following processes: face yarn, middle yarn and bottom yarn are woven through a warp knitting machine to obtain a gray cloth; the obtained gray cloth is sequentially subjected to weight reduction, sanding, dyeing, antibacterial and antifouling finishing in a finishing liquid and setting to obtain the fabric; the finishing agent comprises the following components: octadecyl acrylate, an unsaturated functional monomer, divinylbenzene, butyl acrylate, methyl methacrylate and silica sol; the unsaturated functional monomer contains quaternary ammonium salt and fluorine-containing segments. The unsaturated functional monomer is prepared through the reaction and chlorination of 1-bromoperfluorooctane, 3-(2-chloroethyl)-5,5-dimethylhydantoin and dimethylaminoethyl methacrylate, a perfluorinated long segment is introduced, the fabric is endowed with low surface energy characteristics, quaternary ammonium salt cations and polymerizable carbon-carbon double bonds and N-Cl halamine groups are introduced, and antibacterial function is provided.

Description

Technical Field

[0001] This invention relates to the field of textile treatment technology, specifically to an antibacterial and stain-resistant fabric and its preparation method. Background Technology

[0002] Polyester-nylon fabric is widely used in clothing and home textiles due to its soft hand feel, good drape, and excellent breathability. However, conventional polyester-nylon fabric is prone to staining and bacterial growth in humid environments, affecting wearing comfort and hygiene. With rising living standards and increasing health awareness, multifunctional textiles are gaining widespread attention.

[0003] Existing technologies for imparting functionality to fabrics include coating finishing and post-finishing padding. Coating finishing involves applying a resin layer containing functional components to the fabric surface, providing direct effects but impacting the fabric's breathability and hand feel. Post-finishing padding involves immersing the fabric in a finishing solution containing functional components, followed by drying and curing to firmly adhere the functional components to the fiber surface, minimizing the impact on the fabric's original properties. However, general finishing agents often suffer from the difficulty of simultaneously achieving antibacterial and stain-resistant functions. Therefore, we propose an antibacterial and stain-resistant fabric and its preparation method. Summary of the Invention

[0004] The purpose of this invention is to provide an antibacterial and stain-resistant fabric and its preparation method, so as to solve the problems mentioned in the background art.

[0005] To solve the above-mentioned technical problems, the present invention provides the following technical solution: an antibacterial and stain-resistant fabric, which is obtained by warp knitting of face yarn, middle yarn and bottom yarn; the face yarn is polyester-nylon island yarn, the middle yarn is semi-dull filament, and the bottom yarn is spandex yarn; the surface of the fabric is treated with an antibacterial and stain-resistant finishing agent.

[0006] Furthermore, the yarn is 95D / 36F polyester-nylon island yarn, accounting for 66-70% of the total fabric weight.

[0007] Furthermore, the medium yarn is a 45D / 24F semi-dull filament, accounting for 23-27% of the total fabric weight.

[0008] Furthermore, the base yarn is 40D / 3F spandex yarn, accounting for 5-9% of the total fabric weight.

[0009] Furthermore, the fabric is made of HKS3-M warp knitting, with a gauge of 32 needles, a width of 290 inches, and a pile height of 0.3mm.

[0010] A method for preparing an antibacterial and stain-resistant fabric includes the following processes: S1 weaving: The face yarn, middle yarn and back yarn are woven together by a warp knitting machine to obtain the greige fabric; S2 post-processing: The obtained greige fabric is subjected to weight reduction, napping, dyeing, antibacterial and anti-fouling finishing, and setting in sequence to obtain the fabric.

[0011] Furthermore, the weight reduction treatment employs an enzymatic weight reduction process, with a weight reduction rate of 20-25%. The specific process for reducing enzyme weight is as follows: Immerse the fabric in PET hydrolytic enzyme buffer solution and treat it at 50-60℃ and pH=7.5-8.5 for 90-120 min with a bath ratio of 1:(10-20); after weight reduction, heat to 80-90℃ to inactivate the enzyme for 10-15 min and wash with water until neutral. The PET hydrolase is a keratinase or esterase with an enzyme activity of 500–2000 U / g, and the dosage is 0.5–3.0% of the fabric mass. The buffer solution was 0.05 M Tris-HCl buffer at pH 8.0.

[0012] Furthermore, the sanding process employs a carbon fiber sanding roller with a rotation speed of 1200–1500 r / min and a machine speed of 15–25 m / min.

[0013] Furthermore, the antibacterial and antifouling finishing process employs a two-dip and two-nip process, with the ratio of the greige fabric to the finishing solution (solid-liquid ratio) being 1:(8-15) (g / mL), and the immersion time being 30-90 seconds; the padding residue rate is 60-80%. After impregnation and rolling, pre-dry and bake; pre-drying temperature 90-110℃, pre-drying time 1-3min; baking temperature 150-170℃, baking time 1-3min.

[0014] Further, the finishing agent comprises the following components: by weight, 40-60 parts octadecyl acrylate, 15-30 parts unsaturated functional monomers, 3-8 parts divinylbenzene, 10-20 parts butyl acrylate, 5-10 parts methyl methacrylate, 3-8 parts emulsifier, 0.2-0.8 parts initiator, 5-10 parts silica sol, and 100-300 parts deionized water; pH is 5-6; Unsaturated functional monomers contain quaternary ammonium salts and fluorinated segments; The emulsifiers include OP-10 and cetyltrimethylammonium bromide in a mass ratio of (2-5):(1-3); the initiator is azobisisobutyronitrile.

[0015] Furthermore, the finishing agent is prepared by the following process: Octadecyl acrylate, unsaturated functional monomer, divinylbenzene, butyl acrylate, methyl methacrylate, emulsifier and deionized water are mixed and emulsified at 10,000 to 15,000 rpm for 20 to 30 minutes; silica sol is added and added within 5 to 10 minutes, and emulsification continues for a total emulsification time of 30 to 60 minutes to obtain a pre-emulsion. Heat to 70-80℃, add initiator, keep the reaction at this temperature for 4-6 hours, cool to room temperature, and obtain finishing agent with a solid content of 5-20 wt%.

[0016] Furthermore, the unsaturated functional monomer is prepared by the following process: Step 1: Add 1-bromoperfluorooctane, 3-(2-chloroethyl)-5,5-dimethylhydantoin, and potassium carbonate to N,N-dimethylformamide. Under a nitrogen atmosphere, heat to 60-90°C and stir for 10-16 hours. After the reaction is complete, cool to room temperature, add water and stir to precipitate a solid. Filter, wash with deionized water and anhydrous ethanol, and dry under vacuum at 60°C to obtain the hydantoin brominated product. Step 2: Add the hydantoin bromide and dimethylaminoethyl methacrylate obtained in the previous step to anhydrous ethanol, heat to 70-80°C, and stir under reflux for 16-24 hours; remove the ethanol by vacuum distillation to obtain the fluorine-containing quaternary ammonium salt. Step 3: Mix the fluorinated quaternary ammonium salt and dichloromethane, add tert-butyl hypochlorite at 0-25℃, and add it over 15-30 minutes. Then stir the reaction for 60-90 minutes. After the reaction is complete, wash with water, dry the organic phase, wash with anhydrous diethyl ether, and dry under vacuum at 40-50℃ to obtain the unsaturated functional monomer.

[0017] Further, in step 1, the molar ratio of 1-bromoperfluorooctane, 3-(2-chloroethyl)-5,5-dimethylhydantoin, and potassium carbonate is 1:(1.0-1.1):(1.0-1.2). The ratio of 1-bromoperfluorooctane to N,N-dimethylformamide is 10 g / (40-80) mL.

[0018] Furthermore, in step 2, the mass ratio of hydantoin bromide to dimethylaminoethyl methacrylate is 10:(6-12). In the reaction system, 0.1-0.5 wt% of p-hydroxyanisole, containing hydantoin bromide, is added as a polymerization inhibitor; Add 0.05–0.1 eq potassium iodide (KI) of hydantoin bromide as a catalyst.

[0019] Furthermore, in step 3, the mass ratio of the fluorinated quaternary ammonium salt to tert-butyl hypochlorite is 10:(1.5-2.0). The ratio of fluorine-containing quaternary ammonium salt to dichloromethane is 10 g / (50-100) mL.

[0020] In the above technical solution, 1-bromoperfluorooctane reacts with 3-(2-chloroethyl)-5,5-dimethylhydantoin, and the amino group on the hydantoin ring undergoes nucleophilic substitution with the bromoalkane, introducing a long perfluorinated chain into the hydantoin ring. The product is denoted as the hydantoin bromide. The chloroethyl group on the hydantoin ring is retained and undergoes quaternization with the tertiary amino group in dimethylaminoethyl methacrylate in the next step to obtain a fluorinated quaternary ammonium salt. The hydantoin ring is further chlorinated to form N-Cl. The product is denoted as an unsaturated functional monomer, which has a perfluorinated segment, a hydantoin ring, a quaternary ammonium salt cation, and a carbon-carbon double bond that can participate in free radical copolymerization.

[0021] The unsaturated functional monomers were copolymerized with monomers such as octadecyl acrylate and divinylbenzene to prepare a finishing agent. When applied to the surface of a fabric, the perfluorinated segments impart low surface energy properties, making the fabric hydrophobic and oleophobic, and resistant to wetting and adhesion. Synergistically, the long alkyl chains of octadecyl acrylate effectively improve the fabric's stain resistance. Hydantoin ring chlorination forms haloamines, releasing active chlorine; the quaternary ammonium salt cations can disrupt bacterial cell membranes, achieving contact sterilization and giving the fabric excellent antibacterial properties. Divinylbenzene plays a cross-linking role, helping to improve the fabric's wash resistance. Butyl acrylate provides flexible segments, helping to maintain the fabric's soft hand feel.

[0022] Furthermore, the silica sol is prepared by the following process: Mix 50-60% tetrabutyl orthosilicate and 70-75% anhydrous ethanol by mass, adjust the pH to 5-6 using 0.1M acetic acid, stir for 3-5 hours, and then let stand for 24 hours to age. Add the remaining tetrabutyl orthosilicate and anhydrous ethanol, then add dimethyloctadecyl[3-(trimethoxymethylsilyl)propyl]ammonium chloride, and stir for 2-4 hours; adjust the pH to 3-4, and continue stirring for 20-40 minutes to obtain silica sol.

[0023] Further, the silica sol comprises the following components by mass: 7.2 to 10 parts tetrabutyl orthosilicate, 6 to 10 parts dimethyloctadecyl[3-(trimethoxymethylsilyl)propyl]ammonium chloride, and 70 to 100 parts anhydrous ethanol.

[0024] In the above technical solution, the silica sol is prepared using the sol-gel method. Through hydrolysis, condensation, aging, and quaternary ammonium salt modification, a silica sol containing quaternary ammonium salt cations and long-chain alkyl groups is obtained. When applied in finishing agents, it helps to form a rough surface on the fabric. Synergistically, this, combined with the low surface energy imparted by unsaturated functional monomers, improves the hydrophobic and oleophobic properties of the fabric, thereby further improving its stain-resistant properties. Both quaternary ammonium salt cations and long-chain alkyl groups carry positive charges; electrostatic repulsion promotes the stability of the finishing agent and the uniform dispersion of its components. They can also form electrostatic attraction with negatively charged fibers, enhancing the adhesion of the finishing agent to the fabric surface. The quaternary ammonium salt cations can attract chloride ions, forming a chloride-rich microenvironment, which is beneficial for the retention of activity in the haloamine structure and improves the antibacterial durability.

[0025] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. This invention prepares unsaturated functional monomers by reacting and chlorinating 1-bromoperfluorooctane, 3-(2-chloroethyl)-5,5-dimethylhydantoin, and dimethylaminoethyl methacrylate, introducing perfluorinated long-chain segments to impart low surface energy properties to the fabric; and introducing quaternary ammonium salt cations and polymerizable carbon-carbon double bonds and N-Cl haloamine groups to provide antibacterial functions.

[0026] 2. This invention mixes unsaturated functional monomers with octadecyl acrylate, divinylbenzene, butyl acrylate, methyl methacrylate, and dimethyloctadecyl[3-(trimethoxymethylsilyl)propyl]ammonium chloride-modified silica sol for free radical copolymerization, synergistically constructing a low surface energy surface, endowing the fabric with excellent hydrophobic, oleophobic, and stain-resistant properties, and improving the fabric's washability; the introduction of positively charged quaternary ammonium salt-modified silica sol exerts a synergistic hydrophobic and nanoparticle reinforcing effect, further improving the abrasion resistance and stain-resistant durability of the coating film.

[0027] 3. This invention utilizes a warp-knitted interweaving structure of polyester / nylon island-island yarn, semi-dull filament, and spandex yarn, combined with an HKS3-M warp knitting machine and 32-gauge high-gauge weaving, to obtain an elastic warp-knitted fabric with a high specific surface area microfiber pile layer. The fine fibers formed after the island-island yarn undergoes reduced-weight opening significantly improve the adsorption capacity and adhesion of finishing agents per unit area of ​​the fabric, providing an ideal physical base for subsequent antibacterial and stain-resistant finishing. Detailed Implementation

[0028] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0029] The raw materials involved in this invention are not subject to any special limitations and include, exemplarily, the following: The emulsifiers include OP-10 and hexadecyltrimethylammonium bromide in a mass ratio of 3:2; the initiator is azobisisobutyronitrile; the buffer is 0.05M Tris-HCl buffer at pH 8.0; and tert-butyl hypochlorite is a 70wt% aqueous solution. All "parts" are parts by weight, unless otherwise specified.

[0030] Example 1: A method for preparing an antibacterial and stain-resistant fabric, comprising the following processes: S1 Weaving: The fabric is woven using face yarn, middle yarn, and back yarn on a warp knitting machine. The machine uses HKS3-M warp knitting with a 32-gauge gauge, a width of 290 inches, and a pile height of 0.3mm to obtain the greige fabric. The face yarn is 95D / 36F polyester / nylon island fiber, accounting for 68% of the total fabric weight; the middle yarn is 45D / 24F semi-dull filament, accounting for 25% of the total fabric weight; and the back yarn is 40D / 3F spandex, accounting for 7% of the total fabric weight. S2 Post-treatment: The obtained greige fabric is subjected to weight reduction, napping, dyeing, antibacterial and anti-fouling finishing, and setting in sequence to obtain the fabric. The weight reduction process is as follows: The greige fabric is immersed in PET hydrolase buffer solution at a liquor ratio of 1:15 at 55℃ and pH=8.0 for 90 minutes, with a weight reduction rate of 22%. After weight reduction, the temperature is raised to 85℃ to inactivate the enzyme for 12 minutes, and then washed with water until neutral. The PET hydrolase is keratinase NS51111 with an enzyme activity of 1500U / g, and the dosage is 2.0% of the greige fabric mass. The napping process is as follows: Carbon fiber napping rollers are used with a napping roller speed of 1350r / min and a machine speed of 20m / min. S2.1 Preparation of unsaturated functional monomers: A. 1-Bromoperfluorooctane, 3-(2-chloroethyl)-5,5-dimethylhydantoin, and potassium carbonate were added to N,N-dimethylformamide. The mixture was heated to 60°C under a nitrogen atmosphere and stirred for 16 h. After the reaction was completed, the mixture was cooled to room temperature, water was added and stirred to precipitate a solid. The solid was filtered, washed with deionized water and anhydrous ethanol, and dried under vacuum at 60°C to obtain the hydantoin bromide. The molar ratio of 1-bromoperfluorooctane, 3-(2-chloroethyl)-5,5-dimethylhydantoin, and potassium carbonate was 1:1.0:1.0; the ratio of 1-bromoperfluorooctane to N,N-dimethylformamide was 10 g / 80 mL. B. Take 10 parts of the hydantoin bromide obtained in the previous step and 6 parts of dimethylaminoethyl methacrylate, add them to anhydrous ethanol, add 0.1 wt% p-hydroxyanisole and 0.05 eq potassium iodide, heat to 70℃, stir and reflux for 24 h; remove ethanol by vacuum distillation to obtain fluorinated quaternary ammonium salt; the ratio of hydantoin bromide to anhydrous ethanol is 10 g / 100 mL; C. Mix 10 parts of fluorinated quaternary ammonium salt and dichloromethane, add 1.5 parts of tert-butyl hypochlorite at 0℃, and add the mixture over 15 min. Then stir and react for 90 min. After the reaction is complete, wash with water, dry the organic phase, wash with anhydrous diethyl ether, and dry under vacuum at 45℃ to obtain the unsaturated functional monomer. The ratio of fluorinated quaternary ammonium salt to dichloromethane is 10 g / 100 mL. S2.2 Preparation of silica sol: Mix 5 parts tetrabutyl orthosilicate and 49 parts anhydrous ethanol, adjust the pH to 5 with 0.1M acetic acid, stir for 3 hours, and then let stand for 24 hours; add 5 parts tetrabutyl orthosilicate, 21 parts anhydrous ethanol, and 6 parts dimethyloctadecyl[3-(trimethoxymethylsilyl)propyl]ammonium chloride, stir for 2 hours; adjust the pH to 4, and continue stirring for 20 minutes to obtain silica sol; S2.3 Antibacterial and anti-fouling finish: 60 parts of octadecyl acrylate, 15 parts of unsaturated functional monomers, 3 parts of divinylbenzene, 10 parts of butyl acrylate, 5 parts of methyl methacrylate, 3 parts of emulsifier, and 100 parts of deionized water were mixed and emulsified at 10,000 rpm for 30 min. 5 parts of silica sol were added within 5 min, and emulsification continued for a total emulsification time of 45 min to obtain a pre-emulsion. The mixture was heated to 70℃, 0.2 parts of initiator were added, and the reaction was maintained at this temperature for 4 h. After cooling to room temperature, the pH was adjusted to 5, and water was added to obtain a finishing agent with a solid content of 10 wt%. The finishing process involves two dips and two nips, with the ratio of the greige fabric to the finishing liquid (solid-liquid ratio) being 1:8 (g / mL), and the immersion time being 30 seconds. The padding residue rate is 60%. After immersion and nipsing, the fabric is pre-dried and baked. The pre-drying temperature is 90℃ and the pre-drying time is 3 minutes. The baking temperature is 150℃ and the baking time is 3 minutes. The fabric is then dry-heat set at 180℃ for 60 seconds to obtain the final product.

[0031] Example 2: A method for preparing an antibacterial and stain-resistant fabric, comprising the following processes: S1 and S2 are the same as in Example 1; S2.1 Preparation of unsaturated functional monomers: A. 1-Bromoperfluorooctane, 3-(2-chloroethyl)-5,5-dimethylhydantoin, and potassium carbonate were added to N,N-dimethylformamide. The mixture was heated to 75°C under a nitrogen atmosphere and stirred for 13 h. After the reaction was completed, the mixture was cooled to room temperature, water was added and stirred to precipitate a solid. The solid was filtered, washed with deionized water and anhydrous ethanol, and dried under vacuum at 60°C to obtain the hydantoin bromide. The molar ratio of 1-bromoperfluorooctane, 3-(2-chloroethyl)-5,5-dimethylhydantoin, and potassium carbonate was 1:1.05:1.1; the ratio of 1-bromoperfluorooctane to N,N-dimethylformamide was 10 g / 60 mL. B. Take 10 parts of the hydantoin bromide obtained in the previous step and 9 parts of dimethylaminoethyl methacrylate, add them to anhydrous ethanol, add 0.3 wt% p-hydroxyanisole and 0.08 eq potassium iodide, heat to 75℃, stir and reflux for 20 h; remove ethanol by vacuum distillation to obtain a fluorinated quaternary ammonium salt; the ratio of hydantoin bromide to anhydrous ethanol is 10 g / 80 mL; C. Mix 10 parts of fluorinated quaternary ammonium salt and dichloromethane, add 1.8 parts of tert-butyl hypochlorite at 10℃, and add the mixture over 20 min. Then stir the mixture to react for 75 min. After the reaction is complete, wash with water, dry the organic phase, wash with anhydrous diethyl ether, and dry under vacuum at 45℃ to obtain the unsaturated functional monomer. The ratio of fluorinated quaternary ammonium salt to dichloromethane is 10 g / 75 mL. S2.2 Preparation of silica sol: 4.7 parts of tetrabutyl orthosilicate and 61 parts of anhydrous ethanol were mixed, and the pH was adjusted to 5.5 with 0.1M acetic acid. The mixture was stirred for 4 hours and then allowed to stand for 24 hours. 3.9 parts of tetrabutyl orthosilicate, 23 parts of anhydrous ethanol, and 8 parts of dimethyloctadecyl[3-(trimethoxymethylsilyl)propyl]ammonium chloride were added and stirred for 3 hours. The pH was adjusted to 3.5 and the mixture was stirred for another 30 minutes to obtain silica sol. S2.3 Antibacterial and anti-fouling finish: 50 parts of octadecyl acrylate, 22 parts of unsaturated functional monomers, 5 parts of divinylbenzene, 15 parts of butyl acrylate, 8 parts of methyl methacrylate, 5 parts of emulsifier, and 200 parts of deionized water were mixed and emulsified at 12,000 rpm for 25 minutes. 8 parts of silica sol were added over 8 minutes, and emulsification continued for a total emulsification time of 45 minutes to obtain a pre-emulsion. The mixture was heated to 75°C, 0.5 parts of initiator were added, and the reaction was maintained at this temperature for 5 hours. After cooling to room temperature, the pH was adjusted to 5.5 to obtain a finishing agent with a solid content of 10 wt%. The finishing process involves two dips and two nips, with the ratio of the greige fabric to the finishing solution (solid-liquid ratio) being 1:10 (g / mL), and the immersion time being 65s. The padding residue rate is 70%. After immersion and nipping, the fabric is pre-dried and baked. The pre-drying temperature is 100℃ and the pre-drying time is 2min. The baking temperature is 160℃ and the baking time is 2min. The fabric is then dry-heat set at 190℃ for 45s to obtain the final product.

[0032] Example 3: A method for preparing an antibacterial and stain-resistant fabric, comprising the following processes: S1 and S2 are the same as in Example 1; S2.1 Preparation of unsaturated functional monomers: A. 1-Bromoperfluorooctane, 3-(2-chloroethyl)-5,5-dimethylhydantoin, and potassium carbonate were added to N,N-dimethylformamide. The mixture was heated to 90°C under a nitrogen atmosphere and stirred for 10 h. After the reaction was completed, the mixture was cooled to room temperature, water was added and stirred to precipitate a solid. The solid was filtered, washed with deionized water and anhydrous ethanol, and dried under vacuum at 60°C to obtain the hydantoin bromide. The molar ratio of 1-bromoperfluorooctane, 3-(2-chloroethyl)-5,5-dimethylhydantoin, and potassium carbonate was 1:1.1:1.0; the ratio of 1-bromoperfluorooctane to N,N-dimethylformamide was 10 g / 40 mL. B. Take 10 parts of the hydantoin bromide obtained in the previous step and 12 parts of dimethylaminoethyl methacrylate, add them to anhydrous ethanol, add 0.5 wt% p-hydroxyanisole and 0.1 eq potassium iodide, heat to 80℃, stir and reflux for 16 h; remove ethanol by vacuum distillation to obtain a fluorinated quaternary ammonium salt; the ratio of hydantoin bromide to anhydrous ethanol is 10 g / 60 mL; C. Mix 10 parts of fluorinated quaternary ammonium salt and dichloromethane, add 2.0 parts of tert-butyl hypochlorite at 0℃, and add the mixture over 30 min. Then stir and react for 90 min. After the reaction is complete, wash with water, dry the organic phase, wash with anhydrous diethyl ether, and dry under vacuum at 45℃ to obtain the unsaturated functional monomer. The ratio of fluorinated quaternary ammonium salt to dichloromethane is 10 g / 100 mL. S2.2 Preparation of silica sol: 4.3 parts of tetrabutyl orthosilicate and 75 parts of anhydrous ethanol were mixed, and the pH was adjusted to 6 using 0.1M acetic acid. The mixture was stirred for 5 hours and then allowed to stand for 24 hours. 2.9 parts of tetrabutyl orthosilicate, 25 parts of anhydrous ethanol, and 10 parts of dimethyloctadecyl[3-(trimethoxymethylsilyl)propyl]ammonium chloride were added and stirred for 4 hours. The pH was adjusted to 4 and stirring was continued for 40 minutes to obtain silica sol. S2.3 Antibacterial and anti-fouling finish: 40 parts of octadecyl acrylate, 30 parts of unsaturated functional monomers, 8 parts of divinylbenzene, 20 parts of butyl acrylate, 10 parts of methyl methacrylate, 8 parts of emulsifier, and 300 parts of deionized water were mixed and emulsified at 15,000 rpm for 30 min. 10 parts of silica sol were added within 10 min, and emulsification continued for a total emulsification time of 60 min to obtain a pre-emulsion. The mixture was heated to 80℃, 0.8 parts of initiator were added, and the reaction was maintained at this temperature for 6 h. After cooling to room temperature, the pH was adjusted to 6 to obtain a finishing agent with a solid content of 10 wt%. The finishing process involves two dips and two nips, with the ratio of the greige fabric to the finishing solution (solid-liquid ratio) being 1:15 (g / mL), and the immersion time being 90s. The padding residue rate is 80%. After padding, the fabric is pre-dried and baked. The pre-drying temperature is 110℃ and the pre-drying time is 1min. The baking temperature is 170℃ and the baking time is 1min. The fabric is then dry-heat set at 200℃ for 30s to obtain the final product.

[0033] Comparative Example 1: A method for preparing an antibacterial and stain-resistant fabric, comprising the following processes: S2 post-processing: The obtained greige fabric is sequentially subjected to napping, dyeing, antibacterial and anti-fouling finishing, and setting to obtain the fabric; the other processes of S1 and S2 are the same as in Example 1 to obtain the fabric.

[0034] Comparative Example 2: A method for preparing an antibacterial and stain-resistant fabric, comprising the following processes: S2 post-processing: The obtained greige fabric is successively subjected to napping, dyeing, antibacterial and stain-resistant finishing, and setting to obtain the finished fabric; S2.2 Preparation of silica sol: 7.2 parts of tetrabutyl orthosilicate and 100 parts of anhydrous ethanol were mixed, the pH was adjusted to 5 using 0.1M acetic acid, stirred for 3 hours, and then allowed to stand for aging for 24 hours to obtain silica sol; The other processes in S1 and S2 are the same as in Example 1, resulting in the fabric.

[0035] Comparative Example 3: A method for preparing an antibacterial and stain-resistant fabric, comprising the following processes: S2 post-processing: The obtained greige fabric is successively subjected to napping, dyeing, antibacterial and stain-resistant finishing, and setting to obtain the finished fabric; S2.1 Preparation of unsaturated functional monomers: Take 4.5 parts of 3-(2-chloroethyl)-5,5-dimethylhydantoin and 6 parts of dimethylaminoethyl methacrylate, add them to anhydrous ethanol, add 0.1 wt% p-hydroxyanisole and 0.05 eq potassium iodide, heat to 70℃, stir and reflux for 24 h; remove ethanol by vacuum distillation to obtain fluorinated quaternary ammonium salt; the ratio of 3-(2-chloroethyl)-5,5-dimethylhydantoin to anhydrous ethanol is 10 g / 100 mL; Seven parts of fluorinated quaternary ammonium salt and dichloromethane were mixed, and 1.5 parts of tert-butyl hypochlorite were added at 0°C over 15 minutes. The mixture was then stirred and reacted for 90 minutes. After the reaction was completed, the mixture was washed with water, the organic phase was dried, washed with anhydrous diethyl ether, and dried under vacuum at 45°C to obtain the unsaturated functional monomer. The ratio of fluorinated quaternary ammonium salt to dichloromethane was 10 g / 100 mL. S2.2 Preparation of silica sol: 7.2 parts of tetrabutyl orthosilicate and 100 parts of anhydrous ethanol were mixed, the pH was adjusted to 5 using 0.1M acetic acid, stirred for 3 hours, and then allowed to stand for aging for 24 hours to obtain silica sol; The other processes in S1 and S2 are the same as in Example 1, resulting in the fabric.

[0036] Comparative Example 4: A method for preparing an antibacterial and stain-resistant fabric, comprising the following processes: S2 post-processing: The obtained greige fabric is successively subjected to napping, dyeing, antibacterial and stain-resistant finishing, and setting to obtain the finished fabric; S2.1 Preparation of unsaturated functional monomers: Take 4.5 parts of 3-(2-chloroethyl)-5,5-dimethylhydantoin and 6 parts of dimethylaminoethyl methacrylate, add them to anhydrous ethanol, add 0.1 wt% p-hydroxyanisole and 0.05 eq potassium iodide, heat to 70℃, stir and reflux for 24 h; remove ethanol by vacuum distillation to obtain unsaturated functional monomer; the ratio of 3-(2-chloroethyl)-5,5-dimethylhydantoin to anhydrous ethanol is 10 g / 100 mL; S2.2 Preparation of silica sol: 7.2 parts of tetrabutyl orthosilicate and 100 parts of anhydrous ethanol were mixed, the pH was adjusted to 5 using 0.1M acetic acid, stirred for 3 hours, and then allowed to stand for aging for 24 hours to obtain silica sol; The other processes in S1 and S2 are the same as in Example 1, resulting in the fabric.

[0037] Comparative Example 5: A method for preparing an antibacterial and stain-resistant fabric, comprising the following processes: S2 post-processing: The obtained greige fabric is successively subjected to napping, dyeing, antibacterial and stain-resistant finishing, and setting to obtain the finished fabric; S2.1 Preparation of silica sol: 7.2 parts of tetrabutyl orthosilicate and 100 parts of anhydrous ethanol were mixed, the pH was adjusted to 5 using 0.1M acetic acid, stirred for 3 hours, and then allowed to stand for aging for 24 hours to obtain silica sol; S2.2 Antibacterial and anti-fouling finishing: 60 parts of octadecyl acrylate, 15 parts of trifluoroethyl methacrylate, 3 parts of divinylbenzene, 10 parts of butyl acrylate, 5 parts of methyl methacrylate, 3 parts of emulsifier, and 100 parts of deionized water were mixed and emulsified at 10,000 rpm for 30 min. 5 parts of silica sol were added within 5 min, and emulsification continued for a total emulsification time of 45 min to obtain a pre-emulsion. The mixture was heated to 70℃, 0.2 parts of initiator were added, and the reaction was maintained at this temperature for 4 h. After cooling to room temperature, the pH was adjusted to 5, and water was added to obtain a finishing agent with a solid content of 10 wt%. The other processes in S1 and S2 are the same as in Example 1, resulting in the fabric.

[0038] Experiment: Fabrics obtained in Examples 1-3 and Comparative Examples 1-5 were used to prepare samples. Their properties were tested and the results were recorded. Antifouling performance test: Refer to GB / T 30447-2013, test the water contact angle and oil contact angle of the sample. The water droplet is 2μL and the oil droplet is 2μL of n-hexadecane. The test environment is room temperature. The average value is taken at 5 test points. Antibacterial performance test: Referring to GB / T 20944.3-2008, the shaking method was used to test the antibacterial rate of the sample against Staphylococcus aureus (ATCC 6538) and Escherichia coli (ATCC 25922); Wash resistance test: Refer to AATCC 61-2013, wash with water 20 times, and test the water contact angle and antibacterial properties (Staphylococcus aureus) of the sample again, and calculate the antibacterial retention rate.

[0039] Based on the data in the table above, the following conclusions can be clearly drawn: The fabrics obtained in Examples 1-3 are compared with those obtained in Comparative Examples 1-5. The test results show that: Compared with the comparative examples, the fabrics obtained in Examples 1-3 have superior water contact angle, oil contact angle, and antibacterial rate data, and the water contact angle and antibacterial retention rate data are even better after washing. This fully demonstrates that the present invention has achieved an improvement in the antibacterial, stain-resistant, and durable properties of the fabric.

[0040] Compared to Example 1, the fabric in Comparative Example 1 was not subjected to weight reduction treatment, resulting in a lower amount of finishing agent adhesion and reduced performance data. The fabric in Comparative Example 2 was not subjected to weight reduction treatment, and the silica sol was not modified with quaternary ammonium salt, leading to reduced wash resistance and durability.

[0041] Compared to Comparative Example 2, the unsaturated functional monomers in the finishing agent component of Comparative Example 3 do not contain fluorine; the unsaturated functional monomers in the finishing agent component of Comparative Example 4 do not contain fluorine and have not undergone chlorination; and in Comparative Example 5, the unsaturated functional monomers in the finishing agent component are replaced with an equal mass of trifluoroethyl methacrylate. Compared to Example 1, the fabrics prepared in Comparative Examples 3-5 do not simultaneously possess the water and oil repellency and antibacterial durability. It is evident that the fabric preparation process and the composition of the components used in this invention can promote a comprehensive improvement in its stain resistance, antibacterial properties, and durability.

[0042] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

Claims

1. A method for preparing an antibacterial and stain-resistant fabric, characterized in that: Including the following processes: S1 weaving: The face yarn, middle yarn and back yarn are woven together by a warp knitting machine to obtain the greige fabric; S2 post-treatment: The obtained greige fabric is subjected to enzyme reduction, napping, dyeing, antibacterial and stain-resistant finishing in finishing solution, and setting in sequence to obtain the fabric. The finishing agent comprises the following components: octadecyl acrylate, unsaturated functional monomers, divinylbenzene, butyl acrylate, methyl methacrylate, and silica sol; the unsaturated functional monomers contain quaternary ammonium salts and fluorinated segments.

2. The method for preparing an antibacterial and stain-resistant fabric according to claim 1, characterized in that: The unsaturated functional monomer is prepared by the following process: Step 1: Add 1-bromoperfluorooctane, 3-(2-chloroethyl)-5,5-dimethylhydantoin, and potassium carbonate to N,N-dimethylformamide, heat to 60-90°C under nitrogen atmosphere, and stir for 10-16 h to obtain hydantoin brominated product; Step 2: Add the hydantoin bromide and dimethylaminoethyl methacrylate obtained in the previous step to anhydrous ethanol, heat to 70-80°C, stir and reflux for 16-24 hours to obtain a fluorine-containing quaternary ammonium salt. Step 3: Mix the fluorinated quaternary ammonium salt and dichloromethane, add tert-butyl hypochlorite at 0-25°C, complete the addition within 15-30 minutes, and then stir the reaction for 60-90 minutes to obtain the unsaturated functional monomer.

3. The method for preparing an antibacterial and stain-resistant fabric according to claim 1, characterized in that: The silica sol is prepared by the following process: Mix 50-60% tetrabutyl orthosilicate and 70-75% anhydrous ethanol, adjust the pH to 5-6, stir for 3-5 hours, and let stand for 24 hours to age. Add the remaining tetrabutyl orthosilicate and anhydrous ethanol, then add dimethyloctadecyl[3-(trimethoxymethylsilyl)propyl]ammonium chloride, and stir for 2-4 hours; adjust the pH to 3-4, and continue stirring for 20-40 minutes to obtain silica sol.

4. The method for preparing an antibacterial and stain-resistant fabric according to claim 3, characterized in that: The finishing agent is prepared by the following process: Octadecyl acrylate, unsaturated functional monomer, divinylbenzene, butyl acrylate, methyl methacrylate, emulsifier and deionized water are mixed and emulsified at 10,000 to 15,000 rpm for 20 to 30 minutes; silica sol is added and added within 5 to 10 minutes, and emulsification continues for a total emulsification time of 30 to 60 minutes to obtain a pre-emulsion. Heat to 70-80℃, add initiator, maintain the temperature for 4-6 hours, cool to room temperature, and obtain finishing agent.

5. The method for preparing an antibacterial and stain-resistant fabric according to claim 4, characterized in that: The finishing agent comprises the following components by weight: 40-60 parts octadecyl acrylate, 15-30 parts unsaturated functional monomers, 3-8 parts divinylbenzene, 10-20 parts butyl acrylate, 5-10 parts methyl methacrylate, 3-8 parts emulsifier, 0.2-0.8 parts initiator, 5-10 parts silica sol, and 100-300 parts deionized water; pH is 5-6.

6. The method for preparing an antibacterial and stain-resistant fabric according to claim 1, characterized in that: The antibacterial and antifouling finishing process involves two dips and two nips, with a solid-liquid ratio of 1:(8-15) (g / mL) and a dip time of 30-90 seconds; the nips and nips residue is 60-80%. After impregnation and rolling, pre-dry and bake; pre-drying temperature 90-110℃, pre-drying time 1-3min; baking temperature 150-170℃, baking time 1-3min.

7. The method for preparing an antibacterial and stain-resistant fabric according to claim 3, characterized in that: The silica sol comprises the following components by mass: 7.2 to 10 parts tetrabutyl orthosilicate, 6 to 10 parts dimethyl octadecyl [3-(trimethoxymethylsilyl)propyl]ammonium chloride, and 70 to 100 parts anhydrous ethanol.

8. The method for preparing an antibacterial and stain-resistant fabric according to claim 2, characterized in that: In step 1, the molar ratio of 1-bromoperfluorooctane, 3-(2-chloroethyl)-5,5-dimethylhydantoin, and potassium carbonate is 1:(1.0-1.1):(1.0-1.2). In step 2, the mass ratio of hydantoin bromide to dimethylaminoethyl methacrylate is 10:(6-12). In step 3, the mass ratio of fluorinated quaternary ammonium salt to tert-butyl hypochlorite is 10: (1.5-2.0).

9. The method for preparing an antibacterial and stain-resistant fabric according to claim 1, characterized in that: The face yarn is 95D / 36F polyester-nylon island yarn, accounting for 66-70% of the total fabric weight; The medium yarn is a 45D / 24F semi-dull filament, accounting for 23-27% of the total fabric weight; The base yarn is 40D / 3F spandex yarn, accounting for 5-9% of the total weight of the fabric.

10. An antibacterial and stain-resistant fabric prepared by the preparation method according to any one of claims 1-9.

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