Air-permeable antibacterial fabric and preparation process thereof

Abstract

The application discloses a kind of breathable antibacterial fabric and its preparation process, S1, nylon is used as warp and tension is maintained;S2, spandex is used as weft, and weft and warp are interwoven into grey cloth;S3, the grey cloth is finished by finishing agent, the burr is cut, and the wrinkle is smoothed, to obtain fabric, using hexamethylene diisocyanate, 3-hydroxypropionic acid is reacted to obtain hexamethylene di (carbamate propionic acid), after acyl chloride, and with N-methyl-2,2-diamino diethylamine, benzyl bromide is reacted, to obtain antibacterial finishing agent.It contains a large number of quaternary ammonium salt antibacterial groups, and has inhibitory and killing effect on bacteria such as escherichia coli, and at the same time contains polyamide and urethane structure, and has high affinity and interfacial force between the polyamide molecular chain in the blended fabric and the urethane structure of spandex polyurethane, to improve the firmness of antibacterial finishing agent attached to the surface of fabric and antibacterial time effect.

Description

Technical Field

[0001] The present invention relates to the field of fiber technology, in particular to a breathable antibacterial fabric and a preparation process thereof. Background Art

[0002] Nylon fabric is a common synthetic fiber fabric with good abrasion resistance, heat resistance and warmth retention properties, and is widely used in textiles such as clothing, curtains and home textiles. Spandex fiber has high resilience and hygroscopicity, and is often blended with nylon fiber, cotton fiber, etc. to obtain blended fabrics with excellent performance. Chinese patent CN116479570B discloses a preparation method of a nylon-spandex composite cooling fabric, the fabric and its application in underwear. The nylon-spandex composite cooling fabric prepared using spandex fiber, modified cotton fiber, nylon fiber and mint fiber as raw materials has good biocompatibility, hygroscopicity and other properties. However, the nylon-spandex composite cooling fabric does not have good antibacterial properties. This is not conducive to the practical application of the fabric in the fields of antibacterial clothing, medical textiles, etc.

[0003] Currently, finishing agents are used to treat nylon and spandex fabrics, effectively improving their moisture permeability, breathability, softness, and antibacterial properties. Polyamide finishing agents, in particular, are widely used due to their excellent hydrophilicity and affinity with nylon and other fabrics, resulting in excellent water resistance. However, current polyamide finishing agents lack antibacterial properties and are unable to improve the antibacterial properties of blended fabrics such as nylon. Summary of the Invention

[0004] The invention solves the following technical problems: solves the problem that the blended fabric of nylon and spandex has poor moisture permeability and antibacterial performance.

[0005] The present invention provides the following technical solution: A preparation process of an antibacterial finishing agent is as follows:

[0006] (1) Add solvent, hexamethylene diisocyanate, and 3-hydroxypropionic acid into a flask, stir to react, remove the solvent by rotary evaporation, wash with petroleum ether, and dry to obtain hexamethylene diisocyanate propionic acid.

[0007] (2) Add thionyl chloride and hexamethylenebis(carbamate propionic acid) into a flask and heat to reflux. After the reaction, remove the thionyl chloride by rotary evaporation. Add the product to dimethyl sulfoxide, and then add N-methyl-2,2-diaminodiethylamine and triethylamine to carry out polymerization reaction. The precipitate is filtered, washed with ethanol, and dried to obtain carbamate polyamide.

[0008] (3) Add N,N-dimethylformamide and polyamide carbamate into a flask, mix well and add benzyl bromide. After the reaction, remove the solvent by rotary evaporation, wash with ethanol, and dry to obtain an antibacterial finishing agent.

[0009] Furthermore, the solvent in (1) is any one of tetrahydrofuran, toluene, and 1,4-dioxane.

[0010] Furthermore, the ratio of hexamethylene diisocyanate to 3-hydroxypropionic acid in (1) is 1 mol:(1.9-2.2) mol.

[0011] Furthermore, the reaction temperature in (1) is 60-75°C and the reaction time is 3-6 hours.

[0012] Furthermore, the ratio of thionyl chloride, hexamethylenebis(carbamate propionic acid), N-methyl-2,2-diaminodiethylamine, and triethylamine in (2) is (7-10) mol:1 mol:(1-1.1):(2-2.2) mol.

[0013] Furthermore, the polymerization reaction temperature in (2) is 20-40°C and the time is 24-36 hours.

[0014] Furthermore, the ratio of urethane polyamide to benzyl bromide in (3) is 1 g:(0.66-0.75) g.

[0015] Furthermore, the reaction temperature in (3) is 80-120°C and the reaction time is 24-48 hours.

[0016] Furthermore, the preparation process of the breathable antibacterial fabric is as follows: add the antibacterial finishing agent to distilled water, heat it to 80-95°C, stir it for 20-40 minutes, prepare a finishing liquid with a mass fraction of 35-70g / L, then add the blended fabric of nylon and spandex, perform two dipping and two rolling, and then dry it at 90-100°C for 4-6 minutes; bake it at 165-180°C for 20-60 seconds to obtain the breathable antibacterial fabric.

[0017] Furthermore, the blended fabric of nylon and spandex can be prepared by the following method:

[0018] S1. Use nylon as the warp yarn, pass the warp yarn through the warp stop piece, the heddle eye, the warp guide rod, and then into the mandrel hole of the main warp beam, and fix it on the main warp beam to keep a certain tension on the warp yarn;

[0019] S2, using spandex as weft yarn, interweaving the weft yarn and the warp yarn into a grey cloth;

[0020] S3, finishing the grey cloth with a finishing agent, cutting off the rough edges, and smoothing out the wrinkles to obtain the fabric.

[0021] The present invention has the following technical effects:

[0022] The present invention utilizes hexamethylene diisocyanate and 3-hydroxypropionic acid to produce hexamethylene bis(carbamate propionic acid). This is then chlorinated and polymerized with N-methyl-2,2-diaminodiethylamine to produce carbamate polyamide. Finally, the polyamide is quaternized with benzyl bromide to produce a novel antibacterial finishing agent.

[0023] The antibacterial finishing agent prepared by the present invention contains hydrophilic groups such as polyamide, carbamate, quaternary ammonium salt, etc. After finishing, a hydrophilic layer is formed on the surface of the blended fabric of nylon and spandex, which significantly improves the surface hydrophilicity of the blended fabric, is beneficial to increasing the water vapor permeability of the fabric, and improves the moisture permeability and air permeability.

[0024] The antimicrobial finishing agent of the present invention contains a large number of quaternary ammonium salt antimicrobial groups in its backbone, demonstrating a strong inhibitory and killing effect on bacteria such as Escherichia coli. Furthermore, the antimicrobial finishing agent, which contains polyamide and urethane structures, exhibits high affinity and interfacial forces with the nylon polyamide molecular chains and the urethane structures of spandex polyurethane in blended fabrics. This allows the antimicrobial finishing agent to firmly adhere to the surface of the blended fabric and resist removal even after repeated washings, resulting in long-lasting antimicrobial activity. DETAILED DESCRIPTION

[0025] To make the objectives, technical solutions, and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts shall fall within the scope of protection of the present invention.

[0026] Example 1

[0027] (1) Add toluene solvent, 10 mmol hexamethylene diisocyanate, and 19 mmol 3-hydroxypropionic acid to a flask, heat to 75°C, stir and react for 3 hours, remove the solvent by rotary evaporation, wash with petroleum ether, and dry to obtain hexamethylene diisocyanate. The reaction formula is as follows:

[0028]

[0029] (2) Add 140 mmol of thionyl chloride and 20 mmol of hexamethylenebis(carbamate propionic acid) to a flask, heat to 78°C and reflux for 3 hours. After the reaction, remove the thionyl chloride by rotary evaporation. Add the product to 100 mL of dimethyl sulfoxide, then add 20 mmol of N-methyl-2,2-diaminodiethylamine and 44 mmol of triethylamine. Polymerize at 30°C for 24 hours. Filter the precipitate, wash with ethanol, and dry to obtain carbamate polyamide. The reaction route is as follows:

[0030]

[0031] (3) Add 800 mL of N,N-dimethylformamide and 50 g of polyurethane polyamide to the flask, mix well, add 33 g of benzyl bromide, heat to 80 ° C, react for 48 hours, and then remove the solvent by rotary evaporation. Wash with ethanol and dry to obtain an antibacterial finishing agent. The reaction route is as follows:

[0032]

[0033] (4) The antibacterial finishing agent was added to distilled water, heated to 80 °C, stirred for 40 min, and prepared into a finishing solution with a mass fraction of 35 g / L. Then, the blended fabric of nylon and spandex was added, and two dipping and two rolling were performed. Then, the mixture was dried at 90 °C for 6 min and baked at 170 °C for 40 s to obtain a breathable antibacterial fabric.

[0034] Example 2

[0035] (1) Add tetrahydrofuran solvent, 10 mmol hexamethylene diisocyanate, and 22 mmol 3-hydroxypropionic acid into a flask, heat to 60°C, stir and react for 6 hours, remove the solvent by rotary evaporation, wash with petroleum ether, and dry to obtain hexamethylene di(carbamate propionic acid).

[0036] (2) Add 200 mmol of thionyl chloride and 20 mmol of hexamethylenebis(carbamate propionic acid) into a flask, heat to 78°C and reflux for 3 h. After the reaction, remove the thionyl chloride by rotary evaporation. Add the product into 100 mL of dimethyl sulfoxide, and then add 22 mmol of N-methyl-2,2-diaminodiethylamine and 42 mmol of triethylamine. Carry out polymerization at 20°C for 36 h. The precipitate is filtered, washed with ethanol, and dried to obtain carbamate polyamide.

[0037] (3) Add 800 mL of N,N-dimethylformamide and 50 g of polyurethane polyamide into a flask, mix well, add 37.5 g of benzyl bromide, heat to 120 °C, react for 24 h, and remove the solvent by rotary evaporation after the reaction. Wash with ethanol and dry to obtain an antibacterial finishing agent.

[0038] (4) The antibacterial finishing agent was added to distilled water, heated to 95 °C, stirred for 20 min, and prepared into a finishing solution with a mass fraction of 40 g / L. Then, the blended fabric of nylon and spandex was added, and two immersion and two rolling were performed. Then, the mixture was dried at 90 °C for 6 min and baked at 165 °C for 60 s to obtain a breathable antibacterial fabric.

[0039] Example 3

[0040] (1) Add 1,4-dioxane solvent, 10 mmol hexamethylene diisocyanate, 20 mmol 3-hydroxypropionic acid to a flask, heat to 75°C, stir for 4h, rotary evaporation to remove the solvent, petroleum ether washing, drying, to obtain hexamethylene diurethane propionic acid.

[0041] (2) Add 150 mmol of sulfurous acid chloride, 20 mmol of hexamethylene diurethane propionic acid to a flask, heat to 78°C and reflux for 3h, after reaction, rotary evaporation to remove sulfurous acid chloride, the product is added to 100 mL of dimethyl sulfoxide, then 22 mmol of N-methyl-2,2-diamino diethylamine, 40 mmol of triethylamine are added, and the polymerization reaction is carried out at 30°C for 24h, the precipitate is separated, filtered, washed with ethanol, and dried to obtain a urethane polyamide.

[0042] (3) Add 800 mL of N,N-dimethylformamide, 50 g of urethane polyamide to a flask, mix well, then add 37.5 g of benzyl bromide, heat to 110°C, react for 36h, after reaction, rotary evaporation to remove the solvent, ethanol washing, drying, to obtain an antibacterial finishing agent.

[0043] (4) Add the antibacterial finishing agent to distilled water, heat to 95°C, stir for 30 min, configure a finishing liquid with a mass fraction of 55 g / L, then add a blended fabric of nylon and spandex, carry out two-dip-two-pad, then dry at 100°C for 4 min; 180°C baking for 30s, to obtain a breathable antibacterial fabric.

[0044] Example 4

[0045] (1) Add 1,4-dioxane solvent, 10 mmol hexamethylene diisocyanate, 20 mmol 3-hydroxypropionic acid to a flask, heat to 75°C, stir for 4h, rotary evaporation to remove the solvent, petroleum ether washing, drying, to obtain hexamethylene diurethane propionic acid.

[0046] (2) Add 140 mmol of sulfurous acid chloride, 20 mmol of hexamethylene diurethane propionic acid to a flask, heat to 78°C and reflux for 3h, after reaction, rotary evaporation to remove sulfurous acid chloride, the product is added to 100 mL of dimethyl sulfoxide, then 22 mmol of N-methyl-2,2-diamino diethylamine, 40 mmol of triethylamine are added, and the polymerization reaction is carried out at 40°C for 24h, the precipitate is separated, filtered, washed with ethanol, and dried to obtain a urethane polyamide.

[0047] (3) Add 800 mL of N,N-dimethylformamide and 50 g of polyurethane polyamide into a flask, mix well, add 37.5 g of benzyl bromide, heat to 120 °C, react for 36 h, and remove the solvent by rotary evaporation after the reaction. Wash with ethanol and dry to obtain an antibacterial finishing agent.

[0048] (4) The antibacterial finishing agent was added to distilled water, heated to 95 °C, stirred for 30 min, and prepared into a finishing solution with a mass fraction of 70 g / L. Then, the blended fabric of nylon and spandex was added, and two dipping and two rolling were performed. Then, the mixture was dried at 100 °C for 4 min and baked at 180 °C for 20 s to obtain a breathable antibacterial fabric.

[0049] The difference between Comparative Example 1 and Example 1 is that urethane polyamide is used as the finishing agent.

[0050] Urethane polyamide was added to distilled water, heated to 80°C, stirred for 40 minutes, and prepared into a finishing liquid with a mass fraction of 35 g / L. Then, a blended fabric of nylon and spandex was added, and two dipping and two padding were performed. Then, it was dried at 90°C for 6 minutes and baked at 170°C for 40 seconds to obtain a breathable and antibacterial fabric containing a finishing agent.

[0051] The difference between Comparative Example 2 and Example 1 is that common succinyl chloride is used instead of hexamethylene bis(carbamate propionic acid) when preparing polyamide.

[0052] (1) Add 100 mL of dimethyl sulfoxide, 20 mmol of succinyl chloride, 20 mmol of N-methyl-2,2-diaminodiethylamine, and 44 mmol of triethylamine to a flask and carry out polymerization reaction at 30°C for 24 hours. The precipitate is filtered, washed with ethanol, and dried to obtain polyamide. The reaction route is as follows:

[0053]

[0054] (2) Add 800 mL of N,N-dimethylformamide and 50 g of polyamide to a flask, mix well, add 33 g of benzyl bromide, heat to 80°C, react for 48 hours, remove the solvent by rotary evaporation, wash with ethanol, and dry to obtain an antibacterial finishing agent. The reaction route is as follows:

[0055]

[0056] (3) The antibacterial finishing agent was added to distilled water, heated to 80 °C, stirred for 40 min, and prepared into a finishing solution with a mass fraction of 35 g / L. Then, the blended fabric of nylon and spandex was added, and two dipping and two rolling were performed. Then, the mixture was dried at 90 °C for 6 min and baked at 170 °C for 40 s to obtain a breathable antibacterial fabric.

[0057] Comparative Example 3 is a blended fabric of ordinary nylon and spandex, which is not finished with a finishing liquid.

[0058] The water vapor permeability of the fabric was tested according to the method of GB / T 12704.2-2009, and the test stability was 38℃ and the relative humidity was 50%. Each fabric sample was tested 5 times, and the average value was taken.

[0059] Table 1 Water vapor permeability of the fabric

[0060]

[0061] The water vapor permeability of Examples 1-4 reached 24.23-25.74 g·h -1 ·m -2 This is because the antibacterial finishing agent prepared by the present application contains polyamide, urethane, etc., quaternary ammonium salt, etc. hydrophilic groups, and after finishing, a hydrophilic layer is formed on the surface of the blended fabric of nylon and spandex, significantly improving the surface hydrophilicity of the blended fabric, which is beneficial to improve the moisture permeability and air permeability of the fabric.

[0062] Comparative Example 3 is a common blended fabric of nylon and spandex without finishing, and the water vapor permeability is the lowest, and the moisture permeability and air permeability are poor.

[0063] Comparative Example 1 uses urethane polyamide as a finishing agent, and does not contain quaternary ammonium salt hydrophilic groups. Comparative Example 2 uses common succinyl chloride instead of hexamethylene di(urethane propionic acid) when preparing polyamide. The obtained finishing agent does not contain hydrophilic urethane groups. The water vapor permeability of the blended fabric of the two is lower than that of each example, and the moisture permeability and air permeability are poor.

[0064] The antibacterial performance of the fabric was tested by flask shaking method. Escherichia coli bacterial suspension was added to sterile normal saline and diluted to 5×10 6 cfu / mL. And take 1 mL into the sterilized flask, then add 1 cm×1 cm fabric, 37℃ shaking for 24 h, take 0.2 mL of the shaken solution, dilute by 10 times and 100 times respectively, then take 0.1 mL into a sterile culture dish, add melted agar medium, mix well and cool to solidify. 37℃ constant temperature culture for 24 h, then bacterial counting, calculate the inhibition rate.

[0065] Q=(B-C) / B×100%. C is the average number of bacteria after shaking of the test sample. B is the average number of bacteria after shaking of the blank sample. The common blended fabric of nylon and spandex of Comparative Example 3 was used as the blank sample.

[0066] The fabric was washed 50 times according to the method of GB / T 8629-2001, and then the antibacterial performance test was carried out.

[0067] Table 2 Antibacterial performance test of the fabric

[0068]

[0069] The antibacterial rate of the fabric of Examples 1-4 against E. coli reached 99.81-99.99%. And the bacterial rate after washing also reached 99.24-99.99%. This is because the main chain of the antibacterial finishing agent contains a large number of quaternary ammonium salt antibacterial groups, which have a strong inhibitory and killing effect on bacteria such as E. coli. And the antibacterial finishing agent contains polyamide and urethane structure, which has high affinity and interfacial force with the polyamide molecular chain of the nylon in the blended fabric, and the urethane structure of the spandex polyurethane, so that the antibacterial finishing agent can be firmly attached to the surface of the blended fabric and will not fall off after multiple washes. It has long-term antibacterial ability.

[0070] Comparative Example 1 uses urethane polyamide as the finishing agent, which does not contain antibacterial groups, and the blended fabric does not exhibit antibacterial performance.

[0071] Comparative Example 2 uses common succinyl chloride instead of hexamethylene di(urethane propionic acid) when preparing polyamide and antibacterial finishing agent. The obtained antibacterial finishing agent only contains polyamide molecular chain and does not contain urethane structure. The antibacterial finishing agent has high affinity and interfacial force with the polyamide molecular chain of the nylon in the blended fabric, but has low affinity and interfacial force with the spandex polyurethane, resulting in lower adhesion performance of the antibacterial finishing agent on the surface of the blended fabric than the examples. After multiple washes, the antibacterial finishing agent falls off to a higher extent than the examples, resulting in lower antibacterial rate after washing than the examples.

[0072] The above examples are only used to illustrate the technical solutions of the present application, but not to limit it; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that they can still modify the technical solutions recorded in the foregoing examples, or make equivalent substitutions for part of the technical features; and these modifications or substitutions do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. A breathable antibacterial fabric, characterized in that: The breathable antibacterial fabric is composed of an antibacterial finishing agent, a blended fabric of nylon and spandex; The preparation process of the antibacterial finishing agent is: (1) Adding a solvent, hexamethylene diisocyanate, and 3-hydroxypropionic acid into a flask, stirring to react, rotary evaporation, washing, and drying to obtain hexamethylene bis(carbamate propionic acid); (2) Add thionyl chloride and hexamethylenebis(carbamate propionic acid) into a flask, heat to reflux, and after the reaction, rotary evaporate. Add the product to dimethyl sulfoxide, and then add N-methyl-2,2-diaminodiethylamine and triethylamine to carry out polymerization reaction. The precipitate is filtered, washed, and dried to obtain carbamate polyamide; (3) Add N,N-dimethylformamide and polyamide carbamate into a flask, mix well and then add benzyl bromide. After the reaction, perform rotary evaporation, wash and dry to obtain an antibacterial finishing agent.

2. The breathable antibacterial fabric according to claim 1, characterized in that: The solvent in (1) is any one of tetrahydrofuran, toluene, and 1,4-dioxane.

3. The breathable antibacterial fabric according to claim 1, characterized in that: The ratio of hexamethylene diisocyanate to 3-hydroxypropionic acid in (1) is 1 mol: (1.9-2.2) mol.

4. The breathable antibacterial fabric according to claim 1, characterized in that: The reaction temperature in (1) is 60-75°C and the reaction time is 3-6 hours.

5. The breathable antibacterial fabric according to claim 1, characterized in that: The ratio of thionyl chloride, hexamethylenebis(carbamate propionic acid), N-methyl-2,2-diaminodiethylamine and triethylamine in (2) is (7-10) mol: 1 mol: (1-1.1) mol: (2-2.2) mol.

6. The breathable antibacterial fabric according to claim 1, characterized in that: The polymerization reaction temperature in (2) is 20-40°C and the reaction time is 24-36 hours.

7. The breathable antibacterial fabric according to claim 1, characterized in that: The ratio of the carbamate polyamide to benzyl bromide in (3) is 1 g: (0.66-0.75) g.

8. The breathable antibacterial fabric according to claim 1, characterized in that: The reaction temperature in (3) is 80-120°C and the reaction time is 24-48 hours.

9. A process for preparing the breathable antibacterial fabric according to any one of claims 1 to 8, characterized in that: The preparation process comprises the following steps: adding an antibacterial finishing agent to distilled water, heating the mixture to 80-95°C, stirring the mixture for 20-40 minutes to prepare a finishing solution, then adding a blended fabric of nylon and spandex, performing two dipping and two padding, and then drying the mixture at 90-100°C for 4-6 minutes and baking the mixture at 165-180°C for 20-60 seconds to obtain a breathable antibacterial fabric.

10. The preparation process of the breathable antibacterial fabric according to claim 9, characterized in that: The mass fraction of the finishing liquid is 35-70 g / L.

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