Breathable antibacterial fabric and preparation process thereof

Abstract

The invention discloses a breathable antibacterial fabric and a preparation process thereof. The preparation process comprises the following steps: S1, taking chinlon as warp yarns and keeping tension; s2, spandex serves as weft yarn, and the weft yarn and the warp yarn are interwoven into gray cloth; s3, the gray cloth is finished through a finishing agent, burrs are cut off, wrinkles are smoothed, a fabric is obtained, hexamethylene di (carbamate propionic acid) is obtained through a reaction of hexamethylene diisocyanate and 3-hydracrylic acid, the hexamethylene di (carbamate propionic acid) is subjected to acylating chlorination and reacts with N-methyl-2, 2-diaminodiethylamine and benzyl bromide, and the antibacterial finishing agent is obtained. The antibacterial agent contains a large number of quaternary ammonium salt antibacterial groups, has inhibiting and killing effects on escherichia coli and other bacteria, contains polyamide and carbamate structures, and has very high affinity and interfacial force with chinlon polyamide molecular chains in the blended fabric and the carbamate structure of spandex polyurethane. The firmness and antibacterial aging of the antibacterial finishing agent attached to the surface of the fabric are improved.

Description

Technical Field

[0001] The invention relates to the technical field of fibers, 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, temperature 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 cool fabric, a fabric and its application in underwear. The nylon-spandex composite cool 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 cool fabric does not have good antibacterial properties. It is not conducive to the practical application of fabrics in the fields of antibacterial clothing, medical textiles, etc.

[0003] At present, finishing agents are used to finish nylon fabrics, spandex fabrics, etc., which can effectively improve the moisture permeability, breathability, softness and antibacterial properties of fabrics. Among them, polyamide finishing agents have good hydrophilicity and have a large affinity with nylon and other fabrics. The finished fabrics have excellent water resistance and are a widely used finishing agent. However, the current polyamide finishing does not have antibacterial properties and cannot improve the antibacterial properties of nylon and other blended fabrics. 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 air permeability and antibacterial performance.

[0005] The present invention provides the following technical solution: A preparation process of an antibacterial finishing agent is as follows: (1) Add a 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 di(carbamate propionic acid).

[0006] (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, then add N-methyl-2,2-diaminodiethylamine and triethylamine to carry out polymerization reaction. precipitate, filter, wash with ethanol, and dry to obtain carbamate polyamide.

[0007] (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.

[0008] Furthermore, the solvent in (1) is any one of tetrahydrofuran, toluene and 1,4-dioxane.

[0009] Furthermore, the ratio of hexamethylene diisocyanate to 3-hydroxypropionic acid in (1) is 1 mol:(1.9-2.2) mol.

[0010] Furthermore, the reaction temperature in (1) is 60-75°C and the reaction time is 3-6h.

[0011] Furthermore, in (2), the ratio of thionyl chloride, hexamethylenebis(carbamate propionic acid), N-methyl-2,2-diaminodiethylamine, and triethylamine is (7-10) mol:1 mol:(1-1.1):(2-2.2) mol.

[0012] Furthermore, the polymerization reaction temperature in (2) is 20-40°C and the time is 24-36h.

[0013] Furthermore, in (3), the ratio of urethane polyamide to benzyl bromide is 1 g:(0.66-0.75) g.

[0014] Furthermore, the reaction temperature in (3) is 80-120°C and the reaction time is 24-48h.

[0015] Furthermore, the preparation process of the breathable antibacterial fabric is as follows: add the antibacterial finishing agent to distilled water, heat to 80-95°C, stir for 20-40 minutes, prepare a finishing solution with a mass fraction of 35-70g / L, then add the blended fabric of nylon and spandex, perform double dipping and double rolling, and then dry at 90-100°C for 4-6 minutes; bake at 165-180°C for 20-60 seconds to obtain the breathable antibacterial fabric.

[0016] Furthermore, the blended fabric of nylon and spandex can be prepared by the following method: S1. Use nylon as the warp yarn, pass the warp yarn through the warp stop piece, the heddle eye, the warp guide rod, and the mandrel hole of the main warp beam, and fix it on the main warp beam to keep a certain tension of the warp yarn; S2, using spandex as weft yarn, interweaving the weft yarn and the warp yarn into a grey cloth; S3, finishing the grey cloth with a finishing agent, cutting off the rough edges, and smoothing out the wrinkles to obtain the fabric.

[0017] The present invention has the following technical effects: The present invention utilizes hexamethylene diisocyanate and 3-hydroxypropionic acid to react to obtain hexamethylene di(carbamate propionic acid), which is then chlorinated and polymerized with N-methyl-2,2-diaminodiethylamine to obtain carbamate polyamide, which is then quaternized with benzyl bromide to obtain a novel antibacterial finishing agent.

[0018] 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 improving the water vapor permeability of the fabric, and improves the moisture permeability and air permeability.

[0019] The main chain of the antibacterial finishing agent of the present invention contains a large number of quaternary ammonium salt antibacterial groups, which has a strong inhibitory and killing effect on bacteria such as Escherichia coli. In addition, the antibacterial finishing agent contains polyamide and urethane structures, and has high affinity and interfacial interaction with the nylon polyamide molecular chain in the blended fabric and the urethane structure of 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 washings. It has long-lasting antibacterial ability. DETAILED DESCRIPTION

[0020] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0021] Example 1 (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 di(carbamate propionic acid). The reaction formula is as follows: (2) Add 140mmol of thionyl chloride and 20mmol of hexamethylenebis(carbamate propionic acid) into a flask, heat to 78℃ and reflux for 3h, remove thionyl chloride by rotary evaporation after the reaction, add the product into 100mL of dimethyl sulfoxide, then add 20mmol of N-methyl-2,2-diaminodiethylamine and 44mmol of triethylamine, carry out polymerization reaction at 30℃ for 24h, precipitate, filter, wash with ethanol, and dry to obtain carbamate polyamide. The reaction route is as follows: (3) Add 800 mL of N,N-dimethylformamide and 50 g of carbamate 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: (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. The nylon and spandex blended fabric was then added, double-immersed and double-rolled, and then dried at 90°C for 6 min; and baked at 170°C for 40 s to obtain a breathable antibacterial fabric.

[0022] Example 2 (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).

[0023] (2) Add 200 mmol of thionyl chloride and 20 mmol of hexamethylenebis(carbamate propionic acid) into a flask, heat to 78°C for reflux reaction for 3 h, remove thionyl chloride by rotary evaporation after the reaction, add the product into 100 mL of dimethyl sulfoxide, then add 22 mmol of N-methyl-2,2-diaminodiethylamine and 42 mmol of triethylamine, carry out polymerization reaction at 20°C for 36 h, collect the precipitate, filter it, wash it with ethanol, and dry it to obtain carbamate polyamide.

[0024] (3) Add 800 mL of N,N-dimethylformamide and 50 g of polyamide carbamate into a flask, mix well, add 37.5 g of benzyl bromide, heat to 120 °C, react for 24 h, remove the solvent by rotary evaporation after the reaction, wash with ethanol, and dry to obtain an antibacterial finishing agent.

[0025] (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. The nylon and spandex blended fabric was then added and double-impregnated and double-rolled. The mixture was then dried at 90°C for 6 min and baked at 165°C for 60 s to obtain a breathable antibacterial fabric.

[0026] Example 3 (1) Add 1,4-dioxane solvent, 10 mmol hexamethylene diisocyanate, and 20 mmol 3-hydroxypropionic acid into a flask, heat to 75°C, stir and react for 4 hours, remove the solvent by rotary evaporation, wash with petroleum ether, and dry to obtain hexamethylene di(carbamate propionic acid).

[0027] (2) Add 150 mmol of thionyl chloride and 20 mmol of hexamethylenebis(carbamate propionic acid) into a flask, heat to 78°C for reflux reaction for 3 h, remove thionyl chloride by rotary evaporation after the reaction, add the product into 100 mL of dimethyl sulfoxide, then add 22 mmol of N-methyl-2,2-diaminodiethylamine and 40 mmol of triethylamine, carry out polymerization reaction at 30°C for 24 h, collect the precipitate, filter it, wash it with ethanol, and dry it to obtain carbamate polyamide.

[0028] (3) Add 800 mL of N,N-dimethylformamide and 50 g of polyamide carbamate into a flask, mix well, add 37.5 g of benzyl bromide, heat to 110 °C, react for 36 h, and after the reaction, remove the solvent by rotary evaporation, wash with ethanol, and dry to obtain an antibacterial finishing agent.

[0029] (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 55 g / L. The nylon and spandex blended fabric was then added and double-impregnated and double-rolled. The fabric was then dried at 100°C for 4 min and baked at 180°C for 30 s to obtain a breathable antibacterial fabric.

[0030] Example 4 (1) Add 1,4-dioxane solvent, 10 mmol hexamethylene diisocyanate, and 20 mmol 3-hydroxypropionic acid into a flask, heat to 75°C, stir and react for 4 hours, remove the solvent by rotary evaporation, wash with petroleum ether, and dry to obtain hexamethylene di(carbamate propionic acid).

[0031] (2) Add 140 mmol of thionyl chloride and 20 mmol of hexamethylenebis(carbamate propionic acid) into a flask, heat to 78°C for reflux reaction for 3 h, remove thionyl chloride by rotary evaporation after the reaction, add the product into 100 mL of dimethyl sulfoxide, then add 22 mmol of N-methyl-2,2-diaminodiethylamine and 40 mmol of triethylamine, carry out polymerization reaction at 40°C for 24 h, collect the precipitate, filter it, wash it with ethanol, and dry it to obtain carbamate polyamide.

[0032] (3) Add 800 mL of N,N-dimethylformamide and 50 g of polyamide carbamate into a flask, mix well, add 37.5 g of benzyl bromide, heat to 120 °C, react for 36 h, remove the solvent by rotary evaporation after the reaction, wash with ethanol, and dry to obtain an antibacterial finishing agent.

[0033] (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. The nylon and spandex blended fabric was then added and double-impregnated and double-rolled. The fabric was then dried at 100°C for 4 min and baked at 180°C for 20 s to obtain a breathable antibacterial fabric.

[0034] The difference between Comparative Example 1 and Example 1 is that urethane polyamide is used as the finishing agent.

[0035] Add urethane polyamide to distilled water, heat to 80°C, stir for 40 minutes, prepare a finishing solution with a mass fraction of 35 g / L, then add the blended fabric of nylon and spandex, perform double dipping and double rolling, then dry at 90°C for 6 minutes; bake at 170°C for 40 seconds to obtain a breathable antibacterial fabric containing a finishing agent.

[0036] The difference between Comparative Example 2 and Example 1 is that, when preparing polyamide, common succinyl chloride is used instead of hexamethylene di(carbamate propionic acid).

[0037] (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 into 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: (2) Add 800 mL of N,N-dimethylformamide and 50 g of polyamide into 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: (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. The nylon and spandex blended fabric was then added and double-impregnated and double-rolled. The fabric was then dried at 90°C for 6 min and baked at 170°C for 40 s to obtain a breathable antibacterial fabric.

[0038] Comparative Example 3 is a blended fabric of ordinary nylon and spandex, which is not finished with a finishing liquid.

[0039] The water vapor permeability of fabrics was tested according to the method of GB / T 12704.2-2009, and the test temperature was 38°C and the relative humidity was 50%. Each fabric sample was tested 5 times and the average value was taken.

[0040] Table 1 Water vapor permeability of fabrics The water vapor transmission rate of Examples 1-4 reached 24.23-25.74 g·h -1 ·m -2This is because 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 and is beneficial to improving the moisture permeability and air permeability of the fabric.

[0041] Comparative Example 3 is an ordinary unfinished blended fabric of nylon and spandex, which has the lowest water vapor permeability and poor moisture permeability.

[0042] Comparative Example 1 uses carbamate polyamide as a finishing agent, which does not contain a quaternary ammonium salt hydrophilic group. Comparative Example 2 uses common succinyl chloride to replace hexamethylene di(carbamate propionic acid) when preparing polyamide. The resulting finishing agent does not contain a hydrophilic carbamate group. The water vapor permeability of the blended fabric of the two is lower than that of each embodiment, and the moisture permeability is poor.

[0043] The antibacterial properties of the fabric were tested by the flask oscillation method. The E. coli suspension was added to sterile saline and diluted to 5×10 6 cfu / mL. Take 1 mL and add it to a sterilized flask, then add 1cm×1cm fabric, shake at 37℃ for 24 hours, take 0.2mL of the shaken solution, dilute it 10 times and 100 times respectively, then take 0.1mL and place it in a sterile culture dish, add melted agar medium, mix well and cool to solidify. Incubate at 37℃ for 24 hours, then count the bacteria and calculate the inhibition rate.

[0044] Q = (BC) / B × 100%. C is the average bacterial count of the test sample after shaking. B is the average bacterial count of the blank sample after shaking. The ordinary nylon and spandex blended fabric of Comparative Example 3 is used as the blank sample.

[0045] The fabrics were washed 50 times according to the method of GB / T 8629-2001, and then the antibacterial performance test was carried out.

[0046] Table 2 Antibacterial performance test of fabrics The antibacterial rate of the fabrics of Examples 1-4 against Escherichia 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 Escherichia coli. In addition, the antibacterial finishing agent contains polyamide and urethane structures, and has high affinity and interfacial forces with the nylon polyamide molecular chain in the blended fabric and the urethane structure of 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 washings. It has long-lasting antibacterial ability.

[0047] Comparative Example 1 uses urethane polyamide as a finishing agent, does not contain antibacterial groups, and the blended fabric does not show antibacterial properties.

[0048] In comparative example 2, when preparing polyamide and antibacterial finishing agent, common succinyl chloride was used instead of hexamethylene di(carbamate propionic acid). The obtained antibacterial finishing agent only contained polyamide molecular chains and did not contain carbamate structures. The antibacterial finishing agent had high affinity and interfacial interaction with the nylon polyamide molecular chains in the blended fabric, but had low affinity and interfacial interaction with spandex polyurethane, resulting in the antibacterial finishing agent having lower adhesion performance on the surface of the blended fabric than the embodiments. After multiple washings, the degree of shedding of the antibacterial finishing agent was higher than that of the embodiments, resulting in the antibacterial rate after washing being lower than that of the embodiments.

[0049] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

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 for reaction, rotary evaporation, washing and drying to obtain hexamethylene di(carbamate propionic acid); (2) adding thionyl chloride and hexamethylenebis(carbamate propionic acid) into a flask, heating to reflux, performing rotary evaporation after the reaction, adding the product into dimethyl sulfoxide, and then adding N-methyl-2,2-diaminodiethylamine and triethylamine to carry out polymerization reaction, precipitating the precipitate, filtering, washing, and drying to obtain carbamate polyamide; (3) Add N,N-dimethylformamide and polyamide carbamate into a flask, mix well and 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 3-6h.

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):(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 24-36h.

7. The breathable antibacterial fabric according to claim 1, characterized in that: The ratio of 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 24-48h.

9. A process for preparing the breathable antibacterial fabric according to any one of claims 1 to 8, characterized in that: The preparation process is as follows: adding the antibacterial finishing agent into distilled water, heating to 80-95°C, stirring for 20-40 minutes, preparing a finishing solution, then adding the blended fabric of nylon and spandex, performing double dipping and double rolling, and then drying at 90-100°C for 4-6 minutes; and baking 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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