A multifunctional cotton fabric based on cochineal red-chitosan composite microspheres and preparation method thereof

Abstract

The present invention relates to a multifunctional cotton fabric based on cochineal red-chitosan composite microspheres and a preparation method thereof, and belongs to the technical field of cotton fabrics. The present invention first uses cochineal red, chitosan and polyaziridine to prepare cochineal red-chitosan composite microspheres with uniform size, small size and high balling rate; then sodium periodate, chitosan and sodium borohydride are used to amino-modify cotton fabric, and cochineal red-chitosan composite microspheres are adsorbed on its surface; finally, 1,2,3,4-butanetetracarboxylic acid and sodium hypophosphite are used for modification treatment, so that it can be chemically bonded with cochineal red-chitosan composite microspheres, so as to enhance the fastness of cochineal red-chitosan composite microspheres on cotton fabrics. The prepared multifunctional cotton fabric not only has excellent mildew and antibacterial properties, but also has a red appearance, and the cochineal red-chitosan composite microspheres are stably fixed on the surface of cotton fabrics and are not easy to fall off.

Description

Technical Field

[0001] The invention belongs to the technical field of cotton fabrics, and in particular relates to a multifunctional cotton fabric based on cochineal red-chitosan composite microspheres and a preparation method thereof. Background Art

[0002] Cotton fabrics are widely used in daily life and industrial production due to their softness, breathability, and comfort. However, cotton fabrics have strong hygroscopicity and hydrophilicity, which makes them very easy to breed bacteria and mold, causing odor, discoloration, and even material damage to the fabric, which not only affects the appearance and service life of the product, but may also cause harm to human health. Therefore, it is particularly important to develop cotton fabrics with antibacterial and anti-mildew properties.

[0003] Chitosan is a natural alkaline polysaccharide. Its positive charge can combine with the negatively charged bacterial cell membrane to affect the metabolism of bacteria and produce an antibacterial effect. It has an inhibitory effect on a series of bacteria and fungi. In recent years, the preparation of chitosan into microspheres has gradually become a research hotspot for new green and efficient antibacterial agents. The larger specific surface area makes its antibacterial ability more excellent. At present, traditionally prepared chitosan microspheres generally have the disadvantages of instability, poor size uniformity, large size, poor preparation reproducibility, and poor cross-linking ability. In addition, common chitosan microspheres are mainly colorless or light yellow, and there is little research on colored chitosan microspheres. Furthermore, the direct loading of chitosan microspheres on cotton fabrics is limited, and it is difficult to significantly improve the antibacterial effect.

[0004] Therefore, developing an antibacterial and mildew-proof cotton fabric based on chitosan microspheres is of great significance, but there are great challenges. Summary of the invention

[0005] In order to solve the above technical problems, the present invention provides a multifunctional cotton fabric based on cochineal red-chitosan composite microspheres and a preparation method thereof. First, cochineal red, chitosan and polyaziridine are used to prepare cochineal red-chitosan composite microspheres with uniform size, small size and high balling rate; then, sodium periodate, chitosan and sodium borohydride are used to amino-modify the cotton fabric, and the cochineal red-chitosan composite microspheres are adsorbed on the surface thereof; finally, 1,2,3,4-butanetetracarboxylic acid and sodium hypophosphite are used for modification treatment, so that the cochineal red-chitosan composite microspheres can be chemically bonded to the cochineal red-chitosan composite microspheres, thereby enhancing the fastness of the cochineal red-chitosan composite microspheres on the cotton fabric. The prepared multifunctional cotton fabric not only has excellent mildew and antibacterial properties, but also has a red appearance, and the cochineal red-chitosan composite microspheres are stably fixed on the surface of the cotton fabric and are not easy to fall off.

[0006] The first object of the present invention is to provide a method for preparing a multifunctional cotton fabric based on cochineal red-chitosan composite microspheres, comprising the following steps:

[0007] S1, adding the aqueous phase to the oil phase, then adding the cosurfactant and the cochineal red solution and stirring evenly to obtain an oil-in-water emulsion; finally, adding the polyethylenimine solution to the oil-in-water emulsion for cross-linking reaction to obtain cochineal red-chitosan composite microspheres; the aqueous phase includes the first chitosan, the first surfactant and the acetic acid aqueous solution; the oil phase includes an emulsifier and a phase change material;

[0008] S2, immersing the cotton fabric in a sodium periodate solution, a second chitosan solution and a sodium borohydride solution in sequence to react and obtain a modified cotton fabric;

[0009] S3, dissolving the carmine-chitosan composite microspheres, dispersant and second surfactant described in step S1 in water to obtain a finishing solution, and immersing the modified cotton fabric described in step S2 in the finishing solution for adsorption treatment, and then continuing to add 1,2,3,4-butanetetracarboxylic acid and sodium hypophosphite to the finishing solution for modification treatment, and finally pre-baking and baking to obtain the multifunctional cotton fabric based on carmine-chitosan composite microspheres.

[0010] In one embodiment of the present invention, in step S1, the first surfactant is selected from one or more of Tween 80, sodium dodecyl sulfate, sodium dodecylbenzene sulfonate and fatty acid glyceride;

[0011] The emulsifier is selected from one or more of Span 80, polyoxyethylene stearate and polyvinyl alcohol;

[0012] The co-surfactant is selected from one or more of ethanol, n-butanol and isopropanol;

[0013] The phase change material is selected from one or more of paraffin, cyclohexane and chloroform;

[0014] The mass concentration (w / v) of the first chitosan in the aqueous phase is 1%-4%, and the concentration of the first surfactant is 30g / L-100g / L; the volume concentration of acetic acid in the acetic acid aqueous solution is 0.1%-5%; if the mass concentration of chitosan is too low, the chitosan content of the reaction will be small, and the wall of the synthesized micro-nanosphere will be thin and easy to deform; if the concentration is too high, the viscosity of the solution will be too high, and the small droplets formed in the emulsion will be larger, resulting in the size of the synthesized micro-nanosphere being too large and the ball formation rate being low; if the concentration of the surfactant is too low, the emulsified droplets will be unevenly dispersed, and the size of the synthesized micro-nanosphere will be uneven; if the concentration is too high, it will cause a waste of resources; if the volume concentration of acetic acid is too low, the chitosan cannot be completely dissolved, and if the concentration is too high, the main chain of the chitosan molecule will be destroyed, which is not conducive to the reaction and microsphere formation;

[0015] The concentration of the emulsifier in the oil phase is 10g / L-30g / L;

[0016] The volume ratio of the oil phase to the water phase is (1-20):1; if the ratio is too low, the probability of collision between the droplets formed during the emulsification process will increase, the size of the synthesized micro-nanospheres will be too large, and the spherical rate will be low; if the ratio is too high, the yield will be too low;

[0017] The mass concentration (w / v) of the carmine solution is 0.01%-1%, and the volume ratio of the carmine solution to the water-in-oil emulsion is 1:(10-50); if the concentration of the carmine solution is too low, the final microspheres will be light in color; if the concentration is too high, there will be too much competition for the cross-linking agent, resulting in the formation of irregular lumps;

[0018] The mass concentration (w / v) of the polyethylenimine solution is 1%-10%, and the volume ratio of the polyethylenimine solution to the water-in-oil emulsion is 1:(10-30); if the concentration of the polyethylenimine solution is too low, the cross-linking is incomplete and the structure of the formed microspheres is unstable; if the concentration is too high, large-scale adhesion will occur.

[0019] In one embodiment of the present invention, in step S1, the stirring speed is 300rpm-800rpm, and the time is 10min-120min; if the stirring speed is too low, the water phase cannot be evenly dispersed in the oil phase, and irregular lumps are eventually formed; if the speed is too high, the formed emulsion is unstable and difficult to cross-link and solidify; if the stirring time is too short, the formed emulsion is unstable, and if the time is too long, it will cause a waste of resources;

[0020] The temperature of the cross-linking reaction is 40°C-70°C, the time is 0.5h-6h, and the rotation speed is 300rpm-800rpm; if the cross-linking temperature is too high or too low, the cross-linking activity of polyethylenimine will be affected; if the cross-linking time is too short, the cross-linking curing will be incomplete, the size of the micro-nanospheres will be uneven, and the ball formation rate will be low; if the cross-linking time is too long, the cross-linking will be excessive, and the micro-nanospheres will be easy to stick together; if the cross-linking rotation speed is too high or too low, the cross-linking curing will be incomplete, resulting in uneven size of the micro-nanospheres and low ball formation rate.

[0021] In one embodiment of the present invention, after S1, the process further includes the steps of centrifugation washing and drying the cochineal red-chitosan composite microspheres; the reagents used for the centrifugation washing are petroleum ether and isopropanol, the rotation speed is 1000rpm-4000rpm, and the number of times is 1-6 times; the drying temperature is 40°C-90°C.

[0022] In one embodiment of the present invention, in step S2, the concentration of the sodium periodate solution is 1 g / L-6 g / L; if the concentration of the sodium periodate solution is too low, the cotton oxidation is incomplete, and the subsequent amination is also incomplete, which ultimately leads to low fastness of the chitosan microspheres; if the concentration is too high, the strength of the cotton fabric will be damaged;

[0023] The dipping process in sodium periodate solution is: bath ratio 1: (30-50), temperature 30℃-90℃, time 1h-4h; if the dipping temperature is too low, the reaction rate is low and it takes a long time; if the temperature is too high, the reaction rate is fast and it is difficult to control the reaction process; if the dipping time is too short, the oxidation is incomplete; if the time is too long, the oxidation is excessive and the strength of the cotton fabric is lost;

[0024] The mass concentration (w / v) of the second chitosan solution is 3%-5%;

[0025] The dipping process in the second chitosan solution is: bath ratio 1: (30-50), temperature 30°C-90°C, time 1h-4h;

[0026] The concentration of the sodium borohydride solution is 2g / L-4g / L;

[0027] The immersion process in sodium borohydride solution is: bath ratio is 1: (30-50), time is 1h-4h.

[0028] In one embodiment of the present invention, in step S3, the dispersant is selected from one or more of tea saponin, sodium tripolyphosphate and polyethylene glycol;

[0029] The second surfactant is selected from one or more of Tween 80, sodium dodecyl sulfate, sodium dodecylbenzene sulfonate and fatty acid glyceride;

[0030] The concentration of cochineal red-chitosan composite microspheres in the finishing liquid is 1 g / L-5 g / L, the total concentration of the dispersant and the second surfactant is 5 g / L-15 g / L, and the mass ratio of the dispersant to the surfactant is (2-5):1.

[0031] In one embodiment of the present invention, in step S3, the conditions of the adsorption treatment are: pH 4-7, temperature 40°C-90°C and time 10min-60min.

[0032] In one embodiment of the present invention, in step S3, the amount of 1,2,3,4-butanetetracarboxylic acid added is 50 g / L-100 g / L;

[0033] The added amount of the sodium hypophosphite is 20g / L-50g / L.

[0034] In one embodiment of the present invention, in step S3, the modification treatment time is 5 min-30 min.

[0035] In one embodiment of the present invention, in step S3, the pre-baking is performed at 50°C-100°C for 1 min-5 min, and the baking is performed at 120°C-180°C for 2 min-6 min.

[0036] In one embodiment of the present invention, the molecular weights of the first chitosan and the second chitosan are independently 2 kDa-500 kDa.

[0037] The second object of the present invention is to provide a multifunctional cotton fabric based on cochineal red-chitosan composite microspheres prepared by the preparation method.

[0038] The principle of the invention is as follows: firstly, biomass chitosan contains multiple hydroxyl and amino active sites, cochineal carmine contains carboxyl active sites, and the multifunctional groups in polyethylenimine can generate crosslinking with biomass chitosan and cochineal carmine; an emulsification crosslinking method is adopted to prepare cochineal carmine-chitosan composite microspheres, under stirring and the action of a surfactant, an aqueous phase is dropped into an oil phase to disperse into microdroplets to form an emulsion, a cochineal carmine solution is added, and then a polyethylenimine solution is added, liquids containing different substances collide with each other under stirring and exchange substances therein, and under the action of polyethylenimine, the raw materials are crosslinked to form a three-dimensional network structure, thereby obtaining micron-level cochineal carmine-chitosan composite microspheres; wherein the micro-nanospheres synthesized from biomass chitosan and polyethylenimine are relatively large in size and easy to agglomerate, which limits the application effect, and the size of the micro-nanospheres can be effectively reduced and dispersed by adding a surfactant and a cosurfactant, thereby expanding the application; and due to the addition of cochineal carmine, the microspheres have red color, which is of great significance in the field of textiles. In addition, the cochineal red-chitosan composite microspheres need to be stably dispersed in water to be uniformly adsorbed and fixed on the surface of cotton fabrics. Therefore, a dispersant and a surface active agent are introduced to mix and prepare a finishing liquid. At the same time, the cochineal red-chitosan composite microspheres need 1,2,3,4-butanetetracarboxylic acid and sodium hypophosphite and are stably fixed on the surface of cotton fabrics under certain conditions. In addition, due to the size of the cochineal red-chitosan composite microspheres themselves and the small number of chemical binding sites on cotton fabrics, sodium periodate and chitosan are used to modify cotton so that its surface has a large number of amino groups, so that the cochineal red-chitosan composite microspheres can be chemically bonded to the modified cotton fabric to improve fastness. 1,2,3,4-butanetetracarboxylic acid can react with the amino groups on the cochineal red-chitosan composite microspheres and the amino groups on the modified cotton fabric under the catalysis of sodium hypophosphite, and connect the cochineal red-chitosan composite microspheres and the modified cotton fabric through covalent bonds. The presence of a large number of covalent bonds greatly improves the fastness of the cochineal red-chitosan composite microspheres on the surface of the modified cotton fabric, solves the problem that the cochineal red-chitosan composite microspheres cannot be permanently fixed on the cotton fabric, and broadens the application range of the cochineal red-chitosan composite microspheres.

[0039] The technical solution of the present invention has the following advantages over the prior art:

[0040] (1) The chitosan in the multifunctional cotton fabric based on carmine-chitosan composite microspheres of the present invention has good antibacterial properties; carmine not only has a good red appearance, but also contains carboxyl and hydroxyl groups in its molecular structure, which can be cross-linked with chitosan during the cross-linking process to form stable microspheres. Carmine-chitosan composite microspheres can provide excellent antibacterial properties and good appearance at the same time, and can be widely used in various fabric products, broadening the application field of chitosan microspheres and improving the safety of chitosan microspheres.

[0041] (2) The multifunctional cotton fabric based on cochineal carmine-chitosan composite microspheres of the present invention has durable mildew and antibacterial properties. The cochineal carmine-chitosan composite microspheres are stably fixed on the surface of the modified cotton fabric, and can simultaneously complete dyeing and functional modification, and are not easy to fall off.

[0042] (3) The preparation method of the present invention is environmentally friendly, has no toxic or harmful by-products produced during the processing, has a simple process, and improves the ecological synthesis efficiency, reduces energy consumption and carbon emissions, and saves production costs. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] In order to make the content of the present invention more clearly understood, the present invention is further described in detail below according to specific embodiments of the present invention in conjunction with the accompanying drawings, wherein:

[0044] Figure 1 The SEM images are of the unmodified cotton fabric of Comparative Example 9 in Test Example 1 of the present invention and the multifunctional cotton fabric based on cochineal red-chitosan composite microspheres of Example 4; wherein (a) is Comparative Example 9, and (b) is Example 4;

[0045] Figure 2 These are SEM images of the cochineal red-chitosan composite microspheres in Example 4 and Comparative Examples 1-3 in Test Example 1 of the present invention; wherein (a) is Example 4, (b) is Comparative Example 1, (c) is Comparative Example 2, and (d) is Comparative Example 3. DETAILED DESCRIPTION

[0046] The present invention is further described below in conjunction with the accompanying drawings and specific embodiments so that those skilled in the art can better understand the present invention and implement it. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. It should be understood that the specific embodiments are only used to explain the present invention, but the embodiments are not intended to limit the present invention.

[0047] In the present invention, unless otherwise explained, technical and scientific terms used in the present invention have the same meanings as commonly understood by those skilled in the art to which the present invention belongs.

[0048] In the present invention, unless otherwise stated, the term "and / or" used in the present invention includes any and all combinations of one or more of the associated listed items.

[0049] In the present invention, unless otherwise stated, the experimental methods used in the embodiments of the present invention are conventional methods unless otherwise stated, and the materials, reagents, etc. used are all commercially available unless otherwise stated. Example 1

[0050] The multifunctional cotton fabric based on cochineal red-chitosan composite microspheres and the preparation method thereof of the present embodiment specifically comprise the following steps:

[0051] S1. Dissolve chitosan with a molecular weight of 500 kDa in a 2% (v / v) acetic acid aqueous solution, add Tween 80 to the solution and stir evenly to obtain an aqueous phase with a chitosan mass concentration of 3% (w / v) and a Tween 80 concentration of 90 g / L; add Span 80 dropwise into liquid paraffin and stir evenly to obtain an oil phase with a Span 80 concentration of 20 g / L.

[0052] S2. Slowly drop 4 mL of the aqueous phase into 40 mL of the oil phase, add 4 mL of ethanol, add 1 mL of a 1 g / L carmine aqueous solution, and stir at 600 rpm for 1 h to obtain an oil-in-water emulsion; heat the oil-in-water emulsion to 50°C, and drop 4 mL of a 4% (w / v) polyethylenimine aqueous solution for cross-linking and curing for 4 h to obtain a crude product of carmine-chitosan composite microspheres; the crude product is centrifuged and washed three times at 3000 rpm using petroleum ether and isopropanol, respectively, and dried at 70°C to obtain carmine-chitosan composite microspheres.

[0053] S3. Immerse 1 g of cotton fabric in a 6 g / L sodium periodate solution with a bath ratio of 1:50 and continuously shake at 50°C for 3 h to obtain selectively oxidized cotton fabric; immerse the selectively oxidized cotton fabric in a 4% (w / v) chitosan solution with a bath ratio of 1:50 and shake at 50°C for 2 h, then use a 4 g / L sodium borohydride solution to shake and reduce for 2 h with a bath ratio of 1:50, wash and dry to obtain amino-treated cotton fabric.

[0054] S4. Dissolve carmine-chitosan composite microspheres, tea saponin and Tween 80 in water to prepare a finishing solution, wherein the concentration of carmine-chitosan composite microspheres in the finishing solution is 1 g / L, and the total concentration of polyethylene glycol and Tween 80 is 5 g / L (the mass ratio of polyethylene glycol to Tween 80 is 2:1). Immerse the amino-treated cotton fabric in the finishing solution, add acetic acid to adjust the pH of the solution to 6, shake continuously, raise the temperature to 60°C, and keep warm for 30 minutes; add 1,2,3,4-butanetetracarboxylic acid and sodium hypophosphite to the finishing solution, wherein the concentration of 1,2,3,4-butanetetracarboxylic acid in the finishing solution is 100 g / L, and the concentration of sodium hypophosphite is 50 g / L. After continuous shaking for 15 minutes, take out the cotton fabric, pre-bake at 60°C for 3 minutes, and then bake at 160°C in a setting machine for 3 minutes. After baking, take out, wash and dry to obtain a multifunctional cotton fabric based on carmine-chitosan composite microspheres. Example 2

[0055] The multifunctional cotton fabric based on cochineal red-chitosan composite microspheres and the preparation method thereof of the present embodiment specifically comprise the following steps:

[0056] S1. Dissolve chitosan with a molecular weight of 200 kDa in a 2% (v / v) acetic acid aqueous solution, add Tween 80 to the solution and stir evenly to obtain an aqueous phase with a chitosan mass concentration of 3% (w / v) and a Tween 80 concentration of 50 g / L; add Span 80 dropwise into liquid paraffin and stir evenly to obtain an oil phase with a Span 80 concentration of 20 g / L.

[0057] S2. Slowly drop 4 mL of the aqueous phase into 40 mL of the oil phase, add 4 mL of ethanol, add 1 mL of a 1 g / L carmine aqueous solution, and stir at 600 rpm for 1 h to obtain an oil-in-water emulsion; heat the oil-in-water emulsion to 50°C, and drop 4 mL of a 4% (w / v) polyethylenimine aqueous solution for cross-linking and curing for 6 h to obtain a crude product of carmine-chitosan composite microspheres; wash the crude product three times by centrifugation at 3000 rpm using petroleum ether and isopropanol, respectively, and dry at 70°C to obtain carmine-chitosan composite microspheres.

[0058] S3. Immerse 1 g of cotton fabric in a 6 g / L sodium periodate solution with a bath ratio of 1:50 and continuously shake at 50°C for 3 h to obtain selectively oxidized cotton fabric; immerse the selectively oxidized cotton fabric in a 4% (w / v) chitosan solution with a bath ratio of 1:50 and shake at 50°C for 2 h, then use a 4 g / L sodium borohydride solution to shake and reduce for 2 h with a bath ratio of 1:50, wash and dry to obtain amino-treated cotton fabric.

[0059] S4. Dissolve carmine-chitosan composite microspheres, tea saponin and Tween 80 in water to prepare a finishing solution, wherein the concentration of carmine-chitosan composite microspheres in the finishing solution is 1 g / L, and the total concentration of tea saponin and sodium dodecyl sulfate is 5 g / L (the mass ratio of tea saponin and sodium dodecyl sulfate is 3:1). Immerse the amino cotton fabric in the finishing solution, add acetic acid to adjust the pH of the solution to 6, shake continuously, raise the temperature to 60°C, and keep warm for 30 minutes; add 1,2,3,4-butanetetracarboxylic acid and sodium hypophosphite to the finishing solution, wherein the concentration of 1,2,3,4-butanetetracarboxylic acid in the finishing solution is 100 g / L, and the concentration of sodium hypophosphite is 50 g / L. After continuous shaking for 15 minutes, take out the cotton fabric, pre-bake at 60°C for 3 minutes, and then bake at 160°C for 3 minutes in a setting machine. After baking, take out, wash and dry to obtain a multifunctional cotton fabric based on carmine-chitosan composite microspheres. Example 3

[0060] The multifunctional cotton fabric based on cochineal red-chitosan composite microspheres and the preparation method thereof of the present embodiment specifically comprise the following steps:

[0061] S1. Dissolve chitosan with a molecular weight of 200 kDa in a 2% (v / v) acetic acid aqueous solution, add Tween 80 to the solution and stir evenly to obtain an aqueous phase with a chitosan mass concentration of 3% (w / v) and a Tween 80 concentration of 30 g / L; add polyvinyl alcohol dropwise to liquid paraffin and stir evenly to obtain an oil phase with a polyvinyl alcohol concentration of 20 g / L.

[0062] S2. Slowly drop 4 mL of the aqueous phase into 40 mL of the oil phase, add 4 mL of ethanol, add 1 mL of a 1 g / L carmine aqueous solution, and stir at 600 rpm for 1 h to obtain an oil-in-water emulsion; heat the oil-in-water emulsion to 50°C, and drop 4 mL of a 4% (w / v) polyethylenimine aqueous solution for cross-linking and curing for 4 h to obtain a crude product of carmine-chitosan composite microspheres; wash the crude product three times by centrifugation at 3000 rpm using petroleum ether and isopropanol, respectively, and dry at 70°C to obtain carmine-chitosan composite microspheres.

[0063] S3. Immerse 1 g of cotton fabric in a 6 g / L sodium periodate solution with a bath ratio of 1:50 and continuously shake at 50°C for 3 h to obtain selectively oxidized cotton fabric; immerse the selectively oxidized cotton fabric in a 4% (w / v) chitosan solution with a bath ratio of 1:50 and shake at 50°C for 2 h, then use a 4 g / L sodium borohydride solution to shake and reduce for 2 h with a bath ratio of 1:50, wash and dry to obtain amino-treated cotton fabric.

[0064] S4. Dissolve carmine-chitosan composite microspheres, tea saponin and Tween 80 in water to prepare a finishing solution, wherein the concentration of carmine-chitosan composite microspheres in the finishing solution is 1 g / L, and the total concentration of tea saponin and Tween 80 is 5 g / L (the mass ratio of tea saponin and Tween 80 is 2:1). Immerse the amino cotton fabric in the finishing solution, add acetic acid to adjust the pH of the solution to 6, shake continuously, raise the temperature to 60°C, and keep warm for 30 minutes; add 1,2,3,4-butanetetracarboxylic acid and sodium hypophosphite to the finishing solution, wherein the concentration of 1,2,3,4-butanetetracarboxylic acid in the finishing solution is 80 g / L, and the concentration of sodium hypophosphite is 50 g / L. After continuous shaking for 15 minutes, take out the cotton fabric, pre-bake at 60°C for 3 minutes, and then bake at 160°C in a setting machine for 3 minutes. After baking, take out, wash and dry to obtain a multifunctional cotton fabric based on carmine-chitosan composite microspheres. Example 4

[0065] The multifunctional cotton fabric based on cochineal red-chitosan composite microspheres and the preparation method thereof of the present embodiment specifically comprise the following steps:

[0066] S1. Dissolve chitosan with a molecular weight of 200 kDa in a 2% (v / v) acetic acid aqueous solution, add Tween 80 to the solution and stir evenly to obtain an aqueous phase with a chitosan mass concentration of 3% (w / v) and a Tween 80 concentration of 90 g / L; add Span 80 dropwise into liquid paraffin and stir evenly to obtain an oil phase with a Span 80 concentration of 20 g / L.

[0067] S2. Slowly drop 4 mL of the aqueous phase into 40 mL of the oil phase, add 4 mL of ethanol, add 1 mL of a 1 g / L carmine aqueous solution, and stir at 600 rpm for 1 h to obtain an oil-in-water emulsion; heat the oil-in-water emulsion to 50°C, and drop 4 mL of a 4% (w / v) polyethylenimine aqueous solution for cross-linking and curing for 4 h to obtain a crude product of carmine-chitosan composite microspheres; wash the crude product three times by centrifugation at 3000 rpm using petroleum ether and isopropanol, respectively, and dry at 70°C to obtain carmine-chitosan composite microspheres.

[0068] S3. Immerse 1 g of cotton fabric in a 6 g / L sodium periodate solution with a bath ratio of 1:50 and continuously shake at 50°C for 3 h to obtain selectively oxidized cotton fabric; immerse the selectively oxidized cotton fabric in a 4% (w / v) chitosan solution with a bath ratio of 1:50 and shake at 50°C for 2 h, then use a 4 g / L sodium borohydride solution to shake and reduce for 2 h with a bath ratio of 1:50, wash and dry to obtain amino-treated cotton fabric.

[0069] S4. Dissolve carmine-chitosan composite microspheres, tea saponin and Tween 80 in water to prepare a finishing solution, wherein the concentration of carmine-chitosan composite microspheres in the finishing solution is 1 g / L, and the total concentration of tea saponin and Tween 80 is 5 g / L (the mass ratio of tea saponin to Tween 80 is 2:1). Immerse the amino-treated cotton fabric in the finishing solution, adjust the solution pH to 6, shake continuously, raise the temperature to 60°C, and keep warm for 30 minutes; add 1,2,3,4-butanetetracarboxylic acid and sodium hypophosphite to the finishing solution, wherein the concentration of 1,2,3,4-butanetetracarboxylic acid in the finishing solution is 100 g / L, and the concentration of sodium hypophosphite is 50 g / L. After continuous shaking for 15 minutes, take out the cotton fabric, pre-bake at 60°C for 3 minutes, and then bake at 160°C in a setting machine for 3 minutes. After baking, take out, wash and dry to obtain a multifunctional cotton fabric based on carmine-chitosan composite microspheres. Comparative Example 1

[0070] The method is basically the same as Example 4, except that Tween 80 is not added to the aqueous phase. Comparative Example 2

[0071] The method is basically the same as Example 4, except that the 4% (w / v) polyethylenimine aqueous solution is replaced with a 50% (w / v) glutaraldehyde solution. Comparative Example 3

[0072] The method is basically the same as Example 4, except that the temperature of the water-in-oil emulsion is raised to 80°C instead of the temperature of the water-in-oil emulsion being raised to 50°C. Comparative Example 4

[0073] The method is basically the same as Example 4, except that the 4% (w / v) polyethylenimine aqueous solution is not added. Comparative Example 5

[0074] The method is basically the same as Example 4, except that tea saponin and Tween 80 are not added to the finishing liquid. Comparative Example 6

[0075] The method is basically the same as Example 4, except that 1,2,3,4-butanetetracarboxylic acid is not added. Comparative Example 7

[0076] The method is basically the same as Example 4, except that acetic acid is not used to adjust the pH value of the solution to 6. Comparative Example 8

[0077] The method is basically the same as Example 4, except that the mass ratio of tea saponin to Tween 80 is 1:1. Comparative Example 9

[0078] The method is basically the same as Example 4, except that the cotton fabric is not subjected to modification treatment. Comparative Example 10

[0079] Basically the same as Example 4, except that no sodium hypophosphite was added.

[0080] Test Example 1

[0081] The morphology of the unmodified cotton fabric, the multifunctional cotton fabric based on cochineal red-chitosan composite microspheres prepared in Example 4 and Comparative Example 9 was characterized by a desktop scanning electron microscope (SEM) TM 3030 (Hitachi, USA). The results are as follows: Figure 1 As shown. Figure 1 It can be seen that the cochineal red-chitosan composite microspheres were successfully attached to the surface of cotton fabric, indicating that the modification was successful.

[0082] Based on Example 1 and Comparative Examples 1-3, the morphology of cochineal red-chitosan composite microspheres was characterized. The results are as follows Figure 2 As shown. Figure 2 It can be seen that the size of the cochineal red-chitosan composite microspheres of Example 4 is small and the ball formation rate is good; the size of the cochineal red-chitosan composite microspheres of Comparative Example 1 is very large, because Tween 80 can make the aqueous phase more evenly dispersed in the oil phase, forming smaller and more uniform emulsified droplets, thereby cross-linking and curing into small and uniform microspheres; the size of the cochineal red-chitosan composite microspheres of Comparative Example 2 is relatively large and the ball formation rate is low, because the cross-linking ability of glutaraldehyde is too strong, and the products are easily bonded together during the cross-linking process; the cochineal red-chitosan composite microspheres of Comparative Example 3 are adhered, slightly larger in size, and uneven in size, because the appropriate cross-linking temperature can increase the activity of polyethylenimine, thereby improving its cross-linking activity; and a higher cross-linking temperature will cause the activity of polyethylenimine to show a trend of first increasing and then decreasing.

[0083] Test Example 2

[0084] The multifunctional cotton fabrics based on cochineal red-chitosan composite microspheres prepared in Examples 1-4 and Comparative Examples 1-10 were tested for size, coefficient of variation and antibacterial properties of cochineal red-chitosan composite microspheres.

[0085] Size: tested using NanoSizer ZS90 (Malvern, UK);

[0086] Coefficient of variation: Coefficient of variation = standard deviation / mean value*100%;

[0087] Antibacterial performance: The antibacterial rate of Escherichia coli was determined according to the standard of GBT 20944.3-2008 "Evaluation of antibacterial properties of textiles Part 3: Oscillation method";

[0088] Table 1 shows the final measured size and coefficient of variation of cochineal red-chitosan composite microspheres:

[0089] Table 1

[0090]

[0091] Table 2 shows the final measured Escherichia coli inhibition rate:

[0092] Table 2

[0093]

[0094] As can be seen from Tables 1 and 2, the size of the cochineal red-chitosan composite microspheres of the embodiment is relatively small; at the same time, the coefficient of variation is relatively small, indicating that the size difference between the microspheres is relatively small. As the size of the cochineal red-chitosan composite microspheres decreases, the antibacterial effect is continuously improved. However, the size of the microspheres of the comparative example is relatively large, the size difference between the microspheres is relatively large, and the antibacterial effect is not good.

[0095] Comparison of Example 4 and Comparative Example 1 shows that the size of the cochineal-chitosan composite microspheres in Comparative Example 1 is large, the coefficient of variation is large, and the antibacterial property is poor. This indicates that Tween 80 can disperse the emulsion into smaller droplets when the emulsion is formed, thereby effectively reducing the size of the cochineal-chitosan composite microspheres. When the size of the cochineal-chitosan composite microspheres decreases, their specific surface area increases and the antibacterial effect is enhanced.

[0096] By comparing Example 4 and Comparative Example 2, it can be seen that the cochineal red-chitosan composite microspheres obtained by cross-linking with polyethylenimine are smaller in size, smaller in coefficient of variation, larger in specific surface area, and have better antibacterial effect, which indicates that the cross-linking environment required by polyethylenimine is milder, reducing the waste of resources; while the cross-linking ability of glutaraldehyde is too strong, the size of the prepared cochineal red-chitosan composite microspheres is large, the specific surface area is small, and the antibacterial performance is affected.

[0097] Comparison of Example 4 and Comparative Example 3 shows that the size of the cochineal red-chitosan composite microspheres synthesized at a higher temperature is slightly larger and the coefficient of variation is larger. This is because polyethylenimine is greatly affected by temperature, and the activity of polyethylenimine is affected at a higher temperature, making the size of the cochineal red-chitosan composite microspheres larger, thereby reducing the antibacterial performance.

[0098] Comparison of Example 4 and Comparative Example 5 shows that, since tea saponin and Tween 80 are not added as dispersants, the cochineal red-chitosan composite microspheres aggregate with each other and cannot be evenly distributed on the cotton surface, resulting in a decrease in antibacterial performance.

[0099] By comparing Example 4 and Comparative Example 6, it can be seen that without adding 1,2,3,4-butanetetracarboxylic acid for cross-linking, the cochineal red-chitosan composite microspheres are not chemically bonded to the cotton fabric and are easily detached from the cotton fabric. After the treatment, there is less residue on the cotton fabric, which leads to a decrease in the antibacterial performance.

[0100] By comparing Example 4 and Comparative Example 7, it can be seen that without adjusting the pH value, the cochineal red-chitosan composite microspheres and the cotton fabric did not reach a large opposite surface potential, which was not conducive to the adsorption of the cochineal red-chitosan composite microspheres on the cotton fabric, thereby resulting in a decrease in the antibacterial performance.

[0101] Comparison of Example 4 and Comparative Example 8 shows that the ratio of the dispersant to the surfactant affects the dispersion properties of the cochineal red-chitosan composite microspheres in the solution, causing the microspheres to be unevenly distributed on the surface of the cotton fabric, thereby resulting in a decrease in the antibacterial property.

[0102] Comparison of Example 4 and Comparative Example 9 shows that the unmodified cotton fabric does not have active groups involved in cross-linking, and the cochineal red-chitosan composite microspheres cannot be chemically bonded to the cotton fabric, resulting in a decrease in antibacterial performance.

[0103] Comparison of Example 4 and Comparative Example 10 shows that without the addition of sodium hypophosphite, 1,2,3,4-butanetetracarboxylic acid cannot produce a cross-linking effect, and the cochineal red-chitosan composite microspheres cannot be chemically bonded to the cotton fabric, resulting in a decrease in antibacterial performance.

[0104] Test Example 3

[0105] The multifunctional cotton fabrics based on cochineal red-chitosan composite microspheres prepared in Example 4 and Comparative Examples 4-10 were subjected to mildew resistance and durability tests.

[0106] Anti-mildew performance: The anti-mildew grade is measured by testing Aspergillus niger according to the standard GBT 24346-2009 "Evaluation of Anti-mildew Performance of Textiles".

[0107] Durability: Test the color and mildew resistance of washed fabrics according to GBT 3921-2008 Textiles - Tests for Colour Fastness - Colour Fastness to Washing with Soap.

[0108] Table 3 shows the final measured mildew resistance level and durability performance:

[0109] Table 3

[0110]

[0111] It can be seen from Table 3 that, firstly, the multifunctional cotton fabric based on cochineal red-chitosan composite microspheres of Example 4 has a good mildew-proof effect before and after soaping; while the mildew-proof effect of the comparative example is poor, and the mildew-proof effect decreases again after soaping. Secondly, the a* value of the color light parameter Lab of the multifunctional cotton fabric based on cochineal red-chitosan composite microspheres of Example 4 is 11.4, and the a* value is red-green light. The larger the value, the heavier the red light, which proves that the color of the prepared cochineal red-chitosan composite microspheres is red; after soaping, the a* value of the color light parameter Lab drops to 10.6, that is, the blue color light intensity of the fabric after washing only decreases by 7.1%, which proves that the multifunctional cotton fabric based on cochineal red-chitosan composite microspheres has a higher color fixation rate and color fastness; while in the comparative example, since the adsorption amount of cochineal red-chitosan composite microspheres on cotton fabrics is low, the a* value of the color light parameter Lab of the obtained cotton fabric is low; in addition, in comparative examples 6, 9, and 10, since the cochineal red-chitosan composite microspheres are not combined with cotton fabrics by chemical bonds, the fastness is not high, so the a* value of the color light parameter Lab after soaping decreases more seriously.

[0112] Comparison of Example 4 and Comparative Example 5 shows that when tea saponin and Tween 80 are not added, the cochineal red-chitosan composite microspheres cannot be uniformly adsorbed on the cotton fabric due to severe agglomeration, thereby affecting subsequent cross-linking, and thus the anti-mildew effect is poor.

[0113] Comparison of Example 4 and Comparative Example 6 shows that cross-linking is impossible without the addition of 1,2,3,4-butanetetracarboxylic acid, and the cochineal red-chitosan composite microspheres are only physically adsorbed on the surface of the cotton fabric in small amounts and fall off in large amounts after soaping, so the anti-mildew effect is poor.

[0114] Comparison of Example 4 and Comparative Example 7 shows that when the pH value is not adjusted, the cochineal red-chitosan composite microspheres are less adsorbed on the cotton fabric and less cross-linked to the fabric, so the anti-mildew effect is poor.

[0115] By comparing Example 4 and Comparative Example 8, it can be seen that the ratio of the dispersant to the surfactant affects the dispersion performance of the cochineal red-chitosan composite microspheres in the solution, and the microspheres agglomerate and cannot be uniformly adsorbed on the cotton fabric, thereby affecting the subsequent cross-linking, and thus the anti-mildew effect is poor.

[0116] Comparison of Example 4 and Comparative Example 9 shows that the unmodified cotton fabric does not have active groups involved in cross-linking, and the cochineal red-chitosan composite microspheres cannot be chemically bonded to the cotton fabric, so the mildew-proof effect is poor.

[0117] Comparison of Example 4 and Comparative Example 10 shows that without adding sodium hypophosphite, 1,2,3,4-butanetetracarboxylic acid cannot produce cross-linking effect, and cochineal red-chitosan composite microspheres cannot be chemically bonded to cotton fabric, so the mildew-proof effect is poor.

[0118] Obviously, the above embodiments are merely examples for clear explanation and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived from these are still within the protection scope of the invention.

Claims

1. A method for preparing multifunctional cotton fabric based on cochineal red-chitosan composite microspheres, characterized in that: The following steps are involved: S1, adding the aqueous phase to the oil phase, then adding the cosurfactant and the cochineal red solution and stirring evenly to obtain an oil-in-water emulsion; finally, adding the polyethylenimine solution to the oil-in-water emulsion for cross-linking reaction to obtain cochineal red-chitosan composite microspheres; the aqueous phase includes the first chitosan, the first surfactant and the acetic acid aqueous solution; the oil phase includes an emulsifier and a phase change material; S2, immersing the cotton fabric in a sodium periodate solution, a second chitosan solution and a sodium borohydride solution in sequence to react and obtain a modified cotton fabric; S3, dissolving the carmine-chitosan composite microspheres, dispersant and second surfactant described in step S1 in water to obtain a finishing solution, and immersing the modified cotton fabric described in step S2 in the finishing solution for adsorption treatment, and then continuing to add 1,2,3,4-butanetetracarboxylic acid and sodium hypophosphite to the finishing solution for modification treatment, and finally pre-baking and baking to obtain the multifunctional cotton fabric based on carmine-chitosan composite microspheres.

2. The method for preparing multifunctional cotton fabric based on cochineal red-chitosan composite microspheres according to claim 1, characterized in that: In step S1, the first surfactant is selected from one or more of Tween 80, sodium dodecyl sulfate, sodium dodecylbenzene sulfonate and fatty acid glyceride; The emulsifier is selected from one or more of Span 80, polyoxyethylene stearate and polyvinyl alcohol; The co-surfactant is selected from one or more of ethanol, n-butanol and isopropanol; The phase change material is selected from one or more of paraffin, cyclohexane and chloroform; The mass concentration of the first chitosan in the aqueous phase is 1%-4%, the concentration of the first surfactant is 30g / L-100g / L; the volume concentration of acetic acid in the acetic acid aqueous solution is 0.1%-5%; The concentration of the emulsifier in the oil phase is 10g / L-30g / L; The volume ratio of the oil phase to the water phase is (1-20):1; The mass concentration of the cochineal red solution is 0.01%-1%, and the volume ratio of the cochineal red solution to the water-in-oil emulsion is 1:(10-50); The mass concentration of the polyethylenimine solution is 1%-10%, and the volume ratio of the polyethylenimine solution to the water-in-oil emulsion is 1:(10-30).

3. The method for preparing multifunctional cotton fabric based on cochineal red-chitosan composite microspheres according to claim 1, characterized in that: In step S1, the stirring speed is 300 rpm-800 rpm, and the time is 10 min-120 min; The cross-linking reaction is carried out at a temperature of 40° C.-70° C., for a time of 0.5 h-6 h, and at a rotation speed of 300 rpm-800 rpm.

4. The method for preparing multifunctional cotton fabric based on cochineal red-chitosan composite microspheres according to claim 1, characterized in that: In step S2, the concentration of the sodium periodate solution is 1 g / L-6 g / L; The immersion process in sodium periodate solution is: bath ratio 1: (30-50), temperature 30℃-90℃, time 1h-4h; The mass concentration of the second chitosan solution is 3%-5%; The dipping process in the second chitosan solution is: bath ratio 1: (30-50), temperature 30°C-90°C, time 1h-4h; The concentration of the sodium borohydride solution is 2g / L-4g / L; The immersion process in sodium borohydride solution is: bath ratio is 1: (30-50), time is 1h-4h.

5. The method for preparing multifunctional cotton fabric based on cochineal red-chitosan composite microspheres according to claim 1, characterized in that: In step S3, the dispersant is selected from one or more of tea saponin, sodium tripolyphosphate and polyethylene glycol; The second surfactant is selected from one or more of Tween 80, sodium dodecyl sulfate, sodium dodecylbenzene sulfonate and fatty acid glyceride; The concentration of cochineal red-chitosan composite microspheres in the finishing liquid is 1 g / L-5 g / L, the total concentration of the dispersant and the second surfactant is 5 g / L-15 g / L, and the mass ratio of the dispersant to the surfactant is (2-5):

1.

6. The method for preparing multifunctional cotton fabric based on cochineal red-chitosan composite microspheres according to claim 1, characterized in that: In step S3, the conditions of the adsorption treatment are: pH 4-7, temperature 40°C-90°C, and time 10min-60min.

7. The method for preparing multifunctional cotton fabric based on cochineal red-chitosan composite microspheres according to claim 1, characterized in that: In step S3, the amount of 1,2,3,4-butanetetracarboxylic acid added is 50 g / L-100 g / L; The added amount of the sodium hypophosphite is 20g / L-50g / L.

8. The method for preparing multifunctional cotton fabric based on cochineal red-chitosan composite microspheres according to claim 1, characterized in that: In step S3, the modification treatment time is 5 min-30 min.

9. The method for preparing multifunctional cotton fabric based on cochineal red-chitosan composite microspheres according to claim 1, characterized in that: In step S3, the pre-baking is performed at 50°C-100°C for 1 min-5 min, and the baking is performed at 120°C-180°C for 2 min-6 min.

10. Multifunctional cotton fabric based on cochineal red-chitosan composite microspheres prepared by the preparation method according to any one of claims 1 to 9.

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