Silk fabric modified based on blue chitosan microspheres and preparation method thereof

Abstract

The application provides a silk fabric modified based on blue chitosan microspheres and a preparation method thereof, the preparation method uses biomass genipin and biomass chitosan to prepare full-biomass-based blue chitosan microspheres, uses an emulsification crosslinking method and controls various variables, and fixes the prepared blue chitosan microspheres on the silk fabric through treatment of emulsification crosslinking agents, tannic acid, genipin and alkali metal sodium-containing alkoxy rare earth metal cluster compounds, to obtain the silk fabric modified based on the blue chitosan microspheres. The preparation method has the characteristics of environmental friendliness, and no toxic and harmful by-products are generated in the processing process; the process design is reasonable, the operation process is simple, the silk fabric modified based on the blue chitosan microspheres prepared has the performance of mildew resistance and antibiosis, the blue chitosan microspheres are stably fixed on the surface of the silk fabric, dyeing and functional modification can be simultaneously completed, and the blue chitosan microspheres are not easy to fall off.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of silk fabrics, in particular to a silk fabric modified based on blue chitosan microspheres and a preparation method thereof. BACKGROUND

[0002] Chitosan is a natural alkaline polysaccharide, has a broad-spectrum antibacterial function, has an inhibitory effect on a series of bacteria and fungi, and has low toxicity to mammalian cells, and has a safe natural advantage when used as an antibacterial agent. Therefore, chitosan fibers made of chitosan have excellent antibacterial performance, and are often used as medical antibacterial adjuvants. When chitosan is used as an antibacterial finishing agent for textile fiber products (such as cotton, wool, chemical fibers, etc.), the adsorption amount on the textile fiber is limited, and the antibacterial performance of the chitosan-treated fiber product is greatly limited, especially for textile mildew prevention, which is more difficult than antibacterial finishing.

[0003] In recent years, chitosan has gradually become a research hotspot for new green and efficient antibacterial agents in the form of microspheres, and its excellent antibacterial performance is due to the dual action of chitosan itself and the large specific surface area of chitosan microspheres on bacteria. At present, the traditional preparation of chitosan microspheres generally has the disadvantages of instability, poor size uniformity, large size, poor reproducibility, poor cross-linking ability, inability to withstand high temperature for a long time, easy oxidation and even hydrolysis. In addition, common chitosan antibacterial microspheres are mainly colorless or light yellow, and there are few studies on colored antibacterial chitosan microspheres. Moreover, the existing chitosan microspheres cannot be durably fixed on textile fibers and are prone to falling off. SUMMARY

[0004] To solve the above technical problems, the present application provides a silk fabric modified based on blue chitosan microspheres and a preparation method thereof.

[0005] The above-mentioned purpose of the present application is achieved by the following technical solutions:

[0006] The present application provides a preparation method of a silk fabric modified based on blue chitosan microspheres, comprising the following steps:

[0007] (1) chitosan and a surfactant are added to an acetic acid aqueous solution, and after being mixed uniformly, the mixture is used as an aqueous phase solution; an emulsifier is added to liquid paraffin, and after being mixed uniformly, the mixture is used as an oil phase solution;

[0008] (2) the aqueous phase solution prepared in step (1) is added to the oil phase solution prepared in step (1), and under the condition of 300-800 rpm, a water-in-oil emulsion (W / O emulsion) is formed by stirring, a genipin aqueous solution is added to the water-in-oil emulsion, and cross-linking is carried out under the condition of 20-50℃ and 300-800 rpm, and after centrifugation and drying, blue chitosan microspheres are obtained;

[0009] (3) the blue chitosan microspheres prepared in step (2), a dispersant and a surfactant are dissolved in water to obtain a mixed dispersion liquid, the silk fabric is first immersed in a tannic acid aqueous solution, then the silk fabric is taken out and immersed in the mixed dispersion liquid, genipin and an alkali metal sodium-containing alkoxyl rare earth metal cluster are added at 40-50 DEG C to obtain a mixed dispersion solution, an alkaline substance is added to adjust the pH value to alkaline, the silk fabric is taken out and dried to obtain the silk fabric modified based on the blue chitosan microspheres.

[0010] The raw materials used in the application are all biomass extracts; the selected reaction matrix is biomass chitosan, the biomass chitosan contains multiple amino active sites, and the biomass crosslinking agent genipin is an amino crosslinking agent, and the two are easy to crosslink; the emulsion crosslinking method is used to prepare the blue chitosan microspheres, under the action of vigorous stirring and a surfactant, the aqueous solution is dropped into the oil phase to form microdroplets to form an emulsion, then a water-soluble biomass crosslinking agent is added to diffuse into the microdroplets, and the linear polymer is crosslinked to form a three-dimensional network structure, thereby obtaining microspheres; the size of the micro-nanospheres synthesized by the biomass chitosan and the biomass genipin is large and easy to agglomerate, which limits the application effect, the addition of a certain concentration of surfactant can effectively reduce the size of the micro-nanospheres and disperse them, thereby expanding their application; moreover, the biomass chitosan and genipin crosslinked will produce soft blue, which is of great significance in the textile field. In addition, the microspheres need to be stably dispersed in water to be uniformly adsorbed and fixed on the surface of the silk fabric, therefore, a dispersant and a surfactant are introduced to prepare an emulsion dispersion liquid, at the same time, the chitosan microspheres need to be stably fixed on the surface of the silk fabric under the condition of a certain concentration of genipin, a certain temperature and pH.

[0011] In addition, due to the weak surface charge and gravity of the micron-sized balls, it is difficult to directly adsorb on the silk fabric like dye, therefore, tannic acid is used to regulate the negative charge on the silk fabric, increase the surface zeta potential electronegativity, enhance the adsorption amount of chitosan microspheres on the silk fabric, and make the microspheres closely adhere to the silk fabric. At the same time, genipin and two amino cross-linking mainly includes two steps, the first step is to form a tetrahydropyridine ring by ring opening of dihydropyran ring and amino (fast), the second step is that acetic acid methyl ester can form amide with amino (slow), and because genipin may self-crosslink in the solution, the crosslinking efficiency is poor and the rate is low, therefore, an alkali metal sodium-containing alkoxy rare earth metal cluster compound is selected as a catalyst, and chitosan microspheres are quickly crosslinked to the surface of the silk fabric by genipin and the alkali metal sodium-containing alkoxy rare earth metal cluster compound, thereby improving the crosslinking efficiency and rate. Therefore, tannic acid promotes the adsorption of chitosan microspheres to close, the catalyst improves the reaction efficiency, and the two synergistically crosslink the amino on the chitosan microspheres and the amino on the silk under the action of the catalyst by genipin after the contact, thereby generating covalent reaction, solving the problem that the microspheres cannot be durably fixed on the textile fiber material, and widening the application range of chitosan microspheres.

[0012] Further, in step (1), the molecular weight of the chitosan is 2-100 kDa.

[0013] Further, in step (1), the mass concentration (w / v) of chitosan in the aqueous solution is 0.1%-5%, and the concentration that is too low will make the content of the reaction chitosan less, the wall of the synthesized micro-nanosphere thin and easy to deform; and the concentration that is too high will make the viscosity of the solution too high, the small droplets of the emulsion large, and the size of the synthesized micro-nanosphere too large, thereby resulting in a low sphere formation rate.

[0014] Preferably, in step (1), the mass concentration of chitosan in the aqueous solution is 1%-3%.

[0015] Further, in step (1), the concentration of the surfactant in the aqueous solution is 10-50 g / L, and the concentration that is too low will make the dispersed droplets of the emulsion uneven, and the size of the synthesized micro-nanosphere uneven; and the concentration that is too high will cause waste of resources.

[0016] Further, in steps (1) and (3), the surfactant is preferably Tween 80 (Tween 80).

[0017] Further, in step (1), the volume concentration (v / v) of acetic acid in the aqueous acetic acid solution is 0.1%-5%, and the concentration that is too low will not make chitosan completely dissolved; and the concentration that is too high will damage the molecular main chain of chitosan, which is not conducive to the reaction and the formation of the microspheres.

[0018] Further, in step (1), the concentration of the emulsifier in the oil phase solution is 10-30 g / L.

[0019] Further, in step (1), the emulsifier is preferably Span 80.

[0020] Further, in step (1), the liquid paraffin is 10-80 mL.

[0021] Further, in step (2), the volume ratio of the oil phase solution to the water phase solution is (1-20):1. A ratio that is too low increases the probability of collision between the droplets formed during the emulsification process, resulting in micro-nano spheres with a larger size and a lower ball formation rate. A ratio that is too high results in a lower yield.

[0022] Further, in step (2), during the formation of the W / O emulsion, a too low rotation speed makes the water phase solution unable to be uniformly dispersed in the oil phase solution, ultimately forming irregular lumps. A too high rotation speed makes the formed emulsion unstable and difficult to crosslink and solidify.

[0023] Further, in step (2), the time for forming the W / O emulsion is 10-120 min. A time that is too low results in an unstable emulsion, and a time that is too high causes waste of resources.

[0024] Further, in step (2), the mass concentration (w / v) of genipin in the genipin aqueous solution is 7%-10%.

[0025] Further, in step (2), the volume ratio of the genipin aqueous solution to the W / O emulsion is 1:(10-30).

[0026] Further, in step (2), a too high or too low crosslinking temperature affects the crosslinking activity of genipin.

[0027] Further, in step (2), the crosslinking time is 0.5-6 h. A too short crosslinking time results in incomplete crosslinking and solidification, leading to a non-uniform size of the micro-nano spheres and a low ball formation rate. A too long crosslinking time results in excessive crosslinking, causing the micro-nano spheres to easily adhere.

[0028] Further, in step (2), a too high or too low rotation speed during the crosslinking process results in incomplete crosslinking and solidification, leading to a non-uniform size of the micro-nano spheres and a low ball formation rate.

[0029] Further, in step (2), after the crosslinking is completed to obtain a crude product, the method further includes a step of centrifugally washing the crude product with petroleum ether and isopropyl alcohol, the rotation speed of the centrifugation is 1000-4000 rpm, the washing is performed 1-6 times, and then the blue chitosan microspheres are obtained by drying at 40-90°C.

[0030] Further, in step (3), the concentration of tannic acid in the tannic acid aqueous solution is 0.1-40 g / L.

[0031] Further, in step (3), the mass ratio of the dispersant and the surfactant is (2-5):1, and the total concentration of the dispersant and the surfactant in the mixed dispersion is 5-15 g / L, and the dispersant and the surfactant together act as an emulsified crosslinking agent.

[0032] Further, in step (3), the dispersant is preferably tea saponin.

[0033] Further, in step (3), the concentration of the blue chitosan microspheres in the mixed dispersion is 1-5 g / L.

[0034] Further, in step (3), the concentration of the genipin in the mixed dispersion system is 0.5-2 g / L.

[0035] Further, in step (3), the concentration of the alkali metal sodium-containing alkoxy rare earth metal cluster in the mixed dispersion system is 0.05-0.3 mmol / L, and the molar ratio of the alkali metal sodium-containing alkoxy rare earth metal cluster to the amino group in the system is 1:(50-150).

[0036] Further, in step (3), the alkali metal sodium-containing alkoxy rare earth metal cluster can be a neodymium / sodium hetero-bimetallic complex or a lanthanum / sodium hetero-bimetallic complex, such as Nd2Na8(OCH2CH2NMe2) 12 (OH)2 or La2Na8(OCH2CF3) 14 (THF)6.

[0037] Further, in step (3), sodium bicarbonate is added to adjust the pH value to 7.5-8.5.

[0038] Further, in step (3), silk fabric is added and continuously shaken, and gradually heated to 40-50°C, and then genipin and the alkali metal sodium-containing alkoxy rare earth metal cluster are added and continuously shaken for 5-10 min, and then sodium bicarbonate is added to adjust the pH value to 7.5-8.5, and continuously shaken for 1-1.5 h, and then removed, rinsed and air-dried to obtain the blue chitosan microsphere-based modified silk fabric.

[0039] The second aspect of the present application provides a blue chitosan microsphere-based modified silk fabric prepared by the method of the first aspect, which has a mildew-resistant and antibacterial performance, and the blue chitosan microspheres are stably fixed on the surface of the silk fabric and are not easy to fall off.

[0040] The chitosan microspheres in the prior art are mainly used for antibiosis or drug loading, the blue chitosan microspheres are attached to silk fabric in the application, and dyeing and functional modification can be simultaneously completed. Moreover, the types of blue natural dyes are few, and the preparation of the blue chitosan microspheres also belongs to providing a new biomass blue dye.

[0041] The application has the following beneficial effects:

[0042] (1) The biomass crosslinking agent and the biomass chitosan have good antibacterial properties and good blue appearance, can simultaneously provide excellent antibacterial properties and good appearance, can be widely used in various fabric products, broaden the application field of the chitosan microspheres, and improve the use safety of the chitosan microspheres.

[0043] (2) The synthesis method has the characteristics of environmental friendliness, no toxic and harmful by-products are generated in the processing process, the process design is reasonable, the operation process is simple, the ecological synthesis efficiency is improved, the energy consumption is reduced, the production cost is saved, the energy consumption and carbon emission are reduced.

[0044] (3) The silk fabric modified based on the blue chitosan microspheres prepared by the application has the properties of mildew resistance and antibiosis, the blue chitosan microspheres are stably fixed on the surface of the silk fabric, dyeing and functional modification are simultaneously completed, and the blue chitosan microspheres are not easy to fall off. BRIEF DESCRIPTION OF DRAWINGS

[0045] Figure 1 The SEM images of the unmodified silk fabric and the silk fabric modified based on the blue chitosan microspheres prepared in Example 4.

[0046] Figure 2 The SEM images of the silk fabric modified based on the blue chitosan microspheres prepared in Example 4 and the silk fabric modified based on the chitosan microspheres prepared in Comparative Examples 1-3; wherein (a) is Example 4, (b) is Comparative Example 1, (c) is Comparative Example 2, and (d) is Comparative Example 3. DETAILED DESCRIPTION

[0047] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description of the application herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items.

[0048] The application will be further described below in conjunction with the drawings and specific embodiments, so that those skilled in the art can better understand the application and implement it. However, the embodiments are not limiting of the application.

[0049] The experimental methods used in the following examples are conventional methods, and the materials, reagents, etc. used are commercially available unless otherwise specified.

[0050] Example 1

[0051] A preparation method of a silk fabric modified based on blue chitosan microspheres, comprising the following steps:

[0052] (1) 0.4 g of chitosan with a molecular weight of 100 kDa was dissolved in 2% (v / v) (20 mL) acetic acid aqueous solution, and Tween 80 was added to the solution and stirred uniformly to obtain a 2% (w / v) chitosan acetic acid aqueous solution containing Tween 80 (20 g / L) as an aqueous phase solution; Span 80 (20 g / L) was added dropwise to 40 mL of liquid paraffin and stirred uniformly as an oil phase solution.

[0053] (2) 4 mL of the aqueous phase solution was slowly added dropwise to the oil phase solution, and stirred at a speed of 600 rpm for 1 h to obtain a stable W / O emulsion; the emulsion was heated to 40℃, and 2 mL of 7% (w / v) genipin aqueous solution was added dropwise and crosslinked and solidified for 3 h to obtain a crude product of blue chitosan microspheres; the crude product was washed by centrifugation at a speed of 3000 rpm using petroleum ether and isopropanol respectively for three times, and dried at 70℃ to obtain blue chitosan microspheres.

[0054] (3) The silk fabric was immersed in a 1 g / L tannic acid aqueous solution, taken out after constant oscillation for 15 minutes; the above blue chitosan microspheres were mixed and dispersed with tea saponin and Tween 80 at a mass ratio of 2 to obtain a mixed dispersion liquid, the concentration of blue chitosan microspheres in the mixed dispersion liquid was 1 g / L, and the total concentration of tea saponin and Tween 80 was 5 g / L; the silk fabric was added and oscillated constantly, and the temperature was gradually increased to 50℃; genipin and Nd2Na8(OCH2CH2NMe2) 12 (OH)2 were added to obtain a mixed dispersion system, the concentration of genipin in the mixed dispersion system was 0.5 g / L, and the concentration of Nd2Na8(OCH2CH2NMe2) 12 (OH)2 was 0.2 mmol / L, sodium bicarbonate was added after constant oscillation for 5 min to adjust the pH value to 7.5, and the oscillation was continued for one hour, then the silk fabric modified based on blue chitosan microspheres was taken out, washed and air-dried.

[0055] Example 2

[0056] A preparation method of a silk fabric modified based on blue chitosan microspheres, comprising the following steps:

[0057] (1) Chitosan with a molecular weight of 30 kDa was dissolved in 2% (v / v) (20 mL) acetic acid aqueous solution, and Tween 80 was added to the solution and stirred uniformly to obtain a 3% (w / v) chitosan acetic acid aqueous solution containing Tween 80 (20 g / L) as the aqueous phase solution; Span 80 (20 g / L) was added dropwise to 40 mL of liquid paraffin and stirred uniformly as the oil phase solution.

[0058] (2) 4 mL of the aqueous phase solution was slowly added dropwise to the oil phase solution, and stirred at a speed of 600 rpm for 1 h to obtain a stable W / O emulsion; the emulsion was warmed to 40℃, and 2 mL of a 7% (w / v) genipin aqueous solution was added dropwise and cross-linked and solidified for 3 h to obtain a crude product of blue chitosan microspheres; the crude product was washed with petroleum ether and isopropanol at a speed of 3000 rpm for three times, and dried at 70℃ to obtain blue chitosan microspheres.

[0059] (3) The silk fabric was immersed in a 1 g / L tannic acid aqueous solution, and taken out after oscillation for 15 min; the above blue chitosan microspheres were mixed and dispersed with tea saponin and Tween 80 at a mass ratio of 3, the concentration of the blue chitosan microspheres in the mixed dispersion was 1 g / L, and the total concentration of tea saponin and Tween 80 was 10 g / L; the silk fabric was added and oscillated, and the temperature was gradually increased to 50℃; genipin and Nd2Na8(OCH2CH2NMe2) 12 (OH)2 were added to obtain a mixed dispersion system, the concentration of genipin in the mixed dispersion system was 1 g / L, and the concentration of Nd2Na8(OCH2CH2NMe2) 12 (OH)2 was 0.2 mmol / L, sodium bicarbonate was added after oscillation for 5 min to adjust the pH value to 7.5, and the oscillation was continued for one hour, and then the silk fabric modified based on the blue chitosan microspheres was obtained after taking out, rinsing and air drying.

[0060] Example 3

[0061] A preparation method of a silk fabric modified based on blue chitosan microspheres, comprising the following steps:

[0062] (1) Chitosan with a molecular weight of 30 kDa was dissolved in 2% (v / v) (20 mL) acetic acid aqueous solution, and Tween 80 was added to the solution and stirred uniformly to obtain a 3% (w / v) chitosan acetic acid aqueous solution containing Tween 80 (20 g / L) as the aqueous phase solution; Span 80 (20 g / L) was added dropwise to 40 mL of liquid paraffin and stirred uniformly as the oil phase solution.

[0063] (2) Slowly drop 4 mL of the aqueous phase solution into the oil phase solution, and stir at a speed of 600 rpm for 1 h to obtain a stable W / O emulsion; warm the emulsion to 40°C, and drop 2 mL of a 7% (w / v) genipin aqueous solution to crosslink and solidify for 3 h to obtain a crude product of blue chitosan microspheres; centrifugally wash the crude product with petroleum ether and isopropanol at a speed of 3000 rpm for three times, and dry at 70°C to obtain the blue chitosan microspheres.

[0064] (3) Immerse the silk fabric into a 1 g / L tannic acid aqueous solution, and take it out after oscillation for 15 min; prepare a mixed dispersion liquid by mixing the blue chitosan microspheres with tea saponin and Tween 80 at a mass ratio of 3, wherein the concentration of the blue chitosan microspheres in the mixed dispersion liquid is 1 g / L, and the total concentration of tea saponin and Tween 80 is 10 g / L; add the silk fabric into the mixed dispersion liquid, and oscillate, gradually increasing the temperature to 50°C; add genipin and Nd2Na8(OCH2CH2NMe2) 12 (OH)2 into the mixed dispersion liquid to obtain a mixed dispersion system, wherein the concentration of genipin in the mixed dispersion system is 2 g / L, and the concentration of Nd2Na8(OCH2CH2NMe2) 12 (OH)2 is 0.2 mmol / L; after oscillation for 5 min, add sodium bicarbonate to adjust the pH value to 7.5; continue to oscillate for one hour, and then take out, rinse, and dry in the shade to obtain the silk fabric modified based on the blue chitosan microspheres.

[0065] Example 4

[0066] A method for preparing a silk fabric modified based on blue chitosan microspheres, comprising the following steps:

[0067] (1) Dissolve chitosan with a molecular weight of 30 kDa in 2% (v / v) (20 mL) acetic acid aqueous solution, and add Tween 80 into the solution to stir uniformly to obtain a 1% (w / v) chitosan acetic acid aqueous solution containing Tween 80 (25 g / L) as an aqueous phase solution; drop Span 80 (20 g / L) into 40 mL of liquid paraffin to stir uniformly as an oil phase solution.

[0068] (2) Slowly drop 4 mL of the aqueous phase solution into the oil phase solution, and stir at a speed of 600 rpm for 1 h to obtain a stable W / O emulsion; warm the emulsion to 30°C, and drop 2 mL of a 7% (w / v) genipin aqueous solution to crosslink and solidify for 3 h to obtain a crude product of blue chitosan microspheres; centrifugally wash the crude product with petroleum ether and isopropanol at a speed of 3000 rpm for three times, and dry at 70°C to obtain the blue chitosan microspheres.

[0069] (3) silk fabric was immersed in 1 g / L aqueous solution of tannic acid, and then taken out after 15 minutes of continuous shaking; the blue chitosan microspheres were mixed with tea saponin and Tween 80 at a mass ratio of 3 to prepare a mixed dispersion liquid, the concentration of the blue chitosan microspheres in the mixed dispersion liquid was 1 g / L, and the total concentration of tea saponin and Tween 80 was 10 g / L; the silk fabric was added into the mixed dispersion liquid, and then continuously shaken, and gradually heated to 50°C; genipin and Nd2Na8(OCH2CH2NMe2) 12 (OH)2 were added to obtain a mixed dispersion system, the concentration of genipin in the mixed dispersion system was 2 g / L, and the concentration of Nd2Na8(OCH2CH2NMe2) 12 (OH)2 was 0.2 mmol / L; after 5 minutes of continuous shaking, sodium bicarbonate was added to adjust the pH value to 8.5; after one hour of continuous shaking, the silk fabric modified based on the blue chitosan microspheres was taken out, washed, and dried in the dark.

[0070] Comparative Example 1

[0071] A preparation method of a silk fabric modified based on blue chitosan microspheres was the same as that of Example 4, except that no Tween 80 was added in the preparation of the aqueous solution in step (1).

[0072] Comparative Example 2

[0073] A preparation method of a silk fabric modified based on yellow chitosan microspheres was the same as that of Example 4, except that 7% (v / v) of a genipin aqueous solution was replaced by 50% of a glutaraldehyde solution in step (2).

[0074] The color of the silk fabric modified based on chitosan microspheres prepared in Comparative Example 2 was tested, and the b* value of the color light parameter Lab was 2, which was light yellow.

[0075] Comparative Example 3

[0076] A preparation method of a silk fabric modified based on blue chitosan microspheres was the same as that of Example 4, except that the temperature of cross-linking and solidification was 60°C in step (2).

[0077] Comparative Example 4

[0078] A preparation method of silk fabric modified based on chitosan microspheres, which is the same as the preparation method of Example 4, the difference is that in step (2), 4 mL of aqueous solution is slowly added to the oil phase solution, and stirred at a speed of 600 rpm for 1 h to obtain a stable W / O emulsion; the emulsion is heated to 30℃ and kept for 3 h to obtain a crude product of chitosan microspheres; the crude product is washed with petroleum ether and isopropanol at a speed of 3000 rpm for three times, and dried at 70℃ to obtain chitosan microspheres.

[0079] Comparative Example 5

[0080] A preparation method of silk fabric modified based on blue chitosan microspheres, which is the same as the preparation method of Example 4, the difference is that in step (3), tea saponin and Tween 80 are not added in the preparation of the mixed dispersion, and the chitosan microspheres are directly dispersed in water.

[0081] Comparative Example 6

[0082] A preparation method of silk fabric modified based on blue chitosan microspheres, which is the same as the preparation method of Example 4, the difference is that in step (3), genipin is not added.

[0083] Comparative Example 7

[0084] A preparation method of silk fabric modified based on blue chitosan microspheres, which is the same as the preparation method of Example 4, the difference is that in step (3), sodium bicarbonate is not added to adjust the pH value.

[0085] Comparative Example 8

[0086] A preparation method of silk fabric modified based on blue chitosan microspheres, which is the same as the preparation method of Example 4, the difference is that:

[0087] In step (3), the above blue chitosan microspheres are mixed with tea saponin and Tween 80 in a mass ratio of 3 to prepare a mixed dispersion, the concentration of blue chitosan microspheres in the mixed dispersion is 1 g / L, and the total concentration of tea saponin and Tween 80 is 10 g / L, silk fabric is added, and oscillation is continued, and the temperature is gradually increased to 50℃, genipin is added to obtain a mixed dispersion system, the concentration of genipin in the mixed dispersion system is 2 g / L, after continuous oscillation for 5 min, sodium bicarbonate is added to adjust the pH value to 8.5, and the oscillation is continued for one hour, then the silk fabric modified based on blue chitosan microspheres is obtained after taking out, rinsing and air drying.

[0088] Comparative Example 9

[0089] A preparation method of silk fabric modified based on blue chitosan microspheres, which is the same as the preparation method of Example 4, the difference is that in step (3), the step of "immersing the silk fabric into 1 g / L tannic acid aqueous solution, taking out after oscillating for 15 minutes" is not carried out.

[0090] Comparative Example 10

[0091] A preparation method of silk fabric modified based on blue chitosan microspheres, which is the same as the preparation method of Example 4, the difference is that in step (3), Nd2Na8(OCH2CH2NMe2) 12 (OH)2.

[0092] Test Example

[0093] The silk fabrics modified based on blue chitosan microspheres prepared in Examples 1-4 and the silk fabrics modified based on chitosan microspheres prepared in Comparative Examples 1-10 are tested for performance, and the testing method is as follows:

[0094] Chitosan microsphere size test: tested by using a nanoparticle size potential analyzer NanoSizer ZS90 (Malvern, UK).

[0095] Antibacterial performance test: evaluated according to GBT 20944.3-2008 Evaluation of antibacterial properties of textiles Part 3: oscillation method standard, and common E. coli on textiles was selected to measure the inhibition rate.

[0096] Silk fabric surface morphology: morphology characterization was performed by using a tabletop scanning electron microscope (SEM) TM 3030 (Hitachi, USA).

[0097] Silk fabric mildew resistance test: evaluated according to GBT 24346-2009 Textile mildew resistance standard, and common Aspergillus niger on textiles was selected to measure the mildew resistance grade.

[0098] Durability performance test: the adhesion strength test was tested according to GBT 3921-2008 Textile color fastness test of soaping fastness test, i.e. the color and mildew resistance performance characterization of the fabric after standard washing procedure.

[0099] Test Example 1

[0100] The silk fabrics modified based on blue chitosan microspheres prepared in Examples 1-4 and the silk fabrics modified based on chitosan microspheres prepared in Comparative Examples 1-10 were tested for chitosan microsphere size, deviation rate and antibacterial performance, and the test results of chitosan microsphere size and deviation rate are shown in Table 1:

[0101] Table 1 Test results of chitosan microsphere size and deviation rate

[0102]

[0103]

[0104] The test results of antibacterial performance are shown in Table 2:

[0105] Table 2 Test results of antibacterial performance

[0106]

[0107]

[0108] (1) Comparing the test results of Comparative Example 4 and Comparative Example 1, it can be seen from Table 1 and Table 2 that the blue chitosan antibacterial microspheres synthesized without adding Tween 80 have larger size and larger deviation rate, and poor antibacterial property, which shows that Tween 80 can make the emulsion dispersion into smaller droplets when the emulsion is formed, thereby effectively reducing the size of the synthesized blue chitosan antibacterial microspheres. When the size of the blue chitosan antibacterial microspheres decreases, the specific surface area increases, and the antibacterial effect is enhanced.

[0109] (2) Comparing the test results of Example 4 and Comparative Example 2, it can be seen from Table 1 and Table 2 that the size and deviation rate of the blue chitosan antibacterial microspheres obtained by using genipin crosslinking are smaller, which shows that the crosslinking environment required by genipin is more moderate, and the waste of resources is reduced. Glutaraldehyde can also be used as a crosslinking agent for chitosan, but the crosslinking ability is too strong, and the chitosan microspheres prepared have large size and small specific surface area, and the antibacterial performance is affected. As can be seen from Table 2, the antibacterial performance of the blue antibacterial microspheres synthesized using genipin as a crosslinking agent is good, on the one hand, because the size of the blue chitosan antibacterial microspheres synthesized using genipin as a crosslinking agent is small, the specific surface area is large, and the antibacterial effect is good; on the other hand, not only chitosan but also genipin plays a certain antibacterial role in the antibacterial process, so the antibacterial effect of the chitosan antibacterial microspheres synthesized using genipin as a crosslinking agent is better than that of the chitosan antibacterial microspheres synthesized using glutaraldehyde.

[0110] (3) Comparing the test results of Example 4 and Comparative Example 3, it can be seen from Table 1 and Table 2 that the blue chitosan antibacterial microspheres synthesized at a higher temperature have slightly larger size and larger deviation rate. This shows that genipin is greatly affected by temperature, and the activity of genipin is affected when the temperature is higher, so that the size of the synthesized blue chitosan antibacterial microspheres is larger, thereby reducing the antibacterial performance.

[0111] (4) From Table 2, it can be seen that, in the comparative example 5, tea saponin and Tween 80 are not added, the blue chitosan microspheres on the surface of the silk fabric are aggregated seriously, the microspheres are coated, and the antibacterial performance is reduced; in the comparative example 6, no genipin is added for crosslinking, the fixing property of the blue chitosan microspheres on the silk fabric is poor; in the comparative example 7, the pH value is not adjusted, the crosslinking efficiency of genipin is very low, and only a small amount of crosslinking is achieved; in the comparative examples 8-10, tannic acid and / or Nd2Na8(OCH2CH2NMe2) 12 (OH)2 is not added, the fixing property of the blue chitosan microspheres on the silk fabric is even poorer, and the antibacterial performance is poor.

[0112] Test Example 2

[0113] The silk fabrics modified based on the blue chitosan microspheres prepared in the embodiment 4 and the silk fabrics modified based on the chitosan microspheres prepared in the comparative examples 1-3 are subjected to morphology characterization, and the characterization results are shown in Figs. Figure 1 and Figure 2 .

[0114] (1) Figure 1 is the SEM image of the unmodified silk fabric and the silk fabric modified based on the blue chitosan microspheres prepared in the embodiment 4, and it can be seen from the figure that the blue chitosan microspheres modify the silk fabric.

[0115] (2) Comparing the characterization results of the embodiment 4 and the comparative example 1, it can be seen from Figure 2 that the size of the blue chitosan microspheres obtained in the embodiment 4 is small, and the balling rate is good, which is due to the addition of Tween 80. Tween 80 can make the water phase more uniformly dispersed in the oil phase, forming smaller and more uniform emulsion droplets, thereby crosslinking and solidifying into microspheres with small size and uniformity. The size of the blue chitosan microspheres synthesized in the comparative example 1 without adding Tween 80 is large.

[0116] (3) Comparing the characterization results of the embodiment 4 and the comparative example 2, it can be seen from Figure 2 that the size of the blue chitosan antibacterial micro-nanospheres obtained in the embodiment 4 is small, and the balling rate is good, which is due to the difference of the crosslinking agent. The size, balling rate and color of the chitosan antibacterial micro-nanospheres synthesized by different crosslinking agents are not the same. When glutaraldehyde is used as the crosslinking agent, the size of the chitosan antibacterial micro-nanospheres synthesized in the comparative example 2 is large, the balling rate is low, and the appearance is yellow.

[0117] (4) Comparing the characterization results of the embodiment 4 and the comparative example 3, it can be seen from Figure 2It can be seen that the blue chitosan antibacterial micro-nano spheres obtained in Example 4 have small size and good ball forming rate, which is caused by the temperature during cross-linking and solidification. The appropriate temperature can increase the activity of genipin, thereby increasing the cross-linking activity. When the temperature in Comparative Example 3 is high, the activity of genipin first increases and then decreases, causing the synthesized blue chitosan antibacterial micro-nano spheres to be sticky, slightly large in size, and uneven in size.

[0118] Test Example 3

[0119] The silk fabrics modified based on the blue chitosan microspheres prepared in Example 4 and the silk fabrics modified based on the chitosan microspheres prepared in Comparative Examples 5-10 were subjected to mildew resistance and durability tests, and the test results are shown in Table 3.

[0120] Table 3: Test results of mildew resistance and durability

[0121]

[0122] The color of the silk fabric modified based on the blue chitosan microspheres prepared in Example 4 was tested, and the b* value of the color light parameter Lab was -8.2. The b value is a yellow-blue light, and the greater the negative value, the heavier the blue light. This proves that the color of the prepared chitosan microspheres is blue. After soaping, the b* value of the color light parameter Lab decreased to -7.5, that is, the blue color light intensity of the washed fabric only decreased by 8.5%, which proves that the silk fabric prepared by the present application has high color fastness and color fastness.

[0123] In Comparative Example 5, no emulsifying dispersant was added, causing the chitosan mildew-resistant microspheres to agglomerate and unable to cross-link on the surface of the silk, thus having poor mildew resistance. In Comparative Example 6, no genipin was added for cross-linking. In Comparative Example 7, the pH value was not adjusted, and thus the cross-linking was not good, and the durability was poor.

[0124] In the present application, biomass genipin and biomass chitosan are used to prepare full-biomass blue chitosan antibacterial microspheres. The emulsification cross-linking method is used and various variables are controlled, solving the problems of uneven size, large size, low ball forming rate, toxicity, and single color of the synthesized chitosan antibacterial microspheres. At the same time, it also provides a new idea for improving the antibacterial performance of silk fabrics and biomass blue dyes, and has extremely broad application prospects.

[0125] The above-described examples are only preferred examples for fully illustrating the present application, and the protection scope of the present application is not limited thereto. Any equivalent replacement or transformation made by a person skilled in the art based on the present application is within the protection scope of the present application. The protection scope of the present application is subject to the claims.

Claims

1. A method for preparing silk fabric modified based on blue chitosan microspheres, characterized in that, The method comprises the following steps: (1) adding chitosan and a surfactant into an aqueous acetic acid solution, mixing uniformly to obtain an aqueous phase solution; adding an emulsifier into liquid paraffin, mixing uniformly to obtain an oil phase solution; (2) adding the aqueous phase solution prepared in step (1) into the oil phase solution prepared in step (1), stirring at 300-800 rpm to form a water-in-oil emulsion, adding a genipin aqueous solution into the water-in-oil emulsion, crosslinking at 20-50℃ and 300-800 rpm, centrifuging and drying to obtain blue chitosan microspheres; (3) dissolving the blue chitosan microspheres prepared in step (2), a dispersant and a surfactant in water to obtain a mixed dispersion, immersing silk fabric in a tannic acid aqueous solution, taking out the silk fabric and immersing the silk fabric in the mixed dispersion, adding genipin and an alkali metal sodium-containing alkoxy rare earth metal cluster compound into the mixed dispersion at 40-50℃ to obtain a mixed dispersion system, adjusting the pH value to alkaline by adding an alkaline substance, taking out the silk fabric and drying to obtain the silk fabric modified based on the blue chitosan microspheres.

2. The production method according to claim 1, characterized by, In step (1), the mass concentration of chitosan in the aqueous phase solution is 0.1%-5%, the concentration of the surfactant in the aqueous phase solution is 10-50 g / L, and the volume concentration of acetic acid in the aqueous acetic acid solution is 0.1%-5%.

3. The preparation method according to claim 1, characterized in that, In step (1), the concentration of the emulsifier in the oil phase solution is 10-30 g / L.

4. The method of claim 1, wherein, In step (2), the volume ratio of the oil phase solution to the aqueous phase solution is (1-20):

1.

5. The preparation method according to claim 1, characterized in that, In step (3), the concentration of tannic acid in the tannic acid aqueous solution is 0.1-40 g / L.

6. The method of claim 1, wherein, In step (3), the mass ratio of the dispersant to the surfactant is (2-5):1, and the total concentration of the dispersant and the surfactant in the mixed dispersion is 5-15 g / L.

7. The preparation method according to claim 1, characterized in that, In step (3), the concentration of genipin in the mixed dispersion system is 0.5-2 g / L.

8. The method of claim 1, wherein, In step (3), the concentration of the alkali metal sodium-containing alkoxy rare earth metal cluster compound in the mixed dispersion system is 0.05-0.3 mmol / L.

9. The production method according to claim 8, characterized by, In step (3), the alkali metal sodium containing alkoxide rare earth metal cluster is Nd2Na8(OCH2CH2NMe2) 12 (OH)2or La2Na8(OCH2CF3) 14 (THF)6.

10. The silk fabric modified based on the blue chitosan microspheres prepared by the method of any one of claims 1-9.

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