Antibacterial real silk fabric and preparation method thereof

Abstract

The invention relates to an antibacterial real silk fabric and a preparation method thereof, and belongs to the technical field of functional fabrics. The preparation method comprises the following steps: S1, dispersing a zeolite imidazate skeleton structure material in a rhizoma dioscoreae cirrhosae extract solution, stirring, centrifuging and drying to obtain a zeolite imidazate skeleton / rhizoma dioscoreae cirrhosae extract; s2, the real silk fabric is soaked in the zeolite imidazate framework / dioscorea cirrhosa extract finishing liquid for finishing, and the antibacterial real silk fabric is obtained. A condensed tannin compound is encapsulated in a zeolite imidazate framework structure material, and the zeolite imidazate framework structure material releases the condensed tannin compound to react with the real silk fabric under a weak acid condition; the condensed tannin compound can be combined with protein in bacterial cells through hydrogen bonds, hydrophobic interaction and covalent bonds or can be used for effectively inhibiting the growth of bacteria by destroying cell membranes of the bacteria; in addition, zinc ions released by the SL (at) ZIF-8 have an antibacterial effect, and the antibacterial performance of the real silk fabric is synergistically enhanced.

Description

Technical Field

[0001] The invention belongs to the technical field of functional fabrics, and in particular relates to an antibacterial silk fabric and a preparation method thereof. Background Art

[0002] Silk fiber is widely loved by the public for its comfort and is often used to make summer underwear, bedding textiles and health clothing fabrics. When it is worn as an intimate textile, it is easy to breed bacteria due to direct contact with human skin, affecting the physiological health of the human body. Therefore, it is very important to perform antibacterial finishing on silk textiles. Most of the methods for antibacterial finishing of silk fibers are post-finishing methods, that is, post-finishing of silk fibers with antibacterial agents.

[0003] Chinese invention patent CN 115233445 A discloses a method for visible light catalytic antibacterial and durable finishing of silk, wherein an antibacterial finishing agent with a phenolic structure and a photografting catalyst are selected, and under visible light irradiation, the photografting catalyst is excited and activated, and a photochemical reaction occurs with the amino acid side groups on the macromolecular chain structure of the silk fiber to form an active grafting site; then the phenolic antibacterial finishing agent is combined with the silk fiber through diffusion and adsorption, and a covalent reaction occurs with the active grafting site of the silk, completing the covalent grafting finishing of the phenolic antibacterial finishing agent and the silk. However, the silk fabric finished by this method has poor water wash resistance.

[0004] Based on the above background, it is still necessary to develop antibacterial silk fabrics with excellent washability. Summary of the invention

[0005] In order to solve the above technical problems, the present invention provides an antibacterial silk fabric and a preparation method thereof. Firstly, a yam extract is extracted from the yam tuber by a water immersion method, and then the condensed tannin compounds in the yam extract are used as antibacterial components, and a zeolite imidazolate skeleton structure material is used as a functional carrier of the yam extract to synthesize a nano antibacterial material (denoted as SL@ZIF), and finally the silk fabric is subjected to antibacterial finishing by an immersion method.

[0006] The first object of the present invention is to provide a method for preparing an antibacterial silk fabric, comprising the following steps:

[0007] S1, dispersing the zeolite imidazolate framework material in the Dioscorea scoparia extract solution, stirring, centrifuging and drying to obtain the zeolite imidazolate framework / Dioscorea scoparia extract;

[0008] S2, immersing the silk fabric in a zeolite imidazolate skeleton / Dioscorea scoparia extract finishing solution for finishing to obtain the antibacterial silk fabric; the zeolite imidazolate skeleton / Dioscorea scoparia extract finishing solution comprises the zeolite imidazolate skeleton / Dioscorea scoparia extract described in S1 and water.

[0009] In one embodiment of the present invention, in S1, the zeolite imidazolate framework material is selected from one or more of ZIF-67, ZIF-90 and ZIF-8. Metal-organic framework materials (MOFs) are nanoporous materials assembled by coordinating covalent bonds of zinc ions and organic ligands. Zeolite imidazolate framework material is a commonly used MOFs, composed of zinc ions and ligands, with good thermal stability, hydrothermal stability and excellent biocompatibility. In addition, zinc ions have antibacterial effects, and therefore have great application potential in the fields of textile antibacterial, biomedicine, etc.

[0010] In one embodiment of the present invention, in S1, the preparation of the Dioscorea extract specifically includes the following steps: peeling and chopping fresh Dioscorea tubers, adding deionized water at a solid-liquid ratio of 1: (2-3), crushing into a slurry, and then in a sealed state, oscillating and extracting in a water bath at 60°C-65°C for 2h-2.5h, standing, stratifying, filtering, and drying. Based on the research on Dioscorea tuber extracts, it can be basically considered that the main component of Dioscorea tuber extracts is condensed tannin compounds, which are antibacterial active ingredients. Dioscorea extracts give silk fabrics certain antibacterial properties, which is mainly because natural condensed tannin compounds can combine with proteins in fungal cells through hydrogen bonds, hydrophobic interactions and covalent bonds or by destroying bacterial cell membranes, thereby effectively inhibiting bacterial growth.

[0011] In one embodiment of the present invention, in S1, the mass ratio of the zeolite imidazolate framework material to the Dioscorea scoparia extract is 1:(180-220); the concentration of the Dioscorea scoparia extract solution is 180 mg / mL-220 mg / mL. Due to the high surface area and porosity of the zeolite imidazolate framework material, the Dioscorea scoparia extract can be adsorbed on the surface of the zeolite imidazolate framework material, and the main principle of surface adsorption is interactions such as van der Waals forces and hydrogen bonds.

[0012] In one embodiment of the present invention, in S1, the stirring speed is 140 rpm-160 rpm, and the time is 50 min-70 min.

[0013] In one embodiment of the present invention, in S2, the concentration of the zeolite imidazolate framework / Dioscorea scoparia extract finishing solution is 30 g / L-100 g / L, and the pH value is 4-6.

[0014] In one embodiment of the present invention, the pH adjuster is selected from citric acid and / or disodium hydrogen phosphate.

[0015] In one embodiment of the present invention, in S2, the bath ratio of the silk fabric to the zeolite imidazolate skeleton / Dioscorea scoparia extract finishing solution is 1:(40-50).

[0016] In one embodiment of the present invention, in S2, the finishing is to increase the temperature to 50°C-90°C at a rate of 1.8°C / min-2.2°C / min and keep the temperature for 50min-150min.

[0017] In one embodiment of the present invention, the multiple interactions between the zeolite imidazolate skeleton / Dioscorea extract and the silk fiber include: first, under weakly acidic conditions, there is an ionic interaction between the partially ionized hydroxyl groups in the condensed tannin compounds and the protonated amino groups on the silk fibers; second, the hydroxyl groups on the condensed tannin compounds can combine with the amino groups, amide groups, carboxyl groups and hydroxyl groups on the silk fibers to form hydrogen bonds; third, there is also the effect of van der Waals forces between the condensed tannin compounds and the silk fibers, especially the non-polar van der Waals forces between the benzene rings in the condensed tannin compounds and the aromatic rings containing amino acid residues on the silk fibers; fourth, a small amount of condensed tannin compounds and the silk fibers are combined through covalent bonds, such as the hydroxyl groups in the condensed tannin compounds can react with the amino groups on the silk fibers to form covalent bonds.

[0018] The second object of the present invention is to provide an antibacterial silk fabric prepared by the method.

[0019] The antibacterial mechanism of the present invention is as follows: condensed tannin compounds with antibacterial activity are encapsulated in zeolite imidazolate skeleton structure materials. When antibacterial finishing is performed on silk fabrics by an immersion method under weakly acidic conditions, the zeolite imidazolate skeleton structure materials release condensed tannin compounds to react with the silk fabrics. The condensed tannin compounds can be combined with proteins in fungal cells through hydrogen bonds, hydrophobic interactions and covalent bonds, or by destroying bacterial cell membranes, thereby effectively inhibiting bacterial growth. Furthermore, the zinc ions released by SL@ZIF-8 have an antibacterial effect, which synergistically enhances the antibacterial properties of silk fabrics.

[0020] The technical solution of the present invention has the following advantages over the prior art:

[0021] (1) The preparation method of the present invention first extracts Dioscorea scoparia extract from the tuber of Dioscorea scoparia by water immersion, then uses the condensed tannin compounds in the Dioscorea scoparia extract as antibacterial components and uses the zeolite imidazolate skeleton structure material as a functional carrier of the Dioscorea scoparia extract to synthesize a nano antibacterial material (denoted as SL@ZIF), wherein the zeolite imidazolate skeleton structure material loads the condensed tannin compounds by surface adsorption, and encapsulates the condensed tannin compounds with antibacterial activity in the zeolite imidazolate skeleton structure material; finally, the silk fabric is subjected to antibacterial finishing under weak acid conditions by an immersion method, and the zeolite imidazolate skeleton structure material releases the condensed tannin compounds to react with the silk fabric, and the condensed tannin compounds can combine with proteins in fungal cells through hydrogen bonds, hydrophobic interactions and covalent bonds or by destroying the bacterial cell membrane, thereby effectively inhibiting the growth of bacteria; furthermore, the zinc ions released by SL@ZIF have an antibacterial effect, which synergistically enhances the antibacterial properties of the silk fabric. SL@ZIF was attached to silk fabric via ionic bonding, van der Waals forces, hydrogen bonding, and covalent bonding.

[0022] (2) The preparation method described in the present invention has natural raw materials, convenient process, and is green and environmentally friendly. DETAILED DESCRIPTION

[0023] The present invention is further described below in conjunction with 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.

[0024] 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.

[0025] 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.

[0026] 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.

[0027] In the present invention, unless otherwise specified, the preparation of the Dioscorea extract used in the embodiments of the present invention specifically includes the following steps: peeling and chopping fresh Dioscorea tubers, adding deionized water at a solid-liquid ratio of 1:2.5, crushing the mixture into a slurry, adding it to a sealed conical flask, shaking and extracting it in a water bath at 60°C for 2h, then letting the liquid stand and stratify, and filtering and drying it after it cools to room temperature.

[0028] In the present invention, unless otherwise specified, the preparation of ZIF-8 nanoparticles used in the embodiments of the present invention specifically includes the following steps: 1713.54 mg of zinc nitrate hexahydrate and 9852 mg of 2-methylimidazole are dissolved in 240 mL of methanol respectively, and ultrasonicated for 20 min to obtain a clear solution; at room temperature, 20 mL of the methanol solution of zinc nitrate hexahydrate is slowly poured into 20 mL of the methanol solution of 2-methylimidazole, and reacted for 4 h under magnetic stirring; the product is collected by centrifugation, washed with methanol 3 times, and dried under vacuum conditions.

[0029] Example 1

[0030] The antibacterial silk fabric and the preparation method thereof of the present embodiment specifically include the following steps:

[0031] S1, dispersing 50 mg of ZIF-8 in 50 mL of 200 mg / mL aqueous solution of Dioscorea paniculata extract, and magnetically stirring at 150 rpm for 60 min, centrifuging and drying to obtain SL@ZIF-8;

[0032] S2. Disperse SL@ZIF-8 in water to obtain a SL@ZIF-8 finishing solution with a concentration of 30 g / L; immerse the silk fabric in the SL@ZIF-8 finishing solution for finishing with a bath ratio of 1:50, and adjust the pH value of the SL@ZIF-8 finishing solution to 4.5 using a citric acid / disodium hydrogen phosphate buffer solution; heat from 30°C to 60°C at a rate of 2°C / min and keep warm for 120 min, rinse with deionized water and dry naturally to obtain antibacterial silk fabric.

[0033] Example 2

[0034] The antibacterial silk fabric and the preparation method thereof of the present embodiment specifically include the following steps:

[0035] S1, dispersing 50 mg of ZIF-8 in 50 mL of 200 mg / mL aqueous solution of Dioscorea paniculata extract, and magnetically stirring at 150 rpm for 60 min, centrifuging and drying to obtain SL@ZIF-8;

[0036] S2. Disperse SL@ZIF-8 in water to obtain a SL@ZIF-8 finishing solution with a concentration of 100 g / L; immerse the silk fabric in the SL@ZIF-8 finishing solution for finishing with a bath ratio of 1:50, and adjust the pH value of the SL@ZIF-8 finishing solution to 5 using a citric acid / disodium hydrogen phosphate buffer solution; heat from 30°C to 70°C at a rate of 2°C / min and keep warm for 100 min, rinse with deionized water and dry naturally to obtain antibacterial silk fabric.

[0037] Example 3

[0038] The antibacterial silk fabric and the preparation method thereof of the present embodiment specifically include the following steps:

[0039] S1, dispersing 50 mg of ZIF-8 in 50 mL of 200 mg / mL aqueous solution of Dioscorea paniculata extract, and magnetically stirring at 150 rpm for 60 min, centrifuging and drying to obtain SL@ZIF-8;

[0040] S2. Disperse SL@ZIF-8 in water to obtain a SL@ZIF-8 finishing solution with a concentration of 80 g / L; immerse the silk fabric in the SL@ZIF-8 finishing solution for finishing with a bath ratio of 1:50, and adjust the pH value of the SL@ZIF-8 finishing solution to 5.5 using a citric acid / disodium hydrogen phosphate buffer solution; heat from 30°C to 80°C at a rate of 2°C / min and keep warm for 90 minutes, rinse with deionized water and dry naturally to obtain antibacterial silk fabric.

[0041] Example 4

[0042] The antibacterial silk fabric and the preparation method thereof of the present embodiment specifically include the following steps:

[0043] S1, dispersing 50 mg of ZIF-8 in 50 mL of 200 mg / mL aqueous solution of Dioscorea paniculata extract, and magnetically stirring at 150 rpm for 60 min, centrifuging and drying to obtain SL@ZIF-8;

[0044] S2. Disperse SL@ZIF-8 in water to obtain a SL@ZIF-8 finishing solution with a concentration of 50 g / L; immerse the silk fabric in the SL@ZIF-8 finishing solution for finishing with a bath ratio of 1:50, and adjust the pH value of the SL@ZIF-8 finishing solution to 4.5 using a citric acid / disodium hydrogen phosphate buffer solution; heat from 30°C to 90°C at a rate of 2°C / min and keep warm for 70 minutes, rinse with deionized water and dry naturally to obtain antibacterial silk fabric.

[0045] Comparative Example 1

[0046] The method is basically the same as Example 1, except that ZIF-8 is not added, and specifically comprises the following steps:

[0047] The silk fabric was immersed in an aqueous solution of Dioscorea scoparia extract at a concentration of 200 mg / mL for finishing with a bath ratio of 1:50. The pH value of the Dioscorea scoparia extract aqueous solution was adjusted to 4.5 by a citric acid / disodium hydrogen phosphate buffer solution. The temperature was raised from 30°C to 60°C at a rate of 2°C / min and kept for 120 min. The fabric was rinsed with deionized water and dried naturally to obtain an antibacterial silk fabric.

[0048] Test Case

[0049] The antibacterial properties of the antibacterial silk fabrics prepared in Examples 1-4 and Comparative Example 1 were tested:

[0050] Antibacterial performance: The antibacterial rate of antibacterial silk fabrics was tested according to the standard GB / T 20944.3-2008 "Evaluation of antibacterial properties of textiles Part 3: Oscillation method";

[0051] Washability: The washability of antibacterial silk fabrics was tested according to the standard AATCC 124-2006 "Determination of the smoothness of fabrics after repeated home washing";

[0052] Table 1 shows the relevant properties of the modified silk fabric finally measured:

[0053] Table 1

[0054]

[0055]

[0056] It can be seen from Table 1 that the antibacterial silk fabric of the embodiment has good antibacterial performance and water washing resistance. Comparison of Example 1 and Comparative Example 1 shows that the method of Example 1 improves the antibacterial rate of the antibacterial silk fabric after 50 washings, and the antibacterial silk fabric has good antibacterial durability.

[0057] 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 an antibacterial silk fabric, characterized in that: The following steps are involved: S1, dispersing the zeolite imidazolate framework material in the Dioscorea scoparia extract solution, stirring, centrifuging and drying to obtain the zeolite imidazolate framework / Dioscorea scoparia extract; S2, immersing the silk fabric in a zeolite imidazolate skeleton / Dioscorea scoparia extract finishing solution for finishing to obtain the antibacterial silk fabric; the zeolite imidazolate skeleton / Dioscorea scoparia extract finishing solution comprises the zeolite imidazolate skeleton / Dioscorea scoparia extract described in S1 and water.

2. The method for preparing the antibacterial silk fabric according to claim 1, characterized in that: In S1, the zeolite imidazolate framework material is selected from one or more of ZIF-67, ZIF-90 and ZIF-8.

3. The method for preparing the antibacterial silk fabric according to claim 1, characterized in that: In S1, the preparation of the Dioscorea scoparia extract specifically includes the following steps: peeling and chopping fresh Dioscorea scoparia tubers, adding deionized water at a solid-liquid ratio of 1:(2-3), crushing into a slurry, and then in a sealed state, oscillating and extracting in a water bath at 60°C-65°C for 2h-2.5h, standing, stratifying, filtering, and drying.

4. The method for preparing the antibacterial silk fabric according to claim 1, characterized in that: In S1, the mass ratio of the zeolite imidazolate framework structure material to the Dioscorea scoparia extract is 1:(180-220); the concentration of the Dioscorea scoparia extract solution is 180 mg / mL-220 mg / mL.

5. The method for preparing the antibacterial silk fabric according to claim 1, characterized in that: In S1, the stirring speed is 140 rpm-160 rpm, and the time is 50 min-70 min.

6. The method for preparing the antibacterial silk fabric according to claim 1, characterized in that: In S2, the concentration of the zeolite imidazolate framework / Dioscorea scoparia extract finishing solution is 30 g / L-100 g / L, and the pH value is 4-6.

7. The method for preparing the antibacterial silk fabric according to claim 6, characterized in that: The pH regulator is selected from citric acid and / or disodium hydrogen phosphate.

8. The method for preparing antibacterial silk fabric according to claim 1, characterized in that: In S2, the bath ratio of the silk fabric to the zeolite imidazolate skeleton / Dioscorea scoparia extract finishing solution is 1:(40-50).

9. The method for preparing antibacterial silk fabric according to claim 1, characterized in that: In S2, the finishing is performed by heating the temperature to 50-90°C at a rate of 1.8-2.2°C / min and maintaining the temperature for 50-150 min.

10. Antibacterial silk fabric prepared by the method according to any one of claims 1 to 9.

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