阅读说明：本技术 一种双重抗菌无纺布及其制备方法 (Dual-antibacterial non-woven fabric and preparation method thereof ) 是由 李义涛 王芳 云晧 程堂剑 邓永茂 张凌飞 杨刚 于 2020-06-19 设计创作，主要内容包括：本发明涉及一种双重抗菌无纺布的制备方法,包括：将无纺布置于含有锌盐的溶液中浸泡,干燥；然后置于含有银盐、2-甲基咪唑和粘接剂的溶液中浸泡,干燥；然后置于含有还原剂的溶液中浸泡,干燥。本发明通过原位生长法将ZIF-8结构负载在无纺布上,同时在ZIF-8结构中引入银离子,后续将银离子还原成纳米银,得到了具有双重抗菌性能的无纺布。本发明采用原位生长制备抗菌无纺布的方法,可以保证ZIF-8结构在无纺布上的分散均匀性和附着力,纳米银负载在ZIF-8结构上也避免了传统方法在无纺布上引入纳米银容易团聚的问题,由此得到的抗菌无纺布抗菌持久性能和耐洗性能优异。(The invention relates to a preparation method of a dual-antibacterial non-woven fabric, which comprises the following steps: soaking the non-woven fabric in a solution containing zinc salt, and drying; then placing the mixture into a solution containing silver salt, 2-methylimidazole and adhesive for soaking and drying; then soaking in a solution containing a reducing agent, and drying. According to the invention, the ZIF-8 structure is loaded on the non-woven fabric by an in-situ growth method, silver ions are introduced into the ZIF-8 structure at the same time, and the silver ions are subsequently reduced into nano silver, so that the non-woven fabric with dual antibacterial properties is obtained. According to the invention, the method for preparing the antibacterial non-woven fabric by in-situ growth is adopted, the dispersion uniformity and the adhesive force of the ZIF-8 structure on the non-woven fabric can be ensured, the problem that nano silver is easily agglomerated when being introduced into the non-woven fabric by a traditional method is also avoided when the nano silver is loaded on the ZIF-8 structure, and the obtained antibacterial non-woven fabric has excellent antibacterial lasting property and washing fastness.)

1. A preparation method of a dual-antibacterial non-woven fabric is characterized by comprising the following steps:

(1) soaking the non-woven fabric in a solution containing zinc salt, and drying;

(2) soaking the non-woven fabric treated in the step (1) in a solution containing silver salt, 2-methylimidazole and a binder, and drying;

(3) and (3) soaking the non-woven fabric treated in the step (2) in a solution containing a reducing agent, and drying.

2. The method according to claim 1, wherein the molar ratio of the zinc salt to the silver salt is (1-3): (0.1 to 0.3), preferably 1: (0.1 to 0.2);

preferably, the solution in the step (1) contains zinc salt with the concentration of 0.25-0.75 mmol/mL; the solution in the step (2) contains silver salt with the concentration of 0.015-0.05 mmol/mL.

3. The method according to claim 1, wherein the molar ratio of the zinc salt to 2-methylimidazole is (1 to 3): (6-12), preferably 1: (6-7);

preferably, the solution in the step (2) contains 2-methylimidazole with the concentration of 1-3 mmol/mL.

4. The method according to any one of claims 1 to 3, wherein the soaking in step (1), step (2) and/or step (3) is for 4 to 10 hours;

preferably, the soaking time in the step (1) is 4-8 hours, the soaking time in the step (2) is 6-10 hours, and the soaking time in the step (3) is 4-8 hours.

5. The method according to any one of claims 1 to 3, wherein the binder is at least one selected from the group consisting of PEG, PVA and PVP;

and/or the reducing agent is selected from at least one of sodium citrate, glucose or sodium borohydride.

6. The method according to claim 1, wherein in the step (3), the nonwoven fabric is washed with clean water, dried, and then placed in a solution containing a reducing agent.

7. The method according to claim 1 or 6, wherein the drying is: drying for 10-30 min at 60-120 ℃.

8. The method of claim 1, wherein the nonwoven fabric is subjected to corona or plasma treatment prior to step (1);

preferably, the gram weight of the non-woven fabric is 20-50g/m²The thickness is 0.04 mm-0.1 mm.

9. A dual antibacterial nonwoven fabric prepared by the method of any one of claims 1 to 8.

10. Use of the double antimicrobial nonwoven fabric according to claim 9 in the medical or public health field.

Technical Field

The invention relates to the field of composite materials, in particular to a dual-antibacterial non-woven fabric and a preparation method thereof.

Background

The non-woven fabric is also called non-woven fabric, is formed by oriented or random fibers, is a new generation of environment-friendly material, and has the characteristics of moisture resistance, air permeability, flexibility, light weight, no combustion supporting, easy decomposition, no toxicity, no irritation, rich color, low price, cyclic utilization and the like. At present, the demand of non-woven fabrics in the medical and public health fields is gradually increased, and the antibacterial property is higher. However, the conventional antibacterial nonwoven fabric has a disadvantage in antibacterial property. Especially, under the condition of recycling, the traditional non-woven fabric is more difficult to achieve the effects of washing resistance and lasting antibacterial property.

Disclosure of Invention

The first purpose of the present invention is to overcome the defects of the prior art and provide a method for preparing a dual antibacterial non-woven fabric.

Specifically, the preparation method provided by the invention comprises the following steps:

(1) soaking the non-woven fabric in a solution containing zinc salt, and drying;

(2) soaking the non-woven fabric treated in the step (1) in a solution containing silver salt, 2-methylimidazole and a binder, and drying;

(3) and (3) soaking the non-woven fabric treated in the step (2) in a solution containing a reducing agent, and drying.

The invention adopts an in-situ growth method to prepare ZIF-8 (sodalite type methyl imidazole zinc, SOD- [ Zn (mim))₂],zinc 2-methylimidazolate,2-methylimidazole zinc salt, code MAF-4, also called ZIF-8) structure is loaded on the non-woven fabric, and silver ions are introduced into the ZIF-8 structure at the same time, and then are reduced into nano silver. Firstly, introducing ZIF-8 and nano silver with excellent photocatalytic antibacterial performance to a non-woven fabric to obtain the non-woven fabric with dual antibacterial performance; secondly, the method for preparing the antibacterial non-woven fabric through in-situ growth can ensure the dispersion uniformity and the adhesive force of the ZIF-8 structure on the non-woven fabric; the nano silver is loaded on the ZIF-8 structure, so that the problem that the nano silver is easily agglomerated when being introduced on non-woven fabrics by the traditional method is solved; the antibacterial non-woven fabric obtained by the method has excellent antibacterial lasting property and washing fastness. According to the invention, the specific composition of the soaking solution and the soaking step sequence in each step are limited, so that the nano silver in the final product is loaded on the ZIF-8 structure, and the ZIF-8 structure loaded with the nano silver is uniformly dispersed on the surface of the non-woven fabric.

The zinc salt of the present invention may be at least one selected from zinc nitrate, zinc acetate or zinc sulfate.

The silver salt according to the present invention may be at least one selected from silver nitrate and silver sulfate.

The soaking is carried out at normal temperature.

In a preferred embodiment of the present invention, the molar ratio of the zinc salt to the silver salt is (1 to 3): (0.1 to 0.3), more preferably 1: (0.1-0.2). The main raw materials of the antibacterial agent with the bactericidal effect are limited within a specific proportion range, so that the two bactericidal components in the final product can be ensured to cooperatively play the bactericidal effect in the specific proportion.

As a specific embodiment of the invention, the solution in the step (1) contains zinc salt with a concentration of 0.25-0.75 mmol/mL; the solution in the step (2) contains silver salt with the concentration of 0.015-0.05 mmol/mL.

In a preferred embodiment of the present invention, the molar ratio of the zinc salt to 2-methylimidazole is (1 to 3): (6-12), more preferably 1: (6-7). The raw materials are limited in a specific proportion range, so that the ZIF-8 structure can be ensured to effectively grow in situ and be uniformly distributed on the surface of the non-woven fabric.

As a specific embodiment of the invention, the solution in the step (1) contains zinc salt with a concentration of 0.25-0.75 mmol/mL; the solution in the step (2) contains 1-3 mmol/mL of 2-methylimidazole.

In a preferable embodiment of the present invention, the soaking in step (1) and/or step (2) is performed for 4 to 10 hours. In a specific embodiment, the soaking time in step (1) may be 4 to 8 hours, and the soaking time in step (2) may be 6 to 10 hours. The soaking time is limited within the above range, so that the sterilizing component can be sufficiently deposited on the surface of the non-woven fabric and can be sufficiently grown in situ.

In a preferred embodiment of the present invention, the binder is at least one selected from the group consisting of PEG (polyethylene glycol), PVA (polyvinyl alcohol), and PVP (polyvinyl pyrrolidone). In the invention, the concentration of the binder in the solution in the step (2) is further preferably 0.01-0.1 g/mL, and more preferably 0.03-0.07 g/mL.

The step (3) of the invention aims to reduce silver ions into silver simple substance by using a reducing agent, and form nano silver uniformly loaded on a ZIF-8 structure on the surface of the non-woven fabric, thereby realizing excellent sterilization effect.

In the preferred embodiment of the present invention, in the step (3), the nonwoven fabric may be washed with clean water, the residual components may be washed away, dried, and then reduced in a solution containing a reducing agent.

In a preferred embodiment of the present invention, the reducing agent in step (3) is selected to be capable of converting silver ions (Ag)⁺) Reducing agent to silver simple substance. Specifically, at least one of sodium citrate, glucose and sodium borohydride can be selected.

The soaking time in the step (3) of the invention is enough to carry out the reaction of reducing silver ions into silver simple substance. As a specific implementation mode, the soaking time in the step (3) can be 4-8 hours.

As a preferable scheme of the invention, the drying involved in each step of the invention is specifically as follows: drying for 10-30 min at 60-120 ℃. In a specific embodiment, the drying temperature after the step (1) may be 60 to 100 ℃, the drying temperature after the step (2) may be 80 to 120 ℃, and the drying temperature after the step (3) may be 60 to 100 ℃. The drying temperature after washing with clean water can be 60-100 ℃. By limiting the drying temperature and time within the above ranges, the sterilization components on the surface of the nonwoven fabric can be prevented from being affected while the moisture is sufficiently evaporated.

In a preferred embodiment of the present invention, the nonwoven fabric material used in the present invention is selected from one of PP nonwoven fabric, polyester nonwoven fabric, and nylon nonwoven fabric. The nonwoven fabric may be corona or plasma treated prior to treatment to facilitate the antimicrobial component to better adhere to its surface. The gram weight of the non-woven fabric is preferably 20-50g/m²The thickness is 0.04 mm-0.1 mm, which is more convenient for use. The size of the nonwoven fabric is not particularly limited, and the nonwoven fabric may be completely immersed in the solution.

The second purpose of the invention is to provide the double antibacterial non-woven fabric prepared by the method.

A third object of the present invention is to provide an application of the dual antibacterial non-woven fabric in the medical or public health field.

The double-antibacterial non-woven fabric provided by the invention has excellent double-antibacterial effect, including nano-silver antibacterial effect and ZIF-8 photocatalytic antibacterial property. According to the invention, the ZIF-8 structure loaded with the nano-silver is introduced into the non-woven fabric through an in-situ growth method, so that the dispersion uniformity and the adhesive force of the ZIF-8 on the non-woven fabric are improved, the problem that the nano-silver is directly loaded on the non-woven fabric and is easy to agglomerate is solved, and the obtained antibacterial non-woven fabric has excellent washing resistance and antibacterial durability. The ZIF-8 structure in the non-woven fabric has high porosity, and can ensure good air permeability of the non-woven fabric. The whole process of the multi-antibacterial non-woven fabric prepared by the invention uses water as a solvent, and the preparation process is green and environment-friendly.

Detailed Description

The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.