阅读说明：本技术 一种柔软抗菌无纺布及其制备方法 (Soft antibacterial non-woven fabric and preparation method thereof ) 是由 杨春云 于 2021-08-30 设计创作，主要内容包括：本发明属于纺织面料技术领域,具体涉及一种柔软抗菌无纺布及其制备方法。本发明研制的产品,包括无纺布纤维、柠檬酸和抗菌金属离子；所述抗菌金属离子被柠檬酸螯合吸附；所述无纺布纤维为多孔无纺布纤维,所述多孔无纺布纤维的孔隙为通孔结构,以使所述柠檬酸分布于所述孔隙中,并可与外部接触。另外,在所述孔隙与所述柠檬酸之间,填充有聚多巴胺中间层；并且4、所述无纺布纤维中,包括以下重量份数的不同尺寸无纺布纤维：20-40份长度为3-5cm,长径比为20：1-30：1的1#无纺布纤维；30-40份长度为300-500μm,长径比为10：1-15：1的2#无纺布纤维；还包括无纺布纤维质量3-5％的热塑性弹性体TPE。(The invention belongs to the technical field of textile fabrics, and particularly relates to a soft antibacterial non-woven fabric and a preparation method thereof. The product developed by the invention comprises non-woven fabric fibers, citric acid and antibacterial metal ions; the antibacterial metal ions are chelated and adsorbed by citric acid; the non-woven fabric fibers are porous non-woven fabric fibers, and pores of the porous non-woven fabric fibers are in a through hole structure, so that the citric acid is distributed in the pores and can be in contact with the outside. In addition, between the pores and the citric acid, a polydopamine intermediate layer is filled; and 4, the non-woven fabric fibers comprise the following non-woven fabric fibers with different sizes in parts by weight: 20-40 parts of a material with the length of 3-5cm, the length-diameter ratio of 20: 1-30: 1# nonwoven fiber; 30-40 parts of a material with the length of 300-500 mu m, the length-diameter ratio of 10: 1-15: 1# 2 nonwoven fiber; and the thermoplastic elastomer TPE accounts for 3-5% of the mass of the fibers of the non-woven fabric.)

1. A soft antibacterial non-woven fabric is characterized by comprising non-woven fabric fibers, citric acid and antibacterial metal ions;

the antibacterial metal ions are chelated and adsorbed by citric acid;

the non-woven fabric fibers are porous non-woven fabric fibers, and pores of the porous non-woven fabric fibers are in a through hole structure, so that the citric acid is distributed in the pores and can be in contact with the outside.

2. A soft antimicrobial nonwoven fabric according to claim 1, wherein the antimicrobial metal ions are selected from at least one of silver ions, copper ions or zinc ions.

3. The soft, antibacterial nonwoven fabric of claim 1, wherein an intermediate layer of polydopamine is filled between the pores and the citric acid.

4. A soft and antibacterial nonwoven fabric as claimed in claim 1, characterized in that the nonwoven fabric fibers comprise the following different sizes of nonwoven fabric fibers in parts by weight:

20-40 parts of a material with the length of 3-5cm, the length-diameter ratio of 20: 1-30: 1# nonwoven fiber;

30-40 parts of a material with the length of 300-500 mu m, the length-diameter ratio of 10: 1-15: 1# 2 nonwoven fiber.

5. A soft and antibacterial nonwoven fabric as claimed in claim 1, which further comprises 3-5% by mass of fibers of the nonwoven fabric of thermoplastic elastomer TPE.

6. A preparation method of a soft antibacterial non-woven fabric is characterized by comprising the following specific preparation steps:

preparation of porous non-woven fabric fiber:

mixing nano calcium carbonate and polypropylene slices, and extruding in a screw extruder to obtain blended fibers; soaking the blended fiber in hydrochloric acid solution, ultrasonically soaking, filtering, washing and drying to obtain porous non-woven fabric fiber;

modification treatment of porous non-woven fabric fibers:

soaking the porous non-woven fabric fiber in a dopamine solution, adjusting the pH value of the solution to 7.2-7.5, introducing air into the solution, performing ultrasonic impregnation reaction, taking out the porous non-woven fabric fiber, and drying to obtain a pretreated porous non-woven fabric fiber;

mixing and dissolving citric acid and an antibacterial metal salt solution, adding the pretreated porous non-woven fabric fiber, carrying out ultrasonic impregnation, filtering, and drying to obtain the modified porous non-woven fabric fiber.

7. The method of claim 5, wherein the antibacterial metal salt is at least one selected from the group consisting of silver nitrate, copper sulfate, copper chloride, copper nitrate, zinc sulfate, zinc chloride, and zinc nitrate.

8. The method for preparing a soft antibacterial non-woven fabric according to claim 5, wherein the specific preparation steps further comprise: in the preparation process of the non-woven fabric fiber, when the nano calcium carbonate and the polypropylene slices are mixed, thermoplastic elastomer TPE (thermoplastic elastomer) accounting for 3-5% of the mass of the polypropylene slices is added.

Technical Field

The invention belongs to the technical field of textile fabrics. More particularly, relates to a soft antibacterial non-woven fabric and a preparation method thereof.

Background

The development of antibacterial and antiviral non-woven fabrics and chemical fiber products meets the requirements of consumers on the continuous improvement of product performance, and is also the need of enterprises for obtaining higher product added value, improving product competitiveness and expanding market space.

The core ingredient in the antimicrobial material is an antimicrobial agent. The anti-seeding agents can be roughly classified into three major categories, inorganic, organic and natural, according to their chemical compositions. Natural and organic antibacterial agents belong to the chemical sterilization method, and inorganic antibacterial agents belong to the physical sterilization method. The organic antibacterial agent has the advantages of high sterilization speed, wide antibacterial range and the like, but has the problems of poor heat resistance, easy exudation, toxic dissolved substances, no washing resistance, short service life, easy generation of drug resistance and the like. The inorganic antibacterial agent has good safety, heat resistance and durability, and has the disadvantages of high price, slow antibacterial effect, incapability of rapidly killing bacteria like an organic antibacterial agent, and almost no inhibiting effect on fungi and mould. In addition, the inorganic antibacterial powder has poor compatibility with high molecular materials, is easy to agglomerate in matrix resin, and brings great difficulty to the addition of materials such as spinning, film drawing and the like. The antimicrobial agent may be classified into an extractable type and a non-extractable type in terms of release form, each of which has advantages. The molecular assembly antibacterial technology integrates the advantages of the two technologies, and the antibacterial functional group which has high-efficiency broad-spectrum antibacterial activity, is safe and nontoxic to human bodies and has long-acting effect is assembled on the molecular chain of the matrix resin through chemical reaction, so that the antibacterial master batch is obtained, and can be conveniently applied to the production fields of non-woven fabrics, chemical fibers and the like.

Generally, cell membranes or cell walls of bacteria and fungi contain negatively charged proteins, and assembled antibacterial functional groups have positive charges and are adsorbed to microbial cells under the action of coulomb force to influence the normal respiration and metabolic functions of the cells; or the cell membrane (wall) is broken, and the content flows out, thereby killing the microorganism and achieving the aim of antibiosis. Because the charge environment is the basis for the growth and reproduction of bacteria and fungi, just like air and water are in the human body, and the lack of the charge environment causes the death of the bacteria and fungi, the reason is that the assembled antibacterial technology has broad-spectrum antibacterial performance. But the physical action of the charges has no influence on the human body, thereby ensuring the use safety. Moreover, because the antibacterial functional group is connected with the matrix polymer material through a chemical bond, the use safety is further ensured, and the long-acting property of the antibacterial effect is also ensured.

However, in the actual use process, the antibacterial functional group is easily adsorbed to the bacteria or dust and impurities in the external environment, so that a 'passivation layer' is formed on the surface layer, the bacteria in the environment cannot be effectively killed, frequent cleaning is required to maintain the sterilization effect, and the wide use of the product is affected.

Disclosure of Invention

The invention aims to overcome the defects and shortcomings that bacteria or impurities in an external environment are easily adsorbed on the surface of the existing antibacterial non-woven fabric in the actual use process, so that a passivation layer is formed on the surface and the bacteria in the environment cannot be effectively killed, and provides a soft antibacterial non-woven fabric and a preparation method thereof.

The invention aims to provide a soft antibacterial non-woven fabric.

The invention also aims to provide a preparation method of the soft antibacterial non-woven fabric.

The above purpose of the invention is realized by the following technical scheme:

a soft antibacterial non-woven fabric comprises non-woven fabric fibers, citric acid and antibacterial metal ions;

the antibacterial metal ions are chelated and adsorbed by citric acid;

the non-woven fabric fibers are porous non-woven fabric fibers, and pores of the porous non-woven fabric fibers are in a through hole structure, so that the citric acid is distributed in the pores and can be in contact with the outside.

According to the technical scheme, citric acid chelated with antibacterial metal ions is introduced into the non-woven fabric fibers, and the citric acid is used as an essential raw material in a tricarboxylic acid cycle and participates in the respiration cycle of bacteria in the self respiration process of the microorganisms;

firstly, citric acid has a certain weak antibacterial effect, once bacteria are adsorbed on the surface of the non-woven fabric, the citric acid adsorbed in the non-woven fabric is absorbed by the bacteria and participates in the cycle of the bacterial tricarboxylic acid, so that the citric acid in the non-woven fabric is consumed, after the consumption, metal ions chelated by the citric acid and having the antibacterial effect are released, so that the sterilization effect is exerted, in addition, as the consumption of the citric acid is accompanied in the cycle process of the tricarboxylic acid, new citric acid is generated, the adsorption sites of bacterial thalli on the surface of the non-woven fabric are changed along with the consumption and the cycle regeneration of the citric acid, the dead thalli fall off from the surface of the non-woven fabric due to the change of the adsorption sites and lack of biological activity, and the new citric acid is continuously used as an active component to fix the metal ions having the antibacterial effect on the surface of the non-woven fabric.

Preferably, the antibacterial metal ion is selected from at least one of silver ion, copper ion or zinc ion.

Preferably, between the pores and the citric acid, a polydopamine intermediate layer is filled.

According to the technical scheme, the polydopamine layer is further introduced, and the porous channel of the non-woven fabric fibers is treated by the polydopamine layer, so that the adsorption and fixation effects of the pores of the non-woven fabric on the citric acid are improved, and the citric acid is prevented from being quickly lost in the processes of preparation, storage and use of products.

Preferably, the non-woven fabric fibers comprise the following non-woven fabric fibers with different sizes in parts by weight:

20-40 parts of a material with the length of 3-5cm, the length-diameter ratio of 20: 1-30: 1# nonwoven fiber;

30-40 parts of a material with the length of 300-500 mu m, the length-diameter ratio of 10: 1-15: 1# 2 nonwoven fiber.

According to the technical scheme, the non-woven fabric fibers with different specifications are compounded, and under the condition of the same mass addition, the fibers with relatively smaller specifications can obtain higher bulk density, so that the antibacterial non-woven fabric can obtain a relatively compact antibacterial layer; in addition, the non-woven fabric is formed by stacking fibers in an unordered manner, the long fibers can guarantee the softness and the mechanical property of the product, and after the long fibers and the short fibers are staggered in length, the short fibers are filled in gaps among the long fibers, so that the surface flatness of the non-woven fabric can be improved, and dust stacking is reduced.

Preferably, the thermoplastic elastomer TPE with the mass of non-woven fabric fibers of 3-5% is also included.

A preparation method of a soft antibacterial non-woven fabric comprises the following specific preparation steps:

preparation of porous non-woven fabric fiber:

mixing nano calcium carbonate and polypropylene slices, and extruding in a screw extruder to obtain blended fibers; soaking the blended fiber in hydrochloric acid solution, ultrasonically soaking, filtering, washing and drying to obtain porous non-woven fabric fiber;

modification treatment of porous non-woven fabric fibers:

soaking the porous non-woven fabric fiber in a dopamine solution, adjusting the pH value of the solution to 7.2-7.5, introducing air into the solution, performing ultrasonic impregnation reaction, taking out the porous non-woven fabric fiber, and drying to obtain a pretreated porous non-woven fabric fiber;

mixing and dissolving citric acid and an antibacterial metal salt solution, adding the pretreated porous non-woven fabric fiber, carrying out ultrasonic impregnation, filtering, and drying to obtain the modified porous non-woven fabric fiber.

Preferably, the antibacterial metal salt is selected from at least one of silver nitrate, copper sulfate, copper chloride, copper nitrate, zinc sulfate, zinc chloride, and zinc nitrate.

Preferably, the specific preparation steps further comprise: in the preparation process of the non-woven fabric fiber, when the nano calcium carbonate and the polypropylene slices are mixed, thermoplastic elastomer TPE (thermoplastic elastomer) accounting for 3-5% of the mass of the polypropylene slices is added.

Above-mentioned technical scheme is further in the product preparation process, add thermoplastic elastomer, on the one hand, when the product preparation, in getting into thermoplastic elastomer along with the hydrone, arouse the elastomer to take place certain degree inflation, thereby make porous non-woven fabrics fibre pore contraction, after the drying, the elastomer volume shrinks, certain passageway has been left in the pore, thereby the moisture absorption gas permeability of non-woven fabrics has been guaranteed, good moisture absorption is ventilative, mean that the non-woven fabrics has good mass transfer process inside and outside, do benefit to the transmission of antibiotic component, also can follow the antibiotic persistence of improvement product to a certain extent.

Detailed Description

The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.

Unless otherwise indicated, reagents and materials used in the following examples are commercially available.

Example 1

Preparation of porous non-woven fabric fiber:

according to the weight portion, 5 portions of nano calcium carbonate, 120 portions of polypropylene slices and 3% of thermoplastic elastomer TPE (thermoplastic elastomer) of the polypropylene slices are sequentially added into a mixer, stirred and mixed, poured into a screw extruder for forming, and then sieved out, wherein the length distribution is 3-5cm, and the length-diameter ratio distribution is 20: 1-30: 1, and the length distribution is 300-: 1-15: 1, taking 20 parts of 1# non-woven fabric fiber and 30 parts of 2# non-woven fabric fiber to compound according to parts by weight to obtain blended fiber;

soaking the blend fiber in a hydrochloric acid solution with the mass fraction of 3%, ultrasonically soaking for 60min under the condition that the ultrasonic frequency is 60kHz, filtering, collecting a filter cake, washing the filter cake for 3 times by using deionized water, transferring the washed filter cake into an oven, and drying the filter cake to constant weight under the condition that the temperature is 55 ℃ to obtain porous non-woven fabric fibers;

modification treatment of porous non-woven fabric fibers:

soaking the porous non-woven fabric fibers in a dopamine solution with the concentration of 2g/L, adjusting the pH value of the solution to 7.2, introducing air into the solution at the rate of 30mL/min, continuously introducing the air for 10min, continuously performing ultrasonic treatment at the frequency of 60kHz in the air introduction process, then taking out the porous non-woven fabric fibers, and drying the porous non-woven fabric fibers to constant weight at the temperature of 55 ℃ to obtain pretreated porous non-woven fabric fibers;

citric acid and an antibacterial metal salt solution with the mass fraction of 3% are mixed according to the mass ratio of 1: 10 to obtain a citric acid mixed solution, and mixing the pretreated porous non-woven fabric fibers and the citric acid mixed solution according to a mass ratio of 10: 1, mixing, ultrasonically dipping for 45min under the condition that the ultrasonic frequency is 90kHz, filtering, collecting a filter cake, and drying the obtained filter cake to constant weight under the condition that the temperature is 55 ℃ to obtain modified porous non-woven fabric fibers; the antibacterial metal salt is silver nitrate;

and preparing the soft antibacterial non-woven fabric product from the obtained modified porous non-woven fabric fibers by a spunlace process.

Example 2

Preparation of porous non-woven fabric fiber:

according to the weight portion, sequentially taking 8 portions of nano calcium carbonate, 130 portions of polypropylene slices and 4% of thermoplastic elastomer TPE (thermoplastic elastomer) of the polypropylene slices, adding the materials into a mixer, stirring and mixing the materials, pouring the mixture into a screw extruder for forming, and then screening out the materials with the length of 3-5cm and the length-diameter ratio of 20: 1-30: 1, and a length of 300-500 μm, an aspect ratio of 10: 1-15: the 2# non-woven fabric fiber of 1 is compounded by 30 parts of the 1# non-woven fabric fiber and 35 parts of the 2# non-woven fabric fiber according to the parts by weight to obtain blended fiber;

soaking the blended fibers in a hydrochloric acid solution with the mass fraction of 4%, ultrasonically soaking for 70min under the condition that the ultrasonic frequency is 80kHz, filtering, collecting a filter cake, washing the filter cake for 4 times by using deionized water, transferring the washed filter cake into an oven, and drying at the temperature of 58 ℃ to constant weight to obtain porous non-woven fibers;

modification treatment of porous non-woven fabric fibers:

soaking the porous non-woven fabric fibers in a dopamine solution with the concentration of 3g/L, adjusting the pH value of the solution to 7.4, introducing air into the solution at the rate of 40mL/min, continuously introducing the air for 15min, continuously performing ultrasonic treatment at the frequency of 80kHz in the air introducing process, then taking out the porous non-woven fabric fibers, and drying the porous non-woven fabric fibers at the temperature of 58 ℃ to constant weight to obtain pretreated porous non-woven fabric fibers;

citric acid and an antibacterial metal salt solution with the mass fraction of 4% are mixed according to the mass ratio of 1: 12, mixing and dissolving to obtain a citric acid mixed solution, and mixing the pretreated porous non-woven fabric fibers with the citric acid mixed solution according to a mass ratio of 15: 1, performing ultrasonic impregnation for 55min under the condition that the ultrasonic frequency is 100kHz, filtering, collecting a filter cake, and drying the obtained filter cake to constant weight under the condition that the temperature is 58 ℃ to obtain modified porous non-woven fabric fibers; the antibacterial metal salt is copper sulfate;

and preparing the soft antibacterial non-woven fabric product from the obtained modified porous non-woven fabric fibers by a spunlace process.

Example 3

Preparation of porous non-woven fabric fiber:

according to the weight portion, 10 portions of nano calcium carbonate, 150 portions of polypropylene slices and 5% of thermoplastic elastomer TPE (thermoplastic elastomer) of the polypropylene slices are sequentially added into a mixer, stirred and mixed, poured into a screw extruder for forming, and then sieved out, wherein the length is 3-5cm, and the length-diameter ratio is 20: 1-30: 1, and a length of 300-500 μm, an aspect ratio of 10: 1-15: the 2# non-woven fabric fiber of 1 is compounded by 40 parts of the 1# non-woven fabric fiber and 40 parts of the 2# non-woven fabric fiber according to the parts by weight to obtain blended fiber;

soaking the blended fibers in a hydrochloric acid solution with the mass fraction of 5%, ultrasonically soaking for 80min under the ultrasonic frequency of 90kHz, filtering, collecting a filter cake, washing the filter cake for 5 times by using deionized water, transferring the washed filter cake into an oven, and drying at the temperature of 60 ℃ to constant weight to obtain porous non-woven fibers;

modification treatment of porous non-woven fabric fibers:

soaking the porous non-woven fabric fibers in a dopamine solution with the concentration of 5g/L, adjusting the pH value of the solution to 7.5, introducing air into the solution at the rate of 50mL/min, continuously introducing the air for 20min, continuously performing ultrasonic treatment at the frequency of 90kHz in the air introducing process, then taking out the porous non-woven fabric fibers, and drying the porous non-woven fabric fibers at the temperature of 60 ℃ to constant weight to obtain pretreated porous non-woven fabric fibers;

citric acid and an antibacterial metal salt solution with the mass fraction of 5% are mixed according to the mass ratio of 1: 15 to obtain a citric acid mixed solution, and mixing the pretreated porous non-woven fabric fibers and the citric acid mixed solution according to a mass ratio of 20: 1, mixing, ultrasonically dipping for 60min under the condition that the ultrasonic frequency is 120kHz, filtering, collecting a filter cake, and drying the obtained filter cake to constant weight under the condition that the temperature is 60 ℃ to obtain modified porous non-woven fabric fibers; the antibacterial metal salt is copper nitrate;

and preparing the soft antibacterial non-woven fabric product from the obtained modified porous non-woven fabric fibers by a spunlace process.

Example 4

This example differs from example 1 in that: and replacing the dopamine solution with deionized water with equal mass, and keeping the rest conditions unchanged.

Example 5

This example differs from example 1 in that: the thermoplastic elastomer was not added and the remaining conditions were kept unchanged.

Example 6

Preparation of porous non-woven fabric fiber:

according to the weight portion, 5 portions of nano calcium carbonate, 120 portions of polypropylene slices and 3% of thermoplastic elastomer TPE (thermoplastic elastomer) of the polypropylene slices are sequentially added into a mixer, stirred and mixed, poured into a screw extruder for forming, and then sieved out, wherein the length distribution is 3-5cm, and the length-diameter ratio distribution is 20: 1-30: 1 to obtain blended fiber;

soaking the blend fiber in a hydrochloric acid solution with the mass fraction of 3%, ultrasonically soaking for 60min under the condition that the ultrasonic frequency is 60kHz, filtering, collecting a filter cake, washing the filter cake for 3 times by using deionized water, transferring the washed filter cake into an oven, and drying the filter cake to constant weight under the condition that the temperature is 55 ℃ to obtain porous non-woven fabric fibers;

modification treatment of porous non-woven fabric fibers:

soaking the porous non-woven fabric fibers in a dopamine solution with the concentration of 2g/L, adjusting the pH value of the solution to 7.2, introducing air into the solution at the rate of 30mL/min, continuously introducing the air for 10min, continuously performing ultrasonic treatment at the frequency of 60kHz in the air introduction process, then taking out the porous non-woven fabric fibers, and drying the porous non-woven fabric fibers to constant weight at the temperature of 55 ℃ to obtain pretreated porous non-woven fabric fibers;

citric acid and an antibacterial metal salt solution with the mass fraction of 3% are mixed according to the mass ratio of 1: 10 to obtain a citric acid mixed solution, and mixing the pretreated porous non-woven fabric fibers and the citric acid mixed solution according to a mass ratio of 10: 1, mixing, ultrasonically dipping for 45min under the condition that the ultrasonic frequency is 90kHz, filtering, collecting a filter cake, and drying the obtained filter cake to constant weight under the condition that the temperature is 55 ℃ to obtain modified porous non-woven fabric fibers; the antibacterial metal salt is silver nitrate;

and preparing the soft antibacterial non-woven fabric product from the obtained modified porous non-woven fabric fibers by a spunlace process.

Comparative example 1

This comparative example differs from example 1 in that: EDTA with equal mass is adopted to replace citric acid, and other conditions are kept unchanged.

The products of examples 1-6 and comparative example 1 were tested for performance, and the specific test methods and test results are described below;

taking the concentration of 5.6 multiplied by 10⁵Each 100mL of cfu/mL bacterial suspension (Staphylococcus epidermidis AATCC35982, Escherichia coli) with the final concentration of 5.6X 10⁴cfu/mL) of the sample, the sample is uniformly smeared on the surface of a culture dish containing nutrient agar and having a diameter of 200mm, sample sheets of the non-woven fabric products obtained in each example and each comparative example are respectively taken, a circular sample sheet with a diameter of 6mm is selected as the sample sheet, the sample sheet is placed on the surface of the culture dish, the diameter of a bacteriostatic circle around the sample sheet is measured by a vernier caliper after the sample sheet is placed in a constant temperature incubator at 37 ℃ for standing and culturing for 36 hours, and the specific test results are shown in Table 1:

table 1: product performance test results

	Diameter of zone of inhibition
		Example 1	15.6mm
Example 2	16.2mm
		Example 3	15.9mm
Example 4	14.2mm
		Example 5	13.8mm
Example 6	12.9mm
		Comparative example 1	8.2mm

According to the test results, the scheme of the invention has good bacteriostatic effect and can effectively kill bacteria in the environment.

The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.