阅读说明：本技术 一种持久抗菌聚酰胺面料的制备方法 (Preparation method of polyamide fabric with lasting antibacterial effect ) 是由 王维明 肖燕 于 2020-07-09 设计创作，主要内容包括：本发明公开了一种持久抗菌聚酰胺面料的制备方法,包括：将聚酰胺面料置于无机酸溶液中酸处理,排液,用氢氧化钠溶液中和,水洗至中性,烘干获得改性聚酰胺面料；将十二烷基苯磺酸钠加入到盐酸水溶液中,搅拌,使所述十二烷基苯磺酸钠充分溶解,再加入抗菌剂,搅拌使所述抗菌剂分散均匀,逐渐加入前驱体,待所述前驱体加完之后,继续搅拌,接着升温在搅拌的条件下反应,获得复合抗菌剂；在复合抗菌剂中加入次亚磷酸钠,再用碱剂将pH值调节,采用二浸二轧的方法对所述改性聚酰胺面料进行改性,轧焙烘,水洗,烘干,制成持久抗菌聚酰胺面料。本发明工艺简单、条件易控制,制取的聚酰胺面料具有广谱、高效和持久的抗菌性。(The invention discloses a preparation method of a lasting antibacterial polyamide fabric, which comprises the following steps: placing the polyamide fabric in an inorganic acid solution for acid treatment, discharging liquid, neutralizing with a sodium hydroxide solution, washing with water to be neutral, and drying to obtain a modified polyamide fabric; adding sodium dodecyl benzene sulfonate into a hydrochloric acid aqueous solution, stirring to fully dissolve the sodium dodecyl benzene sulfonate, adding an antibacterial agent, stirring to uniformly disperse the antibacterial agent, gradually adding a precursor, continuing stirring after the precursor is added, and then heating to react under the stirring condition to obtain a composite antibacterial agent; adding sodium hypophosphite into the composite antibacterial agent, adjusting the pH value by using an alkaline agent, modifying the modified polyamide fabric by adopting a two-dipping and two-rolling method, rolling, baking, washing and drying to prepare the durable antibacterial polyamide fabric. The invention has simple process and easily controlled conditions, and the prepared polyamide fabric has broad-spectrum, high-efficiency and lasting antibacterial property.)

1. A preparation method of a lasting antibacterial polyamide fabric is characterized by comprising the following steps:

(1) fiber surface modification treatment: placing polyamide fabric in an inorganic acid solution, carrying out acid treatment for 10-30min at the temperature of 25-35 ℃, discharging liquid, neutralizing with a sodium hydroxide solution, washing with water to be neutral, and drying for 30-60min at the temperature of 80-100 ℃ to obtain modified polyamide fabric;

(2) preparing a composite antibacterial agent: adding sodium dodecyl benzene sulfonate into a hydrochloric acid aqueous solution, stirring for 30-60min at the temperature of 25 ℃ to fully dissolve the sodium dodecyl benzene sulfonate, adding an antibacterial agent, continuously stirring for 30-60min to uniformly disperse the antibacterial agent, gradually adding a precursor within 20-30min, continuously stirring for 20-30min after the precursor is added, heating to 50-60 ℃ at the heating rate of 1-2 ℃/min, and reacting for 3-4h under the stirring condition to obtain a composite antibacterial agent, wherein the stirring rotation speed is 150-;

(3) modified fabric antibacterial finishing: adding sodium hypophosphite into the composite antibacterial agent, adjusting the pH value to 6-7 by using an alkaline agent, modifying the modified polyamide fabric by adopting a two-dipping two-rolling method at room temperature, wherein the rolling residue is 80-100%, baking for 5-15min at the temperature of 80-90 ℃, baking for 1-5min at the temperature of 130-150 ℃, washing with water, and finally drying at the temperature of 80-100 ℃ to prepare the durable antibacterial polyamide fabric.

2. The preparation method of the lasting antibacterial polyamide fabric according to claim 1, characterized in that: the polyamide fabric in the step (1) is any one of a polyamide filament fabric, a polyamide short fiber and polyamide filament interwoven fabric, a polyamide short fiber and polyamide filament core-spun yarn fabric, and a fabric made of a polyamide short fiber and polyamide filament drawing and twisting yarn.

3. The preparation method of the lasting antibacterial polyamide fabric according to claim 1, characterized in that: in the step (1), the mass percentage concentration of the inorganic acid solution is 3-8%, the inorganic acid in the inorganic acid solution is selected from any one of hydrochloric acid, sulfuric acid and nitric acid, and the mass percentage concentration of the sodium hydroxide solution is 1-3%.

4. The preparation method of the lasting antibacterial polyamide fabric according to claim 1, characterized in that: in the step (1), in the acid treatment process, the mass ratio of the polyamide fabric to the inorganic acid solution is 1-150, and in the water washing to neutrality process, the mass ratio of the polyamide fabric to the sodium hydroxide solution is 1-105.

5. The preparation method of the lasting antibacterial polyamide fabric according to claim 1, characterized in that: in the step (2), the antibacterial agent is selected from any one or a mixture of several of a metal antibacterial agent, an organic antibacterial agent and a natural antibacterial agent, wherein the metal antibacterial agent is selected from any one of a silver-series antibacterial agent, a copper-series antibacterial agent and a zinc-series antibacterial agent, the organic antibacterial agent is selected from any one of quaternary ammonium salt or quaternary phosphonium salt containing siloxane groups, and the natural antibacterial agent is selected from chitosan with deacetylation degree of 80-90%.

6. The preparation method of the lasting antibacterial polyamide fabric according to claim 1, characterized in that: the precursor in the step (2) is selected from any one or more of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane and ethyltriethoxysilane.

7. The preparation method of the lasting antibacterial polyamide fabric according to claim 1, characterized in that: in the step (2), the precursor is 20-40g/L, the sodium dodecyl benzene sulfonate is 0.5-1g/L, the hydrochloric acid is 3-5g/L, and the antibacterial agent is 5-10 g/L.

8. The preparation method of the lasting antibacterial polyamide fabric according to claim 1, characterized in that: the particle size of the composite antibacterial agent in the step (2) is 50-100 nm.

9. The preparation method of the lasting antibacterial polyamide fabric according to claim 1, characterized in that: the alkaline agent in the step (3) is sodium hydroxide solution with the mass concentration of 5-10 g/L.

10. The preparation method of the lasting antibacterial polyamide fabric according to claim 1, characterized in that: in the step (3), the sodium hypophosphite is 5-10 g/L.

Technical Field

The invention belongs to the field of textiles, and particularly relates to a processing technology of a durable antibacterial polyamide fabric.

Background

The textile has a loose and porous structure, so that excrement secreted by metabolism of a human body can be easily absorbed, a favorable place and required nutrients are provided for attachment and propagation of microorganisms, and a large amount of germs are propagated. The presence of microorganisms on textiles not only affects their performance (e.g., mildew, catalysis, deterioration, etc.), but also poses serious threats to the health of the wearer (e.g., skin disorders, diseases induced by entry into the body, etc.). Therefore, the antibacterial finishing is carried out on the textile to hinder and inhibit the metabolism and reproduction of microorganisms in the using and storing processes of the textile, and the antibacterial finishing has important significance for protecting human health. In recent years, antibacterial textiles have become a focus of research in the field of functional textiles. New coronavirus has been abused in 2019, and by the time that countries and regions affected by epidemic situations are more than 200, infected persons are over 1100 and over ten thousand, and death persons are over 50 and over ten thousand. The rapid propagation of new coronavirus makes the research and development of antibacterial and antiviral textile fabric become the research focus at home and abroad.

The antibacterial textile is usually realized by adding an antibacterial agent into the textile, and the preparation method mainly comprises a fibril method and a post-finishing method, and also can realize the antibacterial function by a blending or interweaving method. The fibril method is that antibacterial agent is added into spinning solution to prepare antibacterial fiber through a spinning process, and the fabric prepared by the method has obvious and lasting antibacterial property, but has the defects of high technical difficulty, high cost and the like. The blending or interweaving method is to compound the fiber with antibacterial property and the common fiber to prepare the antibacterial fabric, and the antibacterial effect of the fabric is mainly determined by the content of the antibacterial fiber. The post-finishing method is to apply an antibacterial agent to the surface of the fiber by coating or padding to endow the fabric with an antibacterial effect, and is the most studied antibacterial fabric preparation method at present due to simple operation, but the antibacterial durability of the fabric prepared by the method is to be further improved.

The antibacterial finishing agent is one of important factors influencing the antibacterial effect of the fabric. The antibacterial finishing agent can be divided into inorganic antibacterial agent, organic antibacterial agent and natural antibacterial agent according to factors such as the source, action mechanism, composition structure and the like of the antibacterial finishing agent. The inorganic antibacterial agent mainly comprises silver and copper, wherein silver is high in price and is easily oxidized to generate dark silver oxide or black simple substance silver, copper is low in price and has a certain antiviral effect, and the color of the copper can change the color of the fabric. The organic antibacterial agent mainly comprises quaternary ammonium salts, guanidines, halogenated phenols and halogen amines, and the antibacterial agent generally has high toxicity and is easy to cause bacteria to generate drug resistance. The natural antibacterial agent has the advantages of good biocompatibility, natural degradation, no drug resistance of bacteria and the like, and is an antibacterial agent with great development potential. In order to meet the increasing demands of people on health, comfort and safety, an ideal antibacterial finishing agent should have the characteristics of safety, broad spectrum, durability and the like, and simultaneously have no obvious influence on the original excellent characteristics and appearance of textiles.

Therefore, a further solution is necessary to overcome the defects of the existing antibacterial protective fabric.

Disclosure of Invention

The invention aims to provide a preparation method of a polyamide fabric with lasting antibacterial property, and the preparation method is used for solving the problems.

The technical scheme of the invention is as follows:

a preparation method of a lasting antibacterial polyamide fabric comprises the following steps:

(1) fiber surface modification treatment: placing polyamide fabric in an inorganic acid solution, carrying out acid treatment for 10-30min at the temperature of 25-35 ℃, discharging liquid, neutralizing with a sodium hydroxide solution, washing with water to be neutral, and drying for 30-60min at the temperature of 80-100 ℃ to obtain modified polyamide fabric;

(2) preparing a composite antibacterial agent: adding sodium dodecyl benzene sulfonate into a hydrochloric acid aqueous solution, stirring for 30-60min at the temperature of 25 ℃ to fully dissolve the sodium dodecyl benzene sulfonate, adding an antibacterial agent, continuously stirring for 30-60min to uniformly disperse the antibacterial agent, gradually adding a precursor within 20-30min, continuously stirring for 20-30min after the precursor is added, heating to 50-60 ℃ at the heating rate of 1-2 ℃/min, and reacting for 3-4h under the stirring condition to obtain a composite antibacterial agent, wherein the stirring rotation speed is 150-;

(3) modified fabric antibacterial finishing: adding sodium hypophosphite into the composite antibacterial agent, adjusting the pH value to 6-7 by using an alkaline agent, modifying the modified polyamide fabric by adopting a two-dipping two-rolling method at room temperature, wherein the rolling residue is 80-100%, baking for 5-15min at the temperature of 80-90 ℃, baking for 1-5min at the temperature of 130-150 ℃, washing with water, and finally drying at the temperature of 80-100 ℃ to prepare the durable antibacterial polyamide fabric.

Further, the polyamide fabric in the step (1) is selected from any one of a polyamide filament fabric, a polyamide staple fiber and polyamide filament interwoven fabric, a polyamide staple fiber and polyamide filament core spun yarn fabric, and a fabric made of a polyamide staple fiber and polyamide filament drawn and twisted yarn.

Further, in the step (1), the mass percentage concentration of the inorganic acid solution is 3-8%, the inorganic acid in the inorganic acid solution is selected from any one of hydrochloric acid, sulfuric acid and nitric acid, and the mass percentage concentration of the sodium hydroxide solution is 1-3%.

Further, in the step (1), in the acid treatment process, the mass ratio of the polyamide fabric to the inorganic acid solution is 1-150, and in the water washing to neutrality process, the mass ratio of the polyamide fabric to the sodium hydroxide solution is 1-150.

Further, in the step (2), the antibacterial agent is selected from any one or a mixture of several of a metal antibacterial agent, an organic antibacterial agent and a natural antibacterial agent, wherein the metal antibacterial agent is selected from any one of silver-based, copper-based and zinc-based antibacterial agents, the organic antibacterial agent is selected from any one of quaternary ammonium salts or quaternary phosphonium salts containing siloxane groups, and the natural antibacterial agent is selected from chitosan with deacetylation degree of 80-90%.

Further, the precursor in the step (2) is selected from any one or more of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane and ethyltriethoxysilane.

Further, in the step (2), the precursor is 20-40g/L, the sodium dodecyl benzene sulfonate is 0.5-1g/L, the hydrochloric acid is 3-5g/L, and the antibacterial agent is 5-10 g/L.

Further, in the step (2), the composite antibacterial agent takes polysiloxane sol as a carrier, the antibacterial agent is fixed in the grid, and the particle size of the polysiloxane sol is 50-100 nm.

Further, the alkaline agent in the step (3) is sodium hydroxide solution with the mass concentration of 5-10 g/L.

Further, the sodium hypophosphite in the step (3) is 5-10 g/L.

The invention provides a preparation method of a lasting antibacterial polyamide fabric, which adopts polysiloxane sol as a carrier, fixes a plurality of antibacterial agents in grids to prepare a composite antibacterial agent, and then uses the composite antibacterial agent for antibacterial finishing of textiles, and has the following advantages:

1. the process is simple, and the process parameters are stable and easy to control;

2. the fabric has broad-spectrum antibacterial property;

3. the fabric has lasting antibacterial ability and good washability.

Detailed Description

The invention discloses a preparation method of a lasting antibacterial polyamide fabric, which comprises the following specific process steps:

firstly, fiber surface modification treatment

The method specifically comprises the following steps: the method comprises the steps of placing a polyamide fabric in an inorganic acid solution with the mass percentage concentration of 3-8%, wherein the polyamide fabric is one of a polyamide filament fabric, a polyamide short fiber and polyamide filament interwoven fabric, a polyamide short fiber and polyamide filament core-spun yarn fabric, and a fabric made by drawing and twisting polyamide short fiber and polyamide filament, the inorganic acid is any one of hydrochloric acid, sulfuric acid and nitric acid, carrying out acid treatment for 10-30min at the temperature of 25-35 ℃, discharging liquid, neutralizing with a sodium hydroxide solution with the mass percentage concentration of 1-3%, washing with water to be neutral, and drying for 30-60min at the temperature of 80-100 ℃. The mass ratio of the fiber to the treatment liquid in the processes of acid treatment, water washing and neutralization is 1: 5-10.

The principle of the step is as follows: the amido bond in the molecular structure of the nylon fiber is easy to hydrolyze under the acidic condition to generate two reactive groups of amido and carboxyl, the reactivity of the fiber surface and a chemical auxiliary agent can be improved by acid hydrolysis, and common acid agents comprise hydrochloric acid, nitric acid and sulfuric acid. In addition, the acid hydrolysis process is a surface-to-interior process, and can be controlled by conditions, and the acid hydrolysis is utilized to generate a rough structure on the surface of the fiber, so that the specific surface area of the fiber is increased, and the loading capacity of the fiber for the antibacterial agent is further improved.

Preparation of composite antibacterial agent

Adding 0.5-1g/L sodium dodecyl benzene sulfonate into 3-5g/L hydrochloric acid aqueous solution, stirring at 25 deg.C for 30-60min to fully dissolve the sodium dodecyl benzene sulfonate, adding 5-10g/L antibacterial agent selected from one or more of metal antibacterial agent, organic antibacterial agent and natural antibacterial agent, wherein the metal antibacterial agent is preferably silver-based, copper-based or zinc-based antibacterial agent, the organic antibacterial agent is preferably quaternary ammonium salt or quaternary phosphonium salt containing siloxane group, and the natural antibacterial agent is preferably chitosan with deacetylation degree of 80-90%. Stirring for 30-60min to disperse the antibacterial agent uniformly, and gradually adding 20-40g/L precursor selected from one or more of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane and ethyltriethoxysilane within 20-30 min. After the precursor is added, the mixture is continuously stirred for 20-30min, then the temperature is raised to 50-60 ℃ at the speed of 1-2 ℃/min, the mixture reacts for 3-4h under the stirring condition, and the composite antibacterial agent with the particle size of 50-100nm is obtained, wherein the stirring speed in the step is 150-.

The principle of the step is as follows: the invention selects polysiloxane hydrosol as a carrier to prepare the composite antibacterial agent, and the composite antibacterial agent is based on the following points: the polysiloxane hydrosol has good film-forming property, and silicon hydroxyl (-Si-OH) which is not subjected to self-crosslinking can be chemically formed with carboxyl (-COOH) formed by hydrolysis on the surface of fiber to form a film, and a plurality of antibacterial agents are fixed in a sol grid by fiber, alkoxy in siloxane groups is hydrolyzed to generate silicon hydroxyl (Si-OH) to perform chemical reaction, so that firm valence bond combination is formed, and the load fastness of the antibacterial agents on the surface of the fiber is improved; the mesh formed by dehydrating the silicon hydroxyl groups can lock the antibacterial agent and improve the washability of the fabric finished by the antibacterial agent.

Third, modified fabric antibacterial finishing

Adding 5-10g/L sodium hypophosphite into the composite antibacterial agent, adjusting the pH value to 6-7 by using an alkaline agent, wherein the alkaline agent is a sodium hydroxide solution with the mass concentration of 5-10g/L, modifying the fabric by adopting a two-dipping two-rolling method at room temperature, baking the fabric for 5-15min at the temperature of 80-90 ℃ and baking the fabric for 1-5min at the temperature of 130-150 ℃, washing the fabric with water, and baking the fabric at the temperature of 80-100 ℃.

The principle of the step is as follows: the effective hydrolysis of the precursor of the polysiloxane hydrosol is the basis for preparing the silica sol, and the acidity adjustment is beneficial to the hydrolysis of the precursor. However, polyamide fibers are susceptible to hydrolysis under acidic conditions, which in turn affects the performance properties of the fabric. The pH value of the silica sol is adjusted to 6-7, which can not cause the rapid condensation of the sol particles and can not cause obvious influence on the fiber strength.

In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, embodiments accompanying the present invention are further described below. The invention is not limited to the embodiments listed but also comprises any other known variations within the scope of the invention as claimed.

Reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic may be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.

Comparative example

Modifying the polyamide fabric by adopting a two-dipping two-rolling method at room temperature, wherein the dosage of the polysiloxane quaternary ammonium salt antibacterial agent is 10g/L, the rolling residual rate is 90%, baking is carried out for 4min at 90 ℃, baking is carried out for 1min at 130 ℃, washing is carried out, and drying is carried out at 80 ℃.