WO2021232870A1

WO2021232870A1 - Copper-containing, antimicrobial and antiviral non-woven fabric and preparation method therefor

Info

Publication number: WO2021232870A1
Application number: PCT/CN2021/077409
Authority: WO
Inventors: 许东东; 许心愿
Original assignee: 华盛爽朗纺织品（北京）有限公司
Priority date: 2020-05-19
Filing date: 2021-02-23
Publication date: 2021-11-25
Also published as: US20210363689A1; CN113684607A

Abstract

A copper-containing, antimicrobial and antiviral non-woven fabric and a preparation method therefor. The preparation method therefor comprises the following steps: subjecting a fiber material to fiber web formation, pre-wetting and spunlaced reinforcement in order to obtain a spunlaced fiber cloth-based fabric; subjecting the spunlaced fiber cloth-based fabric to padding and sizing in an organic complex copper solution, in order to obtain a copper-containing spunlaced non-woven fabric, with the copper content on the copper-containing spunlaced non-woven fabric being ≥500 ppm; and subjecting the copper-containing spunlaced non-woven fabric obtained from padding and sizing to drying and winding. The method has the advantages of easy industrialization, a simple process and a short production cycle; the copper-containing, antimicrobial and antiviral non-woven fabric prepared by the method has excellent antimicrobial and antiviral properties; and the copper-containing, antimicrobial and antiviral non-woven fabric can be widely used.

Description

Copper-containing antibacterial and antiviral non-woven fabric and preparation method thereof

Technical field

This application relates to the technical field of non-woven fabrics, and more specifically, it relates to a copper-containing antibacterial and antiviral non-woven fabric and a preparation method thereof.

Background technique

With the rapid spread of large-scale, highly infectious diseases, the market demand for antibacterial nonwoven materials has rapidly increased, and higher requirements have been placed on the antibacterial properties of nonwoven materials. Development of nonwoven materials with good antibacterial and antibacterial properties Has become one of the current hot spots in the field of non-woven fabrics.

Spunlace non-woven fabrics are fabrics in which high-pressure fine water jets are sprayed onto one or more layers of fiber webs to entangle the fibers so that the webs can be reinforced and have a certain strength. Because of its advantages of high strength, low fuzz, high moisture absorption and good air permeability, spunlace nonwovens have become one of the fastest technological advancements in the nonwovens industry in recent years, and are widely used in medical and sanitary nonwovens. Fabrics, non-woven fabrics for home decoration, non-woven fabrics for clothing, non-woven fabrics for industrial use, non-woven fabrics for agricultural use, etc. In particular, in recent years, while the demand for medical and health non-woven fabrics has greatly increased, higher requirements have been placed on its antibacterial and antiviral properties.

However, non-woven fabrics are conducive to the adhesion of microorganisms due to their porous shape and the chemical structure of polymer compounds. Therefore, the research and development of antibacterial functions of spunlace non-woven fabrics is of great significance.

Summary of the invention

In view of the shortcomings of the prior art, in the first aspect, this application provides a method for preparing copper-containing antibacterial and antiviral non-woven fabrics, which has good antibacterial properties and a certain degree of antiviral spunlace. The woven fabric has the advantages of simple preparation method, easy realization of industrialization, and simple process.

Specifically, this application provides the following technical solution: a method for preparing a copper-containing antibacterial and antiviral non-woven fabric, including the following steps:

Preparation of spunlace non-woven fabric base fabric: the fiber material is successively subjected to fiber web formation, pre-wetting, and spunlace reinforcement to obtain a spunlace fiber fabric base fabric;

Padding and sizing: the spunlace fiber cloth base fabric is padding sizing in an organic complex copper solution to obtain a copper-containing spunlace non-woven fabric, and the copper content of the copper-containing spunlace non-woven fabric is ≥500ppm;

The copper-containing spunlace non-woven fabric obtained after padding and sizing is dried and wound.

By adopting the above technical solution, the copper element has a strong bactericidal function and a certain antiviral effect. In this application, the spunlace non-woven fabric is padding sizing in the organic complex copper solution. On the one hand, the organic complex copper solution Not only can be coated on the surface of the spunlace non-woven fabric, but also can penetrate into the internal voids of the spunlace non-woven fabric, making the interior of the spunlace non-woven fabric, especially the voids between the fibers and the surface of the spunlace non-woven fabric All have copper ions, which can play a better antibacterial effect. On the other hand, the copper element exists in the form of copper ions between the fibers of the spunlace non-woven fabric, and the antibacterial function is more significant, especially the copper-containing spunlace The control of the copper ion concentration on the non-woven fabric makes the final spunlace non-woven fabric have excellent antibacterial and antiviral effects.

In the process of preparing the spunlace nonwoven fabric in this application, the fibrous material fibers are first formed into a web, then pre-wet, and then reinforced by hydroentanglement. Under the action of hydroentanglement, the fiber web moves, intersperses, entangles, and entangles among the fibers. , Forming countless soft entanglement points, consolidating the fiber web to obtain the spunlace fiber cloth base fabric. The pre-wetting operation compacts the fluffy fiber web, venting the air in the fiber web, so that the fiber web can enter the spunlace area. Effectively absorb the energy of the water jet, strengthen the fiber entanglement effect, and make the copper ions in the organic complex copper solution more firmly embedded in the fiber surface and the fiber during the subsequent padding and sizing, and strengthen the copper ion and the fiber web. Bonding strength, and the resulting spunlace non-woven fabric has excellent antibacterial properties.

In addition, compared to the method of directly using antibacterial fibers, the spunlace non-woven fabric in the present application is directly padding sizing after fiber formation and spunlace reinforcement during the production process. On the one hand, the operation is more simple and convenient, and the process cycle is more convenient. Shorter, large-scale production of spunlace non-woven fabrics in a short period of time, to meet the supply, and can meet the performance of non-woven fabrics, and has excellent antibacterial and antiviral properties. It can be used in disposable medical supplies. It is of great significance to meet the demand and supply of various medical supplies; on the other hand, padding through the organic complex copper solution makes the gaps and areas of the spunlace non-woven fabric evenly infiltrated, and the antibacterial effect is uniform, which can effectively avoid Precipitation of substances in the holes of the spunlace non-woven fabric after drying.

The application is further provided that: the fiber material includes at least one of natural fiber, rayon fiber, rayon protein fiber, polyacrylonitrile fiber, and polyvinyl alcohol fiber.

By adopting the above technical solution, the molecular structure of the fiber material contains open hydroxyl groups, and the formed spunlace fiber cloth base cloth contains open hydroxyl groups. When the spunlace fiber cloth base cloth is dipped in an organic complex copper solution , The complexed copper ions form a chemical chelate with cellulose or protein fibers. The two are firmly combined and are not easy to fall off during use. The spunlace fiber cloth has excellent antibacterial and durable properties.

The application is further set as follows: the fabric obtained after the step of forming the fiber material fiber into the web contains ≥5% cotton fiber, or 5-65% cellulose fiber, or 5-65% protein fiber, or 5-65% poly Acrylonitrile fiber, or 100% low melting point polyvinyl alcohol fiber;

The organic complex copper solution is obtained by adding 5.5 wt% of the initial organic complex copper solution to 10-30 volume multiples of water.

By adopting the above technical scheme, by controlling the fiber content of cotton fiber or cellulose fiber in the cloth obtained after the fiber forming step and the copper ion concentration in the organic complex copper solution, the copper content on the spunlace fiber cloth is finally controlled , Play an excellent anti-bacterial and anti-virus performance.

In addition, when the fabric is 100% low-melting point polyvinyl alcohol fiber, it can be dissolved in low-temperature water, which reduces waste generation, especially for the current medical waste treatment.

This application is further set as: the initial organic complexed copper solution is prepared according to the following method:

Preparation of coordinated ionic liquid: uniformly mix urea, caprolactam and acetamide, and then heat and keep it warm until the caprolactam and urea are uniformly melted and liquefied to obtain the coordinated ionic liquid;

Preparation of organic complex copper solution: add the coordination solid mixture including sodium chloride, potassium permanganate, sodium peroxide and copper powder to the coordination ionic liquid, stir uniformly, react, and pour into pure water after cooling to obtain the copper content It is 5.5wt% of the initial organic copper complex solution.

By adopting the above technical solution, the organic complex copper solution is used in the spunlace non-woven fabric in this application. Compared with inorganic copper, organic copper is safer and more reliable, has good environmental compatibility, and has good compatibility. Its antibacterial effect lasts for a long time, and the copper content on the final spunlace non-woven fabric can be controlled by the copper ion concentration in the initial organic complexed copper solution and the amount of water added, and finally has excellent antibacterial and antiviral properties.

The application is further set as follows: in the step of preparing the coordination ionic liquid, the mixing weight ratio of urea, caprolactam and acetamide is 1: (0.2-0.4): (0.2-0.4), and the heating temperature after uniform mixing is 100-120°C, The holding time is 0.5-1h.

The application is further set as follows: in the step of preparing the organic complex copper solution: the mixing weight ratio of sodium chloride, potassium permanganate, sodium peroxide and copper powder is 1: (1-2): (1-2): ( 2.5-2.9), the mixing weight ratio of the coordination solid mixture and the coordination ionic liquid is 1: (3-3.5).

By adopting the above technical scheme, in the step of preparing the organic complex copper solution, by controlling the mass ratio between sodium chlorate, potassium permanganate, sodium peroxide and copper powder, all the copper powder is oxidized to monovalent ions, which are coordinated with each other. The organics in the ionic liquid chelate to form complex copper.

The application is further configured as follows: when the fiber material is one or more of polyester fiber, polyamide fiber, polyvinyl chloride fiber, and polypropylene fiber, the spunlace fiber cloth base fabric is also shelled before padding and sizing. The dipping step of the glycan-ascorbic acid solution is as follows: the spunlace fiber cloth base cloth is dipped in the chitosan-ascorbic acid solution, and then dried at 150-170℃ for 5-10min, the chitosan-ascorbic acid solution The preparation method is as follows: add 5-10 parts of chitosan powder to 25-30 parts of acetic acid and 60-70 parts of water, magnetically stir until the chitosan is dissolved, then add 3-5 parts of ascorbic acid, and stir evenly.

By adopting the above technical scheme, the molecular structures of chitosan and ascorbic acid both have open hydroxyl groups. The spunlace fiber cloth base fabric is first dipped in a chitosan-ascorbic acid solution, and the chitosan and ascorbic acid are immersed in the spunlace fiber cloth. In the gap, the hydroxyl binding points on the reinforced spunlace fiber cloth base fabric will have more binding sites with the complex copper ions during the subsequent padding in the organic complex copper solution. In addition, compared with divalent copper, the coordination bond of monovalent copper is more covalent, so the stability of monovalent copper complexes is stronger than that of divalent copper complexes. The strong ascorbic acid is used in this application. Reducing, adding ascorbic acid can inhibit the oxidation of monovalent copper to divalent copper, thereby enhancing the antibacterial performance and the durability of antibacterial functions.

Chitosan is also added to the system, and the dissolved chitosan has a strong adsorption capacity. Chitosan can be more firmly attached between the spunlace fiber cloth base cloth, and it can also improve the ascorbic acid and spunlace fiber cloth. The bonding strength between the base fabrics. The addition of acetic acid can dissolve chitosan on the one hand, and on the other hand, it can also enhance the adsorption between chitosan and the spunlace fiber fabric, so that chitosan and ascorbic acid can be more firmly adsorbed on the spunlace fiber fabric. After drying, the chitosan also has certain antibacterial properties and excellent moisture absorption properties, which can further enhance the antibacterial and moisture absorption properties of the spunlace fiber cloth.

The application is further set as follows: the spunlace fiber cloth base cloth is subjected to a soaping step after the chitosan-ascorbic acid solution padding step, and the specific operation is: the dried spunlace fiber cloth base cloth is soaped at 5g/L Medium soaping 5-10min, soaping temperature is 35-40℃, and then drying at 50-60℃.

By adopting the above technical scheme, the spunlace fiber cloth base fabric after the chitosan-ascorbic acid solution is soaked can be soaped, which can remove the weakly bonded chitosan and ascorbic acid on the spunlace fiber cloth base fabric and prevent subsequent soaking. During rolling, chitosan and ascorbic acid enter the organic complexed copper solution and complex with complexed copper ions.

In the second aspect, the present application provides a copper-containing antibacterial and antiviral non-woven fabric, which has the advantages of good antibacterial properties and certain antiviral properties.

Specifically, this application provides the following technical solution: a copper-containing antibacterial and antiviral non-woven fabric prepared by the preparation method according to the first aspect described above.

By adopting the above technical solution, the spunlace nonwoven fabric prepared by the above method has improved antibacterial and antiviral properties on the basis of maintaining excellent air permeability, high moisture absorption and low fluffing of the spunlace nonwoven fabric. The obtained spunlace non-woven fabric has excellent antibacterial and antiviral properties, and has a wide range of applications.

In the third aspect, this application provides an application of a copper-containing antibacterial and antiviral non-woven fabric, which has the advantage of being widely used.

Specifically, this application provides the following technical solution: an application of the above-mentioned copper-containing antibacterial and antiviral non-woven fabric in medical and sanitary products.

By adopting the above technical solution, the non-woven fabric obtained in this application has excellent antibacterial and disease resistance performance, and has a wide range of products in medical and sanitary products such as surgical gowns, surgical masks, medical dressing materials, wound dressings, medical gauze, and masks. Applications.

In summary, this application has the following beneficial effects:

1. In this application, using the bactericidal effect and antiviral effect of copper element, the spunlace non-woven fabric is padding sizing in the organic complex copper solution. On the one hand, the copper element is present in the spunlace in the form of complexed copper ions. The antibacterial function between the fibers of the woven fabric is more significant, especially by controlling the concentration of copper ions on the spunlace non-woven fabric, which has an antibacterial and antiviral effect. In addition, the organic complex copper solution can not only be coated on the spunlace The surface of the non-woven fabric can penetrate into the internal voids of the spunlace non-woven fabric, so that the interior of the spunlace non-woven fabric, especially the voids between the fibers and the surface of the spunlace non-woven fabric, have copper ions, which can Play a better antibacterial effect;

2. Compared with the method of directly using antibacterial fibers, the spunlace non-woven fabric in the present application is directly padding sizing after fiber formation and spunlace reinforcement during the production process. On the one hand, in the organic complex copper solution The padding makes the gaps and areas of the spunlace non-woven fabric evenly infiltrated, and the antibacterial effect is uniform, which can effectively avoid the precipitation of substances in the spunlace non-woven fabric holes after drying; on the other hand, the operation is more simple and convenient. The process cycle is shorter, and the spunlace non-woven fabric can be mass-produced in a short time to meet the supply, and can meet the performance of the non-woven fabric, and has excellent antibacterial and antiviral properties. It can be used in disposable medical products. The demand and supply of various medical supplies during the epidemic is of great significance;

3. The fiber material used for fiber web formation in this application includes at least one of natural fiber, rayon fiber, rayon fiber, polyacrylonitrile fiber, and polyvinyl alcohol fiber, so that the spunlace fiber cloth base fabric contains The open hydroxyl group will form a chemical chelation between the copper complex and the hydroxyl group during subsequent padding in the organic complex copper solution. The two are firmly combined and will not easily fall off during use. The resulting spunlace fiber cloth is antibacterial and durable. Excellent performance.

Detailed ways

The following describes the implementation of the application in detail with reference to the examples, but those skilled in the art will understand that the following examples are only used to illustrate the application, and should not be regarded as limiting the scope of the application. The specific conditions are not indicated in the examples. , In accordance with the conventional conditions or the conditions recommended by the manufacturer.

It should be noted that the spunlace process can process various fibers, such as cotton fiber, nylon fiber, polypropylene fiber, polyester fiber or viscose fiber and other common fibers. Therefore, in the preparation step of the spunlace non-woven fabric base fabric in this application The material of the obtained spunlace non-woven fabric is not limited. It can be cellulose fiber such as viscose fiber, etc., protein fiber such as peanut protein fiber, etc., or polyester fiber (polyester), polyamide fiber ( Nylon/nylon), polyacrylonitrile fiber (acrylic), polyvinyl chloride fiber (chlorinated fiber), polypropylene fiber (polypropylene) or polyvinyl alcohol fiber (Villen), control water by controlling the copper content in the organic complex copper solution The content of copper on the barbed fiber cloth is ≥ 500 ppm, more preferably 1000-8000 ppm.

In order to form a chemical chelation between the complex copper ions in the organic complex copper solution and the fibers of the spunlace fiber cloth, so that the copper ions are not easy to fall off, and the antibacterial and antibacterial durability of the spunlace fiber cloth is more excellent. In the step of barbed fiber cloth base cloth, the fiber material used for fiber formation includes any one of natural fibers or fibers obtained by wet spinning. Specifically, it includes natural fibers such as cotton fibers, man-made cellulose fibers, and man-made fibers. At least one of protein fiber, polyacrylonitrile fiber, and polyvinyl alcohol fiber. The above-mentioned fibers all contain hydroxyl groups, and the fabrics obtained after forming the net on the netting curtain contain open hydroxyl groups, which can form chemical chelation with the complex copper ions when they are paddled in the organic complex copper solution. The combination is more tight, such as the fiber material is only viscose fiber or peanut protein fiber, or a mixture of viscose fiber and peanut protein fiber. More preferably, the fabric obtained after the fiber material fiber web-forming step contains ≥5wt% cotton fiber, or 5-65wt% cellulose fiber, or 5-65wt% protein fiber, or 5-65wt% polyacrylonitrile The fiber, or 100% low-temperature water-soluble polyvinyl alcohol fiber, can use any one of the above-mentioned solutions, but is not limited to the above-mentioned solution. When the fiber material is a mixed fiber material of the above-mentioned hydroxyl-containing fibers and non-hydroxyl-containing fibers, the sum of the hydroxyl-containing fibers in the fabric after the fiber is formed into the web can reach the corresponding minimum content, such as cotton fiber and viscose fiber. When using polyester fiber, you only need to ensure that the sum of cotton fiber and viscose fiber in the fabric is ≥5wt%. The sum of viscose fiber and polyacrylonitrile fiber is between 5 and 65 wt%. Through the control of the content of each fiber in the cloth and the control of the copper content in the organic complex copper solution, the copper content on the final spunlace fiber cloth is controlled.

The low-temperature water-soluble polyvinyl alcohol fiber can be directly dissolved in low-temperature water, and can be dissolved in water at 20-98°C.

When there is no hydroxyl group in the fiber material used for fiber formation, such as the fiber material contains one or more of polyester fiber, polyamide fiber, polyvinyl chloride fiber, and polypropylene fiber, in order to improve the complex copper The bonding strength between the ion and the spunlace fiber cloth. In this application, the chitosan-ascorbic acid solution padding step is also carried out before padding and sizing. Both chitosan and ascorbic acid contain open hydroxyl groups, and then the chitosan is used. The adsorption performance and the addition of acetic acid in the chitosan-ascorbic acid solution make the chitosan and ascorbic acid more firmly adhere to the spunlace fiber cloth base cloth, and complex copper ions in the organic complex copper solution to form chemical chelation to enhance the organic Bond strength between copper and spunlace fiber cloth.

The application will be further described in detail below in conjunction with preparation examples, examples and comparative examples.

Preparation examples 1-5 are preparation examples of the organic complex copper solution.

Preparation Example 1

A preparation method of organic complex copper solution, including the following steps:

S1. Preparation of coordinated ionic liquid: uniformly mix urea, caprolactam and acetamide in a weight ratio of 1:0.2:0.2, then heat to 100°C and keep it at 100°C for 1 hour until the caprolactam and urea are uniformly melted and liquefied to obtain the compound Ionic liquid

S2. Preparation of organic complex copper solution: Weigh sodium chloride, potassium permanganate, sodium peroxide and copper powder according to the mass ratio of 1:1:1:2.5, mix to obtain a coordination solid mixture, and then combine the coordination solid The mixture is added to the coordination ionic liquid and stirred evenly. The mixing weight ratio of the coordination solid mixture and the coordination ionic liquid is 1:3. The reaction completely oxidizes the copper powder to monovalent ions and forms a complex with the organics in the coordination ionic liquid. After cooling, pour it into pure water to prepare an initial organic complex copper solution with a copper content of 5.5%. No precipitation or discoloration occurs after being placed for 3 days. Pour the initial organic complex copper solution into a pure 10 volume multiple In water, prepare an organic complex copper solution.

Preparation Example 2

S1. Preparation of coordination ionic liquid: uniformly mix urea, caprolactam and acetamide in a weight ratio of 1:0.3:0.4, then heat to 110°C and keep at 110°C for 0.5h until the caprolactam and urea are uniformly melted and liquefied to obtain Coordination ionic liquid;

S2. Preparation of organic complex copper solution: Weigh sodium chloride, potassium permanganate, sodium peroxide and copper powder according to the mass ratio of 1:2:1:2.9, mix to obtain a coordination solid mixture, and then combine the coordination solids The mixture is added to the coordination ionic liquid and stirred evenly. The mixing weight ratio of the coordination solid mixture and the coordination ionic liquid is 1:3.5. The reaction completely oxidizes the copper powder to monovalent ions and forms a complex with the organics in the coordination ionic liquid. After cooling, pour it into pure water to prepare an initial organic complex copper solution with a copper content of 5.5%. No precipitation or discoloration occurs after being placed for 3 days. Pour the initial organic complex copper solution into a pure 20 volume multiple In water, prepare an organic complex copper solution.

Preparation Example 3

S1. Preparation of coordination ionic liquid: uniformly mix urea, caprolactam and acetamide in a weight ratio of 1:0.4:0.4, then heat to 120°C and keep at 120°C for 1 hour until the caprolactam and urea are uniformly melted and liquefied to obtain the compound Ionic liquid

S2. Preparation of organic complex copper solution: Weigh sodium chloride, potassium permanganate, sodium peroxide and copper powder according to the mass ratio of 1:2:2:2.9, mix to obtain a coordination solid mixture, and then combine the coordination solid The mixture is added to the coordination ionic liquid and stirred evenly. The mixing weight ratio of the coordination solid mixture and the coordination ionic liquid is 1:3.5. The reaction completely oxidizes the copper powder to monovalent ions and forms a complex with the organics in the coordination ionic liquid. After cooling, pour it into pure water to prepare an initial organic complex copper solution with a copper content of 5.5%. No precipitation or discoloration occurs after being placed for 3 days. Pour the initial organic complex copper solution into a pure volume multiple of 30 In water, prepare an organic complex copper solution.

Preparation Example 4

A preparation method of the organic complex copper solution is carried out according to the method in Preparation Example 2, except that the initial organic complex copper solution is poured into 15 volume multiples of pure water to prepare the organic complex copper solution.

Preparation Example 5

A preparation method of the organic complex copper solution is carried out according to the method in Preparation Example 2, except that the initial organic complex copper solution is poured into 25 volume multiples of pure water to prepare the organic complex copper solution.

Preparation examples 6-10 are preparation examples of chitosan-ascorbic acid solution.

Preparation Example 6

A preparation method of chitosan-ascorbic acid solution includes the following steps:

Add 5 kg of chitosan powder into 25 kg of acetic acid and 60 kg of water, magnetically stir until the chitosan is dissolved, and then add 3 kg of ascorbic acid and stir evenly.

Preparation Example 7

Add 8kg of chitosan powder into 28kg of acetic acid and 65kg of water, magnetically stir until the chitosan is dissolved, and then add 4kg of ascorbic acid and stir evenly.

Preparation Example 8

Add 10kg of chitosan powder into 30kg of acetic acid and 70kg of water, magnetically stir until the chitosan is dissolved, and then add 5kg of ascorbic acid and stir evenly.

Example

Example 1

A method for preparing copper-containing antibacterial and antiviral non-woven fabrics includes the following steps:

Preparation of spunlace non-woven fabric base fabric: the mixed fiber material of viscose fiber and polyester fiber is sequentially subjected to fiber web formation, pre-wetting, and spunlace reinforcement to obtain a spunlace fiber fabric base fabric. The fabric after fiber formation contains 5wt. % Of viscose fiber;

Padding and sizing: the spunlace fiber cloth base fabric is padding sizing in the organic complex copper solution by a sizing machine to obtain a copper-containing spunlace non-woven fabric. The organic complex copper solution in the sizing machine is prepared in Preparation Example 2 The organic complex copper solution;

The copper-containing spunlace non-woven fabric obtained after padding and sizing is dried and wound at a drying temperature of 90°C.

Example 2

Spunlace non-woven fabric base fabric preparation: the viscose fiber, polyacrylonitrile fiber and polyester fiber mixed fiber are sequentially fabricated, pre-wet, and spunlaced to obtain a spunlace fiber fabric base fabric. The sum of viscose fiber and polyester fiber in the cloth is 65wt%;

Padding and sizing: the spunlace fiber cloth base fabric is padding sizing in the organic complex copper solution by a sizing machine to obtain a copper-containing spunlace non-woven fabric. The organic complex copper solution in the sizing machine is prepared in Preparation Example 1 The organic complex copper solution;

The copper-containing spunlace nonwoven fabric obtained after padding and sizing is dried and wound at a drying temperature of 100°C.

Example 3

Spunlace non-woven fabric base fabric preparation: Spunlace fiber fabric base fabric is obtained by combining cotton fiber and polyester fiber mixed fiber through fiber web formation, pre-wetting, and spunlace reinforcement. The cotton fiber content in the fabric after fiber web formation is 5wt%;

Padding and sizing: the spunlace fiber cloth base fabric is padding sizing in the organic complex copper solution through a sizing machine to obtain a copper-containing spunlace non-woven fabric. The organic complex copper solution in the sizing machine is prepared in Preparation Example 5 The organic complex copper solution;

Example 4

A method for preparing copper-containing antibacterial and antiviral non-woven fabrics is carried out according to the method in Example 2, except that:

Preparation of spunlace non-woven fabric base fabric: the soybean fiber and polyester fiber mixed fiber are sequentially subjected to fiber formation, pre-wetting, and spunlace reinforcement to obtain the spunlace fiber fabric base fabric. The content of soybean fiber in the fabric after the fiber formation is 20wt%;

The organic complex copper solution in the sizing machine is the organic complex copper solution prepared in Preparation Example 3.

Example 5

Preparation of spunlace non-woven fabric base fabric: the low-temperature water-soluble polyvinyl alcohol fiber is successively subjected to fiber web formation, pre-wetting, and spunlace reinforcement to obtain the spunlace fiber fabric base fabric. Among them, the low-temperature water-soluble polyvinyl alcohol can be Dissolve in the water temperature;

The organic complex copper solution in the sizing machine is selected from the organic complex copper solution prepared in Preparation Example 4.

Example 6

Preparation of spunlace non-woven fabric base fabric: Spunlace fiber fabric base fabric is obtained after the polypropylene fiber is formed into a web, pre-wet, and spunlace reinforced in sequence;

Chitosan-ascorbic acid solution padding: In the sizing machine, the spunlace fiber cloth is padding in the chitosan-ascorbic acid solution, and then dried at 150°C for 10 minutes. The chitosan-ascorbic acid solution in the sizing machine is selected The chitosan-ascorbic acid solution prepared in Preparation Example 6;

Soaping: the dried spunlace fiber cloth base cloth is soaped in 5g/L soaping agent for 10 minutes, the soaping temperature is 35℃, and then dried at 50℃. Among them, the soaping agent is purchased from Dongguan Spinning Chain New Material Technology Co., Ltd., the brand is Texchain, the model is 605;

Padding and sizing: The soaped spunlace fiber cloth base fabric is padding sizing in the organic complex copper solution through the sizing machine to obtain the copper-containing spunlace non-woven fabric. The preparation example of the organic complex copper solution in the sizing machine The organic complex copper solution prepared in 1;

Example 7

Preparation of spunlace non-woven fabric base fabric: the polyamide fiber is successively subjected to fiber formation, pre-wetting, and spunlace reinforcement to obtain the spunlace fiber fabric base fabric;

Chitosan-ascorbic acid solution padding: In the sizing machine, the spunlace fiber cloth is padding in the chitosan-ascorbic acid solution, and then dried at 160°C for 8 minutes. The chitosan-ascorbic acid solution in the sizing machine is selected The chitosan-ascorbic acid solution prepared in Preparation Example 7;

Soaping: the dried spunlace fiber cloth base fabric is soaped in 5g/L soaping agent for 5 minutes, the soaping temperature is 40℃, and then dried at 55℃. Among them, the soaping agent is purchased from Dongguan Spinning Chain New Material Technology Co., Ltd., the brand is Texchain, the model is 605;

Padding and sizing: The soaped spunlace fiber cloth base fabric is padding sizing in the organic complex copper solution through the sizing machine to obtain the copper-containing spunlace non-woven fabric. The preparation example of the organic complex copper solution in the sizing machine The organic complex copper solution prepared in 2;

Example 8

Preparation of spunlace non-woven fabric base fabric: the polyvinyl chloride fiber is successively subjected to fiber web formation, pre-wetting, and spunlace reinforcement to obtain the spunlace fiber fabric base fabric;

Chitosan-ascorbic acid solution padding: In the sizing machine, the spunlace fiber cloth base cloth is padding in the chitosan-ascorbic acid solution, and then dried at 170℃ for 5 minutes. The chitosan-ascorbic acid solution in the sizing machine is selected The chitosan-ascorbic acid solution prepared in Preparation Example 8;

Soaping: the dried spunlace fiber cloth base cloth is soaped in 5g/L soaping agent for 5 minutes, the soaping temperature is 40 ℃, and then dried at 60 ℃, of which, the soaping agent is purchased from Dongguan Spinning Chain New Material Technology Co., Ltd., the brand is Texchain, the model is 605;

Padding and sizing: The soaped spunlace fiber cloth base fabric is padding sizing in the organic complex copper solution through the sizing machine to obtain the copper-containing spunlace non-woven fabric. The preparation example of the organic complex copper solution in the sizing machine The organic complex copper solution prepared in 3;

Comparison

Comparative example 1

A method for preparing copper-containing antibacterial and antiviral non-woven fabrics is carried out according to the method in Example 2. The difference is that in the padding sizing step, when the organic complex copper solution in the sizing machine is prepared, the initial organic The copper complex solution was poured into pure water of 12 volume multiples, and the rest was the same as in Preparation Example 2.

Comparative example 2

A method for preparing copper-containing antibacterial and antiviral non-woven fabrics is carried out according to the method in Example 2. The difference is that in the padding sizing step, when the organic complex copper solution in the sizing machine is prepared, the initial organic The copper complex solution was poured into pure water of 25 volume multiples, and the rest was the same as in Preparation Example 2.

Comparative example 3

A method for preparing copper-containing antibacterial and antiviral non-woven fabrics is carried out according to the method in Example 2. The difference is that in the padding sizing step, the solution in the sizing machine is not an organic complex copper solution, but 3mol/ L of copper chloride solution.

Performance test

1. Antibacterial test

According to the antibacterial performance of the spunlace fiber cloth obtained in AATCC 100-2012 Textile Antibacterial Performance Test Examples 1-8, the test sample is a disc with a diameter of 4.8 cm. 4 parallel tests are performed, and the average value is taken. The tested strain is Methicillin-resistant Staphylococcus aureus ATCC 33591, the inoculation volume is 1 mL, and the test results are shown in Table 1 below.

Table 1 Examples of antibacterial properties

In the same way, the above-mentioned antibacterial performance test was performed on the spunlace fiber cloth obtained in Comparative Examples 1-3, and the test is shown in Table 2 below.

Table 2 Antibacterial properties of comparative examples

It can be seen from Table 1 that the antibacterial properties of the spunlace nonwoven fabric prepared by the method of this application are good, especially for methicillin-resistant Staphylococcus aureus, which is more toxic and drug resistant, and its antibacterial properties are still relatively good. Strong, the copper ion concentration in the initial organic complexed copper solution in this application is 5.5wt%, adding 10-30 volume multiples of water, combined with the control of the fiber material used for fiber web formation, can control the spunlace nonwoven The amount of copper ions on the cloth is between 500ppm-8000ppm, which has a good antibacterial effect. In combination with Comparative Example 3 and Example 2, it can be seen that the use of organic complexed copper ions in this application has greatly improved antibacterial performance compared with directly adding inorganic copper. Refer to the settings of Comparative Example 1-2 and Example 2. It can be seen that when the concentration of copper ions in the organic complex copper solution is too low, the antibacterial effect is greatly reduced. When the concentration of copper ions is too high, on the one hand, the antibacterial performance remains unchanged, but the cost is increased, and the high copper content is The human body is unfavorable.

In addition, the spunlace non-woven fiber material in Examples 1-5 is a fiber containing hydroxyl groups. When it is directly padded in an organic complex copper solution, its antibacterial effect is high, while the raw material of the spunlace non-woven fabric is synthetic polyester. The fiber does not contain cellulose. It is first dipped in a chitosan-ascorbic acid solution and then dipped in an organic complex copper solution. The final spunlace non-woven fabric also has good antibacterial properties.

2. Lasting performance

The spunlace non-woven fabrics obtained in Example 2, Example 7 and Comparative Examples 1 and 3 were washed 50 times, 100 times and 200 times, respectively, and then referenced to AATCC 100-2012 textile antibacterial performance test. The test sample is the diameter It is a 4.8 cm disc, the tested strain is methicillin-resistant Staphylococcus aureus ATCC 33591, and the volume of the inoculation is 1 mL. In addition, the copper content on the spunlace non-woven fabric is tested to determine the copper content loss, and the test The results are shown in Table 3 below.

Table 3 Durability test

It can be seen from Table 3 above that after 50, 100 and 200 washings, the spunlace non-woven fabric obtained in this application has no significant changes in the antibacterial effect of methicillin-resistant Staphylococcus aureus. This application The spunlace nonwoven fabric obtained by the provided method has excellent antibacterial durability.

3. Anti-virus testing

3.1. Influenza A virus H1N1 virus detection

The spunlace non-woven fabric prepared in Example 2 was tested for influenza A virus H1N1 according to the standard of ISO 18184:2014(E) "Anti-Virus Textile Testing". The experimental group and the control group were set up, and the virus strain was prevented by China Influenza A virus A/PR8/34 (H1N1) provided by the Institute of Virology, Academy of Medical Sciences, the cell line is a continuous canine kidney epithelial cell line MDCK cells, purchased from ATCC, the logarithm value of the virus titer of the test group samples after inoculation and incubation for 24 hours (lgTCID ₅₀ /bottle) The average value is 3.48, the antiviral activity value is 3.08, the antiviral activity rate is 99.92%, and the antiviral activity is good.

3.2 Norovirus detection

Through the British Blu Test Laboratories laboratory, the copper-containing spunlace non-woven fabric prepared in this application was tested and evaluated for anti-virus, and mouse Noro s99 was used instead of human Norovirus to perform the inactivation residual activity test on human skin. It is verified that the copper-containing non-woven fabric can inactivate the virus on the human skin within 4 hours. The experimental group and the control group are set up and 5 parallel tests are carried out. Among them, the skin is provided by the human subcutaneous tissue of the British Tissue Solutions Limited company. The virus is selected in Murine norovirus s99 Berlin strain/RAW cells stored at -80°C and isolated from mouse RAW cells, the virus number is MNV 260315.17, the test steps are as follows:

Use the wet copper-containing spunlace nonwoven fabric prepared in Example 2 to perform standard wiping action on the surface of the subcutaneous tissue sample (1.0×1.0cm): fix the subcutaneous tissue sample with sterile tweezers, and then use the copper-containing spunlace The non-woven fabric wipes 3 times along the surface of the subcutaneous tissue sample, and wipes 3 times at 90°C, and then repeats this process for a duration of 30s. The above-mentioned wiping process is carried out in a separate sterile plastic petri dish;

After incubating for 4 hours at room temperature, inoculate 50 μl of virus suspension onto the surface of the subcutaneous tissue sample for 1 minute;

Transfer the subcutaneous tissue sample to 2.0ml cold cell culture medium (DMEM medium + 5.0% V/V fetal bovine serum, where DMEM medium is Dulbecco's modified Eagle medium) and add 1.0g sterile glass beads, vortex 20 seconds; then filter and separate through a 0.45um filter, and store the filtrate at -20°C overnight. A sample of the filtrate in a volume of 0.1ml was passed through gel filtration (Microspin S-400 HR chromatographic column), and the eluent was serially diluted 10 times for TCID ₅₀ analysis.

_{TCID 50 was} calculated for all 5 groups of parallel experiments.

TCID ₅₀ is calculated according to the Karber method.

The virus in the eluate is calculated as 10 ^(Σn+0.5) ×400 TCID50/ml, where Σn is the sum of the proportions of infected wells ^{from 10 -1} to 10 ^{-6 virus dilution.}

After testing, the murine norovirus s99 Berlin strain/RAW cell was used as a substitute for human norovirus to perform a virus test on human skin. The logarithmic value of the virus titer of the experimental group in Example 2 of this application (lgTCID ₅₀ /bottle) The average value is 4.00, and the antiviral activity is good. And compared with the control group, the biological activity of the virus on the human skin in the experimental group was reduced by 57.32% on average after the copper-containing spunlace non-woven fabric treatment, verifying that the human skin was wiped with the copper-containing spunlace non-woven fabric for 4 hours to inactivate the virus The effect verifies the excellent antiviral performance of the copper-containing spunlace non-woven fabric.

In summary, the spunlace non-woven fabric obtained by the method provided in this application has antibacterial and anti-viral properties, and can be widely used in medical and sanitary non-woven fabrics, non-woven fabrics for home decoration, non-woven fabrics for clothing, and non-woven fabrics for industrial use. Fabrics, agricultural non-woven fabrics and other fields, especially using its antibacterial and antiviral properties in medical and health products such as masks, surgical gowns, etc. have a wide range of applications.

This specific embodiment is only an explanation of the application, and it is not a limitation to the application. After reading this specification, those skilled in the art can make modifications to the embodiment without creative contribution as needed, but as long as the rights of the application are The scope of the requirements is protected by the patent law.

Claims

A preparation method of copper-containing antibacterial and antiviral non-woven fabric is characterized in that it comprises the following steps:

Preparation of spunlace non-woven fabric base fabric: the fiber material is successively subjected to fiber web formation, pre-wetting, and spunlace reinforcement to obtain a spunlace fiber fabric base fabric;

Padding and sizing: the spunlace fiber cloth base fabric is padding sizing in an organic complex copper solution to obtain a copper-containing spunlace non-woven fabric, and the copper content of the copper-containing spunlace non-woven fabric is ≥500ppm;

The copper-containing spunlace non-woven fabric obtained after padding and sizing is dried and wound.
The method for preparing a copper-containing antibacterial and antiviral non-woven fabric according to claim 1, wherein the fiber material comprises natural fiber, man-made cellulose fiber, man-made protein fiber, polyacrylonitrile fiber, polyethylene At least one of alcohol fibers.
The method for preparing a copper-containing antibacterial and antiviral non-woven fabric according to claim 1, wherein the fabric obtained after the step of forming the fiber material fiber into the web contains ≥5% cotton fiber, or 5-65% Cellulose fiber, or 5-65% protein fiber, or 5-65% polyacrylonitrile fiber, or 100% low-temperature water-soluble polyvinyl alcohol fiber;

The organic complex copper solution is obtained by adding 5.5 wt% of the initial organic complex copper solution to 10-30 volume multiples of water.
The method for preparing a copper-containing antibacterial and antiviral non-woven fabric according to claim 3, wherein the initial organic complexed copper solution is prepared according to the following method:

Preparation of coordinated ionic liquid: uniformly mix urea, caprolactam and acetamide, and then heat and keep it warm until the caprolactam and urea are uniformly melted and liquefied to obtain the coordinated ionic liquid;

Preparation of organic complex copper solution: add the coordination solid mixture including sodium chloride, potassium permanganate, sodium peroxide and copper powder to the coordination ionic liquid, stir uniformly, react, and pour into pure water after cooling to obtain the copper content It is 5.5wt% of the initial organic copper complex solution.
The method for preparing a copper-containing antibacterial and antiviral non-woven fabric according to claim 4, wherein in the step of preparing the coordination ionic liquid, the mixing weight ratio of urea, caprolactam and acetamide is 1:(0.2- 0.4): (0.2-0.4), after uniform mixing, the heating temperature is 100-120℃, and the holding time is 0.5-1h.
The method for preparing a copper-containing antibacterial and antiviral non-woven fabric according to claim 4, wherein the step of preparing the organic complex copper solution: sodium chloride, potassium permanganate, sodium peroxide and copper powder The mixing weight ratio is 1:(1-2):(1-2):(2.5-2.9), and the mixing weight ratio of the coordination solid mixture and the coordination ionic liquid is 1:(3-3.5).
The method for preparing a copper-containing antibacterial and antiviral non-woven fabric according to claim 1, wherein when the fiber material is one of polyester fiber, polyamide fiber, polyvinyl chloride fiber, and polypropylene fiber In some cases, the spunlace fiber cloth base cloth is also subjected to the chitosan-ascorbic acid solution padding step before padding and sizing. The specific operation is: padding the spunlace fiber cloth base cloth in the chitosan-ascorbic acid solution , And then dry at 150-170℃ for 5-10min. The preparation method of chitosan-ascorbic acid solution is: add 5-10 parts of chitosan powder to 25-30 parts of acetic acid and 60-70 parts of water, magnetically stir until the shell The glycans are dissolved, and then 3-5 parts of ascorbic acid are added and stirred evenly.
The method for preparing a copper-containing antibacterial and antiviral non-woven fabric according to claim 7, wherein the spunlace fiber fabric is further subjected to a soaping step after the chitosan-ascorbic acid solution padding step, specifically The operation is: the dried spunlace fiber cloth base cloth is soaped in 5g/L soaping agent for 5-10min, the soaping temperature is 35-40℃, and then dried at 50-60℃.
A copper-containing antibacterial and antiviral non-woven fabric, characterized in that it is prepared by the preparation method of claim 1.