CN114232323A - Plasma-treated chitosan antibacterial fiber and preparation method thereof - Google Patents
Plasma-treated chitosan antibacterial fiber and preparation method thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
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- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
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Abstract
The invention provides a preparation method of chitosan antibacterial fiber by plasma treatment. Compared with the prior art, the invention takes the natural chitosan as the antibacterial agent, has better biocompatibility, can generate active groups on the surface of the fiber after plasma treatment, can carry out grafting reaction with the chitosan to ensure that the chitosan is uniformly attached to the outer surface layer of the fiber to form a whole, can ensure that the obtained antibacterial fiber has stronger antibacterial effect and better inhibition on bacterial growth, and has better washability.
Description
Technical Field
The invention belongs to the technical field of textile fabrics, and particularly relates to a chitosan antibacterial fiber treated by plasma and a preparation method thereof.
Background
The antibacterial fiber can be used for resisting staphylococcus aureus bacteria, escherichia coli, candida albicans and the like, and therefore, the antibacterial fiber has wide application fields in sports T-shirts, underwear and socks.
The production process of the antibacterial fiber in the market at present mainly comprises the following steps: the first method adds an antibacterial finishing agent (mainly a chemical finishing agent containing silver and the like) to the surface of the fabric in a soaking and drying mode in a fabric after-finishing mode, and has the advantages that: simple, low cost and the defect of non-washability; secondly, the antibacterial material is implanted into the fiber by a master batch blending method, but most of the antibacterial material added in the blending and finishing is irregular and random on the fiber surface, and the antibacterial agent needs to be on the fiber surface to exert the antibacterial effect; thirdly, a layer of silver is plated on the surface of the fiber in an electroplating antibacterial agent mode, such as silver fiber promoted by Nobo company in America, and X-Static silver wire fiber is widely used on yoga trousers of Lolo lemon, so that the X-Static silver wire fiber has the advantages of good antibacterial effect and the defects of high cost, the selling price of yarn is over 500 yuan/kg, and in addition, simple substance silver is easily oxidized and blackened for a long time in the air; the fourth is a natural antibacterial material, because most of the three antibacterial technologies adopt chemical antibacterial materials such as silver, copper and other metal materials, and when the chemical antibacterial materials contact with human skin, the metal materials have certain influence on human health, so that at present, natural antibacterial materials are proposed by many people, for example, tea leaves, chitosan and other natural materials are used for achieving antibacterial, for example, chitosan viscose fiber and the like proposed by Shandong Haishomol, but the materials fall off due to friction, washing and the like during use, so that the antibacterial performance is reduced.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a plasma-treated chitosan antibacterial fiber with good antibacterial performance and washing resistance, and a preparation method thereof.
The invention provides a preparation method of chitosan antibacterial fiber by plasma treatment, which comprises the following steps:
s1) carrying out plasma treatment on the fiber to obtain a treated fiber;
s2) coating the chitosan antibacterial solution on the treated fibers through atomization spraying, and performing high-temperature treatment to obtain the plasma-treated chitosan antibacterial fibers; the chitosan antibacterial solution comprises chitosan, amino silicone oil and water.
Preferably, the power of the plasma treatment in the step S1) is 50-100W; the gas used is air; the gas flow during plasma treatment is 3-6 cubic meters per second; the passing speed of the fiber during plasma treatment is 50-100 m/min.
Preferably, the plasma treatment in step S1) is performed simultaneously from both left and right sides of the fiber using two plasma generators.
Preferably, the concentration of chitosan in the chitosan antibacterial solution is 30-60 g/L; the concentration of the amino silicone oil is 50-80 g/L.
Preferably, the fiber is selected from nylon, terylene or acrylic fiber; the particle size of the chitosan is 80-100 nm; the molecular weight of the chitosan is 10000-15000; the amino silicone oil is Dow Corning amino silicone oil DG 1000.
Preferably, the chitosan is prepared according to the following steps:
A1) deproteinizing shrimp shells and/or crab shells;
A2) carrying out inorganic salt removal treatment on the shrimp shells and/or the crab shells after the deproteinization treatment;
A3) performing deacetylation treatment on the shrimp shells and/or the crab shells after inorganic salt removal treatment;
A4) and rinsing the deacetylated shrimp shells and/or crab shells to be neutral, drying, and performing ball milling to obtain the chitosan.
Preferably, the step a1) is specifically: heating and soaking shrimp shells and/or crab shells in an alkali metal hydroxide solution for deproteinization treatment; the concentration of the alkali metal hydroxide solution is 2-6%; the temperature for heating and soaking is 85-102 ℃; the heating and soaking time is 8-12 h;
the step A2) is specifically as follows: heating the deproteinized shrimp shells and/or crab shells in an acid solution to remove inorganic salt; the acid solution is 10-20% hydrochloric acid; the heating temperature is 45-80 ℃; the time for inorganic salt removal is 8-12 h;
the step A3) is specifically as follows: heating the shrimp shells and/or crab shells subjected to inorganic salt removal treatment in a sodium hydroxide solution with the concentration of 25-35% for deacetylation treatment; the heating time is 80-100 ℃; the deacetylation treatment time is 4-6 h.
Preferably, the drawing speed of the fiber treated in the atomizing spraying in the step S2) is 10-20 m/min; the length of the working area of the atomized spraying is more than or equal to 30 m; during atomization spraying, 100L of chitosan antibacterial solution is prepared for every 1km of fiber.
Preferably, the temperature of the high-temperature treatment is more than or equal to 200 ℃; the time of high-temperature treatment is more than or equal to 1 min.
The invention also provides the plasma-treated chitosan antibacterial fiber prepared by the preparation method.
The invention provides a preparation method of chitosan antibacterial fiber by plasma treatment, which comprises the following steps: s1) carrying out plasma treatment on the fiber to obtain a treated fiber; s2) coating the chitosan antibacterial solution on the treated fibers through atomization spraying, and performing high-temperature treatment to obtain the plasma-treated chitosan antibacterial fibers; the chitosan antibacterial solution comprises chitosan, amino silicone oil and water. Compared with the prior art, the invention takes the natural material chitosan as the antibacterial agent, has better biocompatibility, can generate active groups on the surface of the fiber after plasma treatment, can be grafted with the chitosan to be uniformly attached to the outer surface layer of the fiber to form a whole, can ensure that the obtained antibacterial fiber has stronger antibacterial effect and better washing resistance, and simultaneously has better washing resistance, adopts the plasma treatment, has high production process efficiency, energy conservation, environmental protection and lower cost, does not influence the mechanical property of the fiber, thereby ensuring that the obtained plasma-treated chitosan antibacterial fiber has high strength, high washing resistance, strong antibacterial property and low cost, can meet the antibacterial standards of various national textile brands such as Japanese antibacterial standard JISL1902, American antibacterial standard AATCC-100, domestic FZ/T73023 and the like, and has short flow, strong antibacterial property and low cost on the preparation process, Low energy consumption and low cost.
Drawings
FIG. 1 is a schematic view of a plasma generator processing fiber according to the present invention;
FIG. 2 is a schematic view of a plasma generating apparatus;
FIG. 3 is a result of measuring the surface components of the plasma-treated chitosan antibacterial fiber obtained in example 1 of the present invention;
fig. 4 is a result of testing the bacteriostatic performance of a cloth prepared from the plasma-treated chitosan antibacterial fiber obtained in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of chitosan antibacterial fiber by plasma treatment, which comprises the following steps: s1) carrying out plasma treatment on the fiber to obtain a treated fiber; s2) coating the chitosan antibacterial solution on the treated fibers through atomization spraying, and performing high-temperature treatment to obtain the plasma-treated chitosan antibacterial fibers; the chitosan antibacterial solution comprises chitosan, amino silicone oil and water.
In the present invention, the sources of all raw materials are not particularly limited, and the raw materials may be commercially available or self-made.
Carrying out plasma treatment on the fiber to obtain a treated fiber; the fibers are preferably single strand fibers; the type of the polyester is preferably nylon, terylene or acrylon, and more preferably terylene; the plasma treatment is preferably a low temperature plasma treatment; the power of the plasma treatment is preferably 50-100W; the plasma treatment is preferably carried out under atmospheric pressure; the gas used is preferably air; the gas flow is preferably 3-6 cubic meters per second; the passing speed of the fiber during plasma treatment is 50-100 m/min; in order to ensure the effect of plasma treatment modification, two plasma generators are preferably adopted to simultaneously carry out the treatment from the left side and the right side of the fiber; referring to fig. 1 and 2, fig. 1 is a schematic view of a plasma generator processing fiber; fig. 2 is a schematic view of a plasma generating apparatus.
Coating the chitosan antibacterial solution on the treated fibers by atomization spraying; wherein the chitosan antibacterial solution comprises chitosan, amino silicone oil and water; the concentration of chitosan in the chitosan antibacterial solution is preferably 30-60 g/L; the preferred particle size of the chitosan is 80-100 nm; the molecular weight of the chitosan is preferably 10000-15000; in the present invention, the chitosan is preferably prepared according to the following steps: a1) Deproteinizing shrimp shells and/or crab shells; A2) carrying out inorganic salt removal treatment on the shrimp shells and/or the crab shells after the deproteinization treatment; A3) performing deacetylation treatment on the shrimp shells and/or the crab shells after inorganic salt removal treatment; A4) and rinsing the deacetylated shrimp shells and/or crab shells to be neutral, drying, and performing ball milling to obtain the chitosan.
In the present invention, the shrimp shell and/or crab shell is preferably fresh shrimp shell and/or crab shell, more preferably obtained by removing heads of shrimps and/or crabs, removing meat, leaving shells thereof, and washing and rinsing.
Deproteinizing shrimp shells and/or crab shells; in the present invention, this step is preferably embodied as follows: heating and soaking shrimp shells and/or crab shells in an alkali metal hydroxide solution for deproteinization treatment; the alkali metal hydroxide solution is preferably sodium hydroxide solution; the concentration of the alkali metal hydroxide solution is 2 to 6 percent, and more preferably 3 to 5 percent; the heating and soaking temperature is preferably 85-102 ℃; the heating and soaking time is 8-12 h.
According to the invention, the deproteinized shrimp shells and/or crab shells are preferably rinsed to neutrality by clear water and then subjected to inorganic salt removal treatment; the inorganic salt removing treatment step preferably comprises the following steps: heating the deproteinized shrimp shells and/or crab shells in an acid solution to remove inorganic salt; the acid solution is preferably 10-20% hydrochloric acid; the heating temperature is preferably 45-80 ℃; the time for the inorganic salt removal treatment is preferably 8-12 h. Inorganic salts with calcium as the main component can be removed completely through inorganic salt removal treatment.
According to the invention, after inorganic salt is removed, the shrimp shell and/or the crab shell are preferably rinsed to be neutral by clear water, then are decolorized and then are deacetylated; the decoloring treatment is preferably performed by soaking in 1-5% glacial acetic acid solution, and more preferably performed by soaking in 2-3% glacial acetic acid solution; the time of the decoloring treatment is preferably 2-4 h; the material can be decolored to pure white through decoloring treatment; the deacetylation treatment is preferably carried out by heating the decolored shrimp shells and/or crab shells in a sodium hydroxide solution with the concentration of 25-35%; the heating time is preferably 80-100 ℃; the deacetylation treatment time is preferably 4-6 h; polymerization also proceeds during the deacetylation treatment.
Rinsing the deacetylated shrimp shells and/or crab shells to neutrality, drying, and performing ball milling to obtain chitosan; the ball milling is preferably carried out using a ball mill. The chitosan is used as an antibacterial functional material, is natural, and has the advantages of skin friendliness and degradability.
The concentration of amino silicone oil in the chitosan solution is preferably 50-80 g/L; the amino silicone oil is preferably Dow Corning amino silicone oil DG 1000. Coating the chitosan antibacterial solution on the treated fibers by atomization spraying; during atomization spraying, 100L of chitosan antibacterial solution is prepared every 1km of fiber; the fibers treated in the invention are preferably subjected to an atomization spraying work area through open-width drawing; the drawing speed of the treated fibers during atomization spraying is preferably 10-20 m/min, and more preferably 15 m/min; the length of the working area of the atomized spray is preferably greater than or equal to 30 m.
After atomization spraying, the chitosan and free radicals generated on the surface of the fiber can be reacted and combined through high-temperature treatment, and the chitosan antibacterial fiber processed by plasma is obtained; the temperature of the high-temperature treatment is preferably more than or equal to 200 ℃; the time of the high-temperature treatment is preferably not less than 1min, and more preferably 2 to 5 min.
The invention takes the natural material chitosan as the antibacterial agent, has better biocompatibility, and the fiber surface after the plasma treatment can generate active groups, can be grafted with chitosan to be attached on the outer surface layer of the fiber, so that the obtained antibacterial fiber has stronger antibacterial effect, can inhibit the growth of bacteria and has better washability, and adopts plasma treatment, the production process has high efficiency, energy conservation, environmental protection and lower cost, does not influence the mechanical property of the fiber, therefore, the obtained plasma-treated chitosan antibacterial fiber has high strength, high washability, strong antibacterial property and low cost, can meet the antibacterial standards of various textile brands of Japan antibacterial standard JISL1902, American antibacterial standard AATCC-100, domestic FZ/T73023 and the like, and has the advantages of short flow, low energy consumption and low cost in the preparation process.
The invention also provides the plasma-treated chitosan antibacterial fiber prepared by the preparation method.
In order to further illustrate the present invention, the following will describe in detail a plasma-treated chitosan antibacterial fiber and a method for preparing the same in accordance with the present invention.
The reagents used in the following examples are all commercially available.
Example 1
The preparation method of the chitosan polyester antibacterial fiber processed by the 75D/72F plasma mainly comprises the following steps:
1.1 preparation of chitosan powder material: mainly adopts crab shells and shrimp shells as raw materials to prepare the chitosan antibacterial liquid material with the particle size of 80 nanometers and the molecular weight of 10000 finally through the processes of taking the shells, removing protein, removing inorganic salt, removing acetyl and the like.
1.2 plasma treatment: firstly, the single-stranded terylene fiber is treated by low-temperature plasma, so that free radicals such as-OH, -COOH, -C-O and the like are generated on the surface of the terylene fiber).
1.3 antibacterial treatment: preparing the chitosan prepared in the step 1.1 into an antibacterial liquid material, coating the antibacterial liquid material in single-stranded yarns in an atomizing and spraying manner, and then realizing reaction and combination with free radicals generated on the surface of the polyester fiber in a high-temperature reaction and drying manner to obtain the chitosan antibacterial fiber treated by the plasma.
The first step of preparing chitosan antibacterial functional powder material is mainly prepared by taking crab shells and shrimp shells as raw materials, and the preparation process is as follows:
(1) taking a shell: removing heads and meats of shrimps and crabs, keeping shells of the shrimps and crabs, and rinsing the shells of the shrimps, the shrimps and the crabs with clean water.
(2) Deproteinization: the method comprises the following steps of carrying out deproteinization treatment on shrimp, shrimp and crab shells rinsed with clear water, and soaking the treated shrimp, shrimp and crab shells by using a NaOH solution with the concentration of about 3% at 85 ℃ for about 8 hours in the working procedure.
(3) Removing inorganic salt: rinsing the soaked materials to be neutral by using clear water; then, inorganic salts are removed, and in the process: HCL (hydrochloric acid) with a concentration of about 10% is used and treated at 45 ℃ for 8 hours until the inorganic salts containing calcium as the main component are completely removed.
(4) Deacetylation: rinsing the material after inorganic salt removal to be neutral, then soaking the material for 2 hours by using glacial acetic acid with the concentration of about 2 percent, and firstly decoloring the material to be pure white; secondly, deacetylating the decolored material, and polymerizing while processing, wherein in the process: the treatment was carried out at 80 ℃ for 4 hours using a caustic sodium hydroxide solution having a concentration of about 25%.
(5) And (3) post-treatment: rinsing the deacetylated material to be neutral by using clear water; and drying the material rinsed to be neutral, and then grinding the dried material into the chitosan antibacterial material by adopting a ball mill.
The second step is a plasma treatment process of the polyester fiber: firstly, carrying out plasma treatment on the terylene single-strand fiber, wherein the chitin antibacterial fiber adopts a low-temperature plasma modification technology, and the process parameters of the plasma treatment comprise: the plasma is low-temperature plasma, the power is 50W, the pressure is atmospheric pressure, the used gas is air, the flow rate of the air flow is 3 cubic meters per second, the passing speed of the single-stranded fiber is 50m/min, and simultaneously, in order to ensure the plasma modification effect, two plasma generating guns are adopted to respectively carry out plasma treatment from the left side and the right side of the fiber.
And thirdly, carrying out grafting reaction on the chitosan antibacterial material prepared in the first step and the polyester fiber subjected to plasma treatment prepared in the second step, wherein yarns enter a treatment area through open-width drawing, the drawing speed is 15m/min, the length of a working area is more than 30 meters, and then, carrying out hot air drying on the yarns, wherein the hot air temperature is 200 ℃, and the drying time is 2 min. Every 1 kilometer of yarn is mixed with 100L of working solution, and the formula of the chitosan antibacterial solution is as follows: 30g/L of chitosan, 50g/L of amino silicone oil DG1000 (Dow Corning), and the balance of water.
Meanwhile, in order to compare the chitin antibacterial fiber prepared by the invention with the blended antibacterial fiber (Taiwan Hua 25035; Shengzhi Bingxiku antibacterial fiber), the chemical assistant treated fiber (the Dow chemical xianban antibacterial finishing agent PM100 is adopted in Shenzhou) and the silver-plated fiber (XT 2 silver fiber produced by Nuobo company in America) which are already in the market, the performances are compared, the polyester fiber yarns with the same specification are arranged and woven into 32S polyester plain cloth, the polyester plain cloth is dyed into white, and then the antibacterial performance and the health compatibility are respectively tested, and the results are shown in the table 1.
TABLE 1 comparison of various antimicrobial fiber properties
From the above table, it can be seen that the chitosan plasma treated antibacterial fiber of the invention has a durable antibacterial effect, can achieve the national standard 3A level antibacterial (highest level) both before washing and after 50 times of washing, and meanwhile, the cloth cover does not have the problems of color change and blackening, and the most important is that the chitosan plasma treated antibacterial fiber is made of natural materials, has the best health compatibility, is low in price, and is suitable for large-scale popularization and use.
The surface components of the plasma-treated chitosan antibacterial fiber obtained in example 1 were measured, and the results are shown in fig. 3, which shows that chitosan had been grafted to the fiber surface.
The plasma-treated chitosan antibacterial fiber obtained in example 1 was prepared into a cloth, and the bacteriostatic properties thereof were measured, and the results are shown in fig. 4.
Example 2
The preparation method of the chitosan polyester antibacterial fiber treated by the 50D/48F plasma mainly comprises the following steps:
2.1 preparation of chitosan powder material: mainly adopts crab shells and shrimp shells as raw materials to prepare the chitosan antibacterial liquid material with the particle size of 80 nanometers and the molecular weight of 11000 finally through the processes of taking the shells, removing protein, removing inorganic salt, removing acetyl and the like.
2.2 plasma treatment: firstly, the single-stranded terylene fiber is treated by low-temperature plasma, so that free radicals such as-OH, -COOH, -C-O and the like are generated on the surface of the terylene fiber).
2.3, antibacterial treatment: and (3) preparing the chitosan prepared in the step (2.1) into an antibacterial liquid material, coating the antibacterial liquid material in the single-strand yarns in an atomizing and spraying manner, and then realizing reaction and combination with free radicals generated on the surface of the polyester fiber in a high-temperature reaction and drying manner.
The first step of preparing chitosan antibacterial functional powder material is mainly prepared by taking crab shells and shrimp shells as raw materials, and the preparation process is as follows:
(1) taking a shell: removing heads and meats of shrimps and crabs, keeping shells of the shrimps and crabs, and rinsing the shells of the shrimps, the shrimps and the crabs with clean water.
(2) Deproteinization: the shrimp, shrimp and crab shells after being rinsed by clear water are deproteinized, and in the working procedure, the processed shrimp, shrimp and crab shells are soaked by NaOH solution with the concentration of about 4 percent, the soaking is carried out at the temperature of 90 ℃, and the processing time is about 9 hours.
(3) Removing inorganic salt: rinsing the soaked materials to be neutral by using clear water; then, inorganic salts are removed, and in the process: HCL (hydrochloric acid) with a concentration of about 9% is used and treated at 50 ℃ for 9 hours until the inorganic salts containing calcium as the main component are completely removed.
(4) Deacetylation: rinsing the material after inorganic salt removal to be neutral, then soaking the material for 3 hours by using glacial acetic acid with the concentration of about 3 percent, and firstly decoloring the material to be pure white; secondly, deacetylating the decolored material, and polymerizing while processing, wherein in the process: the treatment was carried out at 90 ℃ for 5.5 hours using a caustic sodium hydroxide solution having a concentration of about 20%.
(5) And (3) post-treatment: rinsing the deacetylated material to be neutral by using clear water; and drying the material rinsed to be neutral, and then grinding the dried material into the chitosan antibacterial material by adopting a ball mill.
The second step is a plasma treatment process of the polyester fiber: firstly, carrying out plasma treatment on the terylene single-strand fiber, wherein the chitin antibacterial fiber adopts a low-temperature plasma modification technology, and the process parameters of the plasma treatment comprise: the plasma is low-temperature plasma, the power is 60W, the pressure is atmospheric pressure, the used gas is air, the airflow flow is 4 cubic meters per second, the passing speed of the single-strand fiber is 55m/min, and simultaneously, in order to ensure the plasma modification effect, two plasma generating guns are adopted to respectively carry out plasma treatment from the left side and the right side of the fiber.
And thirdly, performing grafting reaction on the chitosan antibacterial material prepared in the first step and the polyester fiber subjected to plasma treatment prepared in the second step, wherein yarns enter a treatment area through open-width drawing, the drawing speed is 15m/min, the length of a working area is more than 50 meters, and then, the yarns are subjected to hot air drying, the hot air temperature is 220 ℃, and the drying time is 4 min. 120L of working solution is prepared from every 1 kilometer of yarn, and the formula of the chitosan antibacterial solution is as follows: 30g/L of chitosan, 60g/L of amino silicone oil DG1000 (Dow Corning), and the balance of water.
Meanwhile, in order to compare the chitin antibacterial fiber prepared by the invention with the blended antibacterial fiber (Taiwan Hua 25035; Shengzhi Bingxiku antibacterial fiber), the chemical assistant treated fiber (the Dow chemical xianban antibacterial finishing agent PM300 is adopted in Shenzhou) and the silver-plated fiber (XT 4 silver fiber produced by Nuobo company in America) which are already in the market, the performances are compared, the polyester fiber yarns with the same specification are arranged and woven into 32S polyester plain cloth, the polyester plain cloth is dyed into white, and then the antibacterial performance and the health compatibility are respectively tested, and the results are shown in the table 2.
TABLE 2 comparison of various antimicrobial fiber properties
From the above table, it can be seen that the chitosan plasma treated antibacterial fiber of the invention has a durable antibacterial effect, can achieve the national standard 3A level antibacterial (highest level) both before washing and after 50 times of washing, and meanwhile, the cloth cover does not have the problems of color change and blackening, and the most important is that the chitosan plasma treated antibacterial fiber is made of natural materials, has the best health compatibility, is low in price, and is suitable for large-scale popularization and use.
Example 3
The preparation method of the chitosan polyester antibacterial fiber treated by the 100D/75F plasma mainly comprises the following steps:
3.1 preparation of chitosan powder material: mainly adopts crab shells and shrimp shells as raw materials to prepare the chitosan antibacterial liquid material with the particle size of 80 nanometers and the molecular weight of 12000 finally through the processes of taking the shells, removing protein, removing inorganic salt, removing acetyl and the like.
3.2 plasma treatment: firstly, the single-stranded terylene fiber is treated by low-temperature plasma, so that free radicals such as-OH, -COOH, -C-O and the like are generated on the surface of the terylene fiber).
3.3, antibacterial treatment: and (3) preparing the chitosan prepared in the step (3.1) into an antibacterial liquid material, coating the antibacterial liquid material in the single-strand yarns in an atomizing and spraying manner, and then realizing reaction and combination with free radicals generated on the surfaces of the polyester fibers in a high-temperature reaction and drying manner.
The first step of preparing chitosan antibacterial functional powder material is mainly prepared by taking crab shells and shrimp shells as raw materials, and the preparation process is as follows:
(1) taking a shell: removing heads and meats of shrimps and crabs, keeping shells of the shrimps and crabs, and rinsing the shells of the shrimps, the shrimps and the crabs with clean water.
(2) Deproteinization: the shrimp, shrimp and crab shells after being rinsed by clear water are deproteinized, and in the working procedure, the processed shrimp, shrimp and crab shells are soaked by NaOH solution with the concentration of about 4 percent, the soaking is carried out at the temperature of 85 ℃, and the processing time is about 9 hours.
(3) Removing inorganic salt: rinsing the soaked materials to be neutral by using clear water; then, inorganic salts are removed, and in the process: HCL (hydrochloric acid) with a concentration of about 10% is used and treated at 50 ℃ for 9 hours until the inorganic salts containing calcium as the main component are completely removed.
(4) Deacetylation: rinsing the material after inorganic salt removal to be neutral, then soaking the material for 4 hours by using glacial acetic acid with the concentration of about 3 percent, and firstly decoloring the material to be pure white; secondly, deacetylating the decolored material, and polymerizing while processing, wherein in the process: the treatment was carried out at 90 ℃ for 5 hours using a caustic sodium hydroxide solution having a concentration of about 25%.
(5) And (3) post-treatment: rinsing the deacetylated material to be neutral by using clear water; and drying the material rinsed to be neutral, and then grinding the dried material into the chitosan antibacterial material by adopting a ball mill.
The second step is a plasma treatment process of the polyester fiber: firstly, carrying out plasma treatment on the terylene single-strand fiber, wherein the chitin antibacterial fiber adopts a low-temperature plasma modification technology, and the process parameters of the plasma treatment comprise: the plasma is low-temperature plasma, the power is 60W, the pressure is atmospheric pressure, the used gas is air, the flow rate of the air flow is 3 cubic meters per second, the passing speed of the single-strand fiber is 55m/min, and simultaneously, in order to ensure the plasma modification effect, two plasma generating guns are adopted to respectively carry out plasma treatment from the left side and the right side of the fiber.
And the third step is that the chitosan antibacterial material prepared in the first step and the polyester fiber after plasma treatment prepared in the second step are subjected to grafting reaction, yarns enter a treatment area through open-width drawing, the drawing speed is 20m/min, the length of a working area is more than 40 meters, and then the yarns are subjected to hot air drying, wherein the hot air temperature is 220 ℃, and the drying time is 3 min. 120L of working solution is prepared from every 1 kilometer of yarn, and the formula of the chitosan antibacterial solution is as follows: 35g/L of chitosan, 60g/L of amino silicone oil DG1000 (Dow Corning), and the balance of water.
Meanwhile, in order to compare the chitin antibacterial fiber prepared by the invention with the blended antibacterial fiber (Taiwan Hua 25035; Shengzhi Bingxiku antibacterial fiber), the chemical assistant treated fiber (the Dow chemical xianban antibacterial finishing agent PM300 is adopted in Shenzhou International), and the silver-plated fiber (Static silver fiber produced by Nuobo corporation in America) which are already in the market, the performances are compared, the polyester fiber yarns with the same specification are arranged and woven into 40S polyester plain cloth, the polyester plain cloth is dyed into white, and then the antibacterial performance and the health compatibility are respectively tested, and the results are shown in table 3.
TABLE 3 comparison of various antimicrobial fiber properties
From the above table, it can be seen that the chitosan plasma treated antibacterial fiber of the invention has a durable antibacterial effect, can achieve the national standard 3A level antibacterial (highest level) both before washing and after 50 times of washing, and meanwhile, the cloth cover does not have the problems of color change and blackening, and the most important is that the chitosan plasma treated antibacterial fiber is made of natural materials, has the best health compatibility, is low in price, and is suitable for large-scale popularization and use.
Claims (10)
1. A preparation method of chitosan antibacterial fiber by plasma treatment is characterized by comprising the following steps:
s1) carrying out plasma treatment on the fiber to obtain a treated fiber;
s2) coating the chitosan antibacterial solution on the treated fibers through atomization spraying, and performing high-temperature treatment to obtain the plasma-treated chitosan antibacterial fibers; the chitosan antibacterial solution comprises chitosan, amino silicone oil and water.
2. The method according to claim 1, wherein the power of the plasma treatment in the step S1) is 50-100W; the gas used is air; the gas flow during plasma treatment is 3-6 cubic meters per second; the passing speed of the fiber during plasma treatment is 50-100 m/min.
3. The method as set forth in claim 1, wherein the plasma treatment in the step S1) is performed simultaneously from both left and right sides of the fiber using two plasma generators.
4. The preparation method according to claim 1, wherein the concentration of chitosan in the chitosan antibacterial solution is 30-60 g/L; the concentration of the amino silicone oil is 50-80 g/L.
5. The method of claim 1, wherein the fibers are selected from nylon, dacron, or acrylon; the particle size of the chitosan is 80-100 nm; the molecular weight of the chitosan is 10000-15000; the amino silicone oil is Dow Corning amino silicone oil DG 1000.
6. The method of claim 1, wherein the chitosan is prepared according to the following steps:
A1) deproteinizing shrimp shells and/or crab shells;
A2) carrying out inorganic salt removal treatment on the shrimp shells and/or the crab shells after the deproteinization treatment;
A3) performing deacetylation treatment on the shrimp shells and/or the crab shells after inorganic salt removal treatment;
A4) and rinsing the deacetylated shrimp shells and/or crab shells to be neutral, drying, and performing ball milling to obtain the chitosan.
7. The preparation method according to claim 6, wherein the step A1) is specifically as follows: heating and soaking shrimp shells and/or crab shells in an alkali metal hydroxide solution for deproteinization treatment; the concentration of the alkali metal hydroxide solution is 2-6%; the temperature for heating and soaking is 85-102 ℃; the heating and soaking time is 8-12 h;
the step A2) is specifically as follows: heating the deproteinized shrimp shells and/or crab shells in an acid solution to remove inorganic salt; the acid solution is 10-20% hydrochloric acid; the heating temperature is 45-80 ℃; the time for inorganic salt removal is 8-12 h;
the step A3) is specifically as follows: heating the shrimp shells and/or crab shells subjected to inorganic salt removal treatment in a sodium hydroxide solution with the concentration of 25-35% for deacetylation treatment; the heating time is 80-100 ℃; the deacetylation treatment time is 4-6 h.
8. The preparation method according to claim 1, wherein the drawing speed of the fiber treated in the atomizing spray in the step S2) is 10 to 20 m/min; the length of the working area of the atomized spraying is more than or equal to 30 m; during atomization spraying, 100L of chitosan antibacterial solution is prepared for every 1km of fiber.
9. The production method according to claim 1, wherein the temperature of the high-temperature treatment is 200 ℃ or higher; the time of high-temperature treatment is more than or equal to 1 min.
10. The plasma-treated chitosan antibacterial fiber prepared by the preparation method of any one of claims 1 to 9.
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| JP2004131600A (en) * | 2002-10-10 | 2004-04-30 | Japan Science & Technology Agency | Method for coating synthetic polymer with chitosan and chitosan-coated formed product |
| US20070161308A1 (en) * | 2006-01-12 | 2007-07-12 | North Carolina State University | Atmospheric pressure plasma-aided antimicrobial finishes of textiles |
| CN106930108A (en) * | 2017-05-09 | 2017-07-07 | 深圳优普莱等离子体技术有限公司 | A kind of method of textile chitosan antibacterial finishing |
| CN111206412A (en) * | 2020-02-28 | 2020-05-29 | 浙江康洁丝新材料科技有限公司 | Plasma modified grafted antibacterial fiber and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004131600A (en) * | 2002-10-10 | 2004-04-30 | Japan Science & Technology Agency | Method for coating synthetic polymer with chitosan and chitosan-coated formed product |
| US20070161308A1 (en) * | 2006-01-12 | 2007-07-12 | North Carolina State University | Atmospheric pressure plasma-aided antimicrobial finishes of textiles |
| CN106930108A (en) * | 2017-05-09 | 2017-07-07 | 深圳优普莱等离子体技术有限公司 | A kind of method of textile chitosan antibacterial finishing |
| CN111206412A (en) * | 2020-02-28 | 2020-05-29 | 浙江康洁丝新材料科技有限公司 | Plasma modified grafted antibacterial fiber and preparation method and application thereof |
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