CN114672894B - Antibacterial nylon yarn and preparation process thereof - Google Patents
Antibacterial nylon yarn and preparation process thereof Download PDFInfo
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- CN114672894B CN114672894B CN202210420761.7A CN202210420761A CN114672894B CN 114672894 B CN114672894 B CN 114672894B CN 202210420761 A CN202210420761 A CN 202210420761A CN 114672894 B CN114672894 B CN 114672894B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
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Abstract
The application relates to the field of functional textiles, and particularly discloses an antibacterial nylon yarn and a preparation process thereof. The antibacterial nylon yarn is prepared from antibacterial master batches and common master batches, wherein the antibacterial master batches are prepared from graphene oxide/nano silver antibacterial agent, antioxidant, dispersing agent and PA6 carrier resin, and the common master batches are prepared from PA6 carrier resin. The preparation process of the antibacterial nylon yarn comprises the following steps: mixing antibacterial master batch, common master batch, dispersing agent and antioxidant in proportion, and melt spinning. The antibacterial nylon yarn has the effects of good antibacterial performance and long antibacterial performance retention time, and when a child wears the nylon fabric made of the antibacterial nylon yarn, the antibacterial agent plays a certain role in inhibiting the growth and propagation of bacteria attached to the antibacterial nylon fabric, so that the problem that the health of the child can be influenced due to the fact that the bacteria are continuously propagated on the nylon fabric is solved to a certain extent.
Description
Technical Field
The application relates to the field of functional textiles, in particular to an antibacterial nylon yarn and a preparation process thereof.
Background
Nylon generally refers to nylon, nylon is the first synthetic fiber in the world, and nylon fiber has high strength, good elasticity and good wear resistance, and is widely applied to the fields of clothing socks, household textiles and the like.
Nylon is prone to generate static electricity. Under the electrostatic adsorption effect, a certain amount of dust can be adsorbed on the nylon surface. A certain amount of bacteria are entrained in the dust, and the bacteria can be attached to the surface of the nylon.
When a user wears nylon clothes, sweat can be discharged from a human body in certain specific occasions, such as hot weather and sports, and the sweat contains water, sodium chloride, a small amount of urea, lactic acid and fatty acid. The warm and moist environment and the nutrients in the sweat provide a good condition for bacteria to multiply, and bacteria continually multiply on the nylon surface.
With respect to the above related art, the applicant believes that when the user of the nylon garment is a young child, on the one hand, the child is on the move and sweat accumulates on the surface of the nylon garment, which provides a good condition for bacterial reproduction, and on the other hand, the child is relatively weak in immunity. The growing bacteria may have a certain impact on the physical health of the child.
Disclosure of Invention
In order to solve the problem that bacteria continuously propagate on nylon clothes and possibly influence health of children, the application provides an antibacterial nylon yarn and a preparation process thereof.
In a first aspect, the application provides an antibacterial nylon yarn, which adopts the following technical scheme:
an antibacterial nylon yarn is prepared from the following raw materials in percentage by mass:
2% -5% of antibacterial master batch;
the common master batch is supplemented to 100 percent;
the antibacterial master batch is prepared from the following raw materials in percentage by mass:
20% of graphene oxide/nano silver antibacterial agent;
0.5% -1% of antioxidant;
0.5% -1% of dispersing agent;
the PA6 carrier resin is supplemented to 100%;
the common master batch is made of PA6 carrier resin.
By adopting the technical scheme, the nano silver has good broad-spectrum antibacterial property, high safety, low toxicity to human cells and difficult generation of drug resistance, but the nano silver has the characteristics of easy oxidative discoloration, easy agglomeration and the like, so that the application of the nano silver is limited to a certain extent. The graphene oxide is a two-dimensional lamellar carbonaceous material, has good antibacterial performance and high safety, has low cytotoxicity to mammals, and contains more oxygen-containing functional groups such as carbonyl, carboxyl, hydroxyl and the like on the surface of the graphene oxide. These oxygen-containing functional groups provide favorable binding sites for nano-silver, and therefore graphene oxide is an ideal carrier for nano-silver.
After graphene oxide is used as a carrier and combined with nano silver particles, nano silver is mainly loaded on a sheet layer of the graphene oxide, so that the nano silver is stabilized and protected, the problem that the nano silver is easy to oxidize and change color is solved to a certain extent, meanwhile, the graphene oxide/nano silver composite material can reduce the release speed of the nano silver, play a slow release role, prolong the action time of the antibacterial nylon yarn, and enable the antibacterial nylon yarn to keep good antibacterial performance for a long time.
The graphene oxide/nano silver is used as an antibacterial agent to prepare antibacterial master batches, and then the antibacterial master batches and the common master batches are used to prepare antibacterial nylon yarns, so that when a child wears the antibacterial nylon fabric prepared from the antibacterial nylon yarns, the antibacterial agent plays a certain role in inhibiting the growth and propagation of bacteria attached to the antibacterial nylon fabric, and the problem that the health of the child can be influenced due to the fact that the bacteria are continuously propagated on the nylon fabric is solved to a certain extent.
Preferably, the graphene oxide/nano silver antibacterial agent is prepared from the following raw materials in parts by mass:
30 parts of graphene oxide powder solution with the concentration of 0.1 g/mL;
60 parts of 0.05g/mL silver nitrate solution;
3-5 parts of a reducing agent;
3-5 parts of a protective auxiliary agent;
3-5 parts of dispersing auxiliary.
By adopting the technical scheme, the reducing agent reduces silver ions in the silver nitrate solution and Ag + The ions are reduced into Ag atoms and grow into simple substance particles, the dispersing auxiliary plays a role in reducing agglomeration among the generated simple substance silver particles, and particle size is reduced, so that nano silver is obtained. The nano silver and the graphene oxide form a graphene oxide/nano silver composite material through electrostatic interaction.
Preferably, the reducing agent is any one of glucose, sodium citrate or ascorbic acid.
By adopting the technical scheme, the selection of the reducing agent is further limited, glucose, sodium citrate and ascorbic acid have reducibility, compared with common reducing agents such as hydrazine hydrate, hydroquinone, sodium borohydride and the like, the glucose, the sodium citrate and the ascorbic acid are nontoxic and green reducing agents, and toxic substances are not generated after the glucose, the sodium citrate and the ascorbic acid are reduced.
Preferably, the dispersing aid is any one of polyethylene glycol, polyvinylpyrrolidone, aniline or gelatin.
By adopting the technical scheme, the specific surface area and free energy of the nano silver particles are higher, the nano silver particles are easy to agglomerate in the aqueous solution, and in order to improve the quality of the graphene oxide/nano silver antibacterial agent as much as possible when the graphene oxide/nano silver antibacterial agent is prepared, the stability of the nano silver particles in water needs to be improved as much as possible, so that a dispersing auxiliary is often needed to prevent the agglomeration during the preparation. Polyethylene glycol, polyvinylpyrrolidone, aniline and gelatin are all dispersing aids. Taking gelatin as a dispersing auxiliary as an example, a part of polypeptide chains of the gelatin are hydrophobic groups, a part of polypeptide chains of the gelatin are hydrophilic groups, and the nano silver particles belong to a hydrophobic system, so that the gelatin can well coat the nano silver particles, the nano silver particles are in a relatively isolated state, a space blocking effect is generated, and aggregation among the nano silver particles can be prevented.
Meanwhile, the gelatin is different from polyethylene glycol, polyvinylpyrrolidone and aniline and is a natural polymer material, and the gelatin is nontoxic and pollution-free and more in line with the production concept of environmental protection.
Preferably, the protection auxiliary agent is sodium alginate and chitosan, and sodium alginate is prepared from the following components in percentage by mass: chitosan is 1:1.
by adopting the technical scheme, the nano silver particles have higher surface energy in the exposed state and cannot be stably stored, sodium alginate and chitosan are natural macromolecules, the sodium alginate contains a large number of hydroxyl groups and carboxyl groups, the molecular chain of the chitosan contains a large number of hydroxyl groups and amino groups, and the oxygen-containing groups provide a plurality of binding sites for the nano silver particles, so that the surface energy of the nano silver particles is reduced, the nano silver is further protected, and the agglomeration of the nano silver is further reduced.
Meanwhile, due to the existence of oxygen-containing functional groups such as hydroxyl, amino, carboxyl and the like, sodium alginate and chitosan have certain reducibility, and can also be used as reducing agents, so that the reduction effect of silver ions in silver nitrate is improved.
Preferably, the graphene oxide/nano silver antibacterial agent is prepared by the following preparation process:
a1, preparing an auxiliary agent of the graphene oxide/nano silver antibacterial agent, respectively dissolving a protection auxiliary agent and a dispersion auxiliary agent in deionized water, mixing the solutions to obtain the auxiliary agent, and regulating the pH value of the auxiliary agent to 8.3-8.4 through an alkaline agent;
a2, preparing a graphene oxide/nano silver antibacterial agent, carrying out ultrasonic treatment on a graphene oxide powder solution for 30min, mixing a silver nitrate solution and the graphene oxide powder solution, carrying out ultrasonic treatment again for 20min, transferring to a water bath at 60 ℃ for heating, adding the auxiliary agent and the reducing agent prepared by the A1 in proportion, stirring for 20min, standing for precipitation for 6h after the reaction is finished, washing the precipitate with ethanol and deionized water in sequence, carrying out suction filtration, and freeze-drying to obtain the graphene oxide/silver particle antibacterial agent.
By adopting the technical scheme, compared with reducing agents such as hydrazine hydrate, hydroquinone, sodium borohydride and the like, the reducing agents such as glucose, sodium citrate and ascorbic acid are relatively weak in reducing property, but the glucose, the sodium citrate and the ascorbic acid are nontoxic and green reducing agents, and toxic substances are not produced after the glucose, the sodium citrate and the ascorbic acid are reduced, so that the reducing agents such as glucose, sodium citrate and ascorbic acid are selected according with the concept of green production.
Since the reducing agents used are nontoxic green reducing agents such as glucose, sodium citrate and ascorbic acid, but these reducing agents are relatively weak in reducibility, the reaction needs to be carried out under heating.
The reducing agents have weaker reducing capability and are more beneficial to the growth of nano silver particles. Ag+ generates Ag atoms in a liquid phase system, and various auxiliaries induce the Ag atoms to gather, so that nano silver with different morphologies is formed. Glucose, sodium citrate and ascorbic acid are relatively weak in reducibility, the rate of silver ions being reduced is relatively slow, and the probability that nano silver particles grow up due to mutual aggregation and the overall specific surface area of nano silver becomes smaller is reduced as much as possible.
Glucose is taken as a reducing agent, the reducing capability of the glucose is weak under acidic and neutral conditions, the reaction with silver ions is slow, the nano silver is not easy to obtain, the pH value and the temperature of the solution are improved, the reducing capability of the glucose can be improved, and the reducing capability of the glucose is improved by adjusting the pH value and the temperature of the solution, so that the nano silver particles with higher quality are obtained. Meanwhile, when gelatin is adopted as a dispersing auxiliary, the viscosity of the blending liquid of gelatin, sodium alginate and chitosan can change along with the temperature, concentration and pH value, gel can be formed when the viscosity is larger, the reaction time is prolonged, the longer the preparation time is, the larger particles are more easily aggregated by nano silver particles, the overall specific surface area of the nano silver is reduced, and the antibacterial rate of the antibacterial nylon yarn is reduced.
The applicant found that when the pH is 8.3-8.4, the blend of gelatin, sodium alginate and chitosan is transparent and has a low viscosity. Meanwhile, when the pH is 8.3-8.4, the reducing capability of glucose is better when the reaction temperature is 60 ℃.
The antibacterial property of the chitosan mainly comes from protonated amino groups on C2 in the molecular structure of the chitosan, but under neutral or alkaline environment, the antibacterial property of the chitosan is greatly weakened due to the reduction of the protonated amino groups, and after the nano silver is combined with the chitosan, the antibacterial defect of the chitosan under the neutral or alkaline environment can be overcome, and the nano silver can be stabilized.
Preferably, the alkaline agent is any one of sodium hydroxide, triethanolamine, disodium hydrogen phosphate or ammonia water.
By adopting the technical scheme, the applicant finds that when ammonia water is used as an alkaline agent and glucose is used as a reducing agent, the prepared graphene oxide/nano silver has good antibacterial performance, and for analysis reasons, ammonium ions in the ammonia water are complexed with silver ions after the ammonia water is added into a solution system to form silver ammonia complex ions, and ammonia molecules are continuously released by the silver ammonia complex ions in the reaction process and are matched with nitrate ions in a silver nitrate solution to form an ammonium nitrate solution consisting of the ammonia water and the ammonium nitrate, so that the alkaline environment of the reaction system is maintained as much as possible, the sustainable progress of the reaction is ensured, and the reduction rate of the silver ions is improved.
In a second aspect, the application provides a preparation process of antibacterial nylon yarn, which adopts the following scheme: and (3) drying the graphene oxide/nano silver antibacterial agent prepared by the A2, PA6 carrier resin and a dispersing agent, and mixing the dried graphene oxide/nano silver antibacterial agent, PA6 carrier resin and the dispersing agent in proportion for melt spinning to obtain the antibacterial nylon yarn.
Preferably, the dispersing agent is polyethylene wax and zinc stearate, and the polyethylene wax is prepared by the following mass ratio: zinc stearate is 1:1.
by adopting the technical scheme, the dispersibility and the fluidity of the graphene oxide/nano silver antibacterial agent in the antibacterial master batch are improved by the polyethylene wax and the zinc stearate, so that the antibacterial agent is uniformly dispersed on the carrier in the high-speed mixing process of raw materials. In addition, zinc ions in the zinc stearate have a certain antibacterial effect, so that the antibacterial performance of the antibacterial nylon yarn is further improved.
In summary, the application has the following beneficial effects:
1. the graphene oxide/nano silver antibacterial agent is prepared by combining graphene oxide serving as a carrier with nano silver particles, and is prepared into the antibacterial nylon yarn in a melt spinning mode, on one hand, the graphene oxide plays a role in stabilizing and protecting the nano silver particles, so that the problem that nano silver can be easily oxidized and discolored is solved, and on the other hand, the release speed of the nano silver particles is reduced by the graphene oxide, so that the antibacterial nylon yarn can keep good antibacterial performance for a long time, and the antibacterial effect of the antibacterial nylon yarn is optimized, on the other hand, the graphene oxide also has a certain antibacterial performance, the antibacterial effect of the antibacterial nylon yarn is further optimized, and when a child wears the nylon fabric prepared from the antibacterial nylon yarn, the antibacterial agent plays a certain role in inhibiting the growth and reproduction of bacteria attached to the antibacterial nylon fabric, so that the problem that the health of the child can be influenced due to the continuous reproduction of the bacteria on the nylon fabric is improved to a certain extent;
2. by limiting the components of the reducing agent and the alkaline agent, for example, glucose is specifically selected as the reducing agent, ammonia water is selected as the alkaline agent, and glucose, ammonia water and silver nitrate solution produce synergistic effect, so that the reaction rate of the silver nitrate solution is increased, the removal of oxygen in the solution is facilitated in the reaction process, and the reduction is facilitated;
3. when gelatin is specifically selected as the dispersing aid, the sodium alginate contains a large amount of hydroxyl groups and carboxyl groups, the molecular chain of the chitosan contains a large amount of hydroxyl groups and amino groups, the nano silver is further protected, the aggregation of the nano silver is further reduced, meanwhile, the gelatin, the sodium alginate and the chitosan all have certain reducibility, the gelatin, the sodium alginate and the chitosan can be used as reducing agents when being used as the dispersing aid, the reducing effect of silver ions in the silver nitrate is improved, the reaction conditions of the dispersing aid and the protecting aid are limited, the pH is 8.3-8.4, the mixed solution of the gelatin, the sodium alginate and the chitosan is transparent and has small viscosity when the reaction temperature is 60 ℃, the reducing capability of glucose is better, meanwhile, the defect of the antibacterial property of the chitosan in a neutral or alkaline environment can be overcome after the nano silver and the chitosan are combined, and the antibacterial effect of the antibacterial nylon yarn is further improved.
Detailed Description
The present application will be described in further detail with reference to preparation examples, examples and comparative examples.
Preparation example
Preparation example 1
Each part of graphene oxide/silver particle antibacterial agent is prepared from the following components in parts by mass:
3000g of graphene oxide powder solution with the concentration of 0.1 g/mL;
6000g of silver nitrate solution with the concentration of 0.05 g/mL;
400g of a reducing agent, specifically 400g of glucose;
400g of dispersing aid, which is specifically 400g of gelatin;
400g of a protective auxiliary agent, which is specifically prepared from 200g of chitosan and 200g of sodium alginate;
3000mL of deionized water.
The graphene oxide/silver particle antibacterial agent is prepared by the following preparation process:
a1, preparing an auxiliary agent of graphene oxide/nano silver antibacterial agent, namely mixing 3000mL of deionized water according to a ratio of 2:2:1:1 is divided into four parts, 400g of glucose is dissolved in 1000mL of deionized water to prepare a glucose solution of 0.4g/mL, similarly, a gelatin solution of 0.4g/mL is prepared, 200g of chitosan is dissolved in 500mL of deionized water to prepare a chitosan solution of 0.4g/mL, similarly, a sodium alginate solution of 0.4g/mL is prepared, and the gelatin solution, the chitosan solution and the sodium alginate solution are mixed to obtain an auxiliary agent, and the pH value of the auxiliary agent is adjusted to 8.3 through ammonia water.
A2, preparing a graphene oxide/nano silver antibacterial agent, namely ultrasonically treating graphene oxide powder solution for 30min through a 40KHz 100W ultrasonic cleaner, mixing 3000mL of graphene oxide powder solution with 6000mL of silver nitrate solution to obtain a mixed solution, ultrasonically treating for 20min through the 40KHz 100W ultrasonic cleaner, transferring into a water bath at 60 ℃, adding the auxiliary agent prepared by the A1 and the glucose solution into the mixed solution, stirring for 20min, standing and precipitating for 6h after the reaction is finished to obtain a precipitate, sequentially cleaning the precipitate with ethanol and deionized water, and fully drying to obtain the graphene oxide/nano silver antibacterial agent.
Preparation example 2
The present preparation example differs from preparation example 1 in that the reducing agent in each part of graphene oxide/silver particle antibacterial agent is 400g of sodium citrate.
Preparation example 3
The present preparation example differs from preparation example 1 in that the reducing agent in each part of graphene oxide/silver particle antibacterial agent is 400g of ascorbic acid.
Preparation example 4
The present preparation example differs from preparation example 1 in that the reducing agent in each of the graphene oxide/silver particle antibacterial agents is 200g of glucose and 200g of sodium citrate.
Preparation example 5
The present preparation example differs from preparation example 1 in that the reducing agent in each part of graphene oxide/silver particle antibacterial agent is 200g of glucose and 200g of ascorbic acid.
Preparation example 6
The present preparation example differs from preparation example 1 in that the reducing agent in each part of graphene oxide/silver particle antibacterial agent is 200g of sodium citrate and 200g of ascorbic acid.
Preparation example 7
The preparation example differs from preparation example 1 in that the dispersing aid in each part of graphene oxide/silver particle antibacterial agent is 400g of polyethylene glycol.
Preparation example 8
The present preparation example differs from preparation example 1 in that the dispersing aid in each part of graphene oxide/silver particle antibacterial agent is 400g of polyvinylpyrrolidone.
Preparation example 9
The present preparation example differs from preparation example 1 in that the dispersing aid in each part of graphene oxide/silver particle antibacterial agent is aniline 400g.
Preparation example 10
The preparation example differs from preparation example 1 in that the alkaline agent for adjusting the pH of the auxiliary agent in each part of graphene oxide/silver particle antibacterial agent is sodium hydroxide.
PREPARATION EXAMPLE 11
The preparation example differs from preparation example 1 in that the alkaline agent for adjusting the pH of the auxiliary agent in each part of graphene oxide/silver particle antibacterial agent is triethanolamine.
Preparation example 12
The preparation example differs from preparation example 1 in that the alkaline agent for adjusting the pH of the auxiliary agent in each part of graphene oxide/silver particle antibacterial agent is disodium hydrogen phosphate.
Preparation example 13
The present preparation example differs from preparation example 1 in that no alkaline agent is added to each part of graphene oxide/silver particle antibacterial agent.
PREPARATION EXAMPLE 14
The present preparation example differs from preparation example 1 in that the pH of the auxiliary agent in each part of graphene oxide/silver particle antibacterial agent is adjusted to 7.5 by means of aqueous ammonia as an alkaline agent.
Preparation example 15
The present preparation example differs from preparation example 1 in that the pH of the auxiliary agent in each part of graphene oxide/silver particle antibacterial agent is adjusted to 9.5 by means of aqueous ammonia as an alkaline agent.
PREPARATION EXAMPLE 16
The preparation example is different from the preparation example 1 in that each part of graphene oxide/silver particle antibacterial agent is prepared from the following components in parts by mass:
3000g of graphene oxide powder solution with the concentration of 0.1 g/mL;
6000g of silver nitrate solution with the concentration of 0.05 g/mL;
300g of reducing agent, specifically 300g of glucose;
300g of dispersing auxiliary, which is specifically gelatin 300g;
300g of protective auxiliary agent, which is specifically prepared from 150g of chitosan and 150g of sodium alginate;
3000mL of deionized water.
The graphene oxide/silver particle antibacterial agent is prepared by the following preparation process:
a1, preparing an auxiliary agent of graphene oxide/nano silver antibacterial agent, namely mixing 3000mL of deionized water according to a ratio of 2:2:1:1 is divided into four parts, 400g of glucose is dissolved in 1000mL of deionized water to prepare a glucose solution of 0.4g/mL, similarly, a gelatin solution of 0.4g/mL is prepared, 150g of chitosan is dissolved in 500mL of deionized water to prepare a chitosan solution of 0.3g/mL, similarly, a sodium alginate solution of 0.3g/mL is prepared, and the gelatin solution, the chitosan solution and the sodium alginate solution are mixed to obtain an auxiliary agent, and the pH value of the auxiliary agent is adjusted to 8.3 through ammonia water.
A2, preparing a graphene oxide/nano silver antibacterial agent, namely ultrasonically treating graphene oxide powder solution for 30min through a 40KHz 100W ultrasonic cleaner, mixing 3000mL of graphene oxide powder solution with 6000mL of silver nitrate solution to obtain a mixed solution, ultrasonically treating for 20min through the 40KHz 100W ultrasonic cleaner, transferring into a water bath at 60 ℃, adding the auxiliary agent prepared by the A1 and the glucose solution into the mixed solution, stirring for 20min, standing and precipitating for 6h after the reaction is finished to obtain a precipitate, sequentially cleaning the precipitate with ethanol and deionized water, and fully drying to obtain the graphene oxide/nano silver antibacterial agent.
Preparation example 17
The preparation example is different from the preparation example 1 in that each part of graphene oxide/silver particle antibacterial agent is prepared from the following components in parts by mass:
3000g of graphene oxide powder solution with the concentration of 0.1 g/mL;
6000g of silver nitrate solution with the concentration of 0.05 g/mL;
500g of a reducing agent, specifically 500g of glucose;
500g of dispersing auxiliary, which is specifically gelatin 500g;
500g of a protective auxiliary agent, which is specifically prepared from 250g of chitosan and 250g of sodium alginate;
3000mL of deionized water.
The graphene oxide/silver particle antibacterial agent is prepared by the following preparation process:
a1, preparing an auxiliary agent of graphene oxide/nano silver antibacterial agent, namely mixing 3000mL of deionized water according to a ratio of 2:2:1:1 is divided into four parts, 500g of glucose is dissolved in 1000mL of deionized water to prepare a glucose solution of 0.5g/mL, similarly, a gelatin solution of 0.5g/mL is prepared, 250g of chitosan is dissolved in 500mL of deionized water to prepare a chitosan solution of 0.5g/mL, similarly, a sodium alginate solution of 0.5g/mL is prepared, and the gelatin solution, the chitosan solution and the sodium alginate solution are mixed to obtain an auxiliary agent, and the pH value of the auxiliary agent is adjusted to 8.3 through ammonia water.
A2, preparing a graphene oxide/nano silver antibacterial agent, namely ultrasonically treating graphene oxide powder solution for 30min through a 40KHz 100W ultrasonic cleaner, mixing 3000mL of graphene oxide powder solution with 6000mL of silver nitrate solution to obtain a mixed solution, ultrasonically treating for 20min through the 40KHz 100W ultrasonic cleaner, transferring into a water bath at 60 ℃, adding the auxiliary agent prepared by the A1 and the glucose solution into the mixed solution, stirring for 20min, standing and precipitating for 6h after the reaction is finished to obtain a precipitate, sequentially cleaning the precipitate with ethanol and deionized water, and fully drying to obtain the graphene oxide/nano silver antibacterial agent.
Examples
Example 1
The embodiment of the application discloses an antibacterial nylon yarn, which is prepared from the following raw materials in parts by mass:
2500g of antibacterial master batch;
47500g of common master batch.
The antibacterial master batch is prepared from the following raw materials in parts by mass:
500g of graphene oxide/nano silver antibacterial agent obtained in preparation example 1;
25g of an antioxidant, specifically 12.5g of an antioxidant 168 and 12.5g of an antioxidant 1076;
25g of a dispersing agent, specifically 12.5g of polyethylene wax and 12.5g of zinc stearate;
1950g of PA6 carrier resin.
The common master batch is made of PA6 carrier resin.
Wherein the PA6 carrier resin is specifically PA6 slice produced by Baling petrochemical industry, and the brand BL3280H.
The specific preparation process of the antibacterial nylon yarn comprises the following steps:
s1, preparing antibacterial master batch, namely taking 500g of graphene oxide/nano silver antibacterial agent, 12.5g of antioxidant 168, 12.5g of antioxidant 1076, 12.5g of polyethylene wax, 12.5g of zinc stearate and 1950gPA6 carrier resin, fully drying and uniformly mixing to obtain a premix, and carrying out melt extrusion granulation on the premix to obtain the antibacterial master batch.
S2, preparing antibacterial nylon yarns, namely 2500g of the antibacterial masterbatch obtained in the step S1, 47500g of the common masterbatch, drying and uniformly mixing to obtain mixed masterbatch, and melt-spinning the mixed masterbatch to obtain the antibacterial nylon yarns.
Wherein the graphene oxide/nano silver antibacterial agent is the graphene oxide/nano silver antibacterial agent prepared in preparation example 1.
Example 2-example 15 differs from example 1 only in that the sources of graphene oxide/nanosilver antimicrobial agent in step S1 are different, and the sources of graphene oxide/nanosilver antimicrobial agent in each example are noted in the following table:
example 18
The difference between this example and example 1 is that each part of antibacterial nylon yarn is made from the following raw materials in parts by mass:
1000g of antibacterial master batch;
49000g of ordinary master batch.
Example 19
The difference between this example and example 1 is that each part of antibacterial nylon yarn is made from the following raw materials in parts by mass:
1750g of antibacterial master batch;
48250g of common master batch.
Comparative example
Comparative example 1
The present comparative example differs from example 1 in that the antibacterial agent in the antibacterial master batch in each antibacterial nylon yarn is only nano silver.
Comparative example 2
The present comparative example is different from example 1 in that the antibacterial agent in the antibacterial master batch in each part of antibacterial nylon yarn is only graphene oxide.
Comparative example 3
The comparative example differs from example 1 in that each part of antibacterial nylon yarn is made from the following raw materials in parts by mass:
3000g of antibacterial master batch;
47000g of common master batch.
Performance test
Antibacterial polyamide yarns of examples 1 to 15 and comparative examples 1 to 2 were subjected to antibacterial tests by referring to AATCC 100-2012 evaluation method for antibacterial textiles, and the test results are shown in tables 1, 2, 3 and 4.
TABLE 1
TABLE 2
TABLE 3 Table 3
TABLE 4 Table 4
It can be seen from examples 1 to 6 that the antibacterial rate of the antibacterial nylon yarn after washing 30 times is highest when glucose is used as a reducing agent. The reason for this analysis is probably because the reducibility of glucose is higher than that of sodium citrate, so that the antibacterial rate of the antibacterial nylon yarn in example 1 is higher than that of the antibacterial nylon yarn in example 2. Secondly, the reducibility of the ascorbic acid is relatively higher than that of glucose, which may lead to a relatively high rate of reduction of silver ions, namely, a relatively high rate of generation of nano silver particles, and the silver nano particles grow up due to mutual agglomeration, so that the overall specific surface area of the nano silver becomes smaller, and the antibacterial rate of the antibacterial nylon yarn is reduced.
The applicant finds that the kind of the reducing agent has a certain influence on the reduced rate of silver ions, the reduced rate of nano silver is related to the antibacterial performance of the final graphene oxide/nano silver antibacterial agent, and the reduced rate of silver ions has a certain threshold interval with the better antibacterial performance of the corresponding graphene oxide/nano silver antibacterial agent. Therefore, glucose is used as a reducing agent, the rate of silver ions being reduced is in a better range, and the graphene oxide/nano silver antibacterial agent has better antibacterial performance.
As can be seen from the combination of the examples 1 and 10-13, when ammonia water is used as an alkaline agent, the antibacterial rate of the antibacterial nylon yarn after washing for 30 times is highest, and the reduction of glucose is weak for analysis reasons, and the antibacterial nylon yarn can be spontaneously performed only in an alkaline environment. After ammonia water is added into a solution system, ammonium ions in the ammonia water are complexed with silver ions to form silver ammonia complex ions, ammonia molecules are continuously released by the silver ammonia complex ions in the reaction process, and the ammonia molecules are matched with nitrate ions in a silver nitrate solution to form an ammonium nitrate solution consisting of the ammonia water and the ammonium nitrate, so that the alkaline environment of the reaction system is maintained as much as possible, the sustainable progress of the reaction is ensured, and the reduction rate of the silver ions is improved, namely the antibacterial quality of the antibacterial nylon yarn is improved.
As can be seen from the combination of the examples 1 and 14-15, the antibacterial rate of the antibacterial nylon yarn after 30 times of washing is highest when the pH value is adjusted to 8.4. For analysis reasons, when the pH value is low, the reaction rate is low, the generated silver crystal nucleus is relatively less, the rate of generating silver crystal nucleus is increased along with the increase of the pH value, silver nano particles are continuously generated in the reaction process, the silver nano particles grow up due to mutual agglomeration, when the pH value is 8.4, the rate of generating the nano silver particles is relatively stable, the particle size of the silver nano particles is relatively minimum, the specific surface area of the nano silver is relatively maximum, and the antibacterial quality of the antibacterial nylon yarn is relatively highest.
It can be seen from the combination of example 1 and comparative examples 1-2 that both graphene oxide and nano silver have a certain antibacterial property, and that the antibacterial property of the graphene oxide/nano silver antibacterial agent is more excellent under the condition that the contents of the graphene oxide, nano silver and graphene oxide/nano silver are the same. The reason for the analysis is probably because after the graphene oxide and the nano silver are combined, the antibacterial effect of the graphene oxide and the nano silver is completed through the coordination effect, and the antibacterial effect is not simply added. On one hand, nano silver is easy to agglomerate in an aqueous solution, and after graphene oxide is used as a substrate of the nano silver, the agglomeration of the nano silver is inhibited, so that the specific surface area of the nano silver is increased; on the other hand, graphene oxide has stronger electronegativity, and the surface of escherichia coli is electronegative, so that the graphene oxide and the escherichia coli mutually repel each other, and the electronegativity of the surface of the graphene oxide material is reduced by introducing nano silver.
It can be seen from the combination of examples 1, examples 18 to 19 and comparative example 3 that the antibacterial performance of the antibacterial nylon yarn is improved as the content of the antibacterial master batch is increased. However, the applicant found that when the content of the antibacterial master batch exceeds 5%, i.e. the content of the graphene oxide/nano silver antibacterial agent exceeds 1%, phenomena such as yarn floating and broken ends occur in the spinning process. Therefore, from the production point of view, the content of the selected antibacterial master batch is 2-5%.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (3)
1. The antibacterial nylon yarn is characterized by being prepared from the following raw materials in percentage by mass: 2% -5% of antibacterial master batch;
the common master batch is supplemented to 100 percent;
the antibacterial master batch is prepared from the following raw materials in percentage by mass: 20% of graphene oxide/nano silver antibacterial agent;
0.5% -1% of antioxidant; 0.5% -1% of dispersing agent;
the PA6 carrier resin is supplemented to 100%;
the common master batch is made of PA6 carrier resin;
the graphene oxide/nano silver antibacterial agent is prepared from the following raw materials in parts by mass:
30 parts of graphene oxide powder solution with the concentration of 0.1 g/mL;
60 parts of 0.05g/mL silver nitrate solution;
3-5 parts of a reducing agent; 3-5 parts of a protective auxiliary agent; 3-5 parts of dispersing auxiliary;
the reducing agent is glucose;
the dispersing auxiliary is gelatin;
the protection auxiliary agent is sodium alginate and chitosan, and sodium alginate is prepared from the following components in percentage by mass: chitosan is 1:1, a step of;
the graphene oxide/nano silver antibacterial agent is prepared by the following preparation process:
a1, preparing an auxiliary agent of the graphene oxide/nano silver antibacterial agent, respectively dissolving a protection auxiliary agent and a dispersion auxiliary agent in deionized water, mixing the solutions to obtain the auxiliary agent, and regulating the pH value of the auxiliary agent to 8.3-8.4 through ammonia water;
a2, preparing a graphene oxide/nano silver antibacterial agent, carrying out ultrasonic treatment on a graphene oxide powder solution, mixing a silver nitrate solution and the graphene oxide powder solution, carrying out ultrasonic treatment again for 20min, transferring to a water bath at 60 ℃ for heating, adding the auxiliary agent and the reducing agent obtained by the preparation of A1, stirring for 20min, standing for precipitation for 6h after the reaction is finished, washing the precipitate with ethanol and deionized water in sequence, carrying out suction filtration, and freeze-drying to obtain the graphene oxide/silver particle antibacterial agent.
2. An antimicrobial nylon yarn according to claim 1, wherein: and (3) drying the graphene oxide/nano silver antibacterial agent prepared by the A2, PA6 carrier resin and a dispersing agent, mixing the dried graphene oxide/nano silver antibacterial agent, PA6 carrier resin, the dispersing agent and an antioxidant in proportion, and carrying out melt extrusion granulation to obtain the antibacterial master batch.
3. An antimicrobial nylon yarn according to claim 2, wherein the dispersing agent is polyethylene wax and zinc stearate, and the polyethylene wax is as follows: zinc stearate is 1:1.
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