CN117799282A - Antibacterial and antiperspirant knitted material, fabric and manufacturing method - Google Patents
Antibacterial and antiperspirant knitted material, fabric and manufacturing method Download PDFInfo
- Publication number
- CN117799282A CN117799282A CN202311521692.XA CN202311521692A CN117799282A CN 117799282 A CN117799282 A CN 117799282A CN 202311521692 A CN202311521692 A CN 202311521692A CN 117799282 A CN117799282 A CN 117799282A
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- antibacterial
- solution
- layer
- fiber
- composite
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Classifications
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Abstract
The invention belongs to the technical field of fabrics, and provides an antibacterial and antiperspirant knitted material, a fabric and a manufacturing method thereof, wherein the manufacturing method comprises the following steps: knitting antibacterial fabric fibers to obtain an antibacterial base layer, dispersing composite nano particles in an ethanol solution of a coupling agent to form an antibacterial dispersion liquid, soaking the antibacterial base layer in the antibacterial dispersion liquid, taking out, cleaning and drying to form a composite nano particle film on the surface of the antibacterial base layer, and thus obtaining an antibacterial composite layer; mixing bamboo carbon fiber, polyester fiber, cotton fiber and deionized water to form spinning solution, heating and melting to obtain spinning solution, spinning the spinning solution to obtain composite yarns, and carrying out double-sided flat knitting on the composite yarns to obtain an antiperspirant base cloth layer; spreading a hot melt adhesive layer and an antibacterial composite layer on the upper layer of the antiperspirant base cloth layer, carrying out hot pressing treatment, cooling, and cleaning and drying to obtain the antibacterial antiperspirant knitted material. The knitted material provided by the invention is formed by compounding the antibacterial composite layer and the antiperspirant base cloth layer, and can simultaneously meet the requirements of people on antibacterial antiperspirant and dryness and comfort.
Description
Technical Field
The invention belongs to the technical field of fabrics, and relates to an antibacterial and antiperspirant knitted material, a fabric and a manufacturing method.
Background
The fabric is a material for making clothing, and the fabric is one of three factors of clothing, can explain the style and the characteristics of the clothing, and directly influences the color, the shape and the expression effect of the clothing. In the clothing field, the clothing fabric is confetti and is different from day to day, but in general, the high-quality and high-grade fabric has the characteristics of comfort in wearing, sweat absorption and ventilation, draping and stiff, noble in vision, soft and beautiful in touch and the like.
Along with the improvement of living standard, the functional textile is more and more favored by people, the moisture-absorbing and quick-drying knitted material adopts brand-new fabric fiber cross-section shape design, and sweat is quickly migrated to the surface of the fabric and diverged by virtue of the functions of wicking, diffusion, transmission and the like of capillary effect generated by micro grooves on the surface of the fiber, so that the purposes of quick water absorption, diffusion, volatilization, quick drying and sweat stopping are realized. The fabric woven by the moisture-absorbing and quick-drying knitted material can absorb sweat rapidly in hot summer when a large amount of sweat is produced by a human body, and the sweat is transferred to the surface of the fabric to volatilize, so that the skin surface is kept dry and comfortable.
CN218115760U discloses a sweat-resistant track, three-dimensional water-conducting knitted fabric, comprising, from inside to outside, a skin-friendly skin layer for contacting skin, a moisture-absorbing sweat-releasing layer for absorbing moisture and releasing sweat, and a sweat-resistant track layer for repelling water and preventing sweat track from being revealed; the moisture absorption and sweat release layer comprises a sweat absorption layer, a plurality of sweat absorption columns are uniformly arranged on the sweat absorption layer at intervals, and water guide grooves are arranged between the sweat absorption columns; the water guide groove is filled with air, and an air layer for circulating water guide is formed between the water guide groove and the skin layer. However, the knitted fabric produced by the technology has a complex structure, is poor in comfort when being used for clothing fabrics, and has no antibacterial effect.
CN212288986U discloses an antibacterial crease-resistant knitted fabric, which comprises an upper knitted fabric, a middle knitted fabric and a lower knitted fabric, wherein the middle knitted fabric is arranged at the lower end of the upper knitted fabric, the lower knitted fabric is arranged at the lower end of the middle knitted fabric, a first antibacterial layer is arranged between the upper knitted fabric and the middle knitted fabric, a second antibacterial layer is arranged between the middle knitted fabric and the lower knitted fabric, bamboo charcoal antibacterial fiber yarns are arranged in the first antibacterial layer, protein fiber yarns are arranged at the lower end of the bamboo charcoal antibacterial fiber yarns, jute antibacterial fiber yarns are arranged in the second antibacterial layer, and polyester fiber yarns are arranged at the lower end of the jute antibacterial fiber yarns. However, the antibacterial crease-resistant knitted fabric produced by the technology has a certain groove-shaped structure on the fiber surface, provides an ideal environment for bacterial breeding and reproduction, makes a wearer more easily suffer from bacterial infection or sweat odor, cannot simultaneously take antibacterial and antiperspirant functions into consideration, has poor comfort when in contact with human skin, and is not suitable for being used as a garment fabric.
Therefore, the prior moisture-absorbing and quick-drying knitted material is endowed with certain antibacterial capability, and particularly when the moisture-absorbing and quick-drying knitted material is used for underwear, bacterial interference and virus infection suffered by human bodies can be directly and effectively reduced.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide an antibacterial and antiperspirant knitted material, a fabric and a manufacturing method thereof.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method of manufacturing an antibacterial antiperspirant knit material, the method comprising:
knitting antibacterial fabric fibers to obtain an antibacterial base layer, dispersing composite nano particles in an ethanol solution of a coupling agent to form an antibacterial dispersion liquid, soaking the antibacterial base layer in the antibacterial dispersion liquid, taking out, cleaning and drying after soaking to form a composite nano particle film on the surface of the antibacterial base layer to obtain an antibacterial composite layer;
(II) mixing bamboo carbon fiber, polyester fiber, cotton fiber and deionized water to form spinning solution, heating and melting the spinning solution to obtain spinning solution, spinning the spinning solution to obtain composite yarn, and finally performing double-sided flat knitting on the composite yarn to obtain an antiperspirant base cloth layer;
And (III) sequentially laying a hot melt adhesive layer and the antibacterial composite layer obtained in the step (I) on the antiperspirant base cloth layer obtained in the step (III), then carrying out hot pressing treatment to bond and composite the antiperspirant base cloth layer and the antibacterial composite layer through the hot melt adhesive layer, cooling, and then washing and drying to obtain the antibacterial antiperspirant knitted material.
The knitted material provided by the invention is formed by compounding the antibacterial composite layer and the antiperspirant base cloth layer, and can simultaneously meet the requirements of people on antibacterial antiperspirant and dryness and comfort. The antibacterial composite layer is used as the surface layer, so that the antibacterial composite layer can effectively resist the bacterial interference of the external environment and can effectively kill bacteria and microorganisms attached to the surface of the fabric; meanwhile, the anti-sweat base cloth layer is used as a bottom layer, the anti-sweat base cloth layer is in direct contact with the skin, and the requirements on the hygroscopicity and the air permeability of the fabric are higher.
The air permeability and the moisture absorption performance are important factors influencing the comfort of fabric body feeling, and the antiperspirant base cloth layer prepared by the method has good air permeability and moisture absorption performance, on one hand, cotton fibers and bamboo charcoal fibers have micropore structures, can quickly absorb moisture emitted by skin, quicken the speed of sweat diffusing to the surrounding environment, and keep the skin dry; the polyester fiber has high strength, good elasticity and smooth surface, and sweat is not easy to adhere, so that the residual quantity of sweat on the antiperspirant base cloth layer is reduced, and the bacteria are prevented from breeding and culturing, thereby being beneficial to the environment. On the other hand, the knitting structure of the knitting material is formed by mutually penetrating loops, so that the knitting material is in a three-dimensional structure, more gaps are formed at the penetrating points, favorable conditions are provided for ventilation and sweat evaporation, and the knitting material has good air permeability and moisture absorption.
As a preferable technical scheme of the invention, in the step (I), the antibacterial textile fiber is prepared by adopting the following method:
(1) Oxidizing the fiber raw material to oxidize hydroxyl groups of fiber molecular chains into carboxyl groups, immersing the oxidized fiber raw material into an amino acid solution for esterification reaction to obtain a modified fiber raw material;
(2) Adding chitosan, tannic acid and silver nitrate into an acetic acid solution, uniformly mixing to obtain a reaction solution, and reacting the reaction solution under a light-shielding condition to obtain an antibacterial solution;
(3) The modified fiber raw material is soaked in the antibacterial solution, taken out and dried to obtain the antibacterial fabric fiber.
According to the invention, firstly, amino acid is grafted onto a fiber raw material through an esterification reaction, and silver ions are loaded onto the surface of the modified fiber raw material under the complexation of amino and sulfhydryl by using the amino acid as an adhesive. The tannic acid is used as a reducing agent of silver ions, silver nitrate can be reduced to obtain silver nano particles, and in addition, the original cytotoxicity of the tannic acid is obviously reduced due to the loading of the silver ions.
The chitosan, the tannic acid and the silver nano particles added in the invention form a composite antibacterial system, and the composite antibacterial system formed by the chitosan and the silver nano particles not only shows the bactericidal effect of silver ions, but also shows the antibacterial effect of chitosan cations, so that the prepared knitted material has more enhanced and durable antibacterial performance. On one hand, the chitosan can be coated on the surface of the silver nano particles, the dispersibility of the Gao Yin nano particles is improved, and meanwhile, the aggregation of the silver nano particles can be effectively relieved, so that the silver nano particles with finer particle size and more uniform dispersion are obtained, and meanwhile, the chitosan is coated to generate a slow release effect, so that the toxicity of silver ions is further weakened; on the other hand, the coating layer formed by chitosan can perform electrostatic interaction with negatively charged residues on the surface of bacteria, so that the permeability of bacterial cell membranes is destroyed, and nutrient substances in bacterial cells such as electrolyte, protein, amino acid, glucose and the like are leaked, so that the normal metabolism of the bacteria is influenced, and the death of the bacteria is finally caused.
In addition, the hydration layer antibacterial film is formed on the surface of the fiber raw material through self-assembly combination of chitosan and tannic acid. Wherein, chitosan can act with groups with negative charges on the surfaces of bacterial cells, thereby changing the fluidity and permeability of bacterial cell membranes; meanwhile, chitosan can form double interference to microorganisms through electrostatic action, so that the permeability of the cell membrane wall of the microorganisms is changed, the osmotic pressure in the cells of the microorganisms is unbalanced, and the aim of inhibiting the growth of the microorganisms is fulfilled; the high concentration chitosan can also induce the hydrolysis of peptidoglycan on the cell wall, resulting in leakage of intracellular electrolytes, firstly potassium ions, phosphate small molecular substances, then macromolecular substances such as DNA, RNA, protein, enzyme and the like, and finally resulting in bacterial death. Tannic acid is a biodegradable water-soluble natural compound which is widely present in plant extracts and has antibacterial, anti-inflammatory, antiviral and antioxidant activities.
Because tannic acid molecules contain a large number of phenolic hydroxyl groups, interaction can occur between the tannic acid molecules and chitosan, and a hydration layer antibacterial film with good hydrophilicity is formed on the surface of the fiber raw material through self-assembly combination, on one hand, the hydration layer antibacterial film can inhibit bacterial adhesion; on the other hand, a small amount of bacteria and microorganisms adhered to the antibacterial film of the hydration layer, because the biological coating contains silver nano particles, the silver nano particles are in direct contact with the bacteria and microorganisms, so that a better antibacterial effect is achieved.
In a preferred embodiment of the present invention, in step (1), the fiber raw material is any one or a combination of at least two of cotton fabric fiber, regenerated cellulose fabric fiber and hemp fabric fiber.
The oxidation treatment process comprises the following steps: immersing the fiber raw material in an oxidizing solution, taking out and drying for standby after immersing.
The amount of the oxidizing solution is 20 to 30mL/g of the fiber raw material, and 20mL, 21mL, 22mL, 23mL, 24mL, 25mL, 26mL, 27mL, 28mL, 29mL or 30mL may be added to each g of the fiber raw material, but the oxidizing solution is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable.
The mass fraction of the oxidizing solution is 10-20wt%, for example, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, 19wt% or 20wt%, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The oxidizing solution is any one or the combination of at least two of hydrogen peroxide solution, potassium permanganate solution and sodium hypochlorite solution.
The soaking time of the fiber raw material in the oxidizing solution is 1 to 5 hours, for example, 1.0 hour, 1.5 hours, 2.0 hours, 2.5 hours, 3.0 hours, 3.5 hours, 4.0 hours, 4.5 hours or 5.0 hours, but the fiber raw material is not limited to the listed values, and other non-listed values in the range of the values are equally applicable.
The concentration of the amino acid solution is 0.15 to 0.25mol/L, and may be, for example, 0.15mol/L, 0.16mol/L, 0.17mol/L, 0.18mol/L, 0.19mol/L, 0.2mol/L, 0.21mol/L, 0.22mol/L, 0.23mol/L, 0.24mol/L or 0.25mol/L, but is not limited to the recited values, and other non-recited values within the range of the values are equally applicable.
Under the oxidation action of the oxidation solution, the C2 position and the C3 position on the molecular chain of the fiber raw material are broken to form dialdehyde groups, and then the dialdehyde groups are continuously oxidized into dicarboxyl groups. The esterification reaction of the primary amino group and the carboxyl group is carried out under the catalysis system of 1-ethyl- (3-dimethyl amino propyl) carbodiimide (EDC) and N-hydroxysuccinimide (NHS), the EDC and the carboxyl group in carboxylated cellulose are coupled to form O-acyl isourea, the O-acyl isourea is easy to attack by the amino group to form amide crosslinking to generate an amide bond, and the NHS can react with the O-acyl isourea to generate a stable intermediate NHS active ester, so that the hydrolysis of the O-acyl isourea is reduced, and the crosslinking reaction efficiency and the product yield are greatly improved.
The amino acid solution is any one or the combination of at least two of lysine solution, arginine solution, histidine solution, tryptophan solution, glycine solution, glutamic acid solution and cysteine solution.
In the present invention, arginine is preferably an arginine solution, which is the most basic amino acid among 20 or more amino acids constituting a protein and has only a guanidine group, the guanidine group has an extremely high positive charge amount, the cell surface of bacteria is negatively charged, and arginine is attached to the cell surface of bacteria by electrostatic adsorption and interacts with functional proteins, DNA, RNA, etc. inside the bacteria cells, thereby exhibiting a strong antibacterial activity.
The esterification reaction temperature is 200-220deg.C, such as 200deg.C, 202 deg.C, 204 deg.C, 206 deg.C, 208 deg.C, 210 deg.C, 212 deg.C, 214 deg.C, 216 deg.C, 218 deg.C or 220 deg.C; the esterification reaction time is 10 to 20 minutes, and may be, for example, 10 minutes, 11 minutes, 12 minutes, 13 minutes, 14 minutes, 15 minutes, 16 minutes, 17 minutes, 18 minutes, 19 minutes or 20 minutes, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In the step (2), the mass concentration of chitosan in the reaction solution is 1 to 10mg/mL, and for example, 1mg/mL, 2mg/mL, 3mg/mL, 4mg/mL, 5mg/mL, 6mg/mL, 7mg/mL, 8mg/mL, 9mg/mL or 10mg/mL may be used, but the present invention is not limited to the above-mentioned values, and other values not shown in the above-mentioned numerical ranges may be used.
The concentration of tannic acid in the reaction solution is 5 to 10mg/mL, for example, 5.0mg/mL, 5.5mg/mL, 6.0mg/mL, 6.5mg/mL, 7.0mg/mL, 7.5mg/mL, 8.0mg/mL, 8.5mg/mL, 9.0mg/mL, 9.5mg/mL or 10.0mg/mL, but the concentration is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned numerical range are applicable.
The invention particularly limits the mass concentration of tannic acid and silver nitrate in the reaction liquid, reduces the toxicity of silver ions in the reaction liquid by adding 5-10mg/mL tannic acid, and ensures the uniform dispersion of the silver nitrate and the tannic acid when the concentration is in the range of 5-10mg/mL, so that a complex generated by the reaction of the silver nitrate and the tannic acid can destroy bacterial cell walls and reduce the damage to normal cells. When the concentration of silver nitrate exceeds 5mg/mL, tannic acid cannot effectively load all of silver nitrate, resulting in greater toxicity. When the concentration of tannic acid exceeds 10mg/mL, only a small portion of the groups of tannic acid can be oxidized during the oxidation-reduction reaction of tannic acid and silver nitrate, and thus the toxicity thereof cannot be effectively reduced.
The concentration of silver nitrate in the reaction solution is 1 to 5mg/mL, and may be, for example, 1.0mg/mL, 1.5mg/mL, 2.0mg/mL, 2.5mg/mL, 3.0mg/mL, 3.5mg/mL, 4.0mg/mL, 4.5mg/mL, or 5.0mg/mL, but the concentration is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned numerical ranges are similarly applicable.
The invention utilizes a large amount of-NH existing in chitosan 2 Can produce complexation coordination with silver ions in the reaction liquid, so that the silver ions are uniformly distributed in molecular chain gaps of chitosan, thereby limiting the activity space of the silver ions in the reaction liquid and providing favorable conditions for the subsequent reduction process of the silver ions. Meanwhile, the collision probability of tannic acid and silver ions can be improved, the reduction reaction rate of the silver ions is accelerated, and the silver ions are reduced into silver nanoparticles with finer particle sizes.
According to the invention, the silver nitrate is reduced by tannic acid to obtain the silver nano particles, the silver nano particles have higher specific surface area, the atomic number in the surface layer is rapidly increased, so that the surface atomic coordination is insufficient, the surface energy of atoms is increased, the biological activity is improved, the silver nano particles can be better combined with microorganisms, when bacteria are close to the silver nano particles, the silver nano particles can be adsorbed on the surfaces of the bacteria and react with bacterial protease, the protease is rapidly deactivated, and the bacteria cannot be propagated and killed; in addition, silver nanoparticles can adsorb onto the cell membrane of microorganisms and enter the cell body, causing microbial cell decomposition, ultimately leading to microbial death.
Because the silver nano particles have smaller scale and poorer dispersibility and are easy to agglomerate in an antibacterial solution, in order to ensure that the newly generated silver nano particles stably exist in the solution and do not agglomerate, chitosan is added in the antibacterial solution, and the amino groups rich in chitosan macromolecules and free silver ions form coordination, so that the activity of the silver ions can be reduced, and the silver ions are subjected to reduction reaction in a limited local space, so that the aim of primarily controlling the particle size of nano silver crystal nuclei is fulfilled. After the nano silver crystal grains are formed, as the surface activity of the nano silver crystal grains is higher, a strong adsorption effect is formed between the nano silver crystal grains and chitosan, so that the chitosan can be wrapped on the surfaces of the nano silver crystal grains to form a coating layer, and the space steric hindrance generated by the coating layer enables gaps to be formed between the nano silver crystal grains, so that the further growth of the nano silver crystal grains is prevented, meanwhile, the aggregation of the nano silver crystal grains can be prevented, fine and uniform silver nano particles can be finally obtained, and the stability and the dispersibility of the silver nano particles in an antibacterial solution are improved.
When the modified fiber raw material is soaked in the antibacterial solution, hydroxyl, carboxyl and amino on the molecular chain of the modified fiber raw material can generate strong adsorption effect with silver nano particles, and the silver nano particles can be firmly embedded in a three-dimensional network structure formed by the modified fiber raw material, so that the loss or falling of the silver nano particles is not easy to cause.
The method is particularly limited in that the mass concentration of silver nitrate in the reaction liquid is 1-5mg/mL, the concentration of the silver nitrate directly influences the particle size and the particle size distribution of silver nanoparticles generated after reduction, when the concentration of the silver nitrate in the reaction liquid exceeds 5mg/mL, the collision probability of the silver ions in the reaction liquid is increased, the generation rate of the silver nanoparticles is accelerated, and the agglomeration rate is also improved, and at the moment, the chitosan cannot timely wrap the newly generated silver nanoparticles, so that the silver nanoparticles are secondarily agglomerated.
The mass fraction of the acetic acid solution is 1 to 5wt%, for example, 1.0wt%, 1.5wt%, 2.0wt%, 2.5wt%, 3.0wt%, 3.5wt%, 4.0wt%, 4.5wt% or 5.0wt%, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
The reaction temperature is 70-80deg.C, such as 70deg.C, 71 deg.C, 72 deg.C, 73 deg.C, 74 deg.C, 75 deg.C, 76 deg.C, 77 deg.C, 78 deg.C, 79 deg.C or 80deg.C; the reaction time is 5 to 10 hours, and may be, for example, 5.0 hours, 5.5 hours, 6.0 hours, 6.5 hours, 7.0 hours, 7.5 hours, 8.0 hours, 8.5 hours, 9.0 hours, 9.5 hours or 10.0 hours, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
The reaction process in the step (2) is divided into three steps, wherein in the first step, a large amount of-NH on a chitosan molecular chain is passed 2 Coordination complex reaction is carried out with silver ions, so that the activity of the silver ions is reduced and the dispersibility of the silver ions in the reaction solution is improved; secondly, reducing silver ions through tannic acid to generate silver nano particles; and thirdly, forming a strong adsorption effect between the chitosan and the silver nano particles, so that the chitosan is wrapped on the surfaces of the silver nano particles to form a coating layer, and the stability and the dispersibility of the silver nano particles in the reaction liquid are improved.
In order to advance the progress of the three steps, the invention particularly limits the reaction temperature to 70-80 ℃, and can promote the dissolution of chitosan macromolecules in acetic acid solution when the reaction temperature is within the temperature range, and simultaneously endow silver ions with enough reaction kinetic energy, thereby being beneficial to the reduction reaction of the silver ions and the coating of chitosan. When the reaction temperature is higher than 80 ℃, the interior of chitosan molecules swells, so that the pore diameter of micropores in the chitosan is reduced, the diffusion resistance of silver ions to chitosan molecule chains is increased, the progress of coordination complex reaction is hindered, and the reaction progress of the second step and the third step is influenced.
In a preferred embodiment of the present invention, in the step (3), the soaking time of the modified fiber raw material in the antibacterial solution is 40-50min, for example, 40min, 41min, 42min, 43min, 44min, 45min, 46min, 47min, 48min, 49min or 50min, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
The drying temperature is 90-100deg.C, such as 90deg.C, 91 deg.C, 92 deg.C, 93 deg.C, 94 deg.C, 95 deg.C, 96 deg.C, 97 deg.C, 98 deg.C, 99 deg.C or 100deg.C; the drying time is 0.5 to 1h, and may be, for example, 0.5h, 0.55h, 0.6h, 0.65h, 0.7h, 0.75h, 0.8h, 0.85h, 0.9h, 0.95h or 1h, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
In a preferred embodiment of the present invention, in the step (i), the coupling agent is at least one of γ -aminopropyl triethoxysilane, γ -aminopropyl trimethoxysilane, γ -aminopropyl methyldiethoxysilane, and aminoethylaminopropyl trimethoxysilane.
The concentration of the coupling agent in ethanol solution is 0.1 to 0.5mmol/mL, and may be, for example, 0.1mmol/mL, 0.15mmol/mL, 0.2mmol/mL, 0.25mmol/mL, 0.3mmol/mL, 0.35mmol/mL, 0.4mmol/mL, 0.45mmol/mL, or 0.5mmol/mL, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The mass fraction of the composite nanoparticle in the antibacterial dispersion liquid is 20-30mg/mL, and for example, 20mg/mL, 21mg/mL, 22mg/mL, 23mg/mL, 24mg/mL, 25mg/mL, 26mg/mL, 27mg/mL, 28mg/mL, 29mg/mL or 30mg/mL may be used, but the present invention is not limited to the recited values, and other values not recited in the range of the values are equally applicable.
The antibacterial base layer is immersed in the antibacterial dispersion for 1 to 3 hours, for example, 1.0 hour, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours, 2.0 hours, 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours or 3.0 hours, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The composite nanoparticle comprises nano titanium dioxide particles and a silicon dioxide coating layer formed on the surfaces of the nano titanium dioxide particles.
The composite nano particles are prepared by the following method:
during the continuous stirring process, the titanium salt solution is dripped into the silicate solution, the pH value of the mixed solution is adjusted to 9-10 by alkali liquor, and for example, the mixed solution can be 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9 or 10.0, but the mixed solution is not limited to the listed values, and other non-listed values in the range of the values are equally applicable; then, sequentially aging, aging and centrifugal sedimentation are carried out on the mixed solution to obtain a precipitate; and finally, sequentially carrying out heating drying and high-temperature roasting on the precipitate to obtain the composite nano particles.
The composite nano particles prepared by the invention consist of nano titanium dioxide particles and a silicon dioxide coating layer, wherein the nano titanium dioxide particles mainly play a role in sterilization and bacteriostasis, and the silicon dioxide coating layer plays a role in improving the dispersibility and stability of the nano titanium dioxide particles. The silicon dioxide coating layer is of a loose porous structure and has micropores of graded structures with different pore diameters, which is beneficial to improving the adsorption effect of the composite nano particles on bacteria and microorganisms.
The composite nanoparticle composed of the nano-titania particles and the silica coating layer has a higher sterilization effect than the nano-titania particles, because:
on the one hand, the composite nano particles have better dispersibility, the agglomeration phenomenon among nano titanium dioxide particles is very serious due to the existence of electrostatic action and capillary action, the proportion of the nano titanium dioxide particles in the form of nano particles is small, only nano titanium dioxide particles have sterilizing effect, and titanium dioxide particles with larger particle size do not have sterilizing function. Therefore, the sterilization effect of the nano titanium dioxide particles is poor; according to the invention, the surface of the nano titanium dioxide particles is coated with the silicon dioxide coating layer, so that the surface energy of the nano titanium dioxide particles is reduced, the agglomeration of the coated composite nano particles is prevented, the composite nano particles are in a good dispersion state in the ethanol solution of the coupling agent, the nano titanium dioxide particles can be ensured to exist in the ethanol solution of the coupling agent stably in a nano scale, and the sterilization effect of the nano titanium dioxide particles is improved.
On the other hand, the transparent silicon dioxide coating layer does not influence the light penetration, and even if the silicon dioxide coating layer exists, the nano titanium dioxide particle inner core can also receive illumination and generate electronic transition to kill bacteria; meanwhile, after the nano titanium dioxide particles are coated with the silicon dioxide coating layer, the nano titanium dioxide particles and silicon dioxide are subjected to bonding action to form a Ti-Si chemical bond, the band gap energy which is needed to be spanned by electrons of Ti from valence band electrons to conduction band electrons is obviously reduced, and electrons of the nano titanium dioxide particles can be promoted to be transited under lower light intensity, so that the aim of sterilization is fulfilled.
In addition, after the nano titanium dioxide particles are compounded with the silicon dioxide, as the nano silicon dioxide contains a large amount of surface hydroxyl groups, the hydroxyl groups can react with electron holes of the nano titanium dioxide particles to form active hydroxyl groups with strong oxidizing property, and the active hydroxyl groups are mutually combined to generate hydrogen peroxide, so that bacteria can be killed.
The silicon dioxide coating layer is of a hydrophobic porous structure, so that the adsorption and capture capacity of the composite nano particles to bacteria can be improved; meanwhile, the composite nano particle has stronger moisture absorption capability, can reduce the environmental humidity of the knitted material, ensures the dryness and ventilation of the fabric, is favorable for inhibiting the growth of bacteria, and increases the hydroxyl number on the surface of the composite nano particle due to the moisture absorbed by the composite nano particle, so that the sterilization effect of the composite nano particle is further improved.
The concentration of the titanium salt solution is 2.5 to 3.5mol/L, and may be, for example, 2.5mol/L, 2.6mol/L, 2.7mol/L, 2.8mol/L, 2.9mol/L, 3.0mol/L, 3.1mol/L, 3.2mol/L, 3.3mol/L, 3.4mol/L or 3.5mol/L, but is not limited to the recited values, and other non-recited values within the range of the values are equally applicable.
The titanium salt solution is titanium tetrachloride solution or titanium sulfate solution.
The concentration of the silicate solution is 2 to 3mol/L, for example, 2.0mol/L, 2.1mol/L, 2.2mol/L, 2.3mol/L, 2.4mol/L, 2.5mol/L, 2.6mol/L, 2.7mol/L, 2.8mol/L, 2.9mol/L or 3.0mol/L, but the silicate solution is not limited to the recited values, and other non-recited values within the recited values are equally applicable.
The silicate solution is sodium silicate solution or potassium silicate solution.
The titanium salt solution and the silicate solution are used in amounts of 1 (0.3-0.5) based on the titanium dioxide and the silicon dioxide respectively, and may be, for example, 1:0.3, 1:0.32, 1:0.34, 1:0.36, 1:0.38, 1:0.4, 1:0.42, 1:0.44, 1:0.46, 1:0.48 or 1:0.5, but are not limited to the recited values, and other non-recited values within the range of the values are equally applicable.
The temperature of the heating and drying is 80-120deg.C, such as 80deg.C, 85deg.C, 90deg.C, 95deg.C, 100deg.C, 105deg.C, 110deg.C, 115deg.C or 120deg.C; the heating and drying time is 8 to 10 hours, for example, 8.0 hours, 8.2 hours, 8.4 hours, 8.6 hours, 8.8 hours, 9.0 hours, 9.2 hours, 9.4 hours, 9.6 hours, 9.8 hours or 10.0 hours, but the time is not limited to the recited values, and other non-recited values within the range are applicable.
The high temperature roasting temperature is 600-800 ℃, such as 600 ℃, 620 ℃, 640 ℃, 660 ℃, 680 ℃, 700 ℃, 720 ℃, 740 ℃, 760 ℃, 780 ℃ or 800 ℃; the high temperature calcination time is 3 to 4 hours, and may be, for example, 3.0 hours, 3.1 hours, 3.2 hours, 3.3 hours, 3.4 hours, 3.5 hours, 3.6 hours, 3.7 hours, 3.8 hours, 3.9 hours or 4.0 hours, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
In the step (ii), the mass ratio of the bamboo charcoal fiber to the polyester fiber to the cotton fiber to the deionized water is 1 (20-30): (40-50): (80-100), for example, may be 1:20:40:80, 1:21:41:82, 1:22:42:84, 1:23:43:86, 1:24:44:88, 1:25:45:90, 1:26:46:92, 1:27:47:94, 1:28:48:96, 1:29:49:98 or 1:30:50:100, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
The invention particularly limits the mass ratio of the bamboo charcoal fiber to the polyester fiber to the cotton fiber to 1 (20-30) (40-50), because when the content of the bamboo charcoal fiber exceeds the upper limit of the numerical range limited by the invention, the longitudinal capillary effect of the antiperspirant base cloth layer is obviously reduced, the transverse capillary effect is not obvious, and the water conductivity of the antiperspirant base cloth layer is reduced. This is because although the surface of the bamboo charcoal fiber has many grooves and micropores, the hygroscopicity of the bamboo charcoal fiber is still between that of the terylene fiber and that of the cotton fiber, and when the addition ratio of the bamboo charcoal fiber is too high, the addition ratio of the cotton fiber is correspondingly reduced, thereby affecting the moisture absorption effect of the whole antiperspirant base cloth layer. However, the addition ratio of the bamboo charcoal fiber cannot be lower than the lower limit of the numerical range defined by the invention, because the air permeability of the bamboo charcoal fiber is highest among the three fibers, and the thickness of the antiperspirant base cloth layer is gradually reduced with the increase of the addition ratio of the bamboo charcoal fiber, so that the air permeability of the fabric is improved. Therefore, in order to balance the air permeability and the moisture absorption of the antiperspirant base cloth layer, the invention particularly limits the mass ratio of the bamboo charcoal fiber to the polyester fiber to the cotton fiber to 1 (20-30) to 40-50.
The temperature of the heating and melting is 340-350deg.C, such as 340 deg.C, 341 deg.C, 342 deg.C, 343 deg.C, 344 deg.C, 345 deg.C, 346 deg.C, 347 deg.C, 348 deg.C, 349 deg.C or 350 deg.C; the time for the heating and melting is 3 to 4 hours, and may be, for example, 3.0 hours, 3.1 hours, 3.2 hours, 3.3 hours, 3.4 hours, 3.5 hours, 3.6 hours, 3.7 hours, 3.8 hours, 3.9 hours or 4.0 hours, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
The spinning speed is 1400-1500 deg.C/min, and may be 1400 deg.C/min, 1410 deg.C/min, 1420 deg.C/min, 1430 deg.C/min, 1440 deg.C/min, 1450 deg.C/min, 1460 deg.C/min, 1470 deg.C/min, 1480 deg.C/min, 1490 deg.C/min or 1500 deg.C/min, for example, but not limited to the values recited, and other values not recited in the range of values are equally applicable.
In a preferred embodiment of the present invention, in step (iii), the material of the hot melt adhesive layer is polyurethane.
The hot pressing temperature may be 100 to 120 ℃, for example, 100 ℃, 102 ℃, 104 ℃, 106 ℃, 108 ℃, 110 ℃, 112 ℃, 114 ℃, 116 ℃, 118 ℃ or 120 ℃, the hot pressing time may be 30 to 60 seconds, for example, 30 seconds, 32 seconds, 34 seconds, 36 seconds, 38 seconds, 40 seconds, 42 seconds, 44 seconds, 46 seconds, 48 seconds, 50 seconds, 52 seconds, 54 seconds, 56 seconds, 58 seconds or 60 seconds, but the hot pressing temperature is not limited to the recited values, and other non-recited values within the range are equally applicable.
Illustratively, the present invention provides a method for manufacturing an antibacterial antiperspirant knit material, comprising the steps of:
(1) Preparing an antibacterial base layer:
(1.1) immersing the fiber raw material in 10-20wt% of oxidizing solution, wherein the dosage of the oxidizing solution is 20-30mL/g of the fiber raw material, hydroxyl groups of fiber molecular chains are oxidized into carboxyl groups, and taking out and drying after soaking for 1-5 h; then, immersing the oxidized fiber raw material into an amino acid solution with the concentration of 0.15-0.25mol/L, and carrying out esterification reaction for 10-20min at the temperature of 200-220 ℃ to obtain a modified fiber raw material;
(1.2) adding chitosan, tannic acid and silver nitrate into acetic acid solution with the weight percent of 1-5%, uniformly mixing to obtain a reaction solution, wherein the mass fraction of the chitosan in the reaction solution is 1-10mg/mL, the mass concentration of the tannic acid is 5-10mg/mL, the mass concentration of the silver nitrate is 1-5mg/mL, and placing the reaction solution in a light-shielding condition with the temperature of 70-80 ℃ for reacting for 5-10 hours to obtain an antibacterial solution;
(1.3) soaking the modified fiber raw material in an antibacterial solution for 40-50min, taking out, and drying at 90-100 ℃ for 0.5-1h to obtain antibacterial fabric fibers;
(1.4) knitting the antibacterial fabric fiber to obtain an antibacterial base layer;
(2) Preparing composite nano particles:
in the continuous stirring process, 2.5-3.5mol/L of titanium salt solution is dripped into 2-3mol/L of silicate solution, and the pH value of the mixed solution is adjusted to 9-10 by alkali liquor; then, sequentially aging, aging and centrifugal sedimentation are carried out on the mixed solution to obtain a precipitate; finally, heating and drying the precipitate for 8-10h at 80-120 ℃, and then placing the dried precipitate in a muffle furnace at 600-800 ℃ for high-temperature roasting for 3-4h to obtain composite nano particles; the composite nano particles comprise nano titanium dioxide particles and a silicon dioxide coating layer formed on the surfaces of the nano titanium dioxide particles, wherein the mass ratio of the titanium dioxide to the silicon dioxide is 1 (0.3-0.5);
(3) Preparing an antibacterial composite layer:
dispersing the composite nano particles obtained in the step (2) in an ethanol solution of a coupling agent with the concentration of 0.1-0.5mmol/mL to form an antibacterial dispersion liquid, wherein the mass fraction of the composite nano particles in the antibacterial dispersion liquid is 20-30mg/mL; soaking the antibacterial base layer obtained in the step (1) in antibacterial dispersion liquid for 1-3 hours, and then taking out, cleaning and drying to form a composite nano particle film on the surface of the antibacterial base layer to obtain an antibacterial composite layer;
(4) Preparing an antiperspirant base fabric layer:
mixing bamboo carbon fiber, polyester fiber, cotton fiber and deionized water according to the mass ratio of 1 (20-30): 40-50): 80-100 to form spinning solution, heating the spinning solution to 340-350 ℃ and preserving heat for 3-4 hours to melt the spinning solution to obtain spinning solution, spinning the spinning solution at the spinning speed of 1400-1500 ℃/min to obtain composite yarn, and finally carrying out double-sided flat knitting on the composite yarn to obtain an antiperspirant base cloth layer;
(5) And (3) sequentially paving a hot melt adhesive layer and the antibacterial composite layer obtained in the step (3) on the antiperspirant base cloth layer obtained in the step (4), and then carrying out hot pressing treatment at 100-120 ℃ for 30-60s, so that the antiperspirant base cloth layer and the antibacterial composite layer are bonded and compounded through the hot melt adhesive layer, and cooling, washing and drying to obtain the antibacterial antiperspirant knitted material.
In a second aspect, the invention provides an antibacterial antiperspirant knitted material prepared by the manufacturing method in the first aspect, wherein the knitted material comprises an antiperspirant base layer, a hot melt adhesive layer and an antibacterial composite layer which are sequentially stacked, and the antibacterial composite layer comprises an antibacterial base layer and a composite nanoparticle film formed on the surface of the antibacterial base layer.
The antiperspirant base cloth layer comprises bamboo carbon fiber, polyester fiber and cotton fiber.
In a third aspect, the invention provides an antibacterial antiperspirant fabric, which is obtained by cutting the knitted material in the second aspect.
Compared with the prior art, the invention has the beneficial effects that:
the knitted material provided by the invention is formed by compounding the antibacterial composite layer and the antiperspirant base cloth layer, and can simultaneously meet the requirements of people on antibacterial antiperspirant and dryness and comfort. The antibacterial composite layer is used as a surface layer, so that bacterial interference of the external environment is effectively resisted, and bacteria and microorganisms attached to the surface of the fabric are effectively killed; meanwhile, the anti-sweat base cloth layer is used as a bottom layer, the anti-sweat base cloth layer is in direct contact with the skin, and the requirements on the hygroscopicity and the air permeability of the fabric are higher.
The air permeability and the moisture absorption performance are important factors influencing the comfort of fabric body, and the antiperspirant base cloth layer prepared by the method has good air permeability and moisture absorption performance, on one hand, cotton fibers and bamboo charcoal fibers have micropore structures, can quickly absorb moisture and sweat emitted by skin and diffuse into the surrounding environment, and keep the skin dry; the polyester fiber has high strength, good elasticity and smooth surface, and sweat is not easy to adhere, so that the residual quantity of sweat on the antiperspirant base cloth layer is reduced, and the bacteria are prevented from breeding and culturing, thereby being beneficial to the environment. On the other hand, the knitting structure of the knitting material is formed by mutually penetrating loops, so that the knitting material is in a three-dimensional structure, more gaps are formed at the penetrating points, favorable conditions are provided for ventilation and sweat evaporation, and the knitting material has good air permeability and moisture absorption.
Drawings
FIG. 1 is a flow chart of the process for preparing the antibacterial antiperspirant knit material provided in examples 1-14;
FIG. 2 is an electron micrograph of the antibacterial composite layer prepared in example 1;
FIG. 3 is an infrared spectrum of the antibacterial composite layer prepared in example 1;
FIG. 4 is a photograph of colonies of the knitted materials prepared in example 1 and comparative example 9 after various wearing times;
Wherein, FIGS. 4 (a) - (d) are colony pictures of the knitted material prepared in example 1 after 5h, 10h, 15h and 20h of wearing; FIGS. 4 (e) - (h) are colony pictures of the knitted material of comparative example 9 after 5h, 10h, 15h and 20h of wearing;
FIG. 5 is a graph showing colonies of the knitted materials prepared in example 1 and comparative example 9 after various washing times;
wherein, FIGS. 5 (a) - (d) are colony pictures after 5 times, 10 times, 15 times and 20 times of washing of the knitted material prepared in example 1; FIGS. 5 (e) - (h) are colony pictures after 5, 10, 15 and 20 washings of the knitted material prepared in comparative example 9.
Detailed Description
The technical scheme of the invention is described in detail below with reference to specific embodiments and attached drawings. The examples described herein are specific embodiments of the present invention for illustrating the concept of the present invention; the description is intended to be illustrative and exemplary in nature and should not be construed as limiting the scope of the invention in its aspects. In addition to the embodiments described herein, those skilled in the art can adopt other obvious solutions based on the disclosure of the claims of the present application and the specification thereof, including those adopting any obvious substitutions and modifications to the embodiments described herein.
Example 1
The embodiment provides a manufacturing method of an antibacterial antiperspirant knitted material, which is shown in fig. 1 and specifically comprises the following steps:
(1) Preparing an antibacterial base layer:
(1.1) immersing a fiber raw material (cotton fabric fiber) in a 10wt% hydrogen peroxide solution, wherein the dosage of the hydrogen peroxide solution is 20mL/g of the fiber raw material, hydroxyl groups of fiber molecular chains are oxidized into carboxyl groups, and taking out and drying after soaking for 1 h; then, immersing the oxidized fiber raw material into 0.15mol/L arginine solution, and carrying out esterification reaction for 20min at 200 ℃ to obtain a modified fiber raw material;
(1.2) adding chitosan, tannic acid and silver nitrate into an acetic acid solution with the weight percent of 1%, uniformly mixing to obtain a reaction solution, wherein the mass fraction of the chitosan in the reaction solution is 1mg/mL, the mass concentration of the tannic acid is 5mg/mL, the mass concentration of the silver nitrate is 1mg/mL, and placing the reaction solution in a light-shielding condition at the temperature of 70 ℃ for reacting for 10 hours to obtain an antibacterial solution;
(1.3) soaking the modified fiber raw material in an antibacterial solution for 40min, taking out, and drying at 90 ℃ for 1h to obtain antibacterial fabric fibers;
(1.4) knitting the antibacterial fabric fiber to obtain an antibacterial base layer;
(2) Preparing composite nano particles:
In the continuous stirring process, 2.5mol/L titanium tetrachloride solution is dripped into 2mol/L sodium silicate solution, and the pH value of the mixed solution is adjusted to 9 through sodium hydroxide solution; then, sequentially aging, aging and centrifugal sedimentation are carried out on the mixed solution to obtain a precipitate; finally, heating and drying the precipitate at 80 ℃ for 10 hours, and then placing the dried precipitate in a muffle furnace at 600 ℃ for high-temperature roasting for 4 hours to obtain composite nano particles; the composite nano particles comprise nano titanium dioxide particles and a silicon dioxide coating layer formed on the surfaces of the nano titanium dioxide particles, wherein the mass ratio of titanium dioxide to silicon dioxide is 1:0.3;
(3) Preparing an antibacterial composite layer:
dispersing the composite nano particles obtained in the step (2) in an ethanol solution of gamma-aminopropyl triethoxysilane with the mass fraction of 20mg/mL to form an antibacterial dispersion liquid; soaking the antibacterial base layer obtained in the step (1) in antibacterial dispersion liquid for 1h, and taking out, washing and drying to form a composite nano particle film on the surface of the antibacterial base layer to obtain an antibacterial composite layer;
(4) Preparing an antiperspirant base fabric layer:
mixing bamboo carbon fiber, polyester fiber, cotton fiber and deionized water according to the mass ratio of 1:20:40:80 to form spinning solution, heating the spinning solution to 340 ℃ and preserving heat for 4 hours to melt the spinning solution to obtain spinning solution, spinning the spinning solution at the spinning speed of 1400 ℃/min to obtain composite yarns, and finally carrying out double-sided flat knitting on the composite yarns to obtain an antiperspirant base cloth layer;
(5) And (3) sequentially laying a hot melt adhesive layer and the antibacterial composite layer obtained in the step (3) on the antiperspirant base cloth layer obtained in the step (4), and then carrying out hot pressing treatment at 100 ℃ for 30 seconds to enable the antiperspirant base cloth layer and the antibacterial composite layer to be bonded and compounded through the hot melt adhesive layer, cooling, and then washing and drying to obtain the antibacterial antiperspirant knitted material.
Scanning electron microscope analysis is carried out on the composite antibacterial layer prepared in the embodiment to obtain an electron microscope photograph shown in fig. 2, and as can be seen from fig. 2, composite nano particles are adhered to the fiber surface of the composite antibacterial layer.
The composite antibacterial layer prepared in this example was subjected to infrared spectroscopic analysis to obtain an infrared spectrum as shown in FIG. 3, and as can be seen from the infrared spectrum of chitosan, the infrared spectrum was calculated as 3200cm -1 To 3500cm -1 The broad peaks of (C) are the stretching vibration absorption peaks of-OH and-NH, 1155cm -1 The peak at the point is a chitosan characteristic peak. As can be seen from the infrared spectrum of tannic acid, at 1600cm -1 At which is the c=o absorption peak formed after oxidation of tannic acid. As can be seen from the infrared spectrum of the composite antibacterial layer, the infrared spectrum of the composite antibacterial layer is similar to that of chitosan, wherein the composite antibacterial layer is 3200cm in length -1 To 3500cm -1 The peak type is sharper than the infrared spectrum of chitosan, which shows that the stretching vibration peak of primary amino is changed into the stretching vibration peak of secondary amino; further, the c=o absorption peak after tannic acid oxidation was observed simultaneously in the infrared spectrum of the composite antibacterial layer. The test results showed successful grafting of tannic acid and chitosan onto the fibers.
Example 2
The embodiment provides a manufacturing method of an antibacterial antiperspirant knitted material, which is shown in fig. 1 and specifically comprises the following steps:
(1) Preparing an antibacterial base layer:
(1.1) immersing a fiber raw material (cotton fabric fiber) in a potassium permanganate solution with the weight percentage of 12 percent, wherein the dosage of the potassium permanganate solution is 25mL/g of the fiber raw material, oxidizing hydroxyl groups of fiber molecular chains into carboxyl groups, immersing for 2 hours, and taking out and drying; then, immersing the oxidized fiber raw material into 0.18mol/L arginine solution, and carrying out esterification reaction at 210 ℃ for 18min to obtain a modified fiber raw material;
(1.2) adding chitosan, tannic acid and silver nitrate into 2wt% acetic acid solution, uniformly mixing to obtain a reaction solution, wherein the mass fraction of the chitosan in the reaction solution is 3mg/mL, the mass concentration of the tannic acid is 6mg/mL, the mass concentration of the silver nitrate is 2mg/mL, and placing the reaction solution in a light-shielding condition at 72 ℃ for reacting for 9 hours to obtain an antibacterial solution;
(1.3) soaking the modified fiber raw material in an antibacterial solution for 40min, taking out, and drying at 95 ℃ for 1h to obtain antibacterial fabric fibers;
(1.4) knitting the antibacterial fabric fiber to obtain an antibacterial base layer;
(2) Preparing composite nano particles:
In the continuous stirring process, 2.8mol/L titanium tetrachloride solution is dripped into 2.3mol/L sodium silicate solution, and the pH value of the mixed solution is adjusted to 9 through sodium hydroxide solution; then, sequentially aging, aging and centrifugal sedimentation are carried out on the mixed solution to obtain a precipitate; finally, heating and drying the precipitate for 9.5 hours at 90 ℃, and then placing the dried precipitate in a muffle furnace at 650 ℃ for high-temperature roasting for 3.8 hours to obtain composite nano particles; the composite nano particles comprise nano titanium dioxide particles and a silicon dioxide coating layer formed on the surfaces of the nano titanium dioxide particles, wherein the mass ratio of titanium dioxide to silicon dioxide is 1:0.35;
(3) Preparing an antibacterial composite layer:
dispersing the composite nano particles obtained in the step (2) in an ethanol solution of gamma-aminopropyl trimethoxysilane with the mass fraction of the composite nano particles being 23mg/mL to form an antibacterial dispersion liquid; soaking the antibacterial base layer obtained in the step (1) in antibacterial dispersion liquid for 1.5 hours, and then taking out, washing and drying the antibacterial base layer to form a composite nano particle film on the surface of the antibacterial base layer to obtain an antibacterial composite layer;
(4) Preparing an antiperspirant base fabric layer:
mixing bamboo carbon fiber, polyester fiber, cotton fiber and deionized water according to the mass ratio of 1:25:40:80 to form spinning solution, heating the spinning solution to 340 ℃ and preserving heat for 3.8 hours to enable the spinning solution to be melted to obtain spinning solution, spinning the spinning solution at the spinning speed of 1400 ℃/min to obtain composite yarns, and finally carrying out double-sided flat knitting on the composite yarns to obtain an antiperspirant base cloth layer;
(5) And (3) sequentially laying a hot melt adhesive layer and the antibacterial composite layer obtained in the step (3) on the antiperspirant base cloth layer obtained in the step (4), and then carrying out hot pressing treatment at 105 ℃ for 40 seconds to enable the antiperspirant base cloth layer and the antibacterial composite layer to be bonded and compounded through the hot melt adhesive layer, cooling, and then washing and drying to obtain the antibacterial antiperspirant knitted material.
Example 3
The embodiment provides a manufacturing method of an antibacterial antiperspirant knitted material, which is shown in fig. 1 and specifically comprises the following steps:
(1) Preparing an antibacterial base layer:
(1.1) immersing a fiber raw material (regenerated cellulose fabric fiber) in a 15wt% sodium hypochlorite solution, wherein the dosage of the sodium hypochlorite solution is 23mL/g of the fiber raw material, hydroxyl groups of fiber molecular chains are oxidized into carboxyl groups, and taking out and drying after soaking for 3 hours; subsequently, immersing the oxidized fiber raw material into a lysine solution with the concentration of 0.2mol/L, and carrying out esterification reaction at the temperature of 210 ℃ for 15min to obtain a modified fiber raw material;
(1.2) adding chitosan, tannic acid and silver nitrate into 3wt% acetic acid solution, uniformly mixing to obtain a reaction solution, wherein the mass fraction of the chitosan in the reaction solution is 5mg/mL, the mass concentration of the tannic acid is 8mg/mL, the mass concentration of the silver nitrate is 3mg/mL, and placing the reaction solution in a light-shielding condition at 75 ℃ for reacting for 8 hours to obtain an antibacterial solution;
(1.3) soaking the modified fiber raw material in an antibacterial solution for 45min, taking out, and drying at 95 ℃ for 0.8h to obtain antibacterial fabric fibers;
(1.4) knitting the antibacterial fabric fiber to obtain an antibacterial base layer;
(2) Preparing composite nano particles:
in the continuous stirring process, 3mol/L of titanium sulfate solution is dripped into 2.5mol/L of sodium silicate solution, and the pH value of the mixed solution is adjusted to 9.5 through sodium hydroxide solution; then, sequentially aging, aging and centrifugal sedimentation are carried out on the mixed solution to obtain a precipitate; finally, heating and drying the precipitate for 9 hours at 100 ℃, and then placing the dried precipitate in a muffle furnace at 700 ℃ for high-temperature roasting for 3.5 hours to obtain composite nano particles; the composite nano particles comprise nano titanium dioxide particles and a silicon dioxide coating layer formed on the surfaces of the nano titanium dioxide particles, wherein the mass ratio of titanium dioxide to silicon dioxide is 1:0.4;
(3) Preparing an antibacterial composite layer:
dispersing the composite nano particles obtained in the step (2) in an ethanol solution of gamma-aminopropyl trimethoxysilane with the mass fraction of the composite nano particles being 25mg/mL to form an antibacterial dispersion liquid; soaking the antibacterial base layer obtained in the step (1) in antibacterial dispersion liquid for 2 hours, and taking out, washing and drying to form a composite nano particle film on the surface of the antibacterial base layer to obtain an antibacterial composite layer;
(4) Preparing an antiperspirant base fabric layer:
mixing bamboo carbon fiber, polyester fiber, cotton fiber and deionized water according to the mass ratio of 1:25:45:90 to form spinning solution, heating the spinning solution to 345 ℃, preserving heat for 3.5 hours to enable the spinning solution to be melted to obtain spinning solution, spinning the spinning solution at the spinning speed of 1450 ℃/min to obtain composite yarns, and finally carrying out double-sided flat knitting on the composite yarns to obtain an antiperspirant base cloth layer;
(5) And (3) sequentially laying a hot melt adhesive layer and the antibacterial composite layer obtained in the step (3) on the antiperspirant base cloth layer obtained in the step (4), and then carrying out hot pressing treatment at 110 ℃ for 45 seconds to enable the antiperspirant base cloth layer and the antibacterial composite layer to be bonded and compounded through the hot melt adhesive layer, cooling, and then washing and drying to obtain the antibacterial antiperspirant knitted material.
Example 4
The embodiment provides a manufacturing method of an antibacterial antiperspirant knitted material, which is shown in fig. 1 and specifically comprises the following steps:
(1) Preparing an antibacterial base layer:
(1.1) immersing a fiber raw material (fibrilia fiber) in an 18wt% hydrogen peroxide solution, wherein the dosage of the hydrogen peroxide solution is 25mL/g of the fiber raw material, hydroxyl groups of a fiber molecular chain are oxidized into carboxyl groups, and taking out and drying after soaking for 4 hours; then, immersing the oxidized fiber raw material into 0.23mol/L histidine solution, and carrying out esterification reaction at 215 ℃ for 12min to obtain a modified fiber raw material;
(1.2) adding chitosan, tannic acid and silver nitrate into an acetic acid solution with the weight percent of 4%, uniformly mixing to obtain a reaction solution, wherein the mass fraction of the chitosan in the reaction solution is 8mg/mL, the mass concentration of the tannic acid is 9mg/mL, the mass concentration of the silver nitrate is 4mg/mL, and placing the reaction solution in a light-shielding condition at the temperature of 78 ℃ for reaction for 6 hours to obtain an antibacterial solution;
(1.3) soaking the modified fiber raw material in an antibacterial solution for 48min, taking out, and drying at 95 ℃ for 0.6h to obtain antibacterial fabric fibers;
(1.4) knitting the antibacterial fabric fiber to obtain an antibacterial base layer;
(2) Preparing composite nano particles:
in the continuous stirring process, 3.2mol/L of titanium sulfate solution is dripped into 2.8mol/L of potassium silicate solution, and the pH value of the mixed solution is adjusted to 9.8 through sodium hydroxide solution; then, sequentially aging, aging and centrifugal sedimentation are carried out on the mixed solution to obtain a precipitate; finally, heating and drying the precipitate at 110 ℃ for 8.5 hours, and then placing the dried precipitate in a muffle furnace at 750 ℃ for high-temperature roasting for 3.2 hours to obtain composite nano particles; the composite nano particles comprise nano titanium dioxide particles and a silicon dioxide coating layer formed on the surfaces of the nano titanium dioxide particles, wherein the mass ratio of titanium dioxide to silicon dioxide is 1:0.45;
(3) Preparing an antibacterial composite layer:
dispersing the composite nano particles obtained in the step (2) in an ethanol solution of gamma-aminopropyl methyl diethoxy silane with the mass fraction of the composite nano particles being 28mg/mL to form an antibacterial dispersion liquid; soaking the antibacterial base layer obtained in the step (1) in antibacterial dispersion liquid for 2.5 hours, and taking out, washing and drying to form a composite nanoparticle film on the surface of the antibacterial base layer to obtain an antibacterial composite layer;
(4) Preparing an antiperspirant base fabric layer:
mixing bamboo carbon fiber, polyester fiber, cotton fiber and deionized water according to the mass ratio of 1:25:45:95 to form spinning solution, heating the spinning solution to 350 ℃, preserving heat for 3.2h to enable the spinning solution to be melted to obtain spinning solution, spinning the spinning solution at the spinning speed of 1450 ℃/min to obtain composite yarns, and finally carrying out double-sided flat knitting on the composite yarns to obtain an antiperspirant base cloth layer;
(5) And (3) sequentially laying a hot melt adhesive layer and the antibacterial composite layer obtained in the step (3) on the antiperspirant base cloth layer obtained in the step (4), and then carrying out hot pressing treatment at 115 ℃ for 50s, so that the antiperspirant base cloth layer and the antibacterial composite layer are bonded and compounded through the hot melt adhesive layer, and cooling, washing and drying to obtain the antibacterial antiperspirant knitted material.
Example 5
The embodiment provides a manufacturing method of an antibacterial antiperspirant knitted material, which is shown in fig. 1 and specifically comprises the following steps:
(1) Preparing an antibacterial base layer:
(1.1) immersing a fiber raw material (fibrilia fiber) in a hydrogen peroxide solution with the weight percent of 20, wherein the dosage of the hydrogen peroxide solution is 30mL/g of the fiber raw material, hydroxyl groups of fiber molecular chains are oxidized into carboxyl groups, and taking out and drying after soaking for 5 hours; subsequently, immersing the oxidized fiber raw material into 0.25mol/L tryptophan solution, and carrying out esterification reaction for 10min at 220 ℃ to obtain a modified fiber raw material;
(1.2) adding chitosan, tannic acid and silver nitrate into 5wt% acetic acid solution, uniformly mixing to obtain a reaction solution, wherein the mass fraction of the chitosan in the reaction solution is 10mg/mL, the mass concentration of the tannic acid is 10mg/mL, the mass concentration of the silver nitrate is 5mg/mL, and placing the reaction solution in a light-shielding condition at 80 ℃ for reacting for 5 hours to obtain an antibacterial solution;
(1.3) soaking the modified fiber raw material in an antibacterial solution for 50min, taking out, and drying at 100 ℃ for 0.5h to obtain antibacterial fabric fibers;
(1.4) knitting the antibacterial fabric fiber to obtain an antibacterial base layer;
(2) Preparing composite nano particles:
In the continuous stirring process, 3.5mol/L of titanium sulfate solution is dripped into 3mol/L of potassium silicate solution, and the pH value of the mixed solution is adjusted to 10 through sodium hydroxide solution; then, sequentially aging, aging and centrifugal sedimentation are carried out on the mixed solution to obtain a precipitate; finally, heating and drying the precipitate for 8 hours at 120 ℃, and then placing the dried precipitate in a muffle furnace at 800 ℃ for high-temperature roasting for 3 hours to obtain composite nano particles; the composite nano particles comprise nano titanium dioxide particles and a silicon dioxide coating layer formed on the surfaces of the nano titanium dioxide particles, wherein the mass ratio of titanium dioxide to silicon dioxide is 1:0.5;
(3) Preparing an antibacterial composite layer:
dispersing the composite nano particles obtained in the step (2) in 0.5mmol/mL of ethanol solution of aminoethylaminopropyl trimethoxysilane to form an antibacterial dispersion liquid, wherein the mass fraction of the composite nano particles in the antibacterial dispersion liquid is 30mg/mL; soaking the antibacterial base layer obtained in the step (1) in antibacterial dispersion liquid for 3 hours, and taking out, washing and drying to form a composite nano particle film on the surface of the antibacterial base layer to obtain an antibacterial composite layer;
(4) Preparing an antiperspirant base fabric layer:
mixing bamboo carbon fiber, polyester fiber, cotton fiber and deionized water according to the mass ratio of 1:30:50:100 to form spinning solution, heating the spinning solution to 350 ℃ and preserving heat for 3 hours to melt the spinning solution to obtain spinning solution, spinning the spinning solution at a spinning speed of 1500 ℃/min to obtain composite yarns, and finally carrying out double-sided flat knitting on the composite yarns to obtain an antiperspirant base cloth layer;
(5) And (3) sequentially laying a hot melt adhesive layer and the antibacterial composite layer obtained in the step (3) on the antiperspirant base cloth layer obtained in the step (4), and then carrying out hot pressing treatment at 120 ℃ for 60 seconds to enable the antiperspirant base cloth layer and the antibacterial composite layer to be bonded and compounded through the hot melt adhesive layer, cooling, and then washing and drying to obtain the antibacterial antiperspirant knitted material.
Comparative example 1
The comparative example provides a method for manufacturing an antibacterial antiperspirant knitted material, which is different from example 1 in that in the step (1.2), the mass fraction of chitosan in the reaction solution is adjusted to 0.5mg/mL, and other process parameters and operation steps are exactly the same as those of example 1.
Comparative example 2
The comparative example provides a method for manufacturing an antibacterial antiperspirant knitted material, which is different from example 1 in that in the step (1.2), the mass fraction of chitosan in the reaction solution is adjusted to 15mg/mL, and other process parameters and operation steps are identical to those of example 1.
Comparative example 3
The comparative example provides a method for producing an antibacterial antiperspirant knitted material, which is different from example 1 in that in step (1.2), the mass concentration of tannic acid in the reaction liquid is adjusted to 1mg/mL, and other process parameters and operation steps are exactly the same as those of example 1.
Comparative example 4
The comparative example provides a method for producing an antibacterial antiperspirant knitted material, which is different from example 1 in that in step (1.2), the mass concentration of tannic acid in the reaction liquid is adjusted to 15mg/mL, and other process parameters and operation steps are exactly the same as those of example 1.
Comparative example 5
The comparative example provides a method for producing an antibacterial antiperspirant knitted material, which is different from example 1 in that in step (1.2), the mass concentration of silver nitrate in the reaction solution is adjusted to 0.1mg/mL, and other process parameters and operation steps are exactly the same as those of example 1.
Comparative example 6
The comparative example provides a method for producing an antibacterial antiperspirant knitted material, which is different from example 1 in that in step (1.2), the mass concentration of silver nitrate in the reaction solution is adjusted to 8mg/mL, and other process parameters and operation steps are exactly the same as those of example 1.
Comparative example 7
The present comparative example provides a method for manufacturing a knitted material for antibacterial and antiperspirant, which is different from example 1 in that in step (1.2), the reaction temperature is adjusted to 60 ℃, and other process parameters and operation steps are exactly the same as those of example 1.
Comparative example 8
The present comparative example provides a method for manufacturing a knitted material for antibacterial and antiperspirant, which is different from example 1 in that in step (1.2), the reaction temperature is adjusted to 90 ℃, and other process parameters and operation steps are exactly the same as those of example 1.
Comparative example 9
This comparative example provides a method of manufacturing a knitted material, differing from example 1 in that steps (1) - (3) and step (5) are omitted, and the antiperspirant base fabric layer prepared in example 1 is used as the finally obtained knitted material.
Evaluation of antimicrobial Properties of textiles according to the current national Standard GB/T20944.2-2007 part 2: absorption method, the antibacterial properties of the knitted materials prepared in examples 1 to 5 and comparative examples 1 to 9 of the present invention were tested and evaluated, and the bacterial strain used for obtaining the antibacterial rate of the knitted material was staphylococcus aureus, and the test results are shown in table 1.
In order to more intuitively evaluate the long-acting sterilization capability of the knitted material in the actual wearing and using processes, the invention tests the antibacterial condition of the knitted material under different wearing times and different cleaning times, and the specific test process is as follows:
(1) The knitted materials prepared in example 1 and comparative example 9 were made into ready-made clothes, and the experimenters were asked to wear for 5H, 10H, 15H and 20H respectively under the same exercise condition and humidity temperature environment, after the corresponding wearing time was reached, the fabric at the neckline of the ready-made clothes was cut off to obtain 8 fabric samples with the same size (including 4 fabric samples corresponding to example 1 and 4 fabric samples corresponding to comparative example 9 under different wearing times), wherein the 4 fabric samples corresponding to example 1 were marked as H5, H10, H15 and H20 respectively, the 4 fabric samples corresponding to comparative example 9 were marked as H5', H10', H15 'and H20' respectively, the 8 fabric samples were soaked in 8 identical LB liquid media respectively, and simultaneously were mixed in a constant temperature shaker at 37 ℃ under shaking at 220rpm, and the 8 LB liquid media were cultured for 3H under the same experiment environment.
The colony pictures shown in the figure 4 are obtained, and the colony pictures corresponding to H5, H10, H15, H20, H5', H10', H15 'and H20' in the figures 4 (a) - (H) respectively, and as can be seen from the figures 4 (a) - (d), no obvious colony is seen all the time along with the extension of the wearing time, the antibacterial antiperspirant knitted material prepared by the invention has long-acting antibacterial capability, and can still maintain higher antibacterial performance within the wearing time of 20H; as can be seen from FIGS. 4 (e) - (h), the colony count increased significantly with prolonged wear time.
(2) The fabric made of the knitted material prepared in example 1 and comparative example 9 was washed 5 times, 10 times, 15 times and 20 times respectively, 8 fabric samples of the same size (including 4 fabric samples corresponding to example 1 and 4 fabric samples corresponding to comparative example 9 and 4 fabric samples corresponding to different washing times) were obtained, wherein the 4 fabric samples corresponding to example 1 were marked as C5, C10, C15 and C20 respectively, the 4 fabric samples corresponding to comparative example 9 were marked as C5', C10', C15 'and C20' respectively, and 8 fabric samples were immersed in 8 identical LB liquid media respectively, and simultaneously mixed by shaking in a constant temperature shaker at 37 ℃ at a rotation speed of 220rpm, and the 8 LB liquid media were cultured for 3 hours in the same experimental environment.
The colony pictures shown in the figure 5 are obtained, and the colony pictures corresponding to C5, C10, C15, C20, C5', C10', C15 'and C20' in the figures 5 (a) - (h) respectively, and as can be seen from the figures 5 (a) - (d), no obvious colony is seen all the time along with the increase of the cleaning times, which shows that the antibacterial antiperspirant knitted material prepared by the invention has excellent antibacterial capability after a plurality of times of cleaning and can still keep higher antibacterial performance after 20 times of cleaning; as can be seen from FIGS. 5 (e) - (h), the number of colonies increased significantly with the increase in the number of washings, which indicates that the knitted material prepared in comparative example 9 lost the antibacterial ability after washing.
The air permeability of the knitted materials prepared in examples 1 to 5 and comparative examples 1 to 9 of the present invention was tested and evaluated according to the current national standard GB/T5453-1997 "determination of air permeability of textile fabrics", and the test results are shown in Table 1.
Evaluation of moisture absorption and quick drying Properties of textiles according to the current national Standard GB/T21655.1-2008, part 1: the moisture absorption and quick drying performances of the knitted materials prepared in examples 1 to 5 and comparative examples 1 to 9 of the present invention were tested and evaluated by a single combination test method to obtain the water absorption and the water evaporation rate of the knitted materials, and the test results are shown in Table 1.
TABLE 1 results of moisture absorption quick drying Property test of knitted materials prepared in examples 1 to 5 and comparative examples 1 to 9
The national standard GB/T21655.1-2008 stipulates that for knitting products, the water absorption rate is greater than or equal to 200%, the evaporation rate is greater than or equal to 0.18g/h, and test data provided by examples 1-5 show that the water absorption rate and the water evaporation rate of the antibacterial and antiperspirant knitting material prepared by the invention meet the national standard requirements. Meanwhile, the antibacterial rates obtained by the preparation of the examples 1-5 are all more than or equal to 99%, which shows that the test sample has good antibacterial performance.
As can be seen from the test data provided in example 1, comparative example 1 and comparative example 2, the antibacterial rate, air permeability, water absorption and water evaporation rate of the knitted material prepared in comparative example 1 are all lower than those of example 1, because the addition amount of chitosan in comparative example 1 is too low, the dispersibility of silver ions in the reaction solution is affected, the silver nanoparticles obtained by the reaction are seriously agglomerated in the reaction solution, the antibacterial property of the knitted material is further affected, and the agglomerated silver nanoparticles also block the air flow channel and the water evaporation channel to a certain extent, so that the air permeability and the water absorption of the knitted material are affected. The antibacterial rate of the knitted material prepared in comparative example 2 is far lower than that of example 1, and the air permeability, water absorption rate and water evaporation rate are slightly lower than those of example 1, because the addition amount of chitosan in comparative example 2 is too high, so that the viscosity of the reaction solution is too high, the dispersion of silver nano particles is not easy, the antibacterial property of the knitted material is further affected, and meanwhile, the air permeability and the water absorption property of the knitted material are also affected to a certain extent.
As can be seen from the test data provided in example 1, comparative example 3 and comparative example 4, the antibacterial rate of the knitted material prepared in comparative example 3 is lower than that of example 1, and the air permeability, water absorption and water evaporation rate are comparable to those of example 1, since the addition amount of tannic acid in comparative example 3 is too low, so that silver ions cannot be completely reduced to silver nanoparticles, thereby affecting the antibacterial property of the knitted material. The antibacterial rate, air permeability, water absorption rate and water evaporation rate of the knitted material prepared in comparative example 4 are all equivalent to those of example 1, but the residual tannic acid still has certain biotoxicity due to the fact that the addition amount of tannic acid in comparative example 4 is too high and cannot react with silver ions completely, and the residual tannic acid is easy to cause damage to human health when used as a clothing fabric.
As can be seen from the test data provided in example 1, comparative example 5 and comparative example 6, the antibacterial rate of the knitted material prepared in comparative example 5 is far lower than that of example 1, and the air permeability, water absorption and water evaporation rate are comparable to those of example 1, because the addition amount of silver nitrate in comparative example 5 is too low to generate silver nanoparticles in an effective antibacterial amount. The antibacterial rate, air permeability, water absorption rate and water evaporation rate of the knitted material prepared in comparative example 6 are all lower than those of example 1, because the addition amount of silver nitrate in comparative example 6 is too high, a large amount of silver nanoparticles are generated, the addition amount of chitosan is relatively reduced, and effective coating of the silver nanoparticles cannot be formed, so that a large amount of silver nanoparticles are agglomerated, and the sterilization capability cannot be exerted; in addition, the agglomerated silver nanoparticles block the air flow channels and the moisture evaporation channels to some extent, thereby affecting the air permeability and hygroscopicity of the knitted material.
As can be seen from the test data provided in example 1, comparative example 7 and comparative example 8, the antibacterial rate of the knitted material prepared in comparative example 7 is lower than that of example 1, and the air permeability, water absorption and water evaporation rate are comparable to those of example 1, since the reaction temperature in comparative example 7 is too low, the solubility of chitosan in the reaction solution is affected, and the dispersibility of silver ions in the reaction solution is deteriorated, thereby affecting the antibacterial performance of the knitted material. The antibacterial rate of the knitted material prepared in comparative example 8 is far lower than that of example 1, and the air permeability, water absorption rate and water evaporation rate are slightly lower than those of example 1, because the reaction temperature in comparative example 8 is too high, so that the inside of chitosan molecules swells, and an air flow channel and a water evaporation channel are blocked to a certain extent, thereby affecting the air permeability and the water absorption of the knitted material; in addition, the resistance of silver ions diffusing to chitosan molecular chains is increased, and the progress of coordination complex reaction is hindered, so that the dispersibility of silver ions is affected, and the antibacterial performance of the knitted material is reduced.
As can be seen from the test data provided in example 1 and comparative example 9, the knitted material prepared in comparative example 9 has an antibacterial rate far lower than that of example 1, and has an air permeability, water absorption rate and water evaporation rate slightly higher than those of example 1, because the antibacterial composite layer is not adhered in comparative example 9, resulting in a decrease in antibacterial performance of the knitted material, but a higher air permeability, water absorption rate and water evaporation rate can be ensured because the air permeability and moisture absorption performance of the antiperspirant base cloth layer are stronger.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (10)
1. A method of manufacturing an antibacterial antiperspirant knit material, said method comprising:
knitting antibacterial fabric fibers to obtain an antibacterial base layer, dispersing composite nano particles in an ethanol solution of a coupling agent to form an antibacterial dispersion liquid, soaking the antibacterial base layer in the antibacterial dispersion liquid, taking out, cleaning and drying after soaking to form a composite nano particle film on the surface of the antibacterial base layer to obtain an antibacterial composite layer;
(II) mixing bamboo carbon fiber, polyester fiber, cotton fiber and deionized water to form spinning solution, heating and melting the spinning solution to obtain spinning solution, spinning the spinning solution to obtain composite yarn, and finally performing double-sided flat knitting on the composite yarn to obtain an antiperspirant base cloth layer;
and (III) sequentially laying a hot melt adhesive layer and the antibacterial composite layer obtained in the step (I) on the antiperspirant base cloth layer obtained in the step (III), then carrying out hot pressing treatment to bond and composite the antiperspirant base cloth layer and the antibacterial composite layer through the hot melt adhesive layer, cooling, and then washing and drying to obtain the antibacterial antiperspirant knitted material.
2. The method of claim 1, wherein in step (i), the antimicrobial textile fiber is prepared by:
(1) Oxidizing the fiber raw material to oxidize hydroxyl groups of fiber molecular chains into carboxyl groups, immersing the oxidized fiber raw material into an amino acid solution for esterification reaction to obtain a modified fiber raw material;
(2) Adding chitosan, tannic acid and silver nitrate into an acetic acid solution, uniformly mixing to obtain a reaction solution, and reacting the reaction solution under a light-shielding condition to obtain an antibacterial solution;
(3) The modified fiber raw material is soaked in the antibacterial solution, taken out and dried to obtain the antibacterial fabric fiber.
3. The method according to claim 2, wherein in the step (1), the fiber raw material is any one or a combination of at least two of cotton fabric fiber, regenerated cellulose fabric fiber and hemp fabric fiber;
the oxidation treatment process comprises the following steps: immersing the fiber raw material in an oxidizing solution, taking out and drying for standby after immersing;
the dosage of the oxidizing solution is 20-30mL/g of fiber raw material;
the mass fraction of the oxidation solution is 10-20wt%;
the oxidation solution is any one or the combination of at least two of hydrogen peroxide solution, potassium permanganate solution and sodium hypochlorite solution;
The soaking time of the fiber raw material in the oxidizing solution is 1-5h;
the concentration of the amino acid solution is 0.15-0.25mol/L;
the amino acid solution is any one or the combination of at least two of lysine solution, arginine solution, histidine solution, tryptophan solution, glycine solution, glutamic acid solution and cysteine solution;
the temperature of the esterification reaction is 200-220 ℃, and the time of the esterification reaction is 10-20min.
4. The method according to claim 2, wherein in the step (2), the mass concentration of chitosan in the reaction solution is 1 to 10mg/mL;
the mass concentration of tannic acid in the reaction liquid is 5-10mg/mL;
the mass concentration of the silver nitrate in the reaction liquid is 1-5mg/mL;
the mass fraction of the acetic acid solution is 1-5wt%;
the temperature of the reaction is 70-80 ℃, and the reaction time is 5-10h.
5. The method according to claim 2, wherein in the step (3), the soaking time of the modified fiber raw material in the antibacterial solution is 40 to 50 minutes;
the drying temperature is 90-100 ℃, and the drying time is 0.5-1h.
6. The method according to claim 1, wherein in the step (i), the coupling agent is at least one of γ -aminopropyl triethoxysilane, γ -aminopropyl trimethoxysilane, γ -aminopropyl methyldiethoxysilane, and aminoethylaminopropyl trimethoxysilane;
The concentration of the ethanol solution of the coupling agent is 0.1-0.5mmol/mL;
the mass fraction of the composite nano particles in the antibacterial dispersion liquid is 20-30mg/mL;
the soaking time of the antibacterial base layer in the antibacterial dispersion liquid is 1-3h;
the composite nano particles comprise nano titanium dioxide particles and a silicon dioxide coating layer formed on the surfaces of the nano titanium dioxide particles;
the composite nano particles are prepared by the following method:
in the continuous stirring process, dropwise adding a titanium salt solution into a silicate solution, and adjusting the pH value of the mixed solution to 9-10 through alkali liquor; then, sequentially aging, aging and centrifugal sedimentation are carried out on the mixed solution to obtain a precipitate; finally, sequentially heating, drying and roasting the precipitate at a high temperature to obtain the composite nano particles;
the concentration of the titanium salt solution is 2.5-3.5mol/L;
the titanium salt solution is titanium tetrachloride solution or titanium sulfate solution;
the concentration of the silicate solution is 2-3mol/L;
the silicate solution is sodium silicate solution or potassium silicate solution;
the mass ratio of the titanium dioxide to the silicon dioxide is 1 (0.3-0.5) based on the generated titanium dioxide and silicon dioxide respectively;
The temperature of the heating and drying is 80-120 ℃, and the time of the heating and drying is 8-10h;
the high-temperature roasting temperature is 600-800 ℃, and the high-temperature roasting time is 3-4h.
7. The manufacturing method according to claim 1, wherein in the step (ii), the mass ratio of the bamboo charcoal fiber, the polyester fiber, the cotton fiber and the deionized water is 1 (20-30): 40-50): 80-100;
the temperature of the heating and melting is 340-350 ℃, and the time of the heating and melting is 3-4h;
the spinning speed is 1400-1500 ℃/min.
8. The method of claim 1, wherein in step (iii), the material of the hot melt adhesive layer is polyurethane;
the hot pressing temperature is 100-120 ℃, and the hot pressing time is 30-60s.
9. An antibacterial antiperspirant knitted material prepared by the manufacturing method according to any one of claims 1 to 8, characterized in that the knitted material comprises an antiperspirant base layer, a hot melt adhesive layer and an antibacterial composite layer which are sequentially laminated, wherein the antibacterial composite layer comprises an antibacterial base layer and a composite nanoparticle film formed on the surface of the antibacterial base layer;
the antiperspirant base cloth layer comprises bamboo carbon fiber, polyester fiber and cotton fiber.
10. An antibacterial and antiperspirant fabric, which is obtained by cutting the knitted material according to claim 9.
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| CN118288643A (en) * | 2024-05-29 | 2024-07-05 | 泉州市集华针纺科技有限公司 | Warm-keeping knitted fabric and processing technology thereof |
| CN118288643B (en) * | 2024-05-29 | 2024-08-13 | 泉州市集华针纺科技有限公司 | Warm-keeping knitted fabric and processing technology thereof |
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