CN113907090A - SiO (silicon dioxide)2Water-soluble gum-based antibacterial agent and preparation method and application thereof - Google Patents

SiO (silicon dioxide)2Water-soluble gum-based antibacterial agent and preparation method and application thereof Download PDF

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CN113907090A
CN113907090A CN202111274526.5A CN202111274526A CN113907090A CN 113907090 A CN113907090 A CN 113907090A CN 202111274526 A CN202111274526 A CN 202111274526A CN 113907090 A CN113907090 A CN 113907090A
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micron
chitosan
antibacterial agent
preparation
stirring
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王维明
罗然
刘雅静
肖燕
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WUJIANG FUHUA WEAVING CO Ltd
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WUJIANG FUHUA WEAVING CO Ltd
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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
    • 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
    • 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
    • A01N25/30—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 characterised by the surfactants
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
    • D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/53—Polyethers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • D06M16/003—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic with enzymes or microorganisms
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34—Polyamides

Abstract

The invention discloses a SiO2A method of preparing a water-soluble gum-based antimicrobial agent comprising the steps of: mixing the micron elemental silver dispersion liquid and the chitosan solution, continuously stirring, precipitating to obtain a crude product of the chitosan/micron elemental silver composite antibacterial agent, washing and filtering to obtain the chitosan/micron elemental silver composite antibacterial agent; adding a surfactant and a defoaming agent into a hydrochloric acid deionized water solution, stirring, adding a chitosan/micron simple substance silver composite antibacterial agent after the surfactant is fully dissolved, adding alkyl siloxane under stirring, and continuously stirring for reaction to obtain SiO2A water-soluble gum-based antimicrobial agent. SiO of the invention2The preparation method of the water-soluble gum base antibacterial agent further reduces the cost on the premise of ensuring the antibacterial property, and the preparation process is green and environment-friendly; the chitosan/micron simple substance silver composite antibacterial agent is combined with alkyl siloxane to prepare SiO2The water-soluble gum-based antibacterial agent is applied to the preparation of the fabric, and the prepared fabric is good in antibacterial property and durability.

Description

SiO (silicon dioxide)2Water-soluble gum-based antibacterial agent and preparation method and application thereof
Technical Field
The invention relates to the technical field of textiles, in particular to SiO2Preparation method of water-soluble gum-based antibacterial agent and SiO prepared by adopting preparation method2A water-soluble gum-based antibacterial agent and application thereof in the preparation process of fabrics.
Background
The textile has a loose and porous structure, so that excrement secreted by metabolism of a human body is easily absorbed, favorable places and required nutrients are provided for attachment and propagation of microorganisms, and pathogenic bacteria propagate in a large quantity. The presence of microorganisms on textiles not only affects their performance (e.g., mildew, catalysis, deterioration, etc.), but also poses serious health risks to the health of the user (e.g., causing skin disorders, entering the body to induce diseases, etc.). Therefore, the antibacterial finishing is carried out on the textile to hinder and inhibit the metabolism and reproduction of microorganisms in the using and storing processes of the textile, and the antibacterial finishing has important significance for protecting human health. In recent years, antibacterial textiles have become a focus of research in the field of functional textiles.
The antibacterial textile is usually realized by adding an antibacterial agent into the textile, the preparation method mainly comprises a primary fiber method and a post-finishing method, and the antibacterial function can also be realized by a blending or interweaving method, wherein the post-finishing method is to adopt a coating or padding method to attach the antibacterial agent to the surface of the fiber to endow the fabric with the antibacterial effect, and the method becomes the preparation method of the antibacterial fabric which is the most researched at present due to simple operation, but the durability of the antibacterial fabric prepared by the method needs to be further improved. The post-finishing method is a method for loading the antibacterial agent on the surface of the fabric by adopting a physical method, a chemical method or a physical and chemical combination method.
The antibacterial agent is a substance capable of effectively inhibiting the growth and reproduction of microorganisms or killing the microorganisms, and the quality of the performance of the antibacterial agent directly determines the antibacterial effect of the textile. Antibacterial agents can be classified into inorganic antibacterial agents, organic antibacterial agents and natural antibacterial agents according to the source, antibacterial mechanism and composition structure. The inorganic antibacterial agent mainly comprises silver and copper, the silver has a good antibacterial effect, but is high in price and easy to oxidize to generate dark silver oxide or black simple substance silver, the copper is low in price and has a certain antiviral effect, and the color of the copper can change the color of the fabric. The organic antibacterial agent mainly comprises quaternary ammonium salts, guanidines, halogenated phenols and halogen amines, and has excellent antibacterial performance, but generally has high toxicity and is easy to cause bacteria to generate drug resistance. The natural antibacterial agent has the advantages of good biocompatibility, natural degradability, no drug resistance of bacteria and the like, so that the natural antibacterial agent has great development potential. Among them, chitosan is a product of chitin with acetyl removed, and has inhibitory effect on Escherichia coli, Staphylococcus aureus, etc., and is one of the most widely studied natural antibacterial agents due to its abundant resources. However, chitosan alone has poor antibacterial ability, and thus, improving antibacterial ability is a key to promote industrial application of chitosan.
At present, chitosan antibacterial agents can be classified into two major types, namely a composite type and a modified type according to a preparation method, wherein the composite chitosan antibacterial agent is concerned due to the simple preparation method and the remarkable antibacterial effect. However, in the application process of the composite chitosan antibacterial agent, an adhesive or a cross-linking agent is still required to be added to improve the bonding force between the composite chitosan antibacterial agent and the fibers, so that the wearability of the fabric is affected. The literature reports that the bond between the fiber and the antibacterial agent is the most effective method for improving the load strength, and the most studied grafting method can bond the fiber and the antibacterial agent, but has the problems of severe process conditions, difficult uniformity control and the like.
Disclosure of Invention
In view of the above, in order to overcome the defects of the prior art, the present invention aims to provide a SiO2Preparation method of water-soluble gum-based antibacterial agent and prepared SiO2The water-soluble gum base antibacterial agent has good effect and good durability.
In order to achieve the aim, aiming at the defects of the existing antibacterial protective fabric, the invention adopts a sol-gel method to prepare the safe, harmless or low-harm high-efficiency composite antibacterial finishing agent which can be bonded with the fiber through valence bond.
The invention adopts the following technical scheme:
SiO (silicon dioxide)2A method of preparing a water-soluble gum-based antimicrobial agent comprising the steps of:
mixing the micron elemental silver dispersion liquid and the chitosan solution, continuously stirring, precipitating to obtain a crude product of the chitosan/micron elemental silver composite antibacterial agent, washing and filtering to obtain the chitosan/micron elemental silver composite antibacterial agent;
adding a surfactant and a defoaming agent into a hydrochloric acid deionized water solution, stirring, adding a chitosan/micron simple substance silver composite antibacterial agent after the surfactant is fully dissolved, adding alkyl siloxane under stirring, and continuously stirring for reaction to obtain SiO2A water-soluble gum-based antimicrobial agent.
In some embodiments of the invention, the hydrosol (SiO) with antimicrobial function2A water-soluble gum-based antimicrobial agent) is prepared as follows: adding 0.1% of surfactant and 0.01% of defoaming agent into 0.46% of hydrochloric acid deionized water solution, stirring at 25 ℃ at a speed of 300r/min for 60min, adding a chitosan/micron simple substance silver composite antibacterial agent with a mass ratio of 15% to alkyl siloxane after sodium dodecyl benzene sulfonate is fully dissolved, continuing to stir for 60min to enable the antibacterial agent to be uniformly dispersed, adding 4% of alkyl siloxane within 5min under the stirring condition of 600r/min, continuing to stir for 60min after the alkyl siloxane is completely added, then heating to 60 ℃ at a heating speed of 2 ℃/minReacting for 30min under the condition of stirring to obtain SiO2Hydrosol-based chitosan/micron elemental silver composite antibacterial agent. The mass concentration in the present invention is the mass concentration of the corresponding substance in the formed solution, and is not the original concentration of the added substance.
According to some preferred embodiments of the present invention, the alkylsiloxane is selected from one or more of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, and γ -aminopropyltriethoxysilane.
According to some preferred embodiments of the present invention, the surfactant is a mixture of sodium dodecylbenzenesulfonate and twain-80 in a mass ratio of 1: 0.1-0.3.
The principle of the step is as follows: the mixture of anionic sodium dodecyl benzene sulfonate and nonionic twain-80 is used as a surfactant, because the addition of the twain-80 does not change the charge quantity of an hydrosol system, but can enhance the strength of a sodium dodecyl benzene sulfonate micelle and effectively reduce the viscosity of the hydrosol, thereby improving the stability of the hydrosol and the uniformity of the particle size; the addition of the defoaming agent can effectively prevent the surfactant from generating foam under the condition of high-speed stirring, and further avoid influencing the dispersibility of the alkyl siloxane and the final antibacterial effect.
According to some preferable implementation aspects of the invention, in the preparation of the chitosan/micron elemental silver composite antibacterial agent, the mass of the added micron elemental silver is 5-10% of that of the chitosan.
According to some preferred embodiments of the invention, the SiO2In the preparation of the water-soluble gum base antibacterial agent, the mass of the added chitosan/micron elementary substance silver composite antibacterial agent is 10-20% of that of the added alkyl siloxane.
According to some preferred aspects of the invention, the chitosan solution is prepared by the following steps: adding chitosan and acetic acid into deionized water to form a chitosan solution, wherein the mass concentration of the chitosan is 2-5%, and the mass concentration of the acetic acid is 1-2%.
According to some preferred aspects of the invention, the micron elemental silver dispersion is prepared by the following steps: adding sodium dodecyl benzene sulfonate and ethanol into deionized water, stirring, adding 5-10% of micron elemental silver by mass of chitosan while stirring after sodium dodecyl benzene sulfonate is completely dissolved, then precipitating a crude product of the micron elemental silver, and washing to obtain the micron elemental silver.
According to some preferred aspects of the invention, the preparation of the micrometric elemental silver comprises the following steps: adding polyvinylpyrrolidone and a reducing agent into deionized water, wherein the mass concentration of the polyvinylpyrrolidone and the mass concentration of the reducing agent in the system are 0.5-1.0% and 1-2%, stirring, after the polyvinylpyrrolidone and the reducing agent are completely dissolved, adjusting the pH of a reaction solution to 3-4 by using a buffer solution, adding silver nitrate with the mass concentration of 2-5% under the stirring condition, continuously stirring after the addition is finished, heating to 40-50 ℃, reacting for 30-60min at a constant temperature, precipitating a micron elementary silver crude product, washing and filtering to obtain micron elementary silver.
In some embodiments of the present invention, the preparation of the chitosan/micron elemental silver composite antibacterial agent comprises the following steps:
1) preparing a chitosan solution: chitosan with the mass concentration of 2-5% and acetic acid with the mass concentration of 1.0-2.0% are added into 200mL of deionized water. The deacetylation degree of the used chitosan is more than or equal to 90 percent.
2) Preparing a micron elemental silver dispersion liquid: adding 0.1-0.2% of sodium dodecyl benzene sulfonate and 2-5mL of ethanol into 50mL of deionized water, stirring at the speed of 300r/min, adding micron elemental silver accounting for 5-10% of the mass of the chitosan while stirring after the sodium dodecyl benzene sulfonate is completely dissolved, precipitating a crude product of the micron elemental silver by using a centrifuge, and washing for 3-5 times by using the deionized water to obtain the micron elemental silver.
3) Preparing a composite antibacterial agent: stirring at the speed of 600r/min at the temperature of 25-30 ℃, slowly adding the micron elemental silver dispersion liquid into the chitosan solution within 10-20min, continuing stirring for 120-240min after the addition is finished, precipitating a crude product of the chitosan/micron elemental silver composite antibacterial agent by using a centrifugal machine, washing for 3-5 times by using deionized water, and performing suction filtration to obtain the chitosan/micron elemental silver composite antibacterial agent.
In some embodiments of the present invention, the preparation of micron elemental silver comprises the steps of: adding 0.5-1.0% of polyvinylpyrrolidone and 1-2% of reducing agent in mass concentration into 200mL of deionized water at 25-30 ℃, stirring at 300r/min, after the polyvinylpyrrolidone and the reducing agent are completely dissolved, adjusting the pH of a reaction solution to 3-4 by using an acetic acid-sodium acetate buffer solution, slowly adding 2-5% of silver nitrate in mass concentration within 5-10min under the stirring condition, continuously stirring for 10-20min after the addition is finished, heating to 40-50 ℃ at 1-2 ℃/min, reacting at constant temperature for 30-60min, precipitating a micron elementary silver crude product by using a centrifugal machine, washing for 3-5 times by using deionized water, and performing suction filtration to obtain micron elementary silver with the particle size of 1-20 mu m.
According to some preferred embodiments of the present invention, the reducing agent used in the preparation process of the micron elemental silver is one or two of trisodium citrate and ascorbic acid.
The invention also provides SiO prepared by the preparation method2A water-soluble gum-based antimicrobial agent.
The invention also provides the SiO2Application of a water-soluble gum-based antibacterial agent in fabric preparation. In some embodiments of the present invention, a method of making a fabric comprises the steps of: carrying out surface modification on the fibers of the fabric by adopting protease under an acidic condition; then preparing polyalkyl siloxane hydrosol; finishing the modified fabric by using the polyalkylsiloxane hydrosol to obtain the fabric; the surfactant used in the preparation of the polyalkylsiloxane hydrosol is a mixture of sodium dodecylbenzenesulfonate and twain-80. The fibers used in the fabric are aliphatic polyamide fibers.
According to some preferred aspects of the invention, the acidic condition is a pH of 3.0 to 4.0, preferably 3.5.
According to some preferred embodiments of the invention, a surfactant is used in modifying the fibers of the fabric, the surfactant being a nonionic surfactant, preferably nonylphenol polyoxyethylene ether and aliphatic polyoxyethylene ether surfactants.
According to some preferred aspects of the invention, a buffer solution consisting of a mixture of 0.1 to 0.3mol/L disodium phosphate and 0.0.5 to 0.2mol/L citric acid is used in modifying the fibers of the fabric. Preferably, the buffer solution is a mixture of 0.2mol/L disodium hydrogen phosphate and 0.1mol/L citric acid in a volume ratio of 3: 7, so that the pH value of the system is maintained at about 3.5.
The principle of fiber surface modification is as follows: modifying the fiber surface, hydrolyzing through amido bond (-COONH-) to generate carboxyl (-COOH) which can react with silicon hydroxyl (-Si-OH) on the surface of the silica hydrosol particles, forming a micro-rough structure on the fiber surface through denudation, and improving the durability of the finishing effect through the dual functions of mechanical nail anchoring and valence bond combination; the optimal application pH value of the acidic protease for modifying the surface of the polyamide fiber is about 3.5, and the acidity and the protease can generate a synergistic effect in the process of hydrolyzing amido bond (-COONH-) in the molecular structure of the polyamide fiber to generate amido group (-NH2) and carboxyl group (-COOH); the pH is adjusted by a buffer solution, and carboxyl (-COOH) generated in the modification process can be effectively neutralized, so that the pH value of the system is always maintained at about 3.5, and the highest effect of the protease is ensured; the hydrolysis of amido bond by organic acid is more moderate than inorganic strong acid, and the condition is easy to control; the addition of the nonionic surfactant can improve the wettability of the fiber surface, accelerate the swelling of the fiber, further improve the spreading of the biological enzyme treatment solution on the fiber surface, and improve the modification efficiency by improving the effective contact area of the biological enzyme and the fiber surface.
According to some preferred embodiments of the present invention, the pH of the deionized water is adjusted to 3.0-4.0 with a buffer solution, and then a surfactant and a protease are added, wherein the amount of the surfactant is 1-1.5 times of the Critical Micelle Concentration (CMC), and the concentration of the protease in the system is 0.02-2.0 g/mL; treating the fabric at a bath ratio of 1: 10-35, and then washing and drying the fabric.
The nonionic surfactant is added when the protease is used for modifying the polyamide fiber, and not only can improve the wettability of the fiber, improve the swelling performance of the fiber, improve the effective contact area of the protease and the surface of the fiber, and improve the treatment efficiency. Meanwhile, the main purpose of the invention is to improve the fixation strength of the finishing agent on the fiber surface by combining the valence bond combination and the mechanical nail anchor dual functions when the fiber surface is finished by the protease modification to generate more carboxyl groups and form a micro-rough structure.
In some embodiments of the invention, the specific steps of modifying the fiber surface are as follows: adjusting pH value of 1L deionized water to 3.5 with 20mL buffer solution, adding surfactant and 0.2-2.0g protease, wherein the dosage of the surfactant is 1-1.5 times of CMC, and treating the fabric at 40 deg.C for 2-6h with bath ratio of 1: 30. After treatment, the fabric is inactivated at 60 ℃ for 10min, taken out, washed with water and dried.
According to some preferred embodiments of the present invention, the protease is papain, and the papain has an optimum pH of 3.0 to 4.0, and the acidity of the pH does not significantly affect the fiber damage, but can act synergistically with the biological enzymes.
According to some preferred embodiments of the present invention, finishing the modified fabric comprises the steps of: and (3) adjusting the pH value of the polyalkylsiloxane hydrosol to 6-7 by using an alkaline agent, finishing the modified fabric by adopting a padding method, and then washing and drying to prepare the fabric.
According to some preferred embodiments of the invention, the alkaline agent is sodium hydroxide solution with a mass concentration of 4-8 g/L.
In some embodiments of the present invention, the modified face fabric polyalkylsiloxane finishing steps are specifically as follows: adjusting the pH value of the polyalkylsiloxane hydrosol to 6-7 by using an alkaline agent at the temperature of 25-30 ℃, finishing the modified polyamide fabric by adopting a two-dipping two-rolling method, wherein the rolling residue rate is 60-100%, drying for 2-5min at the temperature of 80-90 ℃, baking for 3-6min at the temperature of 140-160 ℃, washing with water, and finally drying at the temperature of 80-100 ℃ to prepare the multifunctional polyamide fabric.
The principle of the step is as follows: the polyamide fiber is easy to hydrolyze under acidic condition, thereby affecting the use performance of the fabric. The pH value of the silica sol is adjusted to 6-7, which can not cause the rapid condensation of the sol particles and can not cause obvious influence on the fiber strength.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the beneficial effects that: SiO of the invention2The preparation method of the water-soluble gum base antibacterial agent combines the relevant characteristics of chitosan and micron elemental silver, further reduces the cost on the premise of ensuring the antibacterial property, and has the advantages of green and environment-friendly preparation process and easily controlled conditions; the chitosan/micron simple substance silver composite antibacterial agent is combined with alkyl siloxane to prepare SiO2The water-soluble gum-based antibacterial agent is applied to the preparation of the fabric, and the prepared fabric is good in antibacterial property and durability.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a microscopic, enlarged view of a sample of polyamide fiber used in a preferred embodiment of the present invention;
FIG. 2 is a microscopic enlarged view of polyamide fiber after modification with a bio-enzyme in preferred embodiment 1-1 of the present invention;
FIG. 3 is a comparison picture of the bacteriostatic effect of the fabrics prepared in the preferred embodiment 3-1 and the comparative examples 1-4 to 1-7 of the present invention.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution in the embodiment of the present invention will be clearly and completely described below with reference to the drawings in the embodiment of the present invention, and it is obvious that the described embodiment is only a part of the embodiment of the present invention, and not a whole embodiment. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1-1 fiber surface modification
The pH value of 1L of deionized water is adjusted to 3.5 of the optimal application value of the protease by using 20mL of buffer solution, 1.0g of protease and 1.2 g of CMC nonylphenol polyoxyethylene ether are added, and the mixture is treated for 3 hours at the temperature of 40 ℃ with the bath ratio of 1: 30. After treatment, inactivation is carried out for 10min at 60 ℃, and the fabric is taken out, washed and dried.
Examples 1-2 fiber surface modification
The pH value of 1L of deionized water is adjusted to 3.5 of the optimal application value of the protease by using 20mL of buffer solution, 1.5g of protease and 1.2 g of CMC nonylphenol polyoxyethylene ether are added, and the mixture is treated for 2 hours at the temperature of 40 ℃ with the bath ratio of 1: 35. After treatment, inactivation is carried out for 10min at 60 ℃, and the fabric is taken out, washed and dried.
Examples 1-3 fiber surface modification
The pH value of 1L of deionized water is adjusted to 3.5 of the optimal application value of the protease by using 20mL of buffer solution, 1.0g of protease and 1.2 g of CMC nonylphenol polyoxyethylene ether are added, and the mixture is treated for 3 hours at the temperature of 40 ℃ with the bath ratio of 1: 25. After treatment, inactivation is carried out for 10min at 60 ℃, and the fabric is taken out, washed and dried.
EXAMPLE 2-1 preparation of hydrosol having antibacterial function
1. Preparation of micron elementary silver
Adding 0.7 mass percent of polyvinylpyrrolidone and 1 mass percent of reducing agent into 200mL of deionized water at 25 ℃, stirring at the speed of 300r/min, after the polyvinylpyrrolidone and the reducing agent are completely dissolved, adjusting the pH of a reaction solution to 3-4 by using an acetic acid-sodium acetate buffer solution, slowly adding 3 mass percent of silver nitrate within 8min under the stirring condition, continuing stirring for 15min after the addition is finished, heating to 40 ℃ at the speed of 1.5 ℃/min, reacting at a constant temperature for 50min, precipitating out elemental silver by using a centrifugal machine, washing for 5 times by using the deionized water, and performing suction filtration to obtain the micron elemental silver.
2. Preparation of chitosan/micron elementary silver composite antibacterial agent
Chitosan solution: chitosan with the mass concentration of 3% is added into 200mL of deionized water for dissolution, and acetic acid with the mass concentration of 1.0% is added into the deionized water for dissolution.
Micron elemental silver dispersion: adding 0.15% of surfactant and 3mL of ethanol into 50mL of deionized water, stirring at the speed of 300r/min, and adding micrometer elementary silver accounting for 6% of the mass of the chitosan while stirring after the sodium dodecyl benzene sulfonate is completely dissolved.
Stirring at the speed of 600r/min at the temperature of 25 ℃, slowly adding the micrometer elementary substance silver dispersion liquid into the chitosan solution within 10min, continuing stirring for 150min after the addition is finished, precipitating elementary substance silver by using a centrifugal machine, washing for 5 times by using deionized water, and performing suction filtration to obtain the chitosan/micrometer elementary substance silver composite antibacterial agent.
3、SiO2Preparation of aqueous-based antibacterial agents
Adding 0.1% of surfactant and 0.01% of defoaming agent into 0.46% of hydrochloric acid deionized water solution, stirring at 25 ℃ at the speed of 300r/min for 60min, adding a chitosan/micron simple substance silver composite antibacterial agent with the mass ratio of 15% to alkyl siloxane after sodium dodecyl benzene sulfonate is fully dissolved, continuing to stir for 60min to enable the antibacterial agent to be uniformly dispersed, adding 4% of methyltrimethoxysilane at the mass concentration within 5min under the stirring condition of 600r/min, continuing to stir for 60min after the precursor is added, then heating to 60 ℃ at the heating speed of 2 ℃/min, reacting for 30min under the stirring condition to obtain SiO2A water-soluble gum-based antimicrobial agent. Wherein the surfactant is a mixture of sodium dodecyl benzene sulfonate and twain-80 in a mass ratio of 1: 0.2.
Example 2-2 preparation of hydrosol having antibacterial function
1. Preparation of micron elementary silver
Under the condition of 25 ℃, adding polyvinylpyrrolidone with the mass concentration of 0.5% and reducing agent with the mass concentration of 1.5% into 200mL of deionized water, stirring at the speed of 300r/min, after the polyvinylpyrrolidone and the reducing agent are completely dissolved, adjusting the pH of a reaction solution to 3-4 by using acetic acid-sodium acetate buffer solution, slowly adding silver nitrate with the mass concentration of 5% within 8min under the stirring condition, continuously stirring for 15min after the addition is finished, heating to 40 ℃ at the speed of 1.5 ℃/min, reacting at constant temperature for 30min, precipitating out elemental silver by using a centrifugal machine, washing for 5 times by using the deionized water, and performing suction filtration to obtain the micron elemental silver.
2. Preparation of chitosan/micron elementary silver composite antibacterial agent
Chitosan solution: chitosan with the mass concentration of 3% is added into 200mL of deionized water for dissolution, and acetic acid with the mass concentration of 1.0% is added into the deionized water for dissolution.
Micron elemental silver dispersion: adding 0.15% of surfactant and 3mL of ethanol into 50mL of deionized water, stirring at the speed of 300r/min, and adding micrometer elementary silver accounting for 10% of the mass of the chitosan while stirring after the sodium dodecyl benzene sulfonate is completely dissolved.
Stirring at the speed of 600r/min at the temperature of 25 ℃, slowly adding the micrometer elementary substance silver dispersion liquid into the chitosan solution within 10min, continuing stirring for 200min after the addition is finished, precipitating elementary substance silver by using a centrifugal machine, washing for 5 times by using deionized water, and performing suction filtration to obtain the chitosan/micrometer elementary substance silver composite antibacterial agent.
3、SiO2Preparation of aqueous-based antibacterial agents
Adding 0.16% of surfactant and 0.016% of defoaming agent into 0.5% of hydrochloric acid deionized water solution, stirring at 25 ℃ at 300r/min for 60min, adding a chitosan/micron simple substance silver composite antibacterial agent with the mass ratio of alkyl siloxane being 20% after sodium dodecyl benzene sulfonate is fully dissolved, continuing to stir for 90min to uniformly disperse the antibacterial agent, adding 4% of propyl trimethoxy silane within 5min under the stirring condition of 600r/min, continuing to stir for 60min after the precursor is added, then heating to 40 ℃ at the heating rate of 1.5 ℃/min, and reacting for 30min under the stirring condition to obtain SiO2A water-soluble gum-based antimicrobial agent. Wherein the surfactant is dodecyl benzene sulfonic acidSodium and twain-80 in a mass ratio of 1: 0.3.
Examples 2-3 preparation of hydrosol having antibacterial function
1. Preparation of micron elementary silver
Under the condition of 25 ℃, adding polyvinylpyrrolidone with the mass concentration of 0.7% and reducing agent with the mass concentration of 1% into 200mL of deionized water, stirring at the speed of 300r/min, after the polyvinylpyrrolidone and the reducing agent are completely dissolved, adjusting the pH of a reaction solution to 3-4 by using an acetic acid-sodium acetate buffer solution, slowly adding silver nitrate with the mass concentration of 4% within 10min under the stirring condition, continuously stirring for 15min after the addition is finished, heating to 40 ℃ at the speed of 1.5 ℃/min, reacting at a constant temperature for 40min, precipitating out elemental silver by using a centrifugal machine, washing for 5 times by using the deionized water, and performing suction filtration to obtain the micron elemental silver.
2. Preparation of chitosan/micron elementary silver composite antibacterial agent
Chitosan solution: chitosan with the mass concentration of 3% is added into 200mL of deionized water for dissolution, and acetic acid with the mass concentration of 1.0% is added into the deionized water for dissolution.
Micron elemental silver dispersion: adding 0.1% of surfactant and 3mL of ethanol into 50mL of deionized water, stirring at the speed of 300r/min, and adding micron elementary silver accounting for 8% of the mass of the chitosan while stirring after the sodium dodecyl benzene sulfonate is completely dissolved.
Stirring at the speed of 600r/min at the temperature of 25 ℃, slowly adding the micrometer elementary substance silver dispersion liquid into the chitosan solution within 10min, continuing stirring for 150min after the addition is finished, precipitating elementary substance silver by using a centrifugal machine, washing for 5 times by using deionized water, and performing suction filtration to obtain the chitosan/micrometer elementary substance silver composite antibacterial agent.
3、SiO2Preparation of aqueous-based antibacterial agents
Adding 0.13% surfactant and 0.013% defoaming agent into 0.46% hydrochloric acid deionized water solution, stirring at 25 deg.C at 300r/min for 60min, dissolving sodium dodecylbenzenesulfonate, and adding 20% chitosan/micrometer simple substance silver composite antibacterial agentThe antibacterial agent is uniformly dispersed by continuously stirring for 60min, alkyl siloxane with the mass concentration of 4% (the mass ratio of methyltrimethoxysilane to propyltrimethoxysilane is 3: 1) is added within 5min under the stirring condition of 600r/min, after the precursor is added, the stirring is continuously carried out for 60min, then the temperature is increased to 40 ℃ at the temperature rise speed of 2 ℃/min, the reaction is carried out for 40min under the stirring condition, and SiO is obtained2A water-soluble gum-based antimicrobial agent. Wherein the surfactant is a mixture of sodium dodecyl benzene sulfonate and twain-80 in a mass ratio of 1: 0.1.
Examples 2-1 to 2-3 provide a method for preparing a multifunctional composite antibacterial finishing agent, having the following advantages: the process is simple, and the process parameters are stable and easy to control; the antibacterial finishing agent has excellent antibacterial effect; the finishing fabric has active groups which can be bonded with the fiber surface through valence bonds, and the finishing fabric has a lasting antibacterial effect; the finishing agent can simultaneously endow the finished fabric with good antibacterial property, water repellency and soft hand feeling.
EXAMPLE 3-1 preparation of Fabric
The preparation method of the multifunctional fabric in the embodiment specifically comprises the following steps:
(1) fiber surface modification treatment: modifying the polyamide fabric by adopting the fiber surface modification method in the example 1-1;
(2) preparing a composite antibacterial finishing agent: SiO by the preparation method in example 2-12Hydrosol-based chitosan/micron elemental silver composite antibacterial agent.
(3) Modified fabric polyalkylsiloxane finishing: adjusting the pH value of the polyalkylsiloxane water-soluble gum base antibacterial agent in the step (2) to 6-7 by using an alkaline agent at the temperature of 25 ℃, finishing the modified polyamide fabric in the step (1) by adopting a two-dipping and two-rolling method with the rolling residue rate of 80%, then drying for 2min at the temperature of 80 ℃, then baking for 3min at the temperature of 140 ℃, washing, and finally drying at the temperature of 80 ℃ to prepare the multifunctional polyamide fabric.
EXAMPLE 3-2 preparation of Fabric
The preparation method of the multifunctional fabric in the embodiment specifically comprises the following steps:
(1) fiber surface modification treatment: modifying the polyamide fabric by adopting the fiber surface modification method in the embodiment 1-2;
(2) preparing a composite antibacterial finishing agent: SiO was prepared by the method of example 2-22Hydrosol-based chitosan/micron elemental silver composite antibacterial agent.
(3) Modified fabric polyalkylsiloxane finishing: adjusting the pH value of the polyalkylsiloxane water-soluble gum base antibacterial agent in the step (2) to 6-7 by using an alkaline agent at the temperature of 25 ℃, finishing the modified polyamide fabric in the step (1) by adopting a two-dipping and two-rolling method with the rolling residue rate of 80%, then drying for 2min at the temperature of 80 ℃, then baking for 3min at the temperature of 140 ℃, washing, and finally drying at the temperature of 80 ℃ to prepare the multifunctional polyamide fabric.
Examples 3-3 preparation of fabrics
The preparation method of the multifunctional fabric in the embodiment specifically comprises the following steps:
(1) fiber surface modification treatment: modifying the polyamide fabric by adopting the fiber surface modification method in the examples 1-3;
(2) preparing a composite antibacterial finishing agent: SiO was prepared by the preparation method in examples 2 to 32Hydrosol-based chitosan/micron elemental silver composite antibacterial agent.
(3) Modified fabric polyalkylsiloxane finishing: adjusting the pH value of the polyalkylsiloxane water-soluble gum base antibacterial agent in the step (2) to 6-7 by using an alkaline agent at the temperature of 25 ℃, finishing the modified polyamide fabric in the step (1) by adopting a two-dipping and two-rolling method with the rolling residue rate of 80%, then drying for 2min at the temperature of 80 ℃, then baking for 3min at the temperature of 140 ℃, washing, and finally drying at the temperature of 80 ℃ to prepare the multifunctional polyamide fabric.
Examples 3-1 to 3-3 provide a method for preparing a multifunctional polyamide fabric, having the following advantages: the process is simple, and the process parameters are stable and easy to control; the fabric has excellent hydrophobicity, antistatic property and comfortable hand feeling; the fabric has lasting antibacterial function and good washing fastness.
Comparative examples 1 to 1
This comparative example differs from example 1-1 in that: in the method for modifying the fiber surface of the comparative example, a nonionic surfactant was not added when the modification was performed with the protease. The remaining other steps of this comparative example are substantially identical to those of example 1-1.
Comparative examples 1 to 2
This comparative example differs from example 1-1 in that: in the fiber surface modification method of the present comparative example, the pH of the system was controlled to 4.2. The remaining other steps of this comparative example are substantially identical to those of example 1-1.
Comparative examples 1 to 3
This comparative example differs from example 1-1 in that: in the fiber surface modification method of the present comparative example, the pH of the system was controlled to 2.8. The remaining other steps of this comparative example are substantially identical to those of example 1-1.
Comparative examples 1 to 4
This comparative example differs from example 3-1 in that: in this comparative example, SiO was prepared2When the water-soluble gum base antibacterial agent is used, the chitosan/micron elemental silver composite antibacterial agent is replaced by micron elemental silver, and the rest other steps of the comparative example are basically consistent with those of the examples 2-1 and 3-1.
Comparative examples 1 to 5
This comparative example differs from example 3-1 in that: in this comparative example, SiO was prepared2When the water-soluble gum base antibacterial agent is used, nano-elementary silver is adopted to replace the chitosan/micron-elementary silver composite antibacterial agent, and the rest other steps of the comparative example are basically consistent with those of the examples 2-1 and 3-1.
Comparative examples 1 to 6
This comparative example differs from example 3-1 in that: in this comparative example, SiO was prepared2When the water-soluble gum base antibacterial agent is used, chitosan is used for replacing the chitosan/micron elemental silver composite antibacterial agent, and other steps remained in the comparative example are basically consistent with those in the examples 2-1 and 3-1.
Comparative examples 1 to 7
This comparative example differs from example 3-1 in that: in this comparative example, SiO was prepared2Dissolving in waterWhen the gum base antibacterial agent is used, the chitosan/nano elemental silver composite antibacterial agent is used for replacing the chitosan/micron elemental silver composite antibacterial agent, and the rest other steps in the comparative example are basically the same as those in the examples 2-1 and 3-1. The nano elemental silver is prepared by a conventional method, and the chitosan/nano elemental silver composite antibacterial agent is prepared by the step 2 in the embodiment 2-1.
Comparative examples 1 to 8
This comparative example differs from example 3-1 in that: the method for preparing the facing of this comparative example did not include step (1) of example 3-1, i.e., the comparative example did not surface-modify the fibers. The remaining other steps of this comparative example are substantially identical to those of example 3-1.
Results and discussion
(1) Testing of fiber surface modification Effect
The fiber-modified fabrics prepared in examples 1-1 to 1-3 and comparative examples 1-1 to 1-3 were subjected to the following terminal carboxyl group contents and weight loss ratios. Wherein the test method for the content of terminal carboxyl groups was carried out by the method described on page 13 of the patent specification entitled method for modifying polyamides, application No. 200580018511.5; the weight loss rate test adopts a constant-temperature dry weight method, and the specific method comprises the following steps: drying the fabric in an oven at 105-110 ℃ until the fabric is in constant weight balance (about 4h), weighing the fabric by using an analytical balance, and weighing the fabric with the weight loss rate (W ═0-W1)/W0X 100%, wherein: w0Is the pre-treatment fabric weight; w1Is the treated fabric weight. The results of the modification effect test are shown in table 1 below:
TABLE 1 fiber surface modification Effect test results
Terminal carboxyl group content (mmol/kg) Weight loss rate/%)
Examples 1 to 1 95.2 1.2±0.3
Examples 1 to 2 101.1 1.3±0.3
Examples 1 to 3 97.2 1.2±0.3
Comparative examples 1 to 1 88.6 1.1±0.3
Comparative examples 1 to 2 83.5 0.8±0.3
Comparative examples 1 to 3 84.3 2.0±0.3
The test results in table 1 show that the example treated fibers have significantly higher terminal carboxyl content than the comparative example treated fibers. The terminal carboxyl group content of the treated fiber of example 1-1 was higher than that of the treated fiber of comparative example 1-1, indicating that the addition of the nonionic surfactant increased the hydrolysis rate of the amide bond. The reason why the content of terminal carboxyl groups in the fibers treated in examples 1-2 is the highest is that the fibers are in contact with the biological enzyme efficiently in a unit time because the mass concentration of the protease in examples 1-2 is high.
The terminal carboxyl group content of the fiber treated in comparative example 1-1 was higher than the fiber treated in comparative example 1-2 and comparative example 1-3, probably because the pH of the treatment solution of comparative example 1-1 was within the optimum active pH range for papain, the terminal carboxyl group content of the fiber treated in comparative example 1-1 was the highest among the fibers treated in comparative example. In addition, comparative examples 1-2 have slightly higher terminal carboxyl group content of the treated fibers of comparative examples 1-3 than comparative examples 1-3, probably due to the lower pH (pH 2.8) of the treatment solutions of comparative examples 1-3, the stronger the acidity, the poorer the stability of the amide bond. The weight loss rate of the fiber treated by the comparative example shows that the weight loss of the fiber is caused by the combined action of the acid and the protease, the terminal carboxyl content of the fiber treated by the comparative example 1-1 is the maximum, and the weight loss rate is not the maximum, which shows that the hydrolysis of the amido bond by the protease is more moderate than that under the acid condition, and the molecular chain of the polyamide is not broken to generate micromolecule substances to be separated from the main body of the fiber in a short time.
(2) Antibacterial Rate test
As shown in fig. 3, the fabrics prepared in examples 3-1 to 3-3 and comparative examples 1-4 to 1-7 were subjected to an antibacterial ratio test; the test method of the antibacterial rate refers to GB/T20944.1-2007 evaluation part 1 of the antibacterial performance of textiles: agar plate diffusion method. The results of the antibacterial ratio test are shown in table 2 below:
TABLE 2 antibacterial Rate test results
Figure BDA0003328997720000131
The test results in table 2 show that when the alkyl polysiloxane hydrosol is used as the matrix, the antibacterial property of chitosan is the worst (comparative examples 1-6), the antibacterial property of micro simple substance silver (comparative examples 1-4) and the antibacterial property of nano simple substance silver (comparative examples 1-5) both reach 100%, the antibacterial property of chitosan can be obviously improved by the simple substance silver, and the antibacterial property of chitosan/micro simple substance silver (examples 3-1, 3-2 and 3-3) is similar to that of the simple substance silver (comparative examples 1-4 and comparative examples 1-5) and is better than that of chitosan/nano simple substance silver (comparative examples 1-7). Reason analysis: chitosan is a porous material, when the simple substance silver is compounded with chitosan, one part of the simple substance silver is adsorbed on the surface of the chitosan, the other part of the simple substance silver is adsorbed inside the pores of the chitosan, the smaller the particle size of the simple substance silver is, the higher the probability of being adsorbed inside the pores of the chitosan is, and the simple substance silver is a contact type antibacterial agent, so the antibacterial property of the chitosan/micron simple substance silver (embodiment) is better than that of the chitosan/nano simple substance silver (comparative examples 1-7).
(3) Durability test
The fabrics prepared in examples 3-1 to 3-3 and comparative examples 1-8 were tested for antibacterial rate, hand feel and static contact angle as follows, wherein the antibacterial rate test method refers to evaluation part 1 of antibacterial performance of textiles in GB/T20944.1-2007: agar plate diffusion method; the hand feeling test adopts a hand touch method; the static contact angle is tested by adopting an OCA50Micro type full-automatic single fiber contact angle measuring instrument (Germany Dataphysics instruments GmbH); the washing method refers to the GB/T8629 and 2017 domestic washing and drying program for the textile test. The test results are shown in table 3 below:
TABLE 3 test results
Figure BDA0003328997720000141
Figure BDA0003328997720000151
The test results in table 3 show that when the polyalkylsiloxane water-soluble gum-based antibacterial agent is used for finishing the polyamide fabric, the antibacterial property, the hand feeling and the static contact angle of the fabric (without biological enzyme modification) prepared in the comparative examples 1-8 are similar to those of the fabric (without biological enzyme modification) prepared in the example 3-1, but after 20 times or 50 times of washing, the fabric prepared in the example 3-1 has various performances which are remarkably superior to those of the fabric prepared in the comparative examples 1-8, mainly because the biological enzyme modification can form carboxyl (-COOH) which is bonded with silicon hydroxyl (Si-OH) through valence bond on the surface of the fiber, and can form a micro-coarse structure, and the coarse structure and the polyalkylsiloxane coating have mechanical meshing effect, so that the durability of the finishing effect is improved.
Table 3 also shows that varying the polyalkylsiloxane precursors (i.e., specific species of alkylsiloxanes) can impart different hand to the finished face material (examples 3-1, 3-2 and 3-3), but does not affect the antimicrobial properties (i.e., antimicrobial rate) and the hydrophobic properties (i.e., static contact angle) nor significantly affect the durability of the finish.
In the preparation method, when the fiber is modified, the pH value of the system is controlled to be about 3.5, the acidity and the protease at the time have a synergistic effect on the degradation of the surface of the polyamide fiber, and the degraded fiber not only can effectively increase the adsorption capacity of the fiber to the polyalkylsiloxane hydrosol, but also can achieve the durability of the effect by mechanical anchor effect and valence bond combination (COOH on the fiber and-OH on the polyalkylsiloxane). At the same time, the film formed of polyalkylsiloxane can compensate for damage caused by the strength of the multi-fibers by the denudation effect.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (10)

1. SiO (silicon dioxide)2The preparation method of the water-soluble gum-based antibacterial agent is characterized by comprising the following steps:
mixing the micron elemental silver dispersion liquid and the chitosan solution, stirring, precipitating to obtain a crude product of the chitosan/micron elemental silver composite antibacterial agent, washing and filtering to obtain the chitosan/micron elemental silver composite antibacterial agent;
adding a surfactant and a defoaming agent into a hydrochloric acid deionized water solution, stirring, adding a chitosan/micron simple substance silver composite antibacterial agent after the surfactant is fully dissolved, adding alkyl siloxane under stirring, and continuously stirring for reaction to obtain SiO2A water-soluble gum-based antimicrobial agent.
2. The method according to claim 1, wherein the surfactant is a mixture of sodium dodecylbenzenesulfonate and twain-80 in a mass ratio of 1: 0.1-0.3.
3. The preparation method of claim 1, wherein in the preparation of the chitosan/micron elemental silver composite antibacterial agent, the mass of the added micron elemental silver is 5-10% of that of the chitosan.
4. The method of claim 1, wherein the SiO is2In the preparation of the water-soluble gum base antibacterial agent, the mass of the added chitosan/micron elementary substance silver composite antibacterial agent is 10-20% of that of the added alkyl siloxane.
5. The method according to claim 1, wherein the chitosan solution is prepared by the steps of: adding chitosan and acetic acid into deionized water to form a chitosan solution, wherein the mass concentration of the chitosan is 2-5%, and the mass concentration of the acetic acid is 1-2%.
6. The method according to claim 1, wherein the micron elemental silver dispersion is prepared by the steps of: adding sodium dodecyl benzene sulfonate and ethanol into deionized water, stirring, adding 5-10% of micron elemental silver by mass of chitosan while stirring after sodium dodecyl benzene sulfonate is completely dissolved, then precipitating a crude product of the micron elemental silver, and washing to obtain the micron elemental silver.
7. The method according to claim 1, wherein the preparation of the micron elemental silver comprises the following steps: adding polyvinylpyrrolidone and a reducing agent into deionized water, wherein the mass concentration of the polyvinylpyrrolidone and the mass concentration of the reducing agent in the system are 0.5-1.0% and 1-2%, stirring, after the polyvinylpyrrolidone and the reducing agent are completely dissolved, adjusting the pH of a reaction solution to 3-4 by using a buffer solution, adding silver nitrate with the mass concentration of 2-5% under the stirring condition, continuing stirring after the addition is finished, heating to 40-50 ℃, reacting at a constant temperature for 30-60min, precipitating a micron elementary silver crude product, washing and filtering to obtain micron elementary silver.
8. The preparation method according to claim 7, wherein the reducing agent used in the preparation process of the micron elemental silver is one or two of trisodium citrate and ascorbic acid.
9. SiO prepared by the preparation method according to any one of claims 1 to 82A water-soluble gum-based antimicrobial agent.
10. SiO as claimed in claim 92Application of a water-soluble gum-based antibacterial agent in fabric preparation.
CN202111274526.5A 2021-10-29 2021-10-29 SiO (silicon dioxide)2Water-soluble gum-based antibacterial agent and preparation method and application thereof Pending CN113907090A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114481611A (en) * 2022-02-24 2022-05-13 绍兴集宇化工科技有限公司 Soft antistatic finishing agent and preparation method and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114481611A (en) * 2022-02-24 2022-05-13 绍兴集宇化工科技有限公司 Soft antistatic finishing agent and preparation method and application thereof

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