CN110592938A - Antibacterial modified silk fiber and preparation method thereof - Google Patents

Antibacterial modified silk fiber and preparation method thereof Download PDF

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Publication number
CN110592938A
CN110592938A CN201910879259.0A CN201910879259A CN110592938A CN 110592938 A CN110592938 A CN 110592938A CN 201910879259 A CN201910879259 A CN 201910879259A CN 110592938 A CN110592938 A CN 110592938A
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sericin
silk fiber
antibacterial
modified
preparation
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杨双建
龚琤琤
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JIESHOU SHUANGXIN TEXTILE Co Ltd
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JIESHOU SHUANGXIN TEXTILE Co Ltd
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    • D—TEXTILES; PAPER
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    • D06M11/73—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 carbon or compounds thereof
    • D06M11/76—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 carbon or compounds thereof with carbon oxides or carbonates
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    • 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
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    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/12—Aldehydes; Ketones
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    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
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    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
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    • 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
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    • 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
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    • 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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
    • D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
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    • 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
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    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/10—Animal fibres

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Abstract

The invention discloses an antibacterial modified silk fiber and a preparation method thereof, wherein the preparation method comprises the steps of silk fiber preparation, sericin fixation, modified sericin preparation, antibacterial modifier preparation, silk fiber primary treatment and silk fiber antibacterial modification treatment; in the preparation process, urea is used as an auxiliary agent, glutaraldehyde is used as a cross-linking agent to react with sericin, the antibacterial capacity of sericin is improved, the water solubility of sericin is reduced, the sericin on the surface of silk fiber is fixed, the sericin on the surface of the silk fiber is prevented from being further dissolved and separated in subsequent treatment, then the silk fiber is treated by emulsifying and dispersing organic silicon emulsion with the sericin, the hydrophobic effect and the flexibility of the silk fiber are improved, the silk fiber is further protected, the silk fiber has good water washing resistance, and finally the silk fiber is treated by antibacterial modification, so that the antibacterial modified fiber has good water washing resistance, hydrophilicity and moisture retention.

Description

Antibacterial modified silk fiber and preparation method thereof
Technical Field
The invention belongs to the technical field of textiles, and particularly relates to an antibacterial modified silk fiber and a preparation method thereof.
Background
The silk is one of the earliest utilized animal fibers of human beings, and is derived from silkworm, is a pure natural material, has good biocompatibility, degradability, air permeability and moisture permeability, and has wide application in the biological medicine, cosmetics and textile industries;
since the silk is pure natural animal protein, the processed silk has a poor bacteriostatic effect, and the textile using the silk as a raw material or a main material is easy to rapidly decay and generate peculiar smell under the condition of high humidity and high temperature, so that the use experience of the silk textile is poor, the use range of the silk textile is limited, and the maintenance difficulty of the silk textile is improved; in the prior art, silk fiber needs to be treated, the antibacterial effect of the silk fiber is improved, the strength and other performances are improved, the silk fiber can be effectively used for a long time, the antibacterial performance of the silk fiber is improved mainly by fixing an antibacterial agent on the surface of the silk fiber through reactive resin, fixing the antibacterial agent on the surface of the silk fiber through the adsorption of the antibacterial agent, fixing the antibacterial agent through two mutually-reacted components and other methods, however, on one hand, the problems of poor washing fastness, poor safety and the like of the conventional commonly-used antibacterial agent exist, on the other hand, the effect that the silk has good affinity with a human body is reduced, in order to solve the problem, and sericin produced in the production process of the silk fiber is fully utilized, the invention provides the following technical scheme.
Disclosure of Invention
The invention aims to provide an antibacterial modified silk fiber and a preparation method thereof.
The technical problems to be solved by the invention are as follows:
1. sericin has good affinity, still has good moisturizing nature, properties such as antibiotic mould proof and antistatic, can make the fabrics that uses silk fibre to prepare as raw materials have better property, but simultaneously, sericin is easily dissolved in aqueous, therefore if silk fibre goods, especially silk quilt, when getting damp and not in time dry, easily harden, lead to the cold-proof effect of silk quilt to descend, give a general consideration to, in prior art, the silk of preparation silk fabric or cotton quilt need through degumming treatment in order to detach the most sericin on silk surface, thereby guarantee silk fibre can normal use, but can reduce the utilization ratio of silkworm cocoon on the one hand like this, on the other hand makes the moisturizing nature such as the fabrics that obtains, antibiotic and antistatic greatly descend.
2. In the prior art, in order to improve the antibacterial capacity of silk fibers, methods such as fixing an antibacterial agent on the surface of the silk fibers through reactive resin, fixing the antibacterial agent on the surface of the silk fibers through self adsorption of the antibacterial agent, and fixing the antibacterial agent through two components which react with each other are mainly adopted, but the method leads to poor water washing resistance of the silk fibers on one hand and reduces the affinity of the silk fibers on the other hand.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of antibacterial modified silk fiber comprises the following steps:
step one, preparation of silk fiber
Cutting the silkworm cocoons into pieces, cleaning the surfaces of the silkworm cocoons by using deionized water and then airing, adding the aired silkworm cocoons into ether to be soaked for 24-48h to remove waxy substances on the surfaces of the silkworm cocoons, carrying out solid-liquid separation after soaking, airing the silkworm cocoons, soaking the silkworm cocoons in absolute ethyl alcohol for 8-12h, then replacing the absolute ethyl alcohol to soak for 10-14h, washing the silkworm cocoons with distilled water after solid-liquid separation, and airing to finish degreasing the silkworm cocoons;
adding the degreased silkworm cocoons into a sodium carbonate aqueous solution with the mass concentration of 0.5-0.8%, heating at the temperature of 95-98 ℃, and processing the treated silkworm cocoons to obtain dispersed silk fibers and a sodium carbonate aqueous solution in which sericin is dissolved;
in the step, firstly, removing waxy substances on the surface of the silkworm cocoon through ether soaking treatment, then removing ether on the surface of the silkworm cocoon through ethanol soaking and distilled water washing, and then dissolving sericin on the surface of silk fiber through alkaline solution heating treatment, thereby separating the silk fiber bonded together;
step two, fixing sericin
Fixing residual sericin on the surface of silk fiber by using glutaraldehyde as a cross-linking agent and urea as an auxiliary agent, specifically, preparing a glutaraldehyde aqueous solution with the mass concentration of 0.5-0.8%, adding urea into the glutaraldehyde aqueous solution, wherein the mass concentration of the urea is 0.7-1.6%, so as to obtain a stationary liquid, adjusting the temperature of the stationary liquid to 40-50 ℃, adding the silk fiber obtained by the treatment in the step one into the stationary liquid, and soaking for 6-20 hours;
taking the silk fiber out of the mixed solution, washing the silk fiber by using deionized water at the temperature of 45-60 ℃, removing glutaraldehyde and urea attached to the surface of the silk fiber, and dehydrating and drying to finish fixing the residual sericin on the surface of the silk fiber;
in the step, urea is used as an auxiliary agent, and aldehyde groups of glutaraldehyde react with omega-amino groups in side chains of amino acid residues in sericin molecules, so that the antibacterial capacity of the sericin is improved on one hand, and the water solubility of the sericin can be reduced on the other hand, so that part of the sericin on the surface of the treated silk fiber is preserved;
step three, preparation of modified sericin
S11, adding citric acid into the sericin aqueous solution obtained in the first step to adjust the pH value to be neutral, performing vacuum drying to obtain a sericin aqueous solution with the mass concentration of 5% -15%, then adding glucan into the sericin aqueous solution, and performing microwave intermittent treatment after the glucan is dissolved and stirred uniformly to finish primary modification of sericin;
wherein the mass concentration of the glucan in the sericin aqueous solution is 25-60 g/L;
the specific method of the microwave batch treatment comprises the following steps: treating with 800W microwave, stopping microwave standing after every 30s, circulating for 4-6 times for 20-30s, and finishing microwave intermittent treatment;
in the step, free amino groups of the sericin are grafted with glucan through microwave treatment, so that the emulsibility and the emulsion stability of the sericin are improved;
s12, filtering the sericin protein aqueous solution obtained in the previous step, performing vacuum freeze drying to obtain sericin powder, adding water to rehydrate the sericin powder, and performing freeze drying again to obtain sericin powder with a porous structure;
s13, adding the sericin powder obtained in the previous step into a silver nitrate solution, soaking for 6-10min, continuously stirring in the soaking process to uniformly disperse the sericin powder, irradiating by ultraviolet light after soaking is finished, and after the silver nitrate solution is completely changed into black, performing solid-liquid separation and freeze drying to obtain modified sericin loaded with nano silver;
because sericin has a porous structure by freeze drying in the previous step, sericin is added into a silver nitrate solution for soaking, the silver nitrate solution can be fully absorbed by sericin, and then silver nitrate can be reduced to generate nano silver particles by ultraviolet irradiation, so that the nano silver particles can be uniformly dispersed in the pore structure and the surface of sericin, and the antibacterial ability of sericin is improved;
the preparation method of the silver nitrate solution comprises the following steps:
adding silver nitrate and polyvinylpyrrolidone into N, N-dimethylformamide, and stirring until the silver nitrate is fully dissolved, wherein the mass concentration of the silver nitrate in the N, N-dimethylformamide is 4g/L, and the mass concentration of the polyvinylpyrrolidone in the N, N-dimethylformamide is 4-10 g/L;
step four, preparation of antibacterial modifier
Preparing a polyvinyl alcohol aqueous solution with the mass concentration of 5% -8%, adding the modified sericin loaded with nano-silver obtained in the previous step, mixing and stirring uniformly, adding citric acid, and uniformly mixing to obtain the antibacterial modifier, wherein the mass concentration of the citric acid in the antibacterial modifier is 0.3% -1%, and the addition concentration of the modified sericin in the antibacterial modifier is 4% -8%;
the polyvinyl alcohol is selected from polyvinyl alcohol with the molecular weight of 18-25 ten thousand and the alcoholysis degree of 98%;
citric acid is taken as a cross-linking agent, polyvinyl alcohol and sericin can form a layer of curing film on the surface of the silk fiber, and the curing film hardly generates dissolution loss or has extremely low dissolution rate at the temperature of 30-40 ℃, so that the silk fiber water-washing resistant effect is good, and meanwhile, because the sericin and the polyvinyl alcohol both have hydrophilicity, the moisture absorption and moisture retention type of the silk fiber can not be obviously influenced;
step five, primary treatment of silk fiber
Adding the modified sericin obtained in the third step into the organic silicon emulsion, stirring by a stirring device to emulsify and disperse the sericin in the organic silicon emulsion, adding the silk fiber obtained by the treatment in the second step into the organic silicon emulsion, soaking for 10-15min, taking out, drying and drying;
in the step, modified sericin is emulsified and dispersed in organic silicon emulsion, and silk fibers are treated by the organic silicon emulsion, firstly, sericin in the emulsion is coated on the surface of the silk fibers, silk protein parts exposed in the process of removing the sericin from the silk fibers are covered, and meanwhile, a layer of oil film is coated on the surface of the silk fibers by the organic silicon emulsion, so that the hydrophobic effect and the flexibility of the silk fibers are improved, the silk fibers can be used as further protection, the silk fibers have good water washing resistance, and the hygroscopicity, the moisture retention and the compression resilience of the silk fibers treated by the organic silicon emulsion are all reduced;
step six, antibacterial modification treatment of silk fibers
And adding the silk fiber obtained by the previous step into an antibacterial modifier, soaking for 20-40min, taking out, draining the surface antibacterial modifier, and drying to obtain the silk fiber with antibacterial effect.
The invention has the beneficial effects that:
1. in the preparation process of the antibacterial modified silk fiber, after the silk cocoon is treated to obtain the dispersed silk fiber, firstly, urea is used as an auxiliary agent, aldehyde groups of glutaraldehyde react with omega-amino groups in amino acid residue side chains in sericin molecules, so that the antibacterial capability of sericin is improved, the water solubility of sericin is reduced, the fixation of residual sericin on the surface of the silk fiber is realized, the sericin on the surface of the silk fiber is prevented from being further dissolved and separated in the subsequent treatment, then, the silk fiber is treated by emulsifying the organic silicon emulsion dispersed with the sericin, the sericin in the emulsion is coated on the surface of the silk fiber, the silk fibroin part exposed in the previous sericin removing process of the silk fiber is covered, and meanwhile, the organic silicon emulsion coats a layer of oil film on the surface of the silk fiber, so that the hydrophobic effect and the flexibility of the silk fiber are improved, the silk fiber can be used for further protection, so that the silk fiber has good water washing resistance, and finally the silk fiber is treated through antibacterial modification, so that the antibacterial modified fiber has good water washing resistance, hydrophilicity and moisture retention.
2. In the preparation process of the modified sericin, firstly, the sericin is modified by glucan, specifically, free amino groups of the sericin are grafted with the glucan under the microwave condition, so that the emulsibility and the emulsification stability of the sericin are improved, and the emulsifying and dispersing capacity of the sericin in an organic silicon emulsion is improved, and therefore the sericin in the organic silicon emulsion can be uniformly laid on the surface of silk fibers; sericin through glucan modification has porous structure through freeze-drying, add this sericin and soak in the silver nitrate solution, sericin can fully absorb the silver nitrate solution, then through ultraviolet irradiation, the silver nitrate can restore and generate the nanometer silver granule, make nanometer silver granule homodisperse in sericin's pore structure and surface, thereby promote sericin's antibacterial ability, use this modified sericin at antibiotic modifier and organosilicon emulsion moderate silk fibre and handle, can promote silk fibrous antibiotic effect greatly.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of antibacterial modified silk fiber comprises the following steps:
step one, preparation of silk fiber
Cutting the silkworm cocoons into pieces, cleaning the surfaces of the silkworm cocoons by using deionized water and then airing, adding the aired silkworm cocoons into ether to be soaked for 30 hours so as to remove waxy substances on the surfaces of the silkworm cocoons, carrying out solid-liquid separation after soaking, airing the silkworm cocoons, soaking the aired silkworm cocoons in absolute ethyl alcohol for 10 hours, replacing the absolute ethyl alcohol for soaking for 10 hours, washing the dried silkworm cocoons with distilled water after solid-liquid separation, and airing to finish degreasing the silkworm cocoons;
adding degreased silkworm cocoons into a sodium carbonate aqueous solution with the mass concentration of 0.5%, heating at the temperature of 98 ℃, and processing the treated silkworm cocoons to obtain dispersed silk fibers and a sodium carbonate aqueous solution in which sericin is dissolved;
step two, fixing sericin
Fixing residual sericin on the surface of the silk fiber by using glutaraldehyde as a cross-linking agent and urea as an auxiliary agent, specifically, preparing a glutaraldehyde aqueous solution with the mass concentration of 0.5%, adding urea with the mass concentration of 0.7% to obtain a fixing solution, adjusting the temperature of the fixing solution to 45 ℃, adding the silk fiber obtained by the treatment in the step one, and soaking for 12 hours;
taking the silk fiber out of the mixed solution, washing the silk fiber by using deionized water at the temperature of 50 ℃, removing glutaraldehyde and urea attached to the surface of the silk fiber, and dehydrating and drying to finish the fixation of sericin remained on the surface of the silk fiber;
step three, preparation of modified sericin
S11, adding citric acid into the sericin aqueous solution obtained in the step one to adjust the pH value to be neutral, obtaining a sericin aqueous solution with the mass concentration of 10% through vacuum drying, then adding glucan into the sericin aqueous solution, and after the glucan is dissolved and stirred uniformly, carrying out microwave intermittent treatment to complete primary modification of sericin;
wherein the mass concentration of the glucan in the sericin aqueous solution is 35 g/L;
the specific method of the microwave batch treatment comprises the following steps: treating with 800W power microwave, stopping microwave standing after every 30s, circulating for 5 times for 30s, and finishing microwave intermittent treatment;
s12, filtering the sericin protein aqueous solution obtained in the previous step, performing vacuum freeze drying to obtain sericin powder, adding water to rehydrate the sericin powder, and performing freeze drying again to obtain sericin powder with a porous structure;
s13, adding the sericin powder obtained in the previous step into a silver nitrate solution, soaking for 10min, continuously stirring in the soaking process to uniformly disperse the sericin powder, irradiating by ultraviolet light after soaking is finished, and after the silver nitrate solution is completely changed into black, performing solid-liquid separation and freeze drying to obtain modified sericin loaded with nano silver;
the preparation method of the silver nitrate solution comprises the following steps:
adding silver nitrate and polyvinylpyrrolidone into N, N-dimethylformamide, and stirring until the silver nitrate is fully dissolved, wherein the mass concentration of the silver nitrate in the N, N-dimethylformamide is 4g/L, and the mass concentration of the polyvinylpyrrolidone in the N, N-dimethylformamide is 5 g/L;
step four, preparation of antibacterial modifier
Preparing a polyvinyl alcohol aqueous solution with the mass concentration of 7%, adding the modified sericin loaded with nano-silver obtained in the previous step, mixing and stirring uniformly, adding citric acid, and mixing uniformly to obtain the antibacterial modifier, wherein the mass concentration of the citric acid in the antibacterial modifier is 0.5%, and the mass concentration of the modified sericin in the antibacterial modifier is 8%;
the polyvinyl alcohol is selected from polyvinyl alcohol with the molecular weight of 20-22 ten thousand and the alcoholysis degree of 98%;
step five, primary treatment of silk fiber
Adding the modified sericin obtained in the third step into the organic silicon emulsion, stirring by a stirring device to emulsify and disperse the sericin in the organic silicon emulsion, adding the silk fiber obtained by the treatment in the second step into the organic silicon emulsion, soaking for 15min, taking out, drying and drying;
step six, antibacterial modification treatment of silk fibers
And adding the silk fiber obtained by the previous step into an antibacterial modifier, soaking for 25min, taking out, draining the surface antibacterial modifier, and drying to obtain the silk fiber with an antibacterial effect.
Example 2
A preparation method of antibacterial modified silk fiber comprises the following steps:
step one, preparation of silk fiber
Cutting the silkworm cocoons into pieces, cleaning the surfaces of the silkworm cocoons by using deionized water and then airing, adding the aired silkworm cocoons into ether to be soaked for 30 hours so as to remove waxy substances on the surfaces of the silkworm cocoons, carrying out solid-liquid separation after soaking, airing the silkworm cocoons, soaking the aired silkworm cocoons in absolute ethyl alcohol for 10 hours, replacing the absolute ethyl alcohol for soaking for 10 hours, washing the dried silkworm cocoons with distilled water after solid-liquid separation, and airing to finish degreasing the silkworm cocoons;
adding degreased silkworm cocoons into a sodium carbonate aqueous solution with the mass concentration of 0.5%, heating at the temperature of 98 ℃, and processing the treated silkworm cocoons to obtain dispersed silk fibers and a sodium carbonate aqueous solution in which sericin is dissolved;
step two, fixing sericin
Fixing residual sericin on the surface of the silk fiber by using glutaraldehyde as a cross-linking agent and urea as an auxiliary agent, specifically, preparing a glutaraldehyde aqueous solution with the mass concentration of 0.6%, adding urea with the mass concentration of 0.8% to obtain a fixing solution, adjusting the temperature of the fixing solution to 50 ℃, adding the silk fiber obtained by the treatment in the step one, and soaking for 12 hours;
taking the silk fiber out of the mixed solution, washing the silk fiber by using deionized water at the temperature of 50 ℃, removing glutaraldehyde and urea attached to the surface of the silk fiber, and dehydrating and drying to finish the fixation of sericin remained on the surface of the silk fiber;
step three, preparation of modified sericin
S11, adding citric acid into the sericin aqueous solution obtained in the step one to adjust the pH value to be neutral, obtaining a sericin aqueous solution with the mass concentration of 10% through vacuum drying, then adding glucan into the sericin aqueous solution, and after the glucan is dissolved and stirred uniformly, carrying out microwave intermittent treatment to complete primary modification of sericin;
wherein the mass concentration of the glucan in the sericin aqueous solution is 35 g/L;
the specific method of the microwave batch treatment comprises the following steps: treating with 800W power microwave, stopping microwave standing after every 30s, circulating for 5 times for 30s, and finishing microwave intermittent treatment;
s12, filtering the sericin protein aqueous solution obtained in the previous step, performing vacuum freeze drying to obtain sericin powder, adding water to rehydrate the sericin powder, and performing freeze drying again to obtain sericin powder with a porous structure;
s13, adding the sericin powder obtained in the previous step into a silver nitrate solution, soaking for 10min, continuously stirring in the soaking process to uniformly disperse the sericin powder, irradiating by ultraviolet light after soaking is finished, and after the silver nitrate solution is completely changed into black, performing solid-liquid separation and freeze drying to obtain modified sericin loaded with nano silver;
the preparation method of the silver nitrate solution comprises the following steps:
adding silver nitrate and polyvinylpyrrolidone into N, N-dimethylformamide, and stirring until the silver nitrate is fully dissolved, wherein the mass concentration of the silver nitrate in the N, N-dimethylformamide is 4g/L, and the mass concentration of the polyvinylpyrrolidone in the N, N-dimethylformamide is 5 g/L;
step four, preparation of antibacterial modifier
Preparing a polyvinyl alcohol aqueous solution with the mass concentration of 6%, adding the modified sericin loaded with nano-silver obtained in the previous step, mixing and stirring uniformly, adding citric acid, and uniformly mixing to obtain the antibacterial modifier, wherein the mass concentration of the citric acid in the antibacterial modifier is 0.3% -1%, and the mass concentration of the modified sericin in the antibacterial modifier is 6%;
the polyvinyl alcohol is selected from polyvinyl alcohol with the molecular weight of 20-22 ten thousand and the alcoholysis degree of 98%;
step five, primary treatment of silk fiber
Adding the modified sericin obtained in the third step into the organic silicon emulsion, stirring by a stirring device to emulsify and disperse the sericin in the organic silicon emulsion, adding the silk fiber obtained by the treatment in the second step into the organic silicon emulsion, soaking for 15min, taking out, drying and drying;
step six, antibacterial modification treatment of silk fibers
And adding the silk fiber obtained by the previous step into an antibacterial modifier, soaking for 40min, taking out, draining the surface antibacterial modifier, and drying to obtain the silk fiber with an antibacterial effect.
Comparative example 1
Comparative example 1, except that sericin was not subjected to an immobilization treatment in the second step.
Comparative example 2
Comparative example 1, except that sericin was not modified with dextran in the third step.
Comparative example 3
Comparative example 1, except that sericin was not modified with a silver nitrate solution in the third step.
Comparative example 4
Comparative example 1, except that the operations of step two to step six were not performed, the silk fiber obtained by the step one treatment was used as the experimental subject.
Analysis of Experimental data and results
The antibacterial performance and the water washing resistance of the antibacterial modified fibers prepared in the examples and the comparative examples are tested, wherein the antibacterial performance test method comprises the following steps: sterilizing the fiber by using 75% ethanol steam, testing the bacteriostasis rate of the modified fiber by adopting the GB15979-2002 standard, wherein the bacteriostasis rate is the ratio of the difference between the number of bacterial colonies of the sample before oscillation and the number of bacterial colonies of the sample after oscillation to the number of bacterial colonies of the sample before oscillation, the test strain is escherichia coli, and the specific result is shown in the table 1;
the test method of the water washing resistance comprises the following steps: preparing a sodium carbonate aqueous solution with the mass concentration of 0.2%, adjusting the water temperature to 30 ℃, adding the fibers into the aqueous solution, stirring the mixture for 30min at the rotating speed of 60r/min to obtain a first washing, drying the fibers between two adjacent washing processes, and testing the sericin residual amount on the surface of the fibers after 10 times, 20 times, 30 times and 40 times of washing respectively, wherein the specific results are shown in table 2;
TABLE 1
Group of Example 1 Example 2 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4
Rate of inhibition of bacteria 91％ 93％ 91％ 87％ 47％ 21％
As can be seen from the results in Table 1, the antibacterial modified fiber prepared by the preparation method of the invention has good antibacterial effect on Escherichia coli.
TABLE 2
Number of washes Example 1 Example 2 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4
10 times of 86％ 89％ 87％ 87％ 85％ 41％
20 times (twice) 71％ 75％ 73％ 72％ 73％ 25％
30 times (twice) 66％ 68％ 66％ 57％ 65％ 12％
40 times (twice) 61％ 63％ 52％ 49％ 61％ 7％
The results shown in table 2 show that the silk fibroin surface fixing agent has a good fixing effect on the sericin on the silk fiber surface, and the participation amount of the sericin on the silk fiber surface can be still maintained above 60% after 40 times of washing, so that the silk fiber has good water absorption and water retention.
The foregoing is merely exemplary and illustrative of the present invention and various modifications, additions and substitutions may be made by those skilled in the art to the specific embodiments described without departing from the scope of the invention as defined in the following claims.

Claims (9)

1. A preparation method of antibacterial modified silk fiber is characterized by comprising the following steps:
step one, preparation of silk fiber
Processing and preparing degreased silk fiber and sericin aqueous solution by taking silkworm cocoons as raw materials;
step two, fixing sericin
Preparing a fixing solution by using glutaraldehyde as a cross-linking agent and urea as an auxiliary agent, and fixing sericin remained on the surface of the silk fiber through the fixing solution;
step three, preparation of modified sericin
S11, adding citric acid into the sericin aqueous solution obtained in the step one to adjust the pH value to be neutral, concentrating the sericin aqueous solution, adding glucan into the sericin aqueous solution, and performing microwave intermittent treatment after the glucan is dissolved and stirred uniformly to finish primary modification of the sericin;
s12, filtering the sericin protein aqueous solution obtained in the previous step, performing vacuum freeze drying to obtain sericin powder, adding water to rehydrate the sericin powder, and performing freeze drying again to obtain sericin powder with a porous structure;
s13, adding the sericin powder obtained in the previous step into a silver nitrate solution, soaking for 6-10min, continuously stirring in the soaking process to uniformly disperse the sericin powder, irradiating by ultraviolet light after soaking is finished, and after the silver nitrate solution is completely changed into black, performing solid-liquid separation and freeze drying to obtain modified sericin loaded with nano silver;
step four, preparation of antibacterial modifier
Preparing a polyvinyl alcohol aqueous solution with the mass concentration of 5% -8%, adding the modified sericin loaded with nano-silver obtained in the previous step, mixing and stirring uniformly, adding citric acid, and uniformly mixing to obtain the antibacterial modifier, wherein the mass concentration of the citric acid in the antibacterial modifier is 0.3% -1%, and the addition concentration of the modified sericin in the antibacterial modifier is 4% -8%;
step five, primary treatment of silk fiber
Adding the modified sericin obtained in the third step into the organic silicon emulsion, stirring by a stirring device to emulsify and disperse the sericin in the organic silicon emulsion, adding the silk fiber obtained by the treatment in the second step into the organic silicon emulsion, soaking for 10-15min, taking out, drying and drying;
step six, antibacterial modification treatment of silk fibers
And adding the silk fiber obtained by the previous step into an antibacterial modifier, soaking for 20-40min, taking out, draining the surface antibacterial modifier, and drying to obtain the silk fiber with antibacterial effect.
2. The preparation method of the antibacterial modified silk fiber according to claim 1, wherein the specific method for preparing the silk fiber by taking the silkworm cocoon as the raw material in the first step is as follows:
cutting the silkworm cocoons into pieces, cleaning the surfaces of the silkworm cocoons with deionized water, then airing, adding the aired silkworm cocoons into ether, soaking for 24-48h, performing solid-liquid separation after soaking, airing the silkworm cocoons, soaking the silkworm cocoons in absolute ethyl alcohol for 8-12h, then replacing the absolute ethyl alcohol for soaking for 10-14h, washing the silkworm cocoons with distilled water after the solid-liquid separation, and airing to finish the degreasing of the silkworm cocoons;
adding the degreased silkworm cocoons into a sodium carbonate aqueous solution with the mass concentration of 0.5-0.8%, heating at the temperature of 95-98 ℃, and processing the treated silkworm cocoons to obtain a dispersed silk fiber and sericin protein aqueous solution.
3. The method for preparing antibacterial modified silk fiber according to claim 1, wherein the fixing solution in the second step is prepared from glutaraldehyde, urea and water, wherein the mass concentration of glutaraldehyde in the fixing solution is 0.5% -0.8%, and the mass concentration of urea in the fixing solution is 0.7% -1.6%.
4. The method for preparing the antibacterial modified silk fiber according to claim 1, wherein the method for fixing sericin remaining on the surface of the silk fiber by the fixing solution in the second step comprises the following steps: and (3) adjusting the temperature of the fixing solution to 40-50 ℃, adding the silk fiber obtained by the treatment in the step one into the fixing solution, taking the silk fiber out of the fixing solution after soaking for 6-20h, washing the silk fiber by using deionized water at the temperature of 45-60 ℃, dehydrating and drying, and fixing the residual sericin on the surface of the silk fiber.
5. The method for preparing the antibacterial modified silk fiber according to claim 1, wherein the mass concentration of the sericin aqueous solution after concentration in the step three is 5-15%, and the mass concentration of dextran in the sericin aqueous solution is 25-60 g/L.
6. The preparation method of the antibacterial modified silk fiber according to claim 1, characterized in that the specific method of the microwave batch treatment in the third step is as follows: treating with 800W power microwave, stopping microwave standing for 20-30s after every 30s of microwave treatment, and circulating for 4-6 times.
7. The method for preparing the antibacterial modified silk fiber according to claim 1, wherein the method for preparing the silver nitrate solution in the third step comprises the following steps:
adding silver nitrate and polyvinylpyrrolidone into N, N-dimethylformamide, and stirring until the silver nitrate is fully dissolved, wherein the mass concentration of the silver nitrate in the N, N-dimethylformamide is 4g/L, and the mass concentration of the polyvinylpyrrolidone in the N, N-dimethylformamide is 4-10 g/L.
8. The method for preparing the antibacterial modified silk fiber according to claim 1, wherein the molecular weight of polyvinyl alcohol in the antibacterial modifying agent is 18-25 ten thousand, and the alcoholysis degree is 98%.
9. An antibacterial modified silk fiber, characterized in that it is prepared by the method for preparing an antibacterial modified silk fiber according to any one of claims 1 to 8.
CN201910879259.0A 2019-09-18 2019-09-18 Antibacterial modified silk fiber and preparation method thereof Pending CN110592938A (en)

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CN113279253A (en) * 2021-04-02 2021-08-20 百事基材料（青岛）股份有限公司 Silk large biological fiber containing coffee active component and preparation method thereof
CN113737521A (en) * 2021-09-27 2021-12-03 溧阳市天目湖农业发展有限公司 Long-acting antibacterial natural silk fiber and processing technology thereof
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