CN110682626B - Antibacterial graphene cloth and preparation method thereof - Google Patents

Antibacterial graphene cloth and preparation method thereof Download PDF

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CN110682626B
CN110682626B CN201910950224.1A CN201910950224A CN110682626B CN 110682626 B CN110682626 B CN 110682626B CN 201910950224 A CN201910950224 A CN 201910950224A CN 110682626 B CN110682626 B CN 110682626B
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skin
graphene oxide
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CN110682626A (en
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刘国成
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04Interconnection of layers
    • B32B7/10Interconnection of layers at least one layer having inter-reactive properties
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/047Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material made of fibres or filaments
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating 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
    • D06M11/73Treating 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
    • D06M11/74Treating 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 or graphite; with carbides; with graphitic acids or their salts
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D06M11/00Treating 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
    • D06M11/83Treating 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
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10Treating 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
    • D06M13/184Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/207Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01Treating 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
    • D06M15/15Proteins or derivatives thereof
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/327Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
    • D06M15/333Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00Layers arrangement
    • B32B2250/20All layers being fibrous or filamentary
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/06Vegetal fibres
    • B32B2262/062Cellulose fibres, e.g. cotton
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/06Vegetal fibres
    • B32B2262/062Cellulose fibres, e.g. cotton
    • B32B2262/065Lignocellulosic fibres, e.g. jute, sisal, hemp, flax, bamboo
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/08Animal fibres, e.g. hair, wool, silk
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10Inorganic fibres
    • B32B2262/106Carbon fibres, e.g. graphite fibres
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/20Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/21Anti-static
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/30Properties of the layers or laminate having particular thermal properties
    • B32B2307/304Insulating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/714Inert, i.e. inert to chemical degradation, corrosion
    • B32B2307/7145Rot proof, resistant to bacteria, mildew, mould, fungi
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02Natural fibres, other than mineral fibres
    • D06M2101/04Vegetal fibres
    • D06M2101/06Vegetal fibres cellulosic

Abstract

The invention discloses an antibacterial graphene fabric and a preparation method thereof, wherein the fabric comprises a skin-friendly layer and an antibacterial layer, the antibacterial layer is bonded with the skin-friendly layer through a bonding layer, the antibacterial layer is prepared by uniformly mixing hydrophilic fibers and antibacterial modified fibers, and raw material fibers for preparing the antibacterial modified fibers are hydrophilic fibers; the antibacterial layer is prepared by uniformly mixing hydrophilic fibers and antibacterial modified fibers, wherein the antibacterial modified fibers are prepared by taking the hydrophilic fibers as raw materials, preliminarily modifying the fibers through an inner antibacterial agent, then preparing graphene oxide dispersion liquid by taking graphene oxide with good dispersibility as a raw material, uniformly distributing the graphene oxide on the surfaces of the fibers, reducing the graphene oxide to reduce the graphene oxide on the surfaces of the fibers to graphene, and uniformly distributing the graphene on the surfaces of the fibers, so that the antibacterial property and the hydrophobicity of the antibacterial modified fibers are improved, and the effective service life of the antibacterial modified fibers is prolonged.

Description

Antibacterial graphene cloth and preparation method thereof
Technical Field
The invention belongs to the technical field of textiles, and particularly relates to an antibacterial graphene fabric and a preparation method thereof.
Background
Along with the rapid development of the textile industry, according to the needs of people, the cloth material and the processing technology are improved, so that the prepared cloth can meet the special needs of people, the updating and the development of the textile industry are greatly promoted, in the cloth material with special performance, the antibacterial cloth material has larger practical value in various aspects and is developed more rapidly in the technical field of textile, in the prior art, the antibacterial cloth material is mainly characterized in that a fiber material with antibacterial property is added into the cloth material or the raw material fiber of the cloth material is modified, the fiber with antibacterial property is difficult to be uniformly dispersed and has obvious effect, the fiber with antibacterial property is modified by nano silver in the prior art, the fiber has good antibacterial performance but higher cost, the bonding strength of the nano silver and the fiber is poor, in the using process of the cloth material, the nano silver will gradually fall off, causing the antibacterial effect to be rapidly reduced.
Graphene is a material with a good antibacterial effect, but graphene has a super-hydrophobic property, so that when fibers are treated by graphene, graphene is difficult to disperse in a water environment, and the adoption of an organic solvent can cause problems of processing environment and cloth safety.
Disclosure of Invention
The invention aims to provide an antibacterial graphene fabric and a preparation method thereof.
The technical problems to be solved by the invention are as follows:
in the prior art, when the antibacterial cloth prepared by modifying fiber raw materials through materials such as nano silver has a good antibacterial effect, nano silver particles cannot be tightly combined with fibers, so that the nano silver particles can gradually fall off along with the increase of washing times, and the antibacterial effect of the antibacterial cloth is rapidly and obviously reduced.
The purpose of the invention can be realized by the following technical scheme:
an antibacterial graphene fabric comprises a skin-friendly layer and an antibacterial layer, wherein the antibacterial layer is bonded with the skin-friendly layer through a bonding layer;
the antibacterial layer is prepared by uniformly mixing hydrophilic fibers and antibacterial modified fibers, wherein the weight ratio of the hydrophilic fibers to the antibacterial modified fibers is 4-8:1, the raw material fibers for preparing the antibacterial modified fibers are hydrophilic fibers, the hydrophilic fibers are hydrophilic plant fibers or animal fibers, and specifically, the hydrophilic plant fibers or animal fibers are cotton fibers, hemp fibers, silk or wool fibers;
the fabric is characterized in that the skin-friendly layer is prepared by processing skin-friendly fibers, the skin-friendly fibers are cotton fibers, hemp fibers, silk or wool fibers, and one surface of the skin-friendly layer is attached to the skin of a human body when the fabric is used;
the adhesive layer is prepared by uniformly mixing hot-melt fibers and hollow fibers and then processing, wherein the mass ratio of the hot-melt fibers to the hollow fibers is 1.5-2.2:1, and the lengths of the hot-melt fibers and the hollow fibers are not more than 10 mm;
the preparation method of the antibacterial graphene cloth comprises the following steps:
taking antibacterial modified fiber as a raw material, and forming a needled non-woven fabric through needling hot rolling, wherein the needled non-woven fabric is an antibacterial layer;
step two, uniformly mixing the hot-melt fibers and the hollow fibers to form mixed fibers, and then coagulating the mixed fibers on one surface of the antibacterial layer by an air-laid technology to form an adhesive layer;
and step three, uniformly condensing the skin-friendly fibers on the surface of the bonding layer through an air-laid technology to obtain an intermediate, heating the intermediate to ensure that the hot-melt fibers are heated and softened to achieve the effect of connecting the antibacterial layer and the skin-friendly layer, cooling the intermediate in a low-temperature environment, and finally flattening the intermediate through rolling to obtain the finished antibacterial graphene cloth.
The preparation method of the antibacterial modified fiber comprises the following steps:
s1, adding the powdery bamboo charcoal into a ball mill, wet-milling for 3-5h at the rotating speed of 260-320r/min by using N, N-dimethylformamide as a wetting agent, and reducing the particle size of the powdery bamboo charcoal, wherein the weight ratio of the powdery bamboo charcoal to the N, N-dimethylformamide is 1:0.3-0.5, and the treated powdery bamboo charcoal is not dried;
s2, adding the powdery bamboo charcoal obtained through the processing in the previous step into a silver nitrate solution, soaking for 10-13 minutes, carrying out ultrasonic processing in the soaking process, irradiating the silver nitrate solution through ultraviolet light after the soaking is finished until the silver nitrate solution is completely converted into black, carrying out solid-liquid separation, and drying to obtain powdery bamboo charcoal loaded with nano silver ions;
in the step, the powdery bamboo charcoal is added into a silver nitrate solution, so that the microporous structure of the bamboo charcoal fully absorbs the silver nitrate solution, and then the silver nitrate is reduced to generate nano silver particles through ultraviolet irradiation treatment, so that the nano silver particles are uniformly distributed in the microporous structure of the bamboo charcoal;
s3, preparing a polyvinyl alcohol aqueous solution with the mass concentration of 5% -8%, adding sericin, stirring and mixing until the sericin is completely dissolved, adding the powdery bamboo charcoal loaded with nano silver ions obtained by the previous step, stirring and mixing uniformly, adding citric acid, and mixing uniformly to obtain the lining antibacterial agent, wherein the mass concentration of the citric acid in the lining antibacterial agent is 0.3% -1%, and the addition concentration of the modified sericin in the lining antibacterial agent is 4% -8%;
citric acid is taken as a cross-linking agent, polyvinyl alcohol and sericin can be cross-linked and solidified to form a layer of solidified film, wherein the powdery bamboo charcoal loaded with nano silver particles and the sericin have good antibacterial effect;
s4, adding the raw material fibers into the lining antibacterial agent, soaking for 5-7min, wherein the surfaces of the fiber monofilaments are wetted by the lining antibacterial agent, separating the raw material fibers from the lining antibacterial agent after soaking is finished, and drying the raw material fibers to obtain primary modified fibers;
in the step, the inner antibacterial agent is solidified on the surface of the raw material fiber to form a layer of solidified film, so that good antibacterial capability is provided;
s5, dispersing graphene oxide in deionized water through ultrasonic treatment, wherein the concentration of the graphene oxide in the deionized water is 0.8-1mg/L, the size of the graphene oxide is less than or equal to 10 microns, then adding the primary modified fiber obtained through the previous step into the graphene oxide dispersion liquid, so that the primary modified fiber is completely soaked in the graphene oxide dispersion liquid for 1-1.5 hours, and the graphene oxide can be uniformly dispersed by adopting ultrasonic treatment in the soaking process;
in the step, graphene oxide with good dispersibility is used as a raw material to prepare a graphene oxide dispersion liquid, so that the graphene oxide is uniformly distributed on the surface of the fiber;
s6, taking out the primary modified fiber, draining, drying, loosening, adding into a sealed steam chamber, introducing inert gas into the steam chamber, exhausting air in the sealed steam chamber, introducing high-temperature steam of hydroiodic acid into the sealed steam chamber, wherein the steam temperature is 127-;
reducing graphene oxide to convert the graphene oxide coated on the surface of the fiber into graphene;
and S7, taking out the primary modified fiber obtained in the previous step, and drying to obtain the antibacterial modified fiber.
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.
The invention has the beneficial effects that:
the antibacterial layer is prepared by uniformly mixing hydrophilic fibers and antibacterial modified fibers, wherein the antibacterial modified fibers are prepared by taking the hydrophilic fibers as raw materials, primarily modifying the fibers through an inner antibacterial agent, and secondarily modifying the fibers through graphene, the inner antibacterial agent is prepared by adding powdered bamboo charcoal into a silver nitrate solution to enable a microporous structure of the bamboo charcoal to fully absorb the silver nitrate solution, then reducing the silver nitrate into nano-silver particles through ultraviolet irradiation treatment, so that the uniform distribution of the nano-silver particles in the microporous structure of the bamboo charcoal is realized, the uniform distribution of nano-silver is promoted, then citric acid is used as a cross-linking agent, polyvinyl alcohol and sericin can be cross-linked and cured to form a layer of cured film, and the powdered bamboo charcoal and sericin loaded with the nano-silver particles in the cured film both have good antibacterial effects, meanwhile, the bamboo charcoal and the nano silver in the bamboo charcoal can be fixed through crosslinking and solidification of polyvinyl alcohol and sericin; after that, graphene oxide with good dispersibility is used as a raw material to prepare a graphene oxide dispersion liquid, so that graphene oxide is uniformly distributed on the surface of the fiber, and then the graphene oxide is reduced, so that the graphene oxide coated on the surface of the fiber is converted into graphene, and a graphene layer is formed on the surface of the fiber, so that the antibacterial effect of the fiber is improved, the hydrophobic capability of the fiber is improved, the problem that the solidified film formed by the inner antibacterial agent is in a wet state for a long time, and the aging failure is rapid is solved, meanwhile, the antibacterial modified fiber has good antistatic and warm-keeping effects due to the graphene coated on the surface, and the cloth is suitable for production of textiles close to human skin, such as bed sheets, quilt covers, bed covers, clothes and the like due to the good antibacterial, antistatic and warm-keeping effects.
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
An antibacterial graphene fabric comprises a skin-friendly layer and an antibacterial layer, wherein the antibacterial layer is bonded with the skin-friendly layer through a bonding layer;
the antibacterial layer is prepared by uniformly mixing hydrophilic fibers and antibacterial modified fibers, wherein the weight ratio of the hydrophilic fibers to the antibacterial modified fibers is 6:1, and the raw material fibers for preparing the antibacterial modified fibers are cotton fibers;
the fabric is characterized in that the skin-friendly layer is prepared by processing skin-friendly fibers, the skin-friendly fibers are cotton fibers, and one surface of the skin-friendly layer is attached to the skin of a human body when the fabric is used;
the adhesive layer is prepared by uniformly mixing hot-melt fibers and hollow fibers and then processing, wherein the mass ratio of the hot-melt fibers to the hollow fibers is 1.5:1, and the lengths of the hot-melt fibers and the hollow fibers are not more than 10 mm;
the preparation method of the antibacterial graphene cloth comprises the following steps:
taking antibacterial modified fiber as a raw material, and forming a needled non-woven fabric through needling hot rolling, wherein the needled non-woven fabric is an antibacterial layer;
step two, uniformly mixing the hot-melt fibers and the hollow fibers to form mixed fibers, and then coagulating the mixed fibers on one surface of the antibacterial layer by an air-laid technology to form an adhesive layer;
and step three, uniformly condensing the skin-friendly fibers on the surface of the bonding layer through an air-laid technology to obtain an intermediate, heating the intermediate to ensure that the hot-melt fibers are heated and softened to achieve the effect of connecting the antibacterial layer and the skin-friendly layer, cooling the intermediate in a low-temperature environment, and finally flattening the intermediate through rolling to obtain the finished antibacterial graphene cloth.
The preparation method of the antibacterial modified fiber comprises the following steps:
s1, adding the powdery bamboo charcoal into a ball mill, wet-milling for 5 hours at a rotating speed of 300r/min by using N, N-dimethylformamide as a wetting agent, and reducing the particle size of the powdery bamboo charcoal, wherein the weight ratio of the powdery bamboo charcoal to the N, N-dimethylformamide is 1:0.4, and the treated powdery bamboo charcoal is not dried;
s2, adding the powdery bamboo charcoal obtained through the processing in the previous step into a silver nitrate solution, soaking for 12 minutes, carrying out ultrasonic processing in the soaking process, irradiating the silver nitrate solution through ultraviolet light after the soaking is finished until the silver nitrate solution is completely converted into black, carrying out solid-liquid separation, and drying to obtain powdery bamboo charcoal loaded with nano silver ions;
s3, preparing a polyvinyl alcohol aqueous solution with the mass concentration of 6%, adding sericin, stirring and mixing until the sericin is completely dissolved, adding the powdery bamboo charcoal loaded with nano silver ions obtained by the previous step, stirring and mixing uniformly, adding citric acid, and uniformly mixing to obtain the lining antibacterial agent, wherein the mass concentration of the citric acid in the lining antibacterial agent is 0.4%, and the addition concentration of the modified sericin in the lining antibacterial agent is 5%;
s4, adding the raw material fibers into the lining antibacterial agent, soaking for 6min, wherein the surfaces of the fiber monofilaments are wetted by the lining antibacterial agent, separating the raw material fibers from the lining antibacterial agent after soaking is finished, and drying the raw material fibers to obtain primary modified fibers;
s5, dispersing graphene oxide in deionized water through ultrasonic treatment, wherein the concentration of the graphene oxide in the deionized water is 0.8mg/L, the size of the graphene oxide is less than or equal to 10 microns, then adding the primarily modified fiber obtained through the previous step into the graphene oxide dispersion liquid, so that the primarily modified fiber is completely soaked in the graphene oxide dispersion liquid for 1h, and the graphene oxide can be uniformly dispersed by adopting ultrasonic treatment in the soaking process;
s6, taking out the primary modified fibers, draining, drying, loosening, adding into a sealed steam chamber, introducing inert gas into the steam chamber, exhausting air in the sealed steam chamber, introducing high-temperature steam of hydroiodic acid into the sealed steam chamber, wherein the steam temperature is 130 ℃, and the reaction time is 2 hours;
and S7, taking out the primary modified fiber obtained in the previous step, and drying to obtain the antibacterial modified fiber.
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 6 g/L.
Example 2
The preparation method of the antibacterial modified fiber comprises the following steps:
s1, adding the powdery bamboo charcoal into a ball mill, wet-milling for 5 hours at a rotating speed of 300r/min by using N, N-dimethylformamide as a wetting agent, and reducing the particle size of the powdery bamboo charcoal, wherein the weight ratio of the powdery bamboo charcoal to the N, N-dimethylformamide is 1:0.4, and the treated powdery bamboo charcoal is not dried;
s2, adding the powdery bamboo charcoal obtained through the processing in the previous step into a silver nitrate solution, soaking for 13 minutes, carrying out ultrasonic processing in the soaking process, irradiating the silver nitrate solution through ultraviolet light after the soaking is finished until the silver nitrate solution is completely converted into black, carrying out solid-liquid separation, and drying to obtain powdery bamboo charcoal loaded with nano silver ions;
s3, preparing a polyvinyl alcohol aqueous solution with the mass concentration of 6%, adding sericin, stirring and mixing until the sericin is completely dissolved, adding the powdery bamboo charcoal loaded with nano silver ions obtained by the previous step, stirring and mixing uniformly, adding citric acid, and uniformly mixing to obtain the lining antibacterial agent, wherein the mass concentration of the citric acid in the lining antibacterial agent is 0.5%, and the addition concentration of the modified sericin in the lining antibacterial agent is 4%;
s4, adding the raw material fibers into the lining antibacterial agent, soaking for 7min, wherein the surfaces of the fiber monofilaments are wetted by the lining antibacterial agent, separating the raw material fibers from the lining antibacterial agent after soaking is finished, and drying the raw material fibers to obtain primary modified fibers;
s5, dispersing graphene oxide in deionized water through ultrasonic treatment, wherein the concentration of the graphene oxide in the deionized water is 1mg/L, the size of the graphene oxide is less than or equal to 10 microns, then adding the primary modified fiber obtained through the previous step into the graphene oxide dispersion liquid, so that the primary modified fiber is completely soaked in the graphene oxide dispersion liquid for 1.5 hours, and the graphene oxide can be uniformly dispersed by adopting ultrasonic treatment in the soaking process;
s6, taking out the primary modified fibers, draining, drying, opening, adding into a sealed steam chamber, introducing inert gas into the steam chamber, exhausting air in the sealed steam chamber, introducing high-temperature steam of hydroiodic acid into the sealed steam chamber, wherein the steam temperature is 150 ℃, and the reaction time is 1.5 hours;
and S7, taking out the primary modified fiber obtained in the previous step, and drying to obtain the antibacterial modified fiber.
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 8 g/L.
Comparative example 1
The fibers were not treated with an inner antimicrobial under otherwise identical conditions.
Comparative example 2
The fibers were not treated with the graphene oxide dispersion under the same conditions.
Experimental results and data analysis
The antibacterial performance of the antibacterial modified fibers prepared in the examples and the comparative examples is tested according to the change relationship of the washing times, 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;
TABLE 1
Number of washes 10 times of 20 times (twice) 30 times (twice) 40 times (twice)
Example 1 93% 87% 84% 73%
Example 2 91% 88% 84% 76%
Comparative example 1 82% 76% 49% 36%
Comparative example 2 87% 82% 71% 59%
As can be seen from the results in table 1, the antibacterial graphene fabric of the present invention can still maintain strong antibacterial performance after being washed for more than 30 times.
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 (1)

1. The antibacterial graphene cloth is characterized by comprising a skin-friendly layer and an antibacterial layer, wherein the antibacterial layer is bonded with the skin-friendly layer through a bonding layer, and one surface of the skin-friendly layer is attached to the skin of a human body;
the antibacterial layer is prepared by uniformly mixing hydrophilic fibers and antibacterial modified fibers, wherein the weight ratio of the hydrophilic fibers to the antibacterial modified fibers is 4-8:1, and raw material fibers for preparing the antibacterial modified fibers are hydrophilic fibers;
the skin-friendly layer is prepared by processing skin-friendly fibers;
the adhesive layer is prepared by uniformly mixing hot-melt fibers and hollow fibers and then processing, wherein the mass ratio of the hot-melt fibers to the hollow fibers is 1.5-2.2:1, and the lengths of the hot-melt fibers and the hollow fibers are not more than 10 mm;
the hydrophilic fibers are cotton fibers, hemp fibers, silk or wool fibers, and the skin-friendly fibers are cotton fibers, hemp fibers, silk or wool fibers;
the preparation method of the cloth comprises the following steps:
taking antibacterial modified fiber as a raw material, and forming a needled non-woven fabric through needling hot rolling, wherein the needled non-woven fabric is an antibacterial layer;
step two, uniformly mixing the hot-melt fibers and the hollow fibers to form mixed fibers, and then coagulating the mixed fibers on one surface of the antibacterial layer by an air-laid technology to form an adhesive layer;
uniformly condensing skin-friendly fibers on the surface of the bonding layer through an air-laid technology to obtain an intermediate, heating the intermediate to ensure that the hot-melt fibers are heated and softened to achieve the effect of connecting the antibacterial layer and the skin-friendly layer, cooling the intermediate in a low-temperature environment, and finally flattening the intermediate through rolling to obtain the finished antibacterial graphene cloth;
the preparation method of the antibacterial modified fiber comprises the following steps:
s1, preparing an inner antibacterial agent;
s2, adding the raw material fibers into the lining antibacterial agent, soaking for 5-7min, separating the raw material fibers from the lining antibacterial agent after soaking is finished, and drying the raw material fibers to obtain primary modified fibers;
s3, dispersing graphene oxide in deionized water through ultrasonic treatment, wherein the concentration of the graphene oxide in the deionized water is 0.8-1mg/L, the size of the graphene oxide is less than or equal to 10 microns, then adding the primary modified fiber into the graphene oxide dispersion liquid, and completely soaking the primary modified fiber in the graphene oxide dispersion liquid for 1-1.5 hours, wherein ultrasonic treatment is adopted in the soaking process;
s4, taking out the primary modified fiber, draining, drying, loosening, adding into a sealed steam chamber, introducing inert gas into the steam chamber, exhausting air in the sealed steam chamber, introducing high-temperature steam of hydroiodic acid into the sealed steam chamber, wherein the steam temperature is 127-;
s5, taking out the primary modified fiber obtained in the previous step, and drying to obtain the antibacterial modified fiber;
the preparation method of the inner antibacterial agent comprises the following steps:
SS1, adding the powdery bamboo charcoal into a ball mill, wet-milling for 3-5h at the rotating speed of 260-320r/min by using N, N-dimethylformamide as a wetting agent, wherein the weight ratio of the powdery bamboo charcoal to the N, N-dimethylformamide is 1:0.3-0.5, and the treated powdery bamboo charcoal is not dried;
SS2, adding the powdery bamboo charcoal obtained by the processing in the previous step into silver nitrate solution, soaking for 10-13 minutes, carrying out ultrasonic processing in the soaking process, irradiating by ultraviolet light after the soaking is finished until the silver nitrate solution is completely converted into black, carrying out solid-liquid separation, and drying to obtain powdery bamboo charcoal loaded with nano silver ions;
SS3, preparing a polyvinyl alcohol aqueous solution with the mass concentration of 5% -8%, then adding sericin, stirring and mixing until the sericin is completely dissolved, adding the powdery bamboo charcoal loaded with nano silver ions obtained by the previous step, stirring and mixing uniformly, then adding citric acid, and mixing uniformly to obtain the lining antibacterial agent, wherein the mass concentration of the citric acid in the lining antibacterial agent is 0.3% -1%, and the addition concentration of the modified sericin in the lining antibacterial agent is 4% -8%;
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.
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