CN113005786B - Graphene-based antibacterial fabric and production process thereof - Google Patents

Graphene-based antibacterial fabric and production process thereof Download PDF

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CN113005786B
CN113005786B CN202110207674.9A CN202110207674A CN113005786B CN 113005786 B CN113005786 B CN 113005786B CN 202110207674 A CN202110207674 A CN 202110207674A CN 113005786 B CN113005786 B CN 113005786B
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graphene
fabric
epoxy resin
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CN113005786A (en
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尤恩校
尤恩杰
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Hangzhou Kelida Home Textile Co ltd
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Hangzhou Kelida Home Textile Co ltd
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0006—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using woven fabrics
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/007—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments
    • D06N3/0077—Embossing; Pressing of the surface; Tumbling and crumbling; Cracking; Cooling; Heating, e.g. mirror finish
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/125—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyamides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/18—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials
    • D06N3/183—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials the layers are one next to the other
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    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N7/00—Flexible sheet materials not otherwise provided for, e.g. textile threads, filaments, yarns or tow, glued on macromolecular material
    • D06N7/0094—Fibrous material being coated on one surface with at least one layer of an inorganic material and at least one layer of a macromolecular material
    • D—TEXTILES; PAPER
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    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/16—Properties of the materials having other properties
    • D06N2209/1671—Resistance to bacteria, mildew, mould, fungi
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    • D06N2209/00—Properties of the materials
    • D06N2209/16—Properties of the materials having other properties
    • D06N2209/1685—Wear resistance

Abstract

The application relates to the field of fabrics, and particularly discloses an antibacterial fabric based on graphene and a production process thereof, wherein the fabric sequentially comprises a fabric layer, an adhesive layer, a graphene layer and a protective layer from inside to outside; the fabric layer is woven by cotton fibers; the bonding layer is a structural layer which is formed by finishing the surface of the fabric layer by polyethyleneimine and plays a role of bonding transition; the graphene layer is a structural layer which is formed by hot-pressing graphene oxide on the surface of the bonding layer and has a main antibacterial effect; the protective layer is a structural layer which is formed by crosslinking epoxy resin glue on the surface of the bonding layer and mainly has the protective effect, and the epoxy resin glue is mainly formed by mixing epoxy resin, polyether amine and benzyl alcohol. The graphene antibacterial fabric prepared by the application has good wear resistance on the surface, can be used for a long time, and the graphene layer is not easy to wear or fall off, so that the graphene antibacterial fabric has more durable antibacterial performance.

Description

Graphene-based antibacterial fabric and production process thereof
Technical Field
The application relates to the technical field of fabrics, in particular to an antibacterial fabric based on graphene and a production process thereof.
Background
The antibacterial fabric is taken as a functional fabric, and has gradually entered the lives of people and gradually gets widely applied. The existing antibacterial fabrics are various, such as traditional kapok fiber fabrics, chitosan fiber fabrics, hemp fiber fabrics and the like, and various unique effects of the antibacterial fabrics are gradually applied to different fields along with the development of graphene materials in recent years, and the graphene antibacterial fabrics are novel fabrics prepared by applying the antibacterial capability of graphene.
The first method is to melt and blend slice raw materials and graphene in a spinning stage to prepare fibers containing graphene, and then to weave the fibers into the fabric; and the second method is to combine a layer of graphene on the surface of the fabric by finishing the fabric by a padding method after the fabric is formed by spinning. Compared with the first method, the method for finishing by padding has the advantages of simpler operation process, easy control of graphene content, no aggregation of graphene caused by mixing and melting and the like, and is more favorable for large-scale industrial production.
However, the graphene fabric prepared by the padding finishing method is concentrated on the surface layer of the fabric, so that the graphene is easily abraded or falls off in the using process, and the service life of the graphene fabric is short.
Disclosure of Invention
In order to improve the wear resistance of the graphene layer on the surface of the graphene fabric and enable the graphene layer to have a longer antibacterial effect, the application provides the graphene-based antibacterial fabric and a production process thereof.
In a first aspect, the application provides an antibacterial fabric based on graphene, which adopts the following technical scheme:
the utility model provides an antibiotic surface fabric based on graphite alkene, includes precoat, adhesive linkage, graphite alkene layer and protective layer from inside to outside in proper order.
The fabric layer is woven by cotton fibers; the bonding layer is a structural layer which is formed by finishing the surface of the fabric layer by polyethyleneimine and plays a role in excessive bonding; the graphene layer is a structural layer which is formed by hot-pressing graphene oxide on the surface of the bonding layer and has a main antibacterial effect; the protective layer is a structural layer which is formed by crosslinking epoxy resin glue on the surface of the bonding layer and mainly has the protective effect, and the epoxy resin glue is mainly prepared by mixing epoxy resin, polyether amine and benzyl alcohol.
By adopting the technical scheme, the structural layer based on the fabric layer is the main structural body of the fabric and is responsible for the main functions and properties of the fabric. The surface of the fabric layer is attached with the adhesive layer, the adhesive layer is made of polyethyleneimine, the polyethyleneimine can be attached to the surface of the fabric layer through after-treatment, and due to the fact that a large number of amino groups are arranged in the polyethyleneimine and the graphene oxide contains a large number of epoxy groups, after the graphene oxide acts on the adhesive layer, an open-loop reaction can be generated to enable the graphene oxide to be stably fixed outside the adhesive layer, and the graphene layer with an antibacterial effect is formed.
Finally, through epoxy and polyetheramine to through benzyl alcohol as the solvent, go up one deck protective layer again on graphite alkene layer surface, polyetheramine can react with the epoxy on oxidation graphite alkene and the epoxy simultaneously, makes and produces the crosslinking between epoxy and the graphite alkene to form the protective layer of one deck crosslinking form again on graphite alkene layer surface, improved graphite alkene layer's wearability, make graphite alkene layer be difficult for appearing wearing and tearing after long-time the use, can have long-time antibacterial capacity.
Preferably, in the epoxy resin glue used for the protective layer, the mass fraction of the epoxy resin is 10-15%, the mass fraction of the polyether amine is 15-20%, and the balance is benzyl alcohol.
By adopting the technical scheme, the content of the epoxy resin in the common epoxy resin adhesive is more than 50 percent, and the content of the polyether amine playing a curing role is generally less than that of the epoxy resin. In the application, the content of the epoxy resin in the epoxy resin adhesive is only 10-15%, and the content of the polyether amine is more than that of the epoxy resin, because the protective layer formed by adopting the low content of the epoxy resin can play a role of abrasion resistance and cannot be too hard, so that the fabric can keep flexibility as much as possible. And excessive polyetheramine is beneficial to reacting with an epoxy group on graphene while causing the epoxy resin to generate crosslinking consolidation, so that the epoxy resin and the graphene are better combined. And select the epoxy within proper dosage range for use, still can avoid influencing the bacteriostatic ability on graphite alkene layer because the protective layer is too thick, make the protective layer have wear-resisting protective capability, can not too much influence the bacteriostatic ability on graphite alkene layer again.
Preferably, the epoxy value of the epoxy resin is 0.4 to 0.45.
By adopting the technical scheme, 0.4-0.45 is the better epoxy value range of the epoxy resin, and the epoxy resin using the epoxy value can have more proper fluidity and viscosity and more proper molecular weight, so that the epoxy resin can be better crosslinked on the surface of the graphene layer.
Preferably, the epoxy resin adhesive also contains allyl glycidyl ether, and the mass fraction of the allyl glycidyl ether is 2-3%.
Through adopting above-mentioned technical scheme, allyl glycidyl ether can play the effect of active diluent, when solidifying, can prevent to produce excessive cross-linking between the epoxy to make the surface fabric still can keep better pliability, and still help improving the contact of bacterium and inlayer graphite alkene layer when using, thereby reduce the influence that the protective layer brought the antibiotic effect.
Preferably, the epoxy resin adhesive also contains liquid carboxyl nitrile rubber, and the mass fraction of the liquid carboxyl nitrile rubber is 4-6%.
By adopting the technical scheme, the liquid carboxyl nitrile rubber is used as reactive rubber and can be used for toughening and modifying epoxy resin, the solubility of the liquid carboxyl nitrile rubber and the reactive rubber is similar, so that the liquid carboxyl nitrile rubber can be completely dissolved before reaction, the epoxy resin and the nitrile rubber are gradually separated along with the polymerization and crosslinking reaction of two polymers after heating, a two-phase structure is generated, and finally the nitrile rubber can be gradually separated out from the surface of the epoxy resin and forms cracks and holes in the epoxy resin, so that the toughness of the epoxy resin is further improved, and the protective layer is prevented from being cracked in a brittle manner. And in the same way, the contact between bacteria and the graphene layer on the inner layer is improved, so that the influence of the protective layer on the antibacterial effect is reduced.
Preferably, the molecular weight of the polyethyleneimine used in the adhesive layer is 3000-5000.
By adopting the technical scheme, the polyethyleneimine with the molecular weight can be more effectively attached to the surface of the fabric layer, and can be more effectively crosslinked and fixed with the graphene layer.
In a second aspect, the application provides a production process of an antibacterial fabric based on graphene, which adopts the following technical scheme: the method comprises the following process steps:
s1: performing tatting on cotton fibers serving as warps and wefts to form a fabric layer to obtain a base fabric;
s2: dipping the substrate fabric in a polyethyleneimine solution with the concentration of 3-3.5g/L for 2-2.5h to form an adhesive layer, taking out the adhesive layer, extruding and drying the adhesive layer, dipping the adhesive layer in a graphene oxide solution with the concentration of 40-45g/L, standing the solution at the temperature of 30-35 ℃ for 30-35min to form a graphene layer, taking out the graphene layer, washing and drying the graphene layer to obtain the graphene fabric;
s3: mixing epoxy resin, polyether amine, allyl glycidyl ether, liquid carboxyl nitrile rubber and benzyl alcohol according to the using amount to obtain epoxy resin glue; spraying epoxy resin glue on the surface of graphene oxide, then extruding by using a roller to remove redundant epoxy resin glue, curing at the temperature of 40-50 ℃ for 15-20min, soaking the fabric in ammonia water with the concentration of 10-12mol/L for 5-8min, taking out, extruding to remove redundant ammonia water, curing at the temperature of 70-80 ℃ for 30-40min to form a protective layer, finally scraping and trimming the surface of the fabric by using a scraper, cleaning and drying to obtain the finished product graphene fabric.
By adopting the technical scheme, the matrix fabric is prepared by weaving cotton fibers, then the polyethyleneimine is used for finishing, a bonding layer is generated on the surface of the matrix fabric, then the graphene oxide and the bonding layer generate ring-opening reaction, and the graphene can be stably fixed after crosslinking is generated.
And in step S3 processing protective layer process, after the spraying epoxy glue, earlier carry out primary cure at the lower temperature, then carry out secondary cure again with the surface fabric flooding in aqueous ammonia for a period of time, so handle and can make between epoxy and the oxidation graphite alkene accomplish behind the first crosslinking consolidation, react through aqueous ammonia and fall unnecessary epoxy, prevent that epoxy from producing on graphite alkene layer and explode and gather, make the protective layer more even, can play better protecting effect. And may further prevent the epoxy resin from being excessively crosslinked, thereby preventing the material from being excessively hard after curing.
Preferably, in step S2, the substrate fabric is soaked in NaOH solution with the temperature of 70-80 ℃ and the concentration of 0.4-0.6mol/L for 40-50min, and then the subsequent process is carried out after the substrate fabric is cleaned and dried.
By adopting the technical scheme, the substrate fabric is pretreated by using the sodium hydroxide, so that the reactivity of the fabric layer and the polyethyleneimine can be improved, and the stability of the graphene layer is improved.
In summary, the present application includes at least one of the following beneficial technical effects:
1. the application provides an antibiotic surface fabric based on graphite alkene, through the adhesive linkage, makes precoat and graphite alkene layer laminate firmly to through add in the graphite alkene layer outside and establish the protective layer of being made by epoxy glue, make graphite alkene layer obtain good protection, improved graphite alkene layer's wear resistance, reduce its wearing and tearing that produce in permanent use, thereby make it have long-term antibiotic effect.
2. The application discloses the mass fractions of the epoxy resin and the polyether amine in the epoxy resin adhesive, and by using the epoxy resin with low concentration and using excessive polyether amine, better crosslinking can be generated between the epoxy resin and the graphene oxide, and the good flexibility of the fabric can be kept.
3. According to the preferable scheme of the application, allyl glycidyl ether and liquid carboxyl nitrile rubber are also added into the epoxy resin adhesive, and the allyl glycidyl ether can play a role in reactive dilution on the epoxy resin to prevent the epoxy resin from being excessively crosslinked; the liquid carboxyl nitrile rubber can modify the epoxy resin, so that pores are generated in the cured epoxy resin, and the two substances can improve the flexibility of the protective layer and prevent brittle cracking.
4. The application still provides a production technology of antibiotic surface fabric based on graphite alkene, at the in-process of preparation protective layer, behind the spraying epoxy glue, carries out the primary cure earlier, then uses the aqueous ammonia to handle the protective layer, is carrying out the secondary cure at last, handles the pliability that helps further improve the protective layer like this, prevents the brittle fracture.
5. In a preferred embodiment of the present application, the precoat is pretreated with sodium hydroxide before finishing with polyethyleneimine, which helps to improve the reactivity of polyethyleneimine on the precoat.
Drawings
Fig. 1 is a schematic structural diagram of an embodiment of an antibacterial fabric based on graphene.
In the figure, 1, a fabric layer; 2. an adhesive layer; 3. a graphene layer; 4. and a protective layer.
Detailed Description
Examples
Example 1: an antibacterial fabric based on graphene is shown in figure 1 and sequentially comprises a fabric layer 1, an adhesive layer 2, a graphene layer 3 and a protective layer 4 from inside to outside;
the fabric layer 1 is woven by cotton fibers; the bonding layer 2 is a structural layer which is formed by finishing the surface of the fabric layer by polyethyleneimine and plays a role of bonding transition; the graphene layer 3 is a structural layer which is formed by hot-pressing graphene oxide on the surface of the bonding layer and has a main antibacterial effect; the protective layer 4 is a structural layer which is formed by cross-linking epoxy resin glue on the surface of the bonding layer and mainly has the protective effect, and the epoxy resin glue is mainly prepared by mixing epoxy resin, polyether amine and benzyl alcohol.
The production process comprises the following steps:
s1: performing tatting on cotton fibers serving as warps and wefts to form a fabric layer to obtain a base fabric, wherein the ratio of the warp density to the weft density of the base fabric is 2:1, and the count of the used cotton fibers is 42 s/3;
s2: dipping a substrate fabric in a polyethyleneimine solution with the concentration of 3g/L and the average molecular weight of 5500 for 2 hours to form an adhesive layer, taking out the adhesive layer, extruding and drying the adhesive layer, dipping the adhesive layer in a graphene oxide solution with the concentration of 40g/L, standing the solution for 30 minutes at 30 ℃ to form a graphene layer, taking out the graphene layer, washing the graphene layer with deionized water and drying the graphene layer to obtain a graphene fabric;
s3: mixing epoxy resin, polyether amine and benzyl alcohol according to the using amount to obtain epoxy resin glue, wherein the mass fraction of each component is shown in table 1, the epoxy value of the used epoxy resin is 0.5, and the type of the polyether amine adopts D230; and (3) spraying the epoxy resin glue on the surface of the graphene oxide, and then extruding by using a roller to remove the redundant epoxy resin glue. Curing at 40 ℃ for 15min, soaking the fabric in ammonia water with the concentration of 10mol/L for 5min, taking out, extruding to remove redundant ammonia water, curing at 70 ℃ for 30min to form a protective layer, scraping and finishing the surface of the fabric by using a scraper, cleaning by using clear water, and drying to obtain the finished product graphene fabric.
The process parameters of the components in the above process can be specifically seen in table 1 below.
Example 2: the graphene-based antibacterial fabric is different from the graphene-based antibacterial fabric in example 1 in that various parameters in the process are different, and the specific parameters are shown in the following table 1.
The production process comprises the following steps:
s1: performing tatting on cotton fibers serving as warps and wefts to form a fabric layer to obtain a base fabric, wherein the ratio of the warp density to the weft density of the base fabric is 2:1, and the count of the used cotton fibers is 42 s/3;
s2: dipping the substrate fabric in a polyethyleneimine solution with the concentration of 3.5g/L and the average molecular weight of 2500 for 2.5h to form an adhesive layer, taking out the adhesive layer, extruding and drying the adhesive layer, dipping the adhesive layer in a graphene oxide solution with the concentration of 45g/L, standing the solution for 35min at 35 ℃ to form a graphene layer, taking out the graphene layer, washing the graphene layer with deionized water and drying the graphene layer to obtain the graphene fabric;
s3: mixing epoxy resin, polyether amine and benzyl alcohol according to the using amount to obtain epoxy resin glue, wherein the mass fraction of each component is shown in table 1, the epoxy value of the used epoxy resin is 0.35, and the type of the polyether amine adopts D230; and (3) spraying the epoxy resin glue on the surface of the graphene oxide, and then extruding by using a roller to remove the redundant epoxy resin glue. Curing at 50 ℃ for 20min, soaking the fabric in 12mol/L ammonia water for 8min, taking out, extruding to remove redundant ammonia water, curing at 80 ℃ for 40min to form a protective layer, scraping and finishing the surface of the fabric by using a scraper, cleaning by using clear water, and drying to obtain the finished graphene fabric.
The process parameters of the components in the above process can be specifically seen in table 1 below.
Examples 3 to 4: an antibacterial fabric based on graphene is disclosed,
the difference from example 1 is that the epoxy value of the epoxy resin used is different, and the specific parameters are shown in table 1 below.
Examples 5-6 a graphene-based antimicrobial fabric,
the difference from example 1 is that the epoxy resin adhesive also contains allyl glycidyl ether, and the mass fractions of the components in the epoxy resin adhesive and the parameters of the remaining components are shown in table 1 below.
Step S3 becomes: mixing epoxy resin, polyether amine, allyl glycidyl ether and benzyl alcohol according to the using amount to obtain epoxy resin adhesive, wherein the mass fraction of each component is shown in table 1, the epoxy value of the used epoxy resin is 0.5, and the type of the polyether amine adopts D230; and (3) spraying the epoxy resin glue on the surface of the graphene oxide, and then extruding by using a roller to remove the redundant epoxy resin glue. Curing at 40 ℃ for 15min, soaking the fabric in ammonia water with the concentration of 10mol/L for 5min, taking out, extruding to remove redundant ammonia water, curing at 70 ℃ for 30min to form a protective layer, scraping and finishing the surface of the fabric by using a scraper, cleaning by using clear water, and drying to obtain the finished product graphene fabric.
Examples 7 to 8: an antibacterial fabric based on graphene is disclosed,
the difference from example 1 is that the epoxy resin glue also contains liquid carboxyl nitrile rubber, and the mass fractions of the components and the parameters of the rest components in the epoxy resin glue are shown in the following table 1.
Step S3 becomes: mixing epoxy resin, polyether amine, liquid carboxyl nitrile rubber and benzyl alcohol according to the using amount to obtain epoxy resin glue, wherein the mass fraction of each component is shown in table 1, the epoxy value of the used epoxy resin is 0.5, and the type of the polyether amine adopts D230; and (3) spraying the epoxy resin glue on the surface of the graphene oxide, and then extruding by using a roller to remove the redundant epoxy resin glue. Curing at 40 ℃ for 15min, soaking the fabric in ammonia water with the concentration of 10mol/L for 5min, taking out, extruding to remove redundant ammonia water, curing at 70 ℃ for 30min to form a protective layer, scraping and finishing the surface of the fabric by using a scraper, cleaning by using clear water, and drying to obtain the finished product graphene fabric.
Examples 9 to 10: an antibacterial fabric based on graphene is disclosed,
the difference from example 1 is that the average molecular weight of the polyethyleneimine used in step S2 is different, as shown in table 1 below.
Example 11: an antibacterial fabric based on graphene is disclosed,
the difference from example 1 is that in step S2, the base fabric is pretreated. The process parameters of the components in the process steps can be found in table 1 below.
Step S2 becomes: soaking the substrate fabric in 0.5mol/L NaOH solution at 75 ℃ for 45min, washing with deionized water and drying. And then dipping the substrate fabric in a polyethyleneimine solution with the concentration of 3g/L and the average molecular weight of 5500 for 2 hours to form an adhesive layer, taking out the adhesive layer, extruding and drying the adhesive layer, dipping the adhesive layer in a graphene oxide solution with the concentration of 40g/L, standing the solution for 30 minutes at the temperature of 30 ℃ to form a graphene layer, taking out the graphene layer, washing the graphene layer by using deionized water, and drying the graphene layer to obtain the graphene fabric.
Table 1: each parameter of the raw materials used in the respective steps of examples 1 to 11
Figure BDA0002949866670000061
Figure BDA0002949866670000071
Comparative example
Comparative example 1: an antibacterial fabric based on graphene is disclosed,
the difference from example 1 is that there is no protective layer on the graphene layer surface.
The production process comprises the following steps:
s1: performing tatting on cotton fibers serving as warps and wefts to form a fabric layer to obtain a base fabric, wherein the ratio of the warp density to the weft density of the base fabric is 2:1, and the count of the used cotton fibers is 42 s/3;
s2: soaking the base fabric in a polyethyleneimine solution with the concentration of 3g/L and the average molecular weight of 5500 for 2 hours to form an adhesive layer, taking out the adhesive layer, extruding and drying the adhesive layer, soaking the adhesive layer in a graphene oxide solution with the concentration of 40g/L, standing the solution for 30 minutes at 30 ℃ to form a graphene layer, taking out the graphene layer, washing the graphene layer with deionized water, and drying the graphene layer to obtain the finished fabric.
Comparative example 2: the graphene-based antibacterial fabric is different from the graphene-based antibacterial fabric in example 1 in that the protective layer is formed by crosslinking polyether amine and graphene oxide.
The production process comprises the following steps:
s1: performing tatting on cotton fibers serving as warps and wefts to form a fabric layer to obtain a base fabric, wherein the ratio of the warp density to the weft density of the base fabric is 2:1, and the count of the used cotton fibers is 42 s/3;
s2: dipping a substrate fabric in a polyethyleneimine solution with the concentration of 3g/L and the average molecular weight of 5500 for 2 hours to form an adhesive layer, taking out the adhesive layer, extruding and drying the adhesive layer, dipping the adhesive layer in a graphene oxide solution with the concentration of 40g/L, standing the solution for 30 minutes at 30 ℃ to form a graphene layer, taking out the graphene layer, washing the graphene layer with deionized water and drying the graphene layer to obtain a graphene fabric;
s3: spraying a 10% by mass benzyl alcohol solution of D230 polyether amine on the surface of graphene oxide, and then extruding by using a roller to remove the excess epoxy resin glue. And (3) curing for 50min at the temperature of 70 ℃ to form a protective layer, and drying after cleaning with clean water to obtain the finished graphene fabric.
Comparative example 3: the graphene-based antibacterial fabric is different from that in example 1 in that ammonia water is not used for treatment in step S3.
Step S3 becomes: mixing epoxy resin, polyetheramine and benzyl alcohol according to the using amount to obtain epoxy resin adhesive, wherein the mass fraction of each component is shown in table 1, and the epoxy value of the used epoxy resin is 0.5; and spraying the epoxy resin adhesive on the surface of the graphene oxide, and then extruding by using a roller to remove the redundant epoxy resin adhesive. And curing for 45min at the temperature of 70 ℃ to form a protective layer, finally, scraping and finishing the surface of the fabric by using a scraper, cleaning by using clear water, and drying to obtain the finished graphene fabric.
Comparative example 4: the graphene-based antibacterial fabric is different from the graphene-based antibacterial fabric in example 1 in that the epoxy resin glue used contains different epoxy resin and polyether amine.
Specifically, the epoxy resin adhesive comprises the following components in percentage by mass: 40% of epoxy resin, 10% of polyether amine and 50% of benzyl alcohol. All other parameters and all test steps are the same.
Performance test
Test one: initial antibacterial performance test principle: the antibacterial performance can be compared by inoculating flora on each antibacterial test sample and a pure cotton control sample which is not subjected to antibacterial treatment and comparing the reproduction condition of bacteria on the test samples.
Test subjects: examples 1 to 11, comparative examples 1 to 4.
The test steps are as follows: the original bacteriostasis rate P of the finished graphene fabric prepared in each example and each comparative example is measured according to the national standard GB/T20944.2-2007 of the people's republic of China1. The pure cotton fiber woven fabric is used as a reference sample and a test sample during measurementThe sample and the control sample are both squares with side length of 5cm multiplied by 5 cm; the samples were sterilized by autoclaving before the test, and E.coli was used as the test strain. Original bacteriostasis rate P1The calculation of (a) retained a decimal place, and the test results are shown in table 2 below.
Table 2: p of examples 1 to 11 and comparative examples 1 to 41Value of
Figure BDA0002949866670000081
From the data in table 2, the following analysis can be derived.
By comparing the data of examples 1-11 and comparative example 1 in Table 2, it can be seen that P for examples 1-111The values are all similar to those of comparative example 1 and are all above 95, so that in examples 1-11, after a protective layer is added outside the graphene layer, the antibacterial ability of the graphene layer is not greatly affected, and the fabric still has good antibacterial ability.
Further comparison shows that the P1 values of examples 5-8 are slightly greater than those of examples 1-2, thus indicating that the addition of allyl glycidyl ether and liquid carboxylated nitrile rubber to the epoxy resin adhesive can improve the original antibacterial ability of the fabric. The allyl glycidyl ether can play a role of an active diluent, can prevent epoxy resin from being excessively crosslinked on the surface of the graphene layer, and the liquid carboxyl nitrile rubber can modify the epoxy resin, improve the toughness of the epoxy resin and enable the protective layer to have tiny pores, so that the influence of the protective layer on the graphene layer can be further reduced, and the influence of the protective layer on the original antibacterial effect is minimized.
Comparing the data of examples 1-2 and comparative example 3, P for examples 1-2 can be found1The value is larger than that of comparative example 3, and thus it can be illustrated that the treatment without ammonia water in the curing process of the protective layer in comparative example 3 causes the original antibacterial ability of the cloth to be decreased. This is because unnecessary epoxy is fallen in the aqueous ammonia reaction, prevents that epoxy from producing on graphite alkene layer and explodes and gather, makes the protective layer more even, prevents that the protective layer is too thick and causes the influence to graphite alkene layer.
Comparative example 1Data from-2 and comparative example 4, it is possible to find P for examples 1-21The value is much larger than that of comparative example 4, so that the technical scheme that the dosage of the epoxy resin and the polyether amine in the epoxy resin adhesive used in examples 1-2 is more optimal can be illustrated. The reason is that the content of the epoxy resin in the epoxy resin adhesive of the embodiment 1-2 is only 10-15%, and the content of the polyether amine is more than that of the epoxy resin, because the epoxy resin with low content is adopted, the formed protective layer can play a role of wear resistance and cannot be too hard, and the influence on the bacteriostatic ability of the graphene layer due to the too thick protective layer can be avoided, so that the protective layer has wear resistance and can not influence the bacteriostatic performance of the graphene layer too much.
And (2) test II: the principle of the bacteriostatic ability endurance test is as follows: the surface of the test sample is subjected to simulated abrasion by using a Martindale abrasion resistance tester, the test sample is subjected to simulated washing by using a washing resistance tester, then the antibacterial ability of the test sample is detected, and the durability of the antibacterial ability of the test sample can be judged by comparing the abrasion of the test sample with the change of the antibacterial ability before and after washing.
Test subjects: examples 1 to 11, comparative examples 1 to 4.
Test equipment: DZ-335-4 Martindale abrasion tester, ZL-8041 Water Wash tester.
The test steps are as follows: three squares with the side length of 5cm × 5cm were cut out from the finished graphene fabrics prepared in examples 1 to 11 and comparative examples 1 to 4, respectively, and the test samples were subjected to simulated wear using a martindale wear meter, and both the front and back surfaces of each test sample were subjected to friction, and the number of times of friction on each surface was 500. And then, carrying out simulated water washing on the test sample by using a water washing resistance testing machine, washing each test sample for 10 times, wherein the washing time is 20min each time, the washing temperature is 25 ℃, and then airing. Then, the same detection method is used for detecting the retained bacteriostatic rate P of each test sample by continuously referring to the national standard GB/T20944.2-2007 of the people's republic of China2Finally, combining the data of the first test, calculating the retention rate X (X is P) of the bacteriostasis rate2÷P1X 100), one decimal place is reserved for the calculation results, and the test results are shown in table 3 belowShown in the figure.
Table 3: p of examples 1 to 11, comparative examples 1 to 41、P2And the value of X
Figure BDA0002949866670000091
Figure BDA0002949866670000101
The following analytical conclusions can be drawn in conjunction with the data in table 3.
Comparing the data of examples 1 to 11 and comparative example 1 in table 3, it can be seen that the value of X is much greater for examples 1 to 11 than for comparative example 1. Therefore, it can be shown that in examples 1 to 11, by arranging the protective layer on the surface of the graphene layer, the abrasion resistance and the water washing resistance of the bacteriostatic ability of the fabric can be effectively improved. This is because the protective layer in examples 1 to 11 is formed by ring-opening crosslinking of low-concentration epoxy resin and excess polyetheramine with the epoxy group on the graphene oxide, and a stable network structure can be formed on the surface of the graphene layer by crosslinking, so that the loss of the graphene layer during friction and water washing can be effectively reduced, and the graphene layer has good wear resistance and long-term durability.
Comparing the data of examples 1-11 and comparative example 2 in Table 3, it can be seen that the X values of examples 1-11 are much greater than comparative example 2. Therefore, it can be shown that the epoxy resin also plays a crucial role in the protective layer, and if the epoxy group on the graphene oxide is subjected to ring-opening crosslinking by using the polyether amine alone, the strength of the formed protective layer is insufficient, and it is difficult to play a good anti-wear role.
Comparing the data in Table 3 for examples 1-2 and examples 3-4, it can be seen that the X value for examples 3-4 is greater than for examples 1-2. Therefore, the epoxy value of the epoxy resin used in the epoxy resin adhesives of examples 3 to 4 can be explained as being more preferable. The epoxy value of the epoxy resin directly influences the viscosity, the molecular weight, the epoxy group content and other important properties of the epoxy resin, so that the protective layer can be better formed on the surface of the graphene layer by selecting the epoxy resin with the proper epoxy value, so that the protective layer is more uniform and the wear resistance is better.
Comparing the data in Table 3 for examples 1-2 and examples 5-8, it can be seen that examples 5-8 have a greater value for X than examples 1-2. This is probably because in examples 5-8, because allyl glycidyl ether and liquid carboxylated nitrile rubber are added to the epoxy resin adhesive, the toughness of the protective layer is improved, so that brittle cracks generated on the surface of the protective layer during simulated water washing can be reduced, and obvious larger cracks can be prevented from being formed on the surface of the protective layer, thereby enabling the protective layer to have better protective capability.
Comparing the data in Table 3 for examples 1-2 and examples 9-10, it can be seen that examples 9-10 have a greater X value than examples 1-2. Therefore, it can be said that the molecular weight of the polyethyleneimine used in examples 9 to 10 is more excellent. This is because different molecular weights may affect the adhesion and fixation ability of polyethyleneimine on the fabric layer, and may also affect the ring-opening consolidation ability between polyethyleneimine and graphene oxide, and therefore, selecting polyethyleneimine with an appropriate molecular weight is helpful for improving the stability of the graphene layer.
Comparing the data in Table 3 for examples 1-2 and example 11, it can be seen that example 11 has a greater value for X than examples 1-2. Therefore, the pretreatment of the fabric layer can improve the reactivity of the fabric layer and the polyethyleneimine, so that the stability of the graphene layer is improved.
The specific embodiments are only for explaining the present application and are not limiting to the present application, and those skilled in the art can make modifications to the embodiments without inventive contribution as required after reading the present specification, but all the embodiments are protected by patent law within the scope of the claims of the present application.

Claims (7)

1. The utility model provides an antibiotic surface fabric based on graphite alkene which characterized in that: the adhesive comprises a fabric layer (1), an adhesive layer (2), a graphene layer (3) and a protective layer (4) from inside to outside in sequence;
the fabric layer (1) is woven by cotton fibers; the bonding layer (2) is a structural layer which is formed by finishing the surface of the fabric layer by polyethyleneimine and plays a role in excessive bonding; the graphene layer (3) is a structural layer which is formed by hot-pressing graphene oxide on the surface of the bonding layer and has a main antibacterial effect; the protective layer (4) is a structural layer which is formed by crosslinking epoxy resin glue on the surface of the bonding layer and mainly plays a role in protection, and the epoxy resin glue is mainly prepared by mixing epoxy resin, polyether amine and benzyl alcohol;
in the epoxy resin adhesive used in the protective layer (4), the mass fraction of the epoxy resin is 10-15%, the mass fraction of the polyether amine is 15-20%, and the balance is benzyl alcohol.
2. The graphene-based antibacterial fabric according to claim 1, characterized in that: the epoxy value of the epoxy resin is 0.4-0.45.
3. The graphene-based antibacterial fabric according to claim 1, characterized in that: the epoxy resin adhesive also contains allyl glycidyl ether, and the mass fraction of the allyl glycidyl ether is 2-3%.
4. The graphene-based antibacterial fabric according to claim 1, characterized in that: the epoxy resin adhesive also contains liquid carboxyl nitrile rubber, and the mass fraction of the liquid carboxyl nitrile rubber is 4-6%.
5. The graphene-based antibacterial fabric according to claim 1, characterized in that: the molecular weight of the polyethyleneimine used in the adhesive layer is 3000-5000.
6. The production process of the graphene-based antibacterial fabric as claimed in any one of claims 1 to 5, characterized in that: the method comprises the following process steps:
s1: performing tatting on cotton fibers serving as warps and wefts to form a fabric layer to obtain a base fabric;
s2: dipping the substrate fabric in a polyethyleneimine solution with the concentration of 3-3.5g/L for 2-2.5h to form an adhesive layer, taking out the adhesive layer, extruding and drying the adhesive layer, dipping the adhesive layer in a graphene oxide solution with the concentration of 40-45g/L, standing the solution at the temperature of 30-35 ℃ for 30-35min to form a graphene layer, taking out the graphene layer, washing and drying the graphene layer to obtain the graphene fabric;
s3: mixing epoxy resin, polyether amine, allyl glycidyl ether, liquid carboxyl nitrile rubber and benzyl alcohol according to the using amount to obtain epoxy resin glue; spraying epoxy resin glue on the surface of graphene oxide, then extruding by using a roller to remove redundant epoxy resin glue, curing at the temperature of 40-50 ℃ for 15-20min, soaking the fabric in ammonia water with the concentration of 10-12mol/L for 5-8min, taking out, extruding to remove redundant ammonia water, curing at the temperature of 70-80 ℃ for 30-40min to form a protective layer, finally scraping and trimming the surface of the fabric by using a scraper, cleaning and drying to obtain the finished product graphene fabric.
7. The production process of the graphene-based antibacterial fabric according to claim 6, characterized in that: in step S2, the substrate fabric is soaked in NaOH solution with the temperature of 70-80 ℃ and the concentration of 0.4-0.6mol/L for 40-50min, and then the subsequent process is carried out after the substrate fabric is cleaned and dried.
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Citations (2)

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Publication number Priority date Publication date Assignee Title
CN108146029A (en) * 2017-12-21 2018-06-12 海安科皓纺织有限公司 Exposure suit and the method for preparing the fabric
CN109440475A (en) * 2018-11-19 2019-03-08 苏州吉晟信纺织有限公司 It is a kind of using polyethyleneimine as nano silver/graphene/cellulose fiber composite material of binder and preparation method thereof

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US20180043656A1 (en) * 2017-09-18 2018-02-15 LiSo Plastics, L.L.C. Oriented Multilayer Porous Film

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108146029A (en) * 2017-12-21 2018-06-12 海安科皓纺织有限公司 Exposure suit and the method for preparing the fabric
CN109440475A (en) * 2018-11-19 2019-03-08 苏州吉晟信纺织有限公司 It is a kind of using polyethyleneimine as nano silver/graphene/cellulose fiber composite material of binder and preparation method thereof

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