Washing-resistant long-acting anti-virus graphene fabric and preparation method thereof
阅读说明：本技术 石墨烯耐水洗长效抗病毒织物及其制备方法 (Washing-resistant long-acting anti-virus graphene fabric and preparation method thereof ) 是由 曾伟荣 曾伟城 于 2020-12-25 设计创作，主要内容包括：本发明提供了一种石墨烯耐水洗长效抗病毒织物及其制备方法。首先在石墨烯纳米片表面原位生长聚乙烯吡咯烷酮,然后配制成较稀地的整理液,通过水刺喷射处理将整理液喷射至活化处理后的织物表面,最后热轧干燥,得到石墨烯耐水洗长效抗病毒织物。本发明利用水刺的冲击力,使得织物纤维表面分裂出细小的微纤维,与此同时,细微水流中的石墨烯/聚乙烯吡咯烷酮复合物吸附于纤维表面及内部；最后通过热压干燥,将分裂出的微纤维恢复至织物原状态,并将石墨烯/聚乙烯吡咯烷酮复合物包覆于织物纤维内部；与此同时,石墨烯表面生长的聚乙烯吡咯烷酮具有良好的粘结性,能够与石墨烯一起牢固的粘结于纤维上,从而显著提高石墨烯的负载量和负载牢度。(The invention provides a washing-resistant long-acting antiviral graphene fabric and a preparation method thereof. Firstly, growing polyvinylpyrrolidone on the surface of a graphene nanosheet in situ, then preparing a relatively dilute finishing liquid, spraying the finishing liquid to the surface of the activated fabric through spunlace spraying treatment, and finally hot rolling and drying to obtain the graphene washable long-acting antiviral fabric. According to the method, the impact force of spunlace is utilized, so that fine microfibers are split from the surface of the fabric fiber, and meanwhile, graphene/polyvinylpyrrolidone composites in fine water flow are adsorbed on the surface and inside of the fiber; finally, through hot-pressing drying, the split microfibers are restored to the original state of the fabric, and the graphene/polyvinylpyrrolidone compound is coated inside the fabric fibers; meanwhile, the polyvinylpyrrolidone growing on the surface of the graphene has good cohesiveness and can be firmly bonded on the fiber together with the graphene, so that the loading capacity and the loading fastness of the graphene are obviously improved.)
1. A preparation method of a graphene washable long-acting antiviral fabric is characterized by comprising the following steps:
s1, growing polyvinylpyrrolidone on the surface of graphene in situ to obtain a graphene/polyvinylpyrrolidone compound;
s2, dissolving the graphene/polyvinylpyrrolidone compound obtained in the step S1 in deionized water, and performing ultrasonic dispersion uniformly to obtain a finishing liquid with a solid content of 1-12 wt%;
s3, dipping the fabric to be finished in an alkaline solution, and then washing and drying to obtain an activated fabric;
and S4, carrying out spunlace spraying treatment on the activated fabric obtained in the step S3 by adopting the finishing liquid obtained in the step S2 through a water needle plate, and then carrying out hot-pressing drying to obtain the graphene water-washing-resistant long-acting antiviral fabric.
2. The method for preparing the graphene washable long-acting antiviral fabric as claimed in claim 1, wherein in step S1, the method for preparing the graphene/polyvinylpyrrolidone complex comprises: adding graphene nanosheets with the transverse size of less than 100nm and the thickness of less than 10nm and a dispersing agent into deionized water, and uniformly dispersing by ultrasonic; then adding an N-vinyl pyrrolidone monomer and an initiator, adjusting the pH value of the reaction solution to 9-10, reacting for 5-12 h in a polymerization reaction kettle at 45-60 ℃, centrifuging and drying a polymerization product to obtain the graphene/polyvinylpyrrolidone compound;
wherein the mass ratio of the N-vinyl pyrrolidone monomer to the graphene nanosheets is (0.1-1): 1.
3. The method for preparing the graphene washable long-acting antiviral fabric as claimed in claim 1 or 2, wherein in step S4, the diameter of the water needle holes of the water needle plate is 0.1-0.25 mm, and the arrangement density of the water needle holes of the water needle plate is 24-64/cm2(ii) a The pressure of the spunlace injection treatment is 3-12 Mpa, and the distance between the water needle plate and the activated fabric is 30-35 mm.
4. The method for preparing the graphene water-fast long-acting antiviral fabric according to claim 1 or 3, wherein in step S4, the water jet spraying treatment comprises: adopting five spunlaces, wherein the first spunlace is a front spunlace, and the pressure is 3-4.2 Mpa; the pressure of the second to fifth spunlaces is 4.5-12 Mpa, and the second to fifth spunlaces are front spunlace, back spunlace, front spunlace and back spunlace in sequence.
5. The preparation method of the graphene washable long-acting antiviral fabric as claimed in claim 4, wherein the diameters of the water needle holes of the first to fifth spunlaces are 0.1-0.13 mm, 0.13-0.15 mm, 0.15-0.17 mm, 0.18-0.20 mm and 0.20-0.23 mm respectively.
6. The method for preparing the graphene washable long-acting antiviral fabric according to claim 1, wherein in step S4, the hot-pressing drying comprises: and (3) putting the fabric subjected to the spunlace injection treatment into a hot pressing plate with the pressure of 0.5-2 MPa, and drying at the temperature of 45-80 ℃ for 0.5-2 h.
7. The method for preparing the graphene washable long-acting antiviral fabric as claimed in claim 1, wherein in step S4, the finishing liquid after the activation of the fabric in the spunlace spraying process is collected, and the collected finishing liquid is prepared into a new finishing liquid according to a predetermined concentration and then recycled.
8. The method for preparing the graphene washable long-acting antiviral fabric according to claim 1, wherein in step S3, the fabric to be finished is cotton fabric, polyester-cotton fabric, nylon or spandex.
9. The method for preparing the graphene washable long-acting antiviral fabric as claimed in claim 1, wherein in step S3, the alkaline solution is a sodium hydroxide solution with a concentration of 1-5 mol/L.
10. The graphene washable long-acting antiviral fabric is characterized by being prepared by the preparation method of any one of claims 1 to 9.
Technical Field
The invention relates to the technical field of antiviral fabric after-finishing, in particular to a washing-resistant long-acting antiviral graphene fabric and a preparation method thereof.
Background
Graphene is a hexagonal honeycomb two-dimensional nanomaterial composed of carbon atoms in sp2 hybrid orbitals, and can be regarded as a single-layer graphite sheet. In recent years, antibacterial functions of graphene and derivatives thereof have been researched and verified by the industry, and researchers think that the antibacterial principle is that when micron-sized bacteria migrate on a sharp nano-scale two-dimensional material of graphene, the bacteria are cut through cell walls instantly and die. In addition, graphene can also destroy cell membranes by large-scale direct extraction of phospholipid molecules on the cell membranes to kill bacteria. At present, the graphene antibacterial property is widely applied to underwear, socks, bedding and the like, the strong physical antibacterial property of the graphene antibacterial fiber is continuously accepted by the market, and compared with other antibacterial fiber textile applications in the market, the graphene fiber has great advantages.
At present, the method for compounding graphene and fabric mainly comprises two methods of composite spinning and after-finishing. The composite spinning is to prepare a spinning solution from graphene and a polymer raw material, and then obtain the graphene composite fiber through composite spinning. The loading capacity of the graphene is greatly limited, and the spinning performance of the polymer is influenced by excessive addition, so that the mechanical performance and other properties of the obtained fiber are influenced. A fabric modification method commonly used in after-finishing is to prepare graphene into a modification solution, and then compound the graphene and the fabric through treatment such as dipping adsorption or padding. However, the graphene surface does not contain active groups, and the size is in the nanometer level, so that agglomeration is easy to occur, and effective dispersion and compounding with a fabric substrate are difficult to perform, so that the binding force between the graphene and the fabric substrate is poor, the washing fastness is not high, and the antibacterial and antiviral durability of the fabric is seriously affected. In addition, graphene is oxidized to obtain graphene oxide, so that the surface active groups of the graphene are improved, and the chemical bonding adsorption of the graphene oxide and the fabric is promoted. But researches show that the antibacterial and antiviral performances of the graphene oxide are far lower than those of graphene nano-sheets. Therefore, how to improve the dispersibility of the graphene and the load fastness of the graphene and the fabric substrate are two key factors for obtaining the washing-resistant long-acting antiviral fabric.
In view of the above, there is a need to design an improved method for preparing a graphene washable long-acting antiviral fabric, so as to solve the above problems.
Disclosure of Invention
The invention aims to provide a washing-resistant long-acting antiviral graphene fabric and a preparation method thereof. Firstly, growing polyvinylpyrrolidone on the surface of a graphene nanosheet in situ, then preparing a relatively dilute finishing liquid, spraying the finishing liquid to the surface of the activated fabric through spunlace spraying treatment, and finally hot rolling and drying to obtain the graphene washable long-acting antiviral fabric. According to the invention, the impact force of spunlace and the cohesiveness of polyvinylpyrrolidone are utilized to coat the graphene/polyvinylpyrrolidone compound in the textile fiber; meanwhile, the polyvinylpyrrolidone growing on the surface of the graphene can be firmly bonded on the fiber together with the graphene, so that the loading capacity and the load fastness of the graphene are obviously improved.
In order to realize the purpose, the invention provides a preparation method of a graphene washable long-acting antiviral fabric, which comprises the following steps:
s1, growing polyvinylpyrrolidone on the surface of graphene in situ to obtain a graphene/polyvinylpyrrolidone compound;
s2, dissolving the graphene/polyvinylpyrrolidone compound obtained in the step S1 in deionized water, and performing ultrasonic dispersion uniformly to obtain a finishing liquid with a solid content of 1-12 wt%;
s3, dipping the fabric to be finished in an alkaline solution, and then washing and drying to obtain an activated fabric;
and S4, carrying out spunlace spraying treatment on the activated fabric obtained in the step S3 by adopting the finishing liquid obtained in the step S2 through a water needle plate, and then carrying out hot-pressing drying to obtain the graphene water-washing-resistant long-acting antiviral fabric.
As a further improvement of the present invention, in step S1, the preparation method of the graphene/polyvinylpyrrolidone complex includes: adding graphene nanosheets with the transverse size of less than 100nm and the thickness of less than 10nm and a dispersing agent into deionized water, and uniformly dispersing by ultrasonic; then adding an N-vinyl pyrrolidone monomer and an initiator, adjusting the pH value of the reaction solution to 9-10, reacting for 5-12 h in a polymerization reaction kettle at 45-60 ℃, centrifuging and drying a polymerization product to obtain the graphene/polyvinylpyrrolidone compound;
wherein the mass ratio of the N-vinyl pyrrolidone monomer to the graphene nanosheets is (0.1-1): 1.
As a further improvement of the invention, in step S4, the diameter of the water needle holes of the water needle plate is 0.1-0.25 mm, and the arrangement density of the water needle holes of the water needle plate is 24-64/cm2(ii) a The pressure of the spunlace injection treatment is 3-12 Mpa, and the distance between the water needle plate and the activated fabric is 30-35 mm.
As a further improvement of the present invention, in step S4, the hydroentangling jet process includes: adopting five spunlaces, wherein the first spunlace is a front spunlace, and the pressure is 3-4.2 Mpa; the pressure of the second to fifth spunlaces is 4.5-12 Mpa, and the second to fifth spunlaces are front spunlace, back spunlace, front spunlace and back spunlace in sequence.
As a further improvement of the invention, the diameters of the water needles of the first to fifth spunlaces are respectively 0.1-0.13 mm, 0.13-0.15 mm, 0.15-0.17 mm, 0.18-0.20 mm and 0.20-0.23 mm.
As a further improvement of the present invention, in step S4, the hot press drying includes: and (3) putting the fabric subjected to the spunlace injection treatment into a hot pressing plate with the pressure of 0.5-2 MPa, and drying at the temperature of 45-80 ℃ for 0.5-2 h.
As a further improvement of the present invention, in step S4, the finishing liquor after the activation of the fabric in the spunlace injection process is collected, and the collected finishing liquor is prepared into a new finishing liquor according to a predetermined concentration and then recycled.
As a further improvement of the present invention, in step S3, the fabric to be finished is cotton fabric, polyester-cotton fabric, nylon or spandex.
In a further improvement of the present invention, in step S3, the alkaline solution is a sodium hydroxide solution with a concentration of 1-5 mol/L.
The graphene washable long-acting antiviral fabric is prepared by the preparation method.
The invention has the beneficial effects that:
1. the invention provides a washing-resistant long-acting anti-virus graphene fabric and a preparation method thereof. By the operation, the dispersion uniformity of the graphene nanosheets is improved, and meanwhile, the polyvinylpyrrolidone can serve as a binder between the graphene nanosheets and the fabric to uniformly bind the graphene nanosheets to the surface and the inside of the fabric. According to the invention, the impact force of spunlace is utilized to split fine microfibers from the surface of the fabric fiber, and meanwhile, graphene/polyvinylpyrrolidone composites in fine water flow are adsorbed on the surface and inside of the fiber. Finally, through hot-pressing drying, the split microfibers are restored to the original state of the fabric, and the graphene/polyvinylpyrrolidone compound is coated inside the fabric fibers; meanwhile, the polyvinylpyrrolidone growing on the surface of the graphene has good cohesiveness and can be firmly bonded on the fiber together with the graphene, so that high loading capacity and load fastness of the graphene nanosheet are realized, the antibacterial and antiviral water washing resistance is improved, and the service life is prolonged.
2. According to the invention, the graphene nanosheets with the transverse dimension of less than 100nm and the thickness of less than 10nm are selected as the antibacterial and antiviral substrate material of the fabric, and the nano-scale transverse dimension of the graphene increases the specific surface area of the graphene on one hand, so that the contact probability of the graphene with germs and viruses is increased; on the other hand, the nanometer-scale transverse dimension is combined with the thickness dimension within 10nm, and the edge of the nanometer-scale transverse dimension is sharper than the micrometer-scale transverse dimension, so that the nanometer-scale transverse dimension is easier to pierce the germ cell wall or the virus protein membrane. In order to prevent the problem that the excessive growth amount of polyvinylpyrrolidone on the surface of the graphene nanosheet can cause the excessive coverage of the edge of the graphene nanosheet, the mass ratio of the N-vinyl pyrrolidone monomer to the graphene nanosheet is controlled within the range of (0.1-1): 1. Within this range, the effects of optimal antibacterial and antiviral rates and optimal service life can be achieved.
3. In the invention, in the step of the water jet treatment, the pore diameters of the water needles of the first to fifth water jet are sequentially increased. According to the arrangement, a thinner water needle is selected for spraying initially, more fine microfibers are split from the surface of the fabric fiber, and at the moment, the graphene/polyvinylpyrrolidone compound is adsorbed on the surface of the fine microfibers more; then the aperture of the water needle is gradually increased, and the water flow with larger diameter can promote the mutual entanglement and coating of the fine microfibers generated at the previous stage, so that the graphene/polyvinylpyrrolidone compound is coated inside the fibers, and the strength of the fabric can be improved. After multiple times of hydro-entangled treatment, the graphene/polyvinylpyrrolidone compound can be loaded on each part of the fabric fiber from inside to outside, thereby realizing high-efficiency comprehensive antibiosis and antivirus.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in detail below with reference to specific embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the scheme of the present invention are shown in the specific embodiments, and other details not closely related to the present invention are omitted.
In addition, it is also to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides a preparation method of a graphene washable long-acting antiviral fabric, which comprises the following steps:
s1, growing polyvinylpyrrolidone on the surface of graphene in situ to obtain a graphene/polyvinylpyrrolidone compound.
In step S1, the method for preparing the graphene/polyvinylpyrrolidone complex includes: adding graphene nanosheets with the transverse dimension of less than 100nm and the thickness of less than 10nm and a dispersing agent into deionized water, and ultrasonically dispersing uniformly (the content of graphene is 1-12 wt%); and then adding an N-vinyl pyrrolidone monomer and an initiator, adjusting the pH value of the reaction solution to 9-10, reacting for 5-12 h in a polymerization reaction kettle at 45-60 ℃, and centrifuging and drying the polymerization product to obtain the graphene/polyvinylpyrrolidone compound.
The dispersing agent is selected from one or more of gelatin, cellulose and cellulose ether. The initiator is azobisisobutyronitrile or benzoyl peroxide. The mass ratio of the N-vinyl pyrrolidone monomer to the graphene nanosheets is (0.1-1): 1. In the step, graphene nanosheets with transverse dimensions less than 100nm and thicknesses less than 10nm are selected as antibacterial and antiviral base materials of the fabric, and the nano-scale transverse dimensions increase the specific surface area of the graphene on one hand, so that the contact probability of the graphene with germs and viruses is increased; on the other hand, the nanometer-scale transverse dimension is combined with the thickness dimension within 10nm, and the edge of the nanometer-scale transverse dimension is sharper than the micrometer-scale transverse dimension, so that the nanometer-scale transverse dimension is easier to pierce the germ cell wall or the virus protein membrane. The polyvinylpyrrolidone grows in situ on the surface of the graphene nanosheet, and can be used as a binder between the graphene nanosheet and the fabric while improving the dispersion uniformity of the graphene nanosheet, so that the graphene nanosheet is uniformly bound on the surface and the inside of the fabric, the high loading capacity and the load fastness of the graphene nanosheet are realized, the antibacterial and antiviral water-washing resistance is improved, and the service life of the antibacterial and antiviral water-washing resistance is prolonged. In order to prevent the problem that the excessive growth amount of polyvinylpyrrolidone on the surface of the graphene nano sheet can cause the excessive coverage of the edge of the graphene nano sheet, the mass ratio of the N-vinyl pyrrolidone monomer to the graphene nano sheet is controlled to be (0.1-1): 1, and preferably (0.2-0.5): 1. The experimental result shows that in the range, the optimal effects of the antibacterial and antiviral rates and the optimal service life can be realized.
S2, dissolving the graphene/polyvinylpyrrolidone compound obtained in the step S1 in deionized water to obtain a finishing liquid with a solid content of 1-12 wt%; the solid content is preferably 5 to 10 wt%. When the solid content is too low, the load capacity is reduced; when the solid content is too high, the viscosity of the finishing liquid can be increased, the resistance of subsequent spunlace injection treatment is increased, the load effect is influenced, and the industrial energy consumption is increased.
S3, dipping the fabric to be finished in an alkaline solution, and then washing and drying to obtain the activated fabric.
In step S3, the fabric to be finished is cotton fabric, polyester-cotton fabric, nylon or spandex. The fabric containing active groups is selected and then subjected to alkali impregnation treatment, so that the content of the active groups on the surface of the fabric is increased, the activity of the fabric is improved, and the bonding effect of the polyvinylpyrrolidone and the fabric is improved.
In step S3, the alkaline solution is a sodium hydroxide solution with a concentration of 1-5 mol/L.
And S4, carrying out spunlace spraying treatment on the activated fabric obtained in the step S3 by adopting the finishing liquid obtained in the step S2 through a water needle plate, and then carrying out hot-pressing drying to obtain the graphene water-washing-resistant long-acting antiviral fabric.
In step S4, the diameter of the water needle hole of the water needle plate is 0.1-0.25 mm, and the arrangement density of the water needles of the water needle plate is 24-64/cm2(ii) a The pressure of the spunlace injection treatment is 3-12 Mpa, and the distance between the water needle plate and the activated fabric is 30-35 mm. The diameter of the water needle is small, the arrangement density is large, the finishing liquid containing the graphene/polyvinylpyrrolidone compound is used as the water jet liquid, the invention utilizes the impact force of the water jet to split the surface of the fabric fiber into fine microfibers, and meanwhile, the graphene/polyvinylpyrrolidone compound in the fine water flow is uniformly adsorbed on the surface and the inside of the fiber.
In step S4, the spunlace jetting process includes: adopting five spunlaces, wherein the first spunlace is a front spunlace, and the pressure is 3-4.2 Mpa; the pressure of the second to fifth spunlaces is 4.5-12 Mpa, and the second to fifth spunlaces are front spunlace, back spunlace, front spunlace and back spunlace in sequence. Preferably, the pressure of the second to fifth hydroentangling is gradually increased.
The diameters of the water needles of the first to fifth spunlaces are respectively 0.1-0.13 mm, 0.13-0.15 mm, 0.15-0.17 mm, 0.18-0.20 mm and 0.20-0.23 mm. The pore diameters of the water needles of the first to fifth water jet are sequentially increased, and the arrangement is that a finer water needle is selected for spraying initially, more fine microfibers are split from the surface of the fabric fiber, and at the moment, more graphene/polyvinylpyrrolidone compound is adsorbed on the surface of the fine microfibers; then the aperture of the water needle is gradually increased, and the water flow with larger diameter can promote the mutual entanglement and coating of the fine microfibers generated at the previous stage, so that the graphene/polyvinylpyrrolidone compound is coated inside the fibers, and the strength of the fabric can be improved. After multiple times of hydro-entangled treatment, the graphene/polyvinylpyrrolidone compound can be loaded on each part of the fabric fiber from inside to outside, thereby realizing high-efficiency comprehensive antibiosis and antivirus.
In step S4, the hot press drying includes: and (3) putting the fabric subjected to the spunlace injection treatment into a hot pressing plate with the pressure of 0.5-2 MPa, and drying at the temperature of 45-80 ℃ for 0.5-2 h. Putting the fabric subjected to the spunlace injection treatment into a hot pressing plate with certain pressure, further hot pressing the split microfibers to an original state of the fabric in a drying process, and coating the graphene/polyvinylpyrrolidone composite inside the fabric fibers; meanwhile, the polyvinylpyrrolidone growing on the surface of the graphene has good cohesiveness and can be firmly bonded on the fiber together with the graphene, so that the loading capacity and the loading fastness of the graphene are obviously improved, and the strength of the fabric is improved.
In step S4, the finishing liquid after the activation of the fabric in the spunlace injection process is collected, and the collected finishing liquid is prepared into a new finishing liquid according to a predetermined concentration and then recycled. Through collecting the finishing liquor after spraying, can realize the recycle of finishing liquor, improve the utilization ratio of raw materials, reduce cost.
The graphene washable long-acting antiviral fabric is prepared by the preparation method.
Example 1
A preparation method of a graphene washable long-acting antiviral fabric comprises the following steps:
s1, adding graphene nanosheets with the transverse size of 50nm and the thickness of 3nm and hydroxymethyl cellulose into deionized water, and performing ultrasonic dispersion uniformly (the content of graphene is 7.5 wt%, and the content of hydroxymethyl cellulose is 1.5%); and then adding an N-vinyl pyrrolidone monomer (the mass ratio of the N-vinyl pyrrolidone monomer to the graphene nanosheets is 0.4:1) and azobisisobutyronitrile, adjusting the pH value of the reaction solution to 9-10, reacting for 8 hours in a polymerization reaction kettle at 50 ℃, centrifuging and drying the polymerization product to obtain the graphene/polyvinylpyrrolidone composite.
S2, dissolving the graphene/polyvinylpyrrolidone compound obtained in the step S1 in deionized water to obtain finishing liquid with solid content of 8 wt%.
S3, firstly, soaking the cotton fabric in a sodium hydroxide solution with the concentration of 2.5mol/L for 30min, and then washing and drying to obtain the activated cotton fabric.
S4, carrying out spunlace injection treatment on the activated fabric obtained in the step S3 through a water needle plate by adopting the finishing liquid obtained in the step S2: adopting five spunlaces, wherein the first spunlace is a front spunlace, and the pressure is 3.5 Mpa; the pressure of the second to fifth hydroentangling is 5.5Mpa, 6Mpa, 7.5Mpa and 8.5Mpa in sequence, and the pressure of the second to fifth hydroentangling is front hydroentangling, back hydroentangling, front hydroentangling and back hydroentangling in sequence. The diameters of the water needles of the first to fifth water jet are 0.12mm, 0.14mm, 0.16mm, 0.18mm and 0.22mm in sequence. The arrangement density of the water needles of the water needle plate is 48/cm2(ii) a The distance between the water needle plate and the activated fabric is 32 mm.
And then putting the fabric subjected to the spunlace spraying treatment into a hot pressing plate with the pressure of 1.2MPa, and drying at the temperature of 60 ℃ for 1h to obtain the graphene washable long-acting antiviral fabric.
After the antibacterial and antiviral fabric is washed 30 times by referring to GN/T20944-2008, the fabric is subjected to a textile antiviral activity test by referring to the standard ISO18184:2014(E), and the tested virus is influenza A virus (H1N 1).
The fabrics were tested for breaking strength according to GB/T3923.1-1997 standard.
Table 1 antiviral test results of graphene water-fast washing long-acting antiviral fabric prepared in example 1
It can be seen that after the graphene washable long-acting antiviral fabric prepared in this embodiment is washed by water for 30 times, the antiviral activity rate is still as high as 99.02%, which indicates that the graphene has high loading fastness and good washing resistance. The breaking strength was 689N, whereas the breaking strength of the untreated cotton fabric was 669N. Therefore, the processing method provided by the invention can improve the load fastness of the graphene and can also improve the strength of the fabric.
Example 2
Compared with the embodiment 1, the difference of the preparation method of the graphene washable long-acting antiviral fabric is that in the step S4, the diameters of the water needles of the first to fifth water jet are all 0.12 mm. The rest is substantially the same as that of embodiment 1, and will not be described herein.
After the graphene water-washing-resistant long-acting antiviral fabric prepared in the embodiment is washed for 30 times, the antiviral activity rate is 98.92%, and the breaking strength of the fabric is 665N. It can be seen that the antiviral activity rate is slightly reduced compared to example 1, and the breaking strength of the fabric is lower than that of the untreated cotton fabric. This is probably because when the smaller-pore squirt is used for each of the five hydroentangling jets, the fine microfibers are repeatedly broken from the surface of the fabric, which easily causes fiber breakage, thereby reducing the strength of the fabric. The graphene/polyvinylpyrrolidone complex is also difficult to be coated inside the fiber, and thus the antiviral activity rate is reduced.
Examples 3 to 9
Compared with the embodiment 1, the difference of the preparation method of the graphene washable long-acting antiviral fabric is that the mass ratio of the N-vinyl pyrrolidone monomer to the graphene nanosheets in the step S1 and the solid content of the finishing liquid in the step S2 are shown in Table 2. The rest is substantially the same as that of embodiment 1, and will not be described herein.
Table 2 antiviral test results of graphene water-fast washable long-acting antiviral fabrics prepared in examples 3 to 9
As can be seen from table 2, as the mass ratio of the N-vinylpyrrolidone monomer to the graphene nanoplatelets increases, the antiviral activity increases first and then decreases, and the breaking strength tends to increase gradually. It is shown that when the amount of the N-vinylpyrrolidone monomer is too large, the edge of the graphene nanoplatelet may be covered too much, thereby reducing the antiviral function. When the amount of the N-vinyl pyrrolidone monomer is too small, the bonding fastness of graphene is reduced, so that the washing resistance is reduced, and the fabric strength is reduced accordingly.
With the increase of the solid content of the finishing liquid, the antiviral activity rate and the breaking strength are increased firstly and then reduced. This is because when the solid content of the finishing liquid is too small, the amount of the graphene/polyvinylpyrrolidone complex supported is small, and thus the antiviral activity rate and the breaking strength are small. When the solid content of the finishing liquid is too large, the viscosity of the finishing liquid is increased, the resistance of subsequent spunlace injection treatment is increased, the loading effect is influenced, and the industrial energy consumption is increased.
Comparative example 1
Compared with the embodiment 1, the difference of the preparation method of the graphene water-washing-resistant long-acting antiviral fabric is that the activated fabric obtained in the step S3 is directly soaked in the finishing liquid obtained in the step S2, and then the activated fabric is taken out and dried to obtain the graphene water-washing-resistant long-acting antiviral fabric. The rest is substantially the same as that of embodiment 1, and will not be described herein.
Comparative example 2
Compared with the embodiment 1, the difference of the preparation method of the graphene washable long-acting antiviral fabric is that in the step S4, a hot pressing plate is not adopted, and drying treatment is directly carried out. The rest is substantially the same as that of embodiment 1, and will not be described herein.
Comparative example 3
Compared with the embodiment 1, the difference of the preparation method of the graphene washable long-acting antiviral fabric is that the graphene nanosheets are directly prepared into finishing liquid, namely, polyvinylpyrrolidone does not grow on the surface of the graphene nanosheets. The rest is substantially the same as that of embodiment 1, and will not be described herein.
Comparative example 4
Compared with the embodiment 1, the difference of the preparation method of the graphene water-washing-resistant long-acting antiviral fabric is that a finishing liquid is directly prepared from graphene nanosheets, the activated fabric obtained in the step S3 is immersed in the finishing liquid obtained in the step S2, and then the activated fabric is taken out and dried to obtain the graphene water-washing-resistant long-acting antiviral fabric. The rest is substantially the same as that of embodiment 1, and will not be described herein.
Table 3 antiviral test results of water-washable long-acting antiviral fabrics of example 1 and comparative examples 1 to 4 of graphene
Test specimen
Antiviral Activity Rate (%)
Breaking strength (N)
Example 1
99.02
689
Comparative example 1
97.82
670
Comparative example 2
98.12
675
Comparative example 3
97.01
663
Comparative example 4
96.24
660
As can be seen from table 3, when the conventional impregnation adsorption treatment is adopted, the fabric has lower antiviral and breaking strength than the graphene washable long-acting antiviral fabric prepared by the present invention. According to the invention, fine microfibers are split from the surface of the fabric fiber through the spunlace injection treatment, and the fine microfibers are entangled and coated with each other, so that the graphene/polyvinylpyrrolidone composite is coated inside the fiber, and the water washing resistance and the strength of the fabric are improved. When hot-pressing drying is not adopted, the antiviral and breaking strength is lower than that of example 1, which shows that the hot-pressing drying can further hot-press the split microfibers to the original state of the fabric, and the graphene/polyvinylpyrrolidone composite is coated inside the fabric fibers, so that the water washing resistance and strength of the fabric are improved. When polyvinylpyrrolidone does not grow on the surface of the graphene, the antiviral and breaking strength of the fabric is far lower than that of the fabric in example 1; when the surface of the graphene is not subjected to polyvinylpyrrolidone growth or spunlace spraying treatment, the antiviral and breaking strength of the fabric are far lower than those of the fabric subjected to spunlace spraying treatment in comparative example 3. The solution containing graphene is used as a spunlace liquid to carry out spunlace spraying treatment, so that the loading capacity and the load fastness of graphene and the fabric strength are improved. And by combining with polyvinylpyrrolidone, the antiviral fabric with much lower water resistance and high strength can be obtained. Therefore, the invention provides a new idea for preparing the long-acting washable antiviral fabric, and the preparation method is simple and feasible in operation and high in raw material utilization rate.
In summary, according to the preparation method of the graphene water-washing-resistant long-acting antiviral fabric provided by the invention, firstly, polyvinylpyrrolidone grows in situ on the surface of a graphene nanosheet, then a relatively dilute finishing liquid is prepared, the finishing liquid is sprayed to the surface of the activated fabric through spunlace spraying treatment, and finally, hot rolling and drying are carried out, so that the graphene water-washing-resistant long-acting antiviral fabric is obtained. According to the method, the impact force of spunlace is utilized, so that fine microfibers are split from the surface of the fabric fiber, and meanwhile, graphene/polyvinylpyrrolidone composites in fine water flow are adsorbed on the surface and inside of the fiber; finally, through hot-pressing drying, the split microfibers are restored to the original state of the fabric, and the graphene/polyvinylpyrrolidone compound is coated inside the fabric fibers; meanwhile, the polyvinylpyrrolidone growing on the surface of the graphene has good cohesiveness and can be firmly bonded on the fiber together with the graphene, so that the loading capacity and the loading fastness of the graphene are obviously improved.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the spirit and scope of the present invention.