CN118007407A - Long-acting super-hydrophobic fabric and preparation method thereof - Google Patents
Long-acting super-hydrophobic fabric and preparation method thereof Download PDFInfo
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- CN118007407A CN118007407A CN202410204633.8A CN202410204633A CN118007407A CN 118007407 A CN118007407 A CN 118007407A CN 202410204633 A CN202410204633 A CN 202410204633A CN 118007407 A CN118007407 A CN 118007407A
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- 239000004744 fabric Substances 0.000 title claims abstract description 149
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title description 2
- 239000000835 fiber Substances 0.000 claims abstract description 153
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 54
- 239000002994 raw material Substances 0.000 claims abstract description 47
- 239000002131 composite material Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 238000012986 modification Methods 0.000 claims abstract description 20
- 230000004048 modification Effects 0.000 claims abstract description 20
- 238000001020 plasma etching Methods 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 238000009941 weaving Methods 0.000 claims abstract description 11
- 238000002074 melt spinning Methods 0.000 claims abstract description 6
- 238000009987 spinning Methods 0.000 claims description 22
- 239000000839 emulsion Substances 0.000 claims description 10
- 239000004814 polyurethane Substances 0.000 claims description 10
- 229920002635 polyurethane Polymers 0.000 claims description 8
- 229920000058 polyacrylate Polymers 0.000 claims description 7
- 239000012510 hollow fiber Substances 0.000 claims description 6
- 125000005005 perfluorohexyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 claims description 6
- 230000005923 long-lasting effect Effects 0.000 claims description 2
- 210000001595 mastoid Anatomy 0.000 abstract description 18
- 239000004753 textile Substances 0.000 abstract description 7
- 240000002853 Nelumbo nucifera Species 0.000 abstract description 2
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- 239000012528 membrane Substances 0.000 abstract 1
- 229920000728 polyester Polymers 0.000 description 87
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 9
- 229910052731 fluorine Inorganic materials 0.000 description 9
- 239000011737 fluorine Substances 0.000 description 9
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
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- 238000005470 impregnation Methods 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 4
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 4
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 4
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- 229920002647 polyamide Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
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- 229920000747 poly(lactic acid) Polymers 0.000 description 1
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- Woven Fabrics (AREA)
Abstract
The invention belongs to the technical field of textile fabrics, and provides a long-acting super-hydrophobic fabric and a preparation method thereof, wherein the method comprises the steps of selecting at least two hydrophobic fibers with different heat shrinkage rates as raw materials; slicing the raw materials, carrying out melt spinning, preparing radiation type composite fibers, weaving the radiation type composite fibers into a fabric, carrying out heat treatment in a relaxed state, preparing the fabric with a micrometer structure, and then carrying out plasma etching to prepare the fabric with a micro-nano double-layer structure; and (3) immersing the fabric with the micro-nano double-layer structure in a hydrophobic finishing agent, and performing grafting modification to prepare the long-acting super-hydrophobic fabric. The invention simulates a micron-sized mastoid structure, a nano-fluff structure and surface wax on the surface of lotus leaf, prepares the long-acting super-hydrophobic fabric which has a micro-nano double-layer structure and a hydrophobic membrane on the surface and is bio-friendly.
Description
Technical Field
The application relates to the technical field of textile fabrics, in particular to a long-acting super-hydrophobic fabric and a preparation method thereof.
Background
Most of the hydrophobic fabrics in the current market are finished by adopting a hydrophobic finishing agent, only have a simple waterproof function, have no self-cleaning property, and most of the existing hydrophobic finishing agents contain long-chain fluorine. Although the fluorine-containing hydrophobic finishing agent has good stability and good hydrophobic performance, the fluorine-containing hydrophobic finishing agent contains FPOS (perfluorooctanesulfonyl compound), PFOA (perfluorooctanoic acid) and other chemical substances, and can be released under the conditions of heating, water soaking, ultraviolet irradiation and the like, so that the fluorine-containing hydrophobic finishing agent has strong migration and high bioaccumulation, can generate great harm to ecological environment, and the hydrophobic grade of the fabric subjected to repeated washing and after-finishing can be obviously reduced.
Based on this, the existing research is continuously improving the hydrophobic finishing agent, for example, glycerol Monostearate (GMO) with long alkyl hydrophobic chain segments is introduced into the organosilicon modified aqueous polyurethane (WPU) structure, and the glycerol monostearate modified silicon-based aqueous polyurethane emulsion with good water repellency of GMO and softness of the organosilicon chain segments is developed to replace the application of fluorine-containing emulsion on fabrics so as to obtain durable hydrophobicity. However, the water contact angle of the fabric finished by the modified emulsion is less than 150 degrees, the performance index of the super-hydrophobic fabric is not reached, and the self-cleaning property is poor.
Besides improving the hydrophobic finishing agent, the existing research also improves the raw materials of the fabric to improve the hydrophobic effect, for example, the patent with the publication number CN112899818B provides a preparation method for preparing micro-bulge high-density hydrophobic knitted fabric by using potential shrinkage composite fibers, the micro-bulge formed by the loop structure formed by the shrinkage difference of the components constituting the fibers and the split fiber generated by post-treatment sanding is formed by the prepared fabric, the micro-bulge is woven in the fabric, the micro-bulge fastness is good, the number of micro-bulge parts is increased along with the increase of the friction times in the use process, and the hydrophobic effect is better. In the method, the arrangement form of the raw material A and the raw material B is X+1 or X+X or 1+X, wherein X is a positive integer greater than 3, and the arrangement form refers to the arrangement form of the raw material A and the raw material B on the section of a spinneret plate of a spinning component. By means of special cross-section design, the specific surface area of the raw materials A, B can be effectively increased due to the composition and proportion of the two components, and micro-bulges are easily formed on the surfaces of the fibers and the fabrics when any one of the high-shrinkage raw materials is shrunk, so that water repellency is facilitated. However, the method also needs to be cured and shaped after roughening, requires more finishing agent and does not involve the problem of hydrophobic durability.
However, the method provides a thought of utilizing the shrinkage difference of fiber components, and based on the thought, the raw materials of the fabric can be further selected, for example, the patent with publication number CN110644173B discloses a frosted fabric with three-dimensional layering effect and a preparation method thereof, and the difference of heat shrinkage rates among fibers serving as the raw materials is not less than 5%; the fiber having the largest heat shrinkage percentage is not less than 10% of the fibers as the raw material. In the method, polylactic acid fibers, viscose fibers or modal fibers are selected for the frosted fabric, but a certain direction is provided for the selection of the difference of the heat shrinkage rate.
In sum, if the raw materials can be further selected based on the shrinkage difference of the fiber components so as to be suitable for the hydrophobic fabric, and the structure of the fiber is improved so as to obtain the long-acting superhydrophobic performance, and the dosage of the finishing agent is reduced in the preparation process, the development of the bio-friendly long-acting superhydrophobic fabric is facilitated.
Disclosure of Invention
In view of the shortcomings of the technology, the invention provides a long-acting super-hydrophobic fabric and a preparation method thereof, which are used for solving the problems that the existing hydrophobic fabric in the prior art is poor in durability, does not have self-cleaning property, and is large in environmental hazard due to the use of a long-chain fluorine-containing hydrophobic finishing agent.
In order to achieve the above and related objects, the present invention adopts the following technical scheme:
the invention provides a preparation method of a long-acting super-hydrophobic fabric, which comprises the following steps:
(1) Raw material selection: selecting at least two hydrophobic fibers with different heat shrinkage rates as raw materials;
(2) Spinning and weaving: slicing the raw materials, performing melt spinning, preparing radial composite fibers and weaving the radial composite fibers into a fabric;
(3) And (3) heat treatment: carrying out heat treatment on the fabric in a relaxed state to shrink the fabric, so as to prepare the fabric with the mastoid having a micrometer structure;
(4) Plasma etching: plasma etching is carried out on the fabric with the mastoid of the micrometer structure to prepare the fabric with the micro-nano double-layer structure of the nanometer structure and the micrometer structure;
(5) Modification: and (3) immersing the fabric with the micro-nano double-layer structure in a hydrophobic finishing agent, and performing grafting modification to prepare the long-acting super-hydrophobic fabric.
In one embodiment of the present application, the difference in heat shrinkage between the hydrophobic fibers as the raw material is not less than 5%.
In one embodiment of the present application, in the step (2), the radial type composite fiber is hollow fiber and/or non-hollow fiber;
And/or when the raw materials are two kinds of fibers, the parts of the two kinds of fibers in the radial composite fiber cross-section structure are X and X, or X and (X+1), wherein X is a positive integer greater than 3.
In one embodiment of the present application, in the step (3), the heat treatment temperature is 95-100 ℃;
and/or the heat treatment time is 15-20 min.
In one embodiment of the present application, the plasma etching in step (4) is electron cyclotron resonance plasma etching.
In one embodiment of the present application, the hydrophobic finish in step (5) is a fluorinated polyacrylate emulsion or a fluorinated polyurethane containing short chain perfluorohexyl segments.
In one embodiment of the present application, in the step (5), the mass concentration of the hydrophobic finishing agent is 1.5-2.5 g/L;
And/or the dipping time is 20-40 s;
and/or the impregnation bath ratio is 1: (10-40).
In one embodiment of the present application, the melt spinning in the step (2) is melt parallel composite spinning, and the prepared facing is a high-count high-density facing.
The second aspect of the invention provides a long-acting super-hydrophobic fabric prepared according to the preparation method of the long-acting super-hydrophobic fabric.
In an embodiment of the application, the surface of the fabric has a micro-nano double-layer structure and a hydrophobic film.
The invention has the beneficial technical effects that:
the invention simulates a micron-sized mastoid structure, a nano-fluff structure and surface wax on the surface of lotus leaf, prepares the long-acting super-hydrophobic fabric which has a micro-nano double-layer structure and a hydrophobic wax film on the surface and is bio-friendly.
According to the invention, at least two hydrophobic fibers with different heat shrinkage rates are selected as raw materials, and micro-bulges are formed on the surfaces of the fibers and the fabric during heat treatment by utilizing the shrinkage difference of fiber components so as to obtain a high-density micro-bulge structure, thereby constructing the fabric with the mastoid with a micrometer structure. Meanwhile, the invention controls the difference value of the heat shrinkage rate so as to improve the efficiency of constructing the micrometer structure and the dimensional stability of the fabric.
The invention prepares the radial composite fiber containing two structures of hollow and non-hollow by melting and parallel composite spinning, and the hollow structure is utilized to promote fiber splitting during heat treatment, so that the internal structure of the fabric is relatively fluffy, and the warmth retention property and the air permeability of the fabric are further improved. In addition, the invention controls the proportion of two hydrophobic fibers, further increases the specific surface area of the fiber section, and when any high shrinkage hydrophobic fiber in the component is shrunk, micro-bulges are easily formed on the surfaces of the fiber and the fabric so as to improve the hydrophobic performance.
In addition, the invention uses microwave electron cyclotron resonance plasma etching technology to perform surface activation on the mastoid fabric with the micrometer structure, thereby facilitating subsequent grafting modification, constructing a micro-nano double-layer structure, obtaining a nano-scale fluff structure and further improving hydrophobicity.
According to the invention, the environment-friendly hydrophobic finishing agent is selected to carry out surface grafting modification on the fabric with the micro-nano double-layer structure, short-chain fluorine-containing functional groups are introduced, the surface energy is reduced, the harm to the environment is reduced, and the washing resistance and the hydrophobic performance are improved.
The invention prepares the super-hydrophobic fabric under the synergistic effect of spinning, heat treatment, plasma etching and grafting modification, and has long-acting property, self-cleaning function and biological friendliness.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the application as claimed.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and together with the description, serve to explain the principles of the application. It is evident that the drawings in the following description are only some embodiments of the present application and that other drawings may be obtained from these drawings without inventive effort for a person of ordinary skill in the art. In the drawings:
Fig. 1 is a schematic cross-sectional view of a radial type composite fiber according to an embodiment of the present application.
Detailed Description
Unless defined otherwise, all technical and/or scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It is appreciated that certain features of the invention, which are, for clarity, described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention, which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable combination or in any other described embodiment of the invention as appropriate. Certain features described in the context of various embodiments will not be considered essential features of those embodiments unless the embodiments are not operable without those elements. The present invention will be further described with reference to the following specific examples, but it should be understood that the specific process conditions, results, etc. described in the examples of the present invention are only for illustrating the present invention, and are not intended to limit the scope of the present invention, and all equivalent changes or modifications according to the spirit of the present invention should be included in the scope of the present invention.
The invention provides a preparation method of a long-acting super-hydrophobic fabric, which comprises the following steps:
(1) Raw material selection: selecting at least two hydrophobic fibers with different heat shrinkage rates as raw materials;
In this step, the difference in heat shrinkage between the hydrophobic fibers as the raw material is not less than 5%, and the hydrophobic fibers include, but are not limited to, polyesters (intrinsic viscosity 0.650 dL/g), high shrinkage polyesters (intrinsic viscosity 0.692 dL/g), polyamides, high shrinkage polyamides.
In this step, the mass percentage of the fiber with large heat shrinkage is 10 to 40 weight percent.
(2) Spinning: slicing the raw materials, and carrying out melt spinning to prepare radial composite fibers;
In the step, the melt spinning is melt parallel composite spinning;
in this step, as shown in fig. 1, the radial type composite fiber is hollow fiber and/or non-hollow fiber;
In this step, when the raw material is two kinds of fibers, the parts of the two kinds of fibers in the radial composite fiber cross-section structure are X and X, or X and (x+1), wherein X is a positive integer greater than 3. For example, when X is 4, as shown in fig. 1 (a), in the fiber cross section, one raw material is uniformly divided into 4 equal parts by the other raw material, one raw material may be split into a fan shape, and the other raw material may be split into a cross shape;
when X is 8, as shown in fig. 1 (b), in the fiber cross section, one raw material is uniformly divided into 8 equal parts by the other raw material, one raw material may be split into a fan shape, and the other raw material may be split into a rice shape.
Specifically, at least two kinds of hydrophobic fibers are sliced, dried, melted and metered respectively, conveyed into the same spinning assembly, converged at a spinneret plate and extruded, and stretched to obtain the radial composite fiber. The main technological parameters of spinning and stretching are shown in table 1.
Table 1 spinning process parameters table
( And (3) injection: PTT is polytrimethylene terephthalate fiber and PET is polyethylene terephthalate fiber )
Weaving: the radial composite fiber is woven into a high-count high-density fabric, wherein the denier of the fabric is 60-80D, and the density is 70-80 g/m 2.
(3) And (3) heat treatment: carrying out heat treatment on the high-count high-density fabric in a relaxed state to shrink the high-count high-density fabric, so as to prepare the mastoid fabric with a micrometer structure;
In the step, the heat treatment temperature is 95-100 ℃, and the heat treatment time is 15-20 min.
(4) Plasma etching: plasma etching is carried out on the mastoid fabric with the micrometer structure to prepare the micro-nano double-layer structure fabric with the nanometer structure and the micrometer structure;
In this step, the plasma etching is microwave electron cyclotron resonance plasma etching.
(5) Modification: dipping the micro-nano double-layer structure fabric into a hydrophobic finishing agent for grafting modification to prepare a long-acting super-hydrophobic fabric;
In the step, the hydrophobic finishing agent is fluorinated polyacrylate emulsion or fluorinated polyurethane containing short-chain perfluorohexyl chain segments;
in particular, fluorine-containing compounds are widely used for modification of hydrophilic polymers because of their stable C-F bonds and low surface energy. Long chain perfluoroalkyl groups degrade to perfluorooctanoic acid (PFOA) which can accumulate in human and animal tissues, thus limiting its use in the textile field. And ZHAO J, etc., synthesizes a fluorine-containing polyurethane (C6 FPU) containing short-chain perfluorohexyl chain segment (-C6F 13), and introduces it as hydrophobic agent into PU spinning solution, and obtains environment-friendly C6FPU/PU waterproof moisture-permeable film by electrostatic spinning method. Thus, the present invention may use a fluorochemical polyurethane containing a short chain perfluorohexyl segment in place of the fluorinated polyacrylate emulsion.
In the step, the mass concentration of the hydrophobic finishing agent is 1.5-2.5 g/L; the dipping time is 20-40 s; the impregnation bath ratio was 1: (10-40);
in the step, after the grafting modification is completed, baking is carried out for 3min at 180 ℃ to prepare the long-acting super-hydrophobic fabric.
The invention also provides the long-acting super-hydrophobic fabric prepared by the preparation method of the long-acting super-hydrophobic fabric, and the surface of the long-acting super-hydrophobic fabric is provided with a micro-nano double-layer structure and a hydrophobic film.
The present invention will be described in detail with reference to specific exemplary examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, as many insubstantial modifications and variations are within the scope of the invention as would be apparent to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
Example 1
(1) Raw material selection: selecting polyester fiber with heat shrinkage rate of 3 percent and high-shrinkage polyester fiber with heat shrinkage rate of 35 percent as raw materials, wherein the mass percent of the high-shrinkage polyester fiber is 20 percent and the mass percent of the polyester fiber is 80 percent.
(2) Spinning and weaving: the method comprises the steps of slicing polyester fibers and high-shrinkage polyester fibers, drying, melting and metering the polyester fibers, conveying the polyester fibers and the high-shrinkage polyester fibers to the same spinning assembly, converging the polyester fibers and the high-shrinkage polyester fibers at a spinneret plate, extruding the converging polyester fibers and the high-shrinkage polyester fibers, and stretching the converging polyester fibers to obtain the radial type composite fibers, wherein the parts of the polyester fibers and the high-shrinkage polyester fibers are 4 and 5 in the cross-section structure of the radial type composite fibers.
The radial composite fiber is woven into a high-count high-density fabric, specifically a 70D polyester fabric, and the fabric density is 76g/m 2.
(3) And (3) treating the high-count high-density fabric in a relaxed state at 100 ℃ for 15min to prepare the mastoid fabric with the micrometer structure.
(4) And (3) performing microwave electron cyclotron resonance plasma etching on the fabric with the mastoid with the micrometer structure to prepare the micro-nano double-layer structure fabric with the nanometer structure and the micrometer structure.
(5) The fabric with the micro-nano double-layer structure is impregnated with fluorinated polyacrylate emulsion with the mass concentration of 2g/L for 30s, the impregnation bath ratio is 1-20, grafting modification is carried out, and the fabric is baked for 3min at 180 ℃ to prepare the long-acting super-hydrophobic fabric.
Example 2
(1) Raw material selection: selecting polyester fiber with 3% of heat shrinkage rate and 40% of high-shrinkage polyester fiber with the heat shrinkage rate as raw materials, wherein the mass percentage of the high-shrinkage polyester fiber is 30wt% and the mass percentage of the polyester fiber is 70wt%.
(2) Spinning and weaving: the method comprises the steps of slicing polyester fibers and high-shrinkage polyester fibers, drying, melting and metering the polyester fibers, conveying the polyester fibers and the high-shrinkage polyester fibers to the same spinning assembly, converging the polyester fibers and the high-shrinkage polyester fibers at a spinneret plate, extruding the converging polyester fibers and the high-shrinkage polyester fibers, and stretching the extruded polyester fibers to obtain the hollow radial type composite fibers, wherein the parts of the polyester fibers and the high-shrinkage polyester fibers are 8 and 9 in the cross-section structure of the hollow radial type composite fibers.
The radial composite fiber is woven into a high-count high-density fabric, specifically a 70D polyester fabric, and the fabric density is 76g/m 2.
(3) And (3) treating the high-count high-density fabric in a relaxed state at 100 ℃ for 15min to prepare the mastoid fabric with the micrometer structure.
(4) And (3) performing microwave electron cyclotron resonance plasma etching on the fabric with the mastoid with the micrometer structure to prepare the micro-nano double-layer structure fabric with the nanometer structure and the micrometer structure.
(5) The fabric with the micro-nano double-layer structure is impregnated with fluorinated polyacrylate emulsion with the mass concentration of 2g/L for 30s, the impregnation bath ratio is 1-30, grafting modification is carried out, and the fabric is baked for 3min at 180 ℃ to prepare the long-acting super-hydrophobic fabric.
Example 3
(1) Raw material selection: selecting polyester fiber with heat shrinkage rate of 3 percent and high-shrinkage polyester fiber with heat shrinkage rate of 35 percent as raw materials, wherein the mass percent of the high-shrinkage polyester fiber is 20 percent and the mass percent of the polyester fiber is 80 percent.
(2) Spinning and weaving: the method comprises the steps of slicing polyester fibers and high-shrinkage polyester fibers, drying, melting and metering the polyester fibers, conveying the polyester fibers and the high-shrinkage polyester fibers to the same spinning assembly, converging the polyester fibers and the high-shrinkage polyester fibers at a spinneret plate, extruding the converging polyester fibers and the high-shrinkage polyester fibers, and stretching the converging polyester fibers to obtain the radial type composite fibers, wherein the parts of the polyester fibers and the high-shrinkage polyester fibers are 4 and 5 in the cross-section structure of the radial type composite fibers.
The radial composite fiber is woven into a high-count high-density fabric, specifically a 70D polyester fabric, and the fabric density is 76g/m 2.
(3) And (3) treating the high-count high-density fabric in a relaxed state at 100 ℃ for 15min to prepare the mastoid fabric with the micrometer structure.
(4) And (3) performing microwave electron cyclotron resonance plasma etching on the fabric with the mastoid with the micrometer structure to prepare the micro-nano double-layer structure fabric with the nanometer structure and the micrometer structure.
(5) The fabric with the micro-nano double-layer structure is impregnated with fluorinated polyurethane containing short-chain perfluorohexyl chain segments with the mass concentration of 2g/L for 30s, the impregnation bath ratio is 1-20, grafting modification is carried out, and the fabric is baked for 3min at 180 ℃ to prepare the long-acting super-hydrophobic fabric.
Comparative example 1
(1) Raw material selection: selecting polyester fiber with heat shrinkage rate of 3 percent and high-shrinkage polyester fiber with heat shrinkage rate of 35 percent as raw materials, wherein the mass percent of the high-shrinkage polyester fiber is 20 percent and the mass percent of the polyester fiber is 80 percent.
(2) Spinning and weaving: the method comprises the steps of slicing polyester fibers and high-shrinkage polyester fibers, drying, melting and metering the polyester fibers, conveying the polyester fibers and the high-shrinkage polyester fibers to the same spinning assembly, converging the polyester fibers and the high-shrinkage polyester fibers at a spinneret plate, extruding the converging polyester fibers and the high-shrinkage polyester fibers, and stretching the converging polyester fibers to obtain the radial type composite fibers, wherein the parts of the polyester fibers and the high-shrinkage polyester fibers are 4 and 5 in the cross-section structure of the radial type composite fibers.
The radial composite fiber is woven into a high-count high-density fabric, specifically a 70D polyester fabric, and the fabric density is 76g/m 2.
(3) And (3) treating the high-count high-density fabric in a relaxed state at 100 ℃ for 15min to prepare the mastoid fabric with the micrometer structure.
(4) The fabric with the mastoid with the micrometer structure is immersed in the fluorinated polyacrylate emulsion with the mass concentration of 2g/L for 30s, the immersion bath ratio is 1-20, grafting modification is carried out, and the fabric is baked for 3min at 180 ℃ to prepare the hydrophobic fabric.
Comparative example 2
(1) Raw material selection: selecting polyester fiber with heat shrinkage rate of 3 percent and high-shrinkage polyester fiber with heat shrinkage rate of 35 percent as raw materials, wherein the mass percent of the high-shrinkage polyester fiber is 20 percent and the mass percent of the polyester fiber is 80 percent.
(2) Spinning and weaving: the method comprises the steps of slicing polyester fibers and high-shrinkage polyester fibers, drying, melting and metering the polyester fibers, conveying the polyester fibers and the high-shrinkage polyester fibers to the same spinning assembly, converging the polyester fibers and the high-shrinkage polyester fibers at a spinneret plate, extruding the converging polyester fibers and the high-shrinkage polyester fibers, and stretching the converging polyester fibers to obtain the radial type composite fibers, wherein the parts of the polyester fibers and the high-shrinkage polyester fibers are 4 and 5 in the cross-section structure of the radial type composite fibers.
The radial composite fiber is woven into a high-count high-density fabric, specifically a 70D polyester fabric, and the fabric density is 76g/m 2.
(3) And (3) treating the high-count high-density fabric in a relaxed state at 100 ℃ for 15min to prepare the mastoid fabric with the micrometer structure.
(4) And (3) performing microwave electron cyclotron resonance plasma etching on the mastoid fabric with the micrometer structure to prepare the hydrophobic fabric.
Performance testing
Waterproof performance test: the fabrics of examples 1 to 3 and comparative examples 1 to 2 were tested for water resistance according to GB/T4745-2012 Water resistance test and evaluation method for textile Water resistance, and the test results are shown in Table 2.
Wash fastness test: according to GB/T3921-2008 "fastness to washing of textiles" fastness to soaping ", the fabrics of examples 1 to 3 and comparative examples 1 to 2 were subjected to washing tests using a SW-12JG type fastness to washing machine, and the test results are shown in Table 2.
Abrasion resistance test: according to GB/T3920-2008 "rubbing fastness to textile color fastness test", the fabrics of examples 1-3 and comparative examples 1-2 were subjected to wear resistance test by using a Y571N type dyeing rubbing fastness machine, and the test results are shown in Table 2.
Water permeation resistance test: according to GB/T4744-2013 "test and evaluation of Water resistance of textiles hydrostatic pressure method", the fabrics of examples 1-3 and comparative examples 1-2 after 15 times of washing were tested for water permeability resistance by using YG (B) 812D digital water permeability tester, and the test results are shown in Table 2.
Table 2 results of the performance test of the fabrics of examples and comparative example 1
| Test object | Water dip rating | Fastness to soaping | Fastness to dry rubbing | Wet rub fastness | Water contact angle/° | Roll angle/° |
| Example 1 | Grade 5 | 4-5 Grade | 4-5 Grade | Grade 4 | 153.3 | 9 |
| Example 2 | Grade 5 | 4-5 Grade | 4-5 Grade | Grade 4 | 155.4 | 8 |
| Example 3 | Grade 5 | Grade 5 | 4-5 Grade | Grade 4 | 155.9 | 8 |
| Comparative example 1 | 3-4 Grade | 3 Grade | Level 2 | Level 2 | 109.6 | 18 |
| Comparative example 2 | 3-4 Grade | 3 Grade | 2-3 Grade | 2-3 Grade | 112.4 | 15 |
As can be seen from Table 2, the long-acting super-hydrophobic fabrics prepared by the method have water wetting grades of 5 grades and soaping fastness of more than 4 grades, which indicates that the long-acting super-hydrophobic fabrics have excellent anti-wetting performance and hydrophobic performance; the dry friction fastness and the wet friction fastness are both more than 4 grades, which indicates that the long-acting super-hydrophobic fabric has good wear resistance, small influence on a water contact angle and good waterproof durability; after washing for 15 times, the Contact Angles (CA) of the water drops on the surface of the fabric prepared by the invention are all more than 150 degrees, and the rolling angles are all less than 10 degrees, which shows that the fabric prepared by the invention has long-acting, durability and self-cleaning effect.
The fabric prepared in the comparative example 1 is not subjected to plasma etching, the surface of the fabric is not provided with a nano fluff structure, the fabric is not activated, and the grafting rate is low; the fabric prepared in comparative example 2 is not grafted with the hydrophobic finishing agent, and the surface energy is higher, so that the water dipping grades, the soaping fastness, the dry rubbing fastness, the wet rubbing fastness and the water contact angle of the fabrics in comparative example 1 and comparative example 2 are smaller than those of the fabrics in the examples of the invention, and the rolling angle is larger than those of the fabrics in the examples of the invention. The fabrics prepared in comparative examples 1 and 2 do not have long-lasting hydrophobic properties and do not have self-cleaning effect.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (10)
1. The preparation method of the long-acting super-hydrophobic fabric is characterized by comprising the following steps of:
(1) Raw material selection: selecting at least two hydrophobic fibers with different heat shrinkage rates as raw materials;
(2) Spinning and weaving: slicing the raw materials, performing melt spinning, preparing radial composite fibers and weaving the radial composite fibers into fabrics;
(3) And (3) heat treatment: carrying out heat treatment on the fabric in a relaxed state to prepare the fabric with the micrometer structure;
(4) Plasma etching: carrying out plasma etching on the fabric with the micrometer structure to prepare the fabric with the micro-nano double-layer structure;
(5) Modification: and immersing the fabric with the micro-nano double-layer structure in a hydrophobic finishing agent for grafting modification to prepare the long-acting super-hydrophobic fabric.
2. The method of producing a long-lasting super-hydrophobic fabric according to claim 1, wherein the difference in heat shrinkage between the hydrophobic fibers as a raw material is not less than 5%.
3. The method for preparing a long-acting superhydrophobic fabric according to claim 1, wherein in the step (2), the radial composite fiber is hollow fiber and/or non-hollow fiber;
And/or when the raw materials are two kinds of fibers, the parts of the two kinds of fibers in the radial composite fiber cross-section structure are X and X, or X and (X+1), wherein X is a positive integer greater than 3.
4. The method for preparing the long-acting superhydrophobic fabric according to claim 1, wherein in the step (3), the heat treatment temperature is 95-100 ℃;
and/or the heat treatment time is 15-20 min.
5. The method for preparing the long-acting superhydrophobic fabric according to claim 1, wherein the plasma etching in the step (4) is electron cyclotron resonance plasma etching.
6. The method for preparing the long-acting super-hydrophobic fabric according to claim 1, wherein the hydrophobic finishing agent in the step (5) is fluorinated polyacrylate emulsion or fluorinated polyurethane containing short-chain perfluorohexyl chain segments.
7. The method for preparing a long-acting superhydrophobic fabric according to claim 1, wherein in the step (5), the mass concentration of the hydrophobic finishing agent is 1.5-2.5 g/L.
8. The method for preparing the long-acting superhydrophobic fabric according to claim 1, wherein the fabric prepared in the step (2) is a high-count high-density fabric.
9. The long-acting superhydrophobic fabric prepared by the preparation method of the long-acting superhydrophobic fabric according to any one of claims 1 to 8.
10. The long-acting superhydrophobic fabric according to claim 9, wherein the surface of the fabric has a micro-nano double-layer structure and a hydrophobic film.
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