CN110670363A - Preparation method of flexible wearable conductive spandex/polyurethane composite material - Google Patents

Preparation method of flexible wearable conductive spandex/polyurethane composite material Download PDF

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CN110670363A
CN110670363A CN201910978793.7A CN201910978793A CN110670363A CN 110670363 A CN110670363 A CN 110670363A CN 201910978793 A CN201910978793 A CN 201910978793A CN 110670363 A CN110670363 A CN 110670363A
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spandex
conductive
fibers
composite material
fiber
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洪剑寒
韩潇
胡铖烨
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University of Shaoxing
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/026—Wholly aromatic polyamines
    • C08G73/0266—Polyanilines or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/61—Polyamines polyimines
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01B—MEASURING LENGTH, THICKNESS OR SIMILAR LINEAR DIMENSIONS; MEASURING ANGLES; MEASURING AREAS; MEASURING IRREGULARITIES OF SURFACES OR CONTOURS
    • G01B7/00—Measuring arrangements characterised by the use of electric or magnetic techniques
    • G01B7/16—Measuring arrangements characterised by the use of electric or magnetic techniques for measuring the deformation in a solid, e.g. by resistance strain gauge
    • G01B7/18—Measuring arrangements characterised by the use of electric or magnetic techniques for measuring the deformation in a solid, e.g. by resistance strain gauge using change in resistance
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/38—Polyurethanes

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Abstract

The invention discloses a preparation method of a flexible wearable conductive spandex/polyurethane composite material, which comprises the following steps: step 1, soaking spandex fibers in an aniline monomer for 60 seconds, taking out the spandex fibers, uniformly extruding the spandex fibers, standing the spandex fibers, and determining the mass of adsorbed aniline by means of front and back weighing; step 2, adding ammonium persulfate into doping acid, stirring to form reaction liquid, then adding the spandex obtained in the step 1 into the reaction liquid, sealing, and carrying out gas bath constant-temperature oscillation reaction for 2 hours; step 3, sequentially putting the spandex fiber reacted in the step 2 into tap water and distilled water to wash twice to obtain spandex/polyaniline conductive fiber; and 4, fixing two ends of three equal-length conductive spandex fibers on copper wires by using conductive adhesive, horizontally straightening and placing the fibers on a polytetrafluoroethylene board, pouring an aqueous polyurethane solution onto the fibers, standing for 24 hours, drying in a 40 ℃ oven for 1 hour to form a cured film, and cutting off the redundant part of the polyurethane film to prepare the conductive spandex/polyurethane composite material.

Description

Preparation method of flexible wearable conductive spandex/polyurethane composite material
Technical Field
The invention belongs to the field of functional materials, and particularly relates to a preparation method of a flexible wearable conductive spandex/polyurethane composite material.
Background
The conductive fiber is an important functional fiber and plays an important role in the fields of static elimination, electromagnetic wave absorption and the like. With the continuous progress of the scientific and technological level and the continuous improvement of the requirements of people on the functions of textiles and clothes, the application of the conductive fibers in the fields of stress sensors, gas sensors, humidity sensors, intelligent clothes and the like is more and more emphasized by people. At present, various conductive fibers such as metal fibers, carbon fibers, conductive polymer fibers and the like are applied to sensors and intelligent clothing.
The fiber and the conductive polymer aniline are combined, the advantages of the fiber material, such as small density, light weight, softness and capability of weaving, of a one-dimensional structure are fully utilized, and the PANI has unique advantages in the development of wearable sensors by combining with excellent conductive performance. For example, spandex fiber has excellent elongation and elastic recovery capability, and the acquisition of electric conductivity can enable the spandex fiber to have excellent electric signal transmission capability, so that the spandex fiber is an ideal raw material for a strain sensor. If the LiWen adopts spandex as a base material, after polyaniline is coated on the surface of the base material, the sensing performance of the LiWen is tested, and the LiWen has certain strain sensing capability. However, polyaniline distributed on the surface of the fiber is easily broken and falls off from the surface of the fiber due to the difference between the deformation capacity of the polyaniline and the matrix fiber when being stretched, thereby affecting the sensing repeatability of the polyaniline.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a flexible wearable conductive spandex/polyurethane composite material, which solves the problems that the preparation of fiber materials by fibers and conductive polymers is complicated, a large amount of waste liquid is easily generated, the demand of aniline solution is greatly reduced by adsorbing aniline monomers, the process difficulty is reduced, and the sensing repeatability of the conductive fibers as sensing devices under the condition of large strain is greatly improved.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a preparation method of a flexible wearable conductive spandex/polyurethane composite material comprises the following steps:
step 1, soaking spandex fibers in an aniline monomer for 60 seconds, taking out the spandex fibers, uniformly extruding the spandex fibers, standing the spandex fibers, and determining the mass of adsorbed aniline by means of front and back weighing;
step 2, adding ammonium persulfate into doping acid, stirring to form reaction liquid, then adding the spandex obtained in the step 1 into the reaction liquid, sealing, and carrying out gas bath constant-temperature oscillation reaction for 2 hours;
step 3, sequentially putting the spandex fiber reacted in the step 2 into tap water and distilled water to wash twice to obtain spandex/polyaniline conductive fiber;
and 4, fixing two ends of three equal-length conductive spandex fibers on copper wires by using conductive adhesive, horizontally straightening and placing the fibers on a polytetrafluoroethylene board, pouring an aqueous polyurethane solution onto the fibers, standing for 24 hours, drying in a 40 ℃ oven for 1 hour to form a cured film, and cutting off the redundant part of the polyurethane film to prepare the conductive spandex/polyurethane composite material.
The mass ratio of the spandex fiber to the aniline in the step 1 is 1: 1.
The concentration of the ammonium persulfate in the step 2 in the reaction liquid is 30g/L, the doping acid is hydrochloric acid, and the concentration in the reaction liquid is 10 mol/L.
The volume mass ratio of the reaction liquid in the step 2 to the mass of the aniline adsorbed in the step 1 is 100mL:1 g.
The temperature of the gas bath constant temperature oscillation reaction in the step 2 is 22 ℃.
And (3) placing the spandex/polyaniline conductive fiber in the step (3) in a constant-temperature and constant-humidity chamber for more than 24 hours for humidifying, wherein the temperature of the constant-temperature and constant-humidity chamber is 20 ℃, and the humidity is 65%.
The parameters of the conductive spandex/polyurethane composite material in the step 4 are as follows: the distance between copper wires is 100mm, the width is 8mm, and the thickness is 0.8 mm.
From the above description, it can be seen that the present invention has the following advantages:
1. the problems that the preparation of fiber materials by fibers and conductive polymers is complicated and a large amount of waste liquid is easily generated are solved, the demand of aniline solution is greatly reduced by adsorbing aniline monomers, the process difficulty is reduced, and the sensing repeatability of the conductive fibers as sensing devices under the condition of large strain is greatly improved.
2. According to the invention, a compact polyaniline conductive layer is formed on the surface of the spandex fiber by adopting an in-situ polymerization method, so that the spandex is endowed with excellent conductivity, and the conductivity of the spandex can reach 0.6S/cm.
3. The conductive spandex/polyurethane composite material has better strain sensing repeatability than a pure conductive spandex fiber, solves the problem of easy cracking in the stretching process of the conductive spandex, and utilizes the elasticity of polyurethane to form a good protection effect on polyaniline.
Drawings
FIG. 1 is a scanning electron microscope image of spandex fibers of an embodiment of the invention before and after conductive treatment;
FIG. 2 is an infrared spectrum of the composite fiber before and after the conductive treatment;
fig. 3 is a graph of the resistance change of conductive spandex under 10%, 20%, 50%, and 100% reciprocating stretch-recovery.
Fig. 4 shows the change of the polyaniline structure on the surface of the spandex/polyaniline composite conductive fiber after multiple times of stretching.
Fig. 5 is a graph of the strain sensing performance of the conductive spandex/polyurethane composite under conditions of 10% strain and 100% strain.
Detailed Description
An embodiment of the present invention is described in detail with reference to fig. 1 to 4, but the present invention is not limited in any way by the claims.
Example 1
Weighing spandex fibers, placing the spandex fibers in an aniline monomer, soaking for 60s, taking out, uniformly extruding the spandex fibers, controlling the mass ratio of the spandex fibers to the aniline monomer to be 1:1, and standing the extruded spandex fibers in a beaker for 2h to enable the spandex fibers to fully adsorb the aniline monomer. Weighing the mass of the spandex fiber adsorbed with the aniline monomer after 2 hours, and subtracting the original mass of the spandex fiber to obtain the mass of the adsorbed aniline.
Ammonium persulfate is used as an oxidant, and hydrochloric acid is used as doping acid to prepare a reaction solution. The concentration of ammonium persulfate in the reaction liquid is 30g/L, the concentration of hydrochloric acid is 1.0mol/L, and the mass-volume ratio of An to the reaction liquid is 1 g: 100 ml. And putting the spandex fiber into the reaction liquid, sealing the beaker, and putting the beaker into a 24-DEG C gas bath constant-temperature oscillator for uniform oscillation to ensure that the aniline monomer and the reaction liquid fully react.
And taking out the spandex fiber in the reaction solution after 2 hours, washing twice with tap water, and then washing twice with deionized water to remove suspended matters on the surface of the fiber.
And finally, placing the prepared spandex/polyaniline composite conductive fiber for natural drying, and then placing the spandex/polyaniline composite conductive fiber in a constant temperature and humidity chamber for humidifying for more than 24 hours for later use.
Fixing two ends of three isometric conductive spandex fibers on copper wires by conductive adhesive, horizontally straightening and placing the conductive spandex fibers on a polytetrafluoroethylene board, pouring an aqueous polyurethane solution onto the fibers to enable the aqueous polyurethane solution to completely wrap the conductive spandex fibers and the copper wires, standing for 24 hours, drying for 1 hour in a 40-DEG C oven to enable polyurethane to be dried into a film, cutting off the redundant part of the polyurethane film, and preparing the conductive spandex/polyurethane composite material, wherein the distance between the copper wires is 100mm, the width is 8mm, and the thickness is 0.8 mm.
Performance detection
FIG. 1 shows the surface topography of spandex before and after conductive treatment. The untreated spandex fiber has a smooth surface and is cylindrical. After in-situ polymerization treatment, a layer of film is attached to the surface of the fiber, and the film consists of particles, has a compact structure and completely coats the spandex fiber.
FIG. 2 is an infrared spectrum of the composite fiber before and after the conductive treatment. Compared with untreated spandex, the spandex/polyaniline composite conductive fiber after conductive treatment still contains the characteristic peak of the spandex fiber and is 1296.08cm at the same time-1，1136.07cm-1And 819.09cm-1New characteristic peaks appear. The three characteristic peaks respectively correspond to C-N stretching vibration, in-plane bending vibration of a benzene ring and C-H out-of-plane bending vibration of a 1, 4-substituted benzene ring. Although polyaniline corresponds to 1500cm-1Stretching vibration peak sum of left and right benzene type structure N-B-N1600 cm-1Left and right quinoid structures N ═The stretching vibration peak of Q-N is covered by the characteristic peak of spandex, but the three obvious characteristic peaks can still prove that the film generated on the surface of the fiber is polyaniline.
After the surface of the spandex fiber is coated with polyaniline, the spandex fiber obtains conductive performance, and the conductivity is from 10-10～10-9The S/cm is improved to 6.26 multiplied by 10-1S/cm, improved by 8-9 orders of magnitude, as shown in the following table:
number of tests Resistance value/omega conductivity/S.cm-1
1 2.53×104 5.85×10-1
2 2.65×104 5.59×10-1
3 2.68×104 5.53×10-1
4 2.65×104 5.59×10-1
5 2.06×104 7.19×10-1
6 2.01×104 7.37×10-1
7 1.94×104 7.64×10-1
8 2.32×104 6.39×10-1
9 2.83×104 5.23×10-1
10 2.40×104 6.17×10-1
Mean value of 2.41×104 6.26×10-1
Fig. 3 is a graph of the resistance change of conductive spandex under 10%, 20%, 50%, and 100% reciprocating stretch-recovery. In the figure R0Is the initial resistance value of the conductive fiber before stretching, R is the real-time change value of the resistance, R/R0Is a multiple of the resistance change. It can be seen that the resistance increases with the elongation of spandex, and after the spandex is recovered by elongation, the resistance decreases again, showing unidirectional sensing performance.
Conducting stretch-recovery circulation on conductive spandex for 1, 5, 10 and 20 times under four different strain conditions to obtain R/R0The changes in (A) are shown in the following table. As can be seen from fig. 3 and the following table, when the strain is 10%, the initial stretching increases the resistance to 2.38 times the initial value, and after returning to the original length, the resistance value is 1.73 times the original value, and the resistance value cannot return to the initial value. R/R after 10 cycles of stretch-cycling0The value is basically stabilized at 1.7-1.8 times, and the recovery time is 1.4-1.5 times. It can be seen that under the 10% cyclic stretch recovery effect, the resistance value of the conductive spandex fiber is basically stable in a certain range, and the conductive spandex fiber has better strain sensing repeatability.
Figure BDA0002234514180000051
As the strain of the fiber increases, it can be seen that the strain sensing repeatability of the conductive spandex is significantly reduced. When the strain is 20%, R/R increases with the number of times of stretching0The value increased from 5.91 times the initial draw to 8.98 times the 20 draws, and the R/R after fiber recovery0The value also increased from 1.39 times of the first recovery to 3.59 times of the 20 th recovery; R/R after 10 elongations at 100% strain0The value is increased to 238.8 times, the value is improved by 300 percent compared with 60.07 times of the initial stretching, and the R/R is recovered after 10 times of stretching0The value is 28.56 times and only 2.78 times after the initial stretch recovery, indicating that the greater the strain, the poorer the ability of the conductive spandex to recover to its initial resistance value, i.e., the poorer its strain sensing repeatability.
Due to the pi conjugated structure, the polyaniline macromolecules have high rigidity and small breaking elongation of about 2%, and when the strain exceeds the limit value, the polyaniline film on the surface of the fiber is easy to break, so that the carrier channel is interrupted, and the resistance is increased.
After multiple times of stretching, the change condition of the polyaniline structure on the surface of the spandex/polyaniline composite conductive fiber is shown in fig. 4, when the strain is 10%, it can be seen that some fine cracks are generated on the polyaniline film, but the cracks do not have great influence on the whole structure of the film, and the film still keeps a fine and complete structure; when the strain is 20%, the cracks of the polyaniline film are increased, the structural roughness of the surface is improved, a more obvious granular structure is presented, and the gaps among the granules are smaller; when the strain is 50%, the granular structure of the polyaniline film is further enhanced, and gaps among granules are obviously increased when the polyaniline film is stretched by 20%; when the strain is 100%, the polyaniline film structure is further damaged, and the number of cracks, the granular structure and gaps among granules are obviously increased and improved. The damage of the polyaniline film structure causes the reduction of the conductive capability of the polyaniline film structure, and the polyaniline film structure is difficult to recover when the fiber is deformed and recovered, so that the larger the elongation is, the larger the resistance of the stretched fiber is, namely, the smaller the repeatability of the strain sensing performance of the fiber is. It can also be inferred from the resistance change that the destruction of the polyaniline conductive layer has a cumulative effect, the more the number of times of stretching, the greater the destruction of the conductive layer, and the more this cumulative destruction is evident at higher strains.
The polyaniline conductive layer on the surface of the conductive spandex fiber is protected by polyurethane to prepare the conductive spandex/polyurethane composite material, and the strain sensing performance is shown in fig. 5 under the conditions that the strain is 10% and 100%. As can be seen from the graph, when the strain is 10%, the R/R0 value of the composite material is basically stabilized at about 1.5 after the composite material is stretched for multiple times, and the R/R0 value of the composite material is basically stabilized at about 1.25 after the composite material is stretched and recovered, compared with conductive spandex, the strain sensing repeatability of the composite material is improved, but the change is small; at 100% strain, the R/R0 values of the composite material in the first stretching and the first recovery are 60 and 2.77 respectively, which are close to that of conductive spandex, but after multiple stretching, the resistance change of the composite material and the conductive spandex fiber is greatly different, and although the resistance of the composite material shows an increasing trend along with the increase of the stretching times, the change range of the resistance change is much smaller than that of the conductive spandex, for example, the resistance value after 10 times of stretching is 87 times of the original value, and the resistance value after 10 times of stretching is 15.5 times of the original value, while the resistance value of the conductive spandex fiber under the same conditions is 238.8 times and 28.56 times respectively.
The polyurethane has excellent elasticity, and wraps polyaniline on the surface of spandex fibers, so that the polyaniline is well protected during stretching. Although the breakage of polyaniline is still unavoidable during stretching, the position of the polyaniline can be relatively fixed in the polyurethane, and when the polyaniline is stretched and recovered, the polyaniline can still be recovered to the original position, so that the chance of the polyaniline breakage structure to be contacted again is increased, the cumulative effect of polyaniline damage is relieved or avoided, and the polyaniline fiber has better strain sensing repeatability than the conductive spandex fiber.
In summary, the invention has the following advantages:
1. the invention solves the problems that the preparation of fiber materials by fibers and conductive polymers is complicated and a large amount of waste liquid is easily generated, greatly reduces the demand of aniline solution by adsorbing aniline monomers, reduces the process difficulty, and simultaneously greatly improves the sensing repeatability of the conductive fibers as sensing devices under the condition of large strain.
2. According to the invention, a compact polyaniline conductive layer is formed on the surface of the spandex fiber by adopting an in-situ polymerization method, so that the spandex is endowed with excellent conductivity, and the conductivity of the spandex can reach 0.6S/cm.
3. The conductive spandex/polyurethane composite material has better strain sensing repeatability than a pure conductive spandex fiber, solves the problem of easy cracking in the stretching process of the conductive spandex, and utilizes the elasticity of polyurethane to form a good protection effect on polyaniline.
It should be understood that the detailed description of the invention is merely illustrative of the invention and is not intended to limit the invention to the specific embodiments described. It will be appreciated by those skilled in the art that the present invention may be modified or substituted equally as well to achieve the same technical result; as long as the use requirements are met, the method is within the protection scope of the invention.

Claims (7)

1. A preparation method of a flexible wearable conductive spandex/polyurethane composite material is characterized by comprising the following steps: the method comprises the following steps:
step 1, soaking spandex fibers in an aniline monomer for 60 seconds, taking out the spandex fibers, uniformly extruding the spandex fibers, standing the spandex fibers, and determining the mass of adsorbed aniline by means of front and back weighing;
step 2, adding ammonium persulfate into doping acid, stirring to form reaction liquid, then adding the spandex obtained in the step 1 into the reaction liquid, sealing, and carrying out gas bath constant-temperature oscillation reaction for 2 hours;
step 3, sequentially putting the spandex fiber reacted in the step 2 into tap water and distilled water to wash twice to obtain spandex/polyaniline conductive fiber;
and 4, fixing two ends of three equal-length conductive spandex fibers on copper wires by using conductive adhesive, horizontally straightening and placing the fibers on a polytetrafluoroethylene board, pouring an aqueous polyurethane solution onto the fibers, standing for 24 hours, drying in a 40 ℃ oven for 1 hour to form a cured film, and cutting off the redundant part of the polyurethane film to prepare the conductive spandex/polyurethane composite material.
2. The preparation method of the flexible wearable conductive spandex/polyurethane composite material according to claim 1, characterized in that: the mass ratio of the spandex fiber to the aniline in the step 1 is 1: 1.
3. The preparation method of the flexible wearable conductive spandex/polyurethane composite material according to claim 1, characterized in that: the concentration of the ammonium persulfate in the step 2 in the reaction liquid is 30g/L, the doping acid is hydrochloric acid, and the concentration in the reaction liquid is 10 mol/L.
4. The preparation method of the flexible wearable conductive spandex/polyurethane composite material according to claim 1, characterized in that: the volume mass ratio of the reaction liquid in the step 2 to the mass of the aniline adsorbed in the step 1 is 100mL:1 g.
5. The preparation method of the flexible wearable conductive spandex/polyurethane composite material according to claim 1, characterized in that: the temperature of the gas bath constant temperature oscillation reaction in the step 2 is 22 ℃.
6. The preparation method of the flexible wearable conductive spandex/polyurethane composite material according to claim 1, characterized in that: and (3) placing the spandex/polyaniline conductive fiber in the step (3) in a constant-temperature and constant-humidity chamber for more than 24 hours for humidifying, wherein the temperature of the constant-temperature and constant-humidity chamber is 20 ℃, and the humidity is 65%.
7. The preparation method of the flexible wearable conductive spandex/polyurethane composite material according to claim 1, characterized in that: the parameters of the conductive spandex/polyurethane composite material in the step 4 are as follows: the distance between copper wires is 100mm, the width is 8mm, and the thickness is 0.8 mm.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115182091A (en) * 2022-07-19 2022-10-14 希纺新材料发展(南通)有限公司 Novel extremely-soft extremely-pasted milk skin velvet high-performance material and production method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115182091A (en) * 2022-07-19 2022-10-14 希纺新材料发展(南通)有限公司 Novel extremely-soft extremely-pasted milk skin velvet high-performance material and production method thereof

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