CN114622406A - Piezoresistive yarn preparation method and piezoresistive yarn prepared by piezoresistive yarn preparation method - Google Patents

Piezoresistive yarn preparation method and piezoresistive yarn prepared by piezoresistive yarn preparation method Download PDF

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CN114622406A
CN114622406A CN202210304067.9A CN202210304067A CN114622406A CN 114622406 A CN114622406 A CN 114622406A CN 202210304067 A CN202210304067 A CN 202210304067A CN 114622406 A CN114622406 A CN 114622406A
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piezoresistive
yarn
coating
storage tank
preparation
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CN114622406B (en
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罗屹东
王国忠
李玉柱
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Kunshan Shuimu Yuankun Technology Co.,Ltd.
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Foshan Southern China Institute For New Materials
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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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/44—Yarns or threads characterised by the purpose for which they are designed
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
    • D—TEXTILES; PAPER
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    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
    • D06M13/2246—Esters of unsaturated carboxylic acids
    • 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
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides 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
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D06M15/05—Cellulose or derivatives thereof
    • D06M15/09—Cellulose ethers
    • 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
    • G01L1/00—Measuring force or stress, in general
    • G01L1/18—Measuring force or stress, in general using properties of piezo-resistive materials, i.e. materials of which the ohmic resistance varies according to changes in magnitude or direction of force applied to the material
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    • 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
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
    • D06M2101/28—Acrylonitrile; Methacrylonitrile
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    • 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
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    • 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
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    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/50—Modified hand or grip properties; Softening compositions

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The invention discloses a preparation method of piezoresistive yarns, which comprises the following steps: mixing a conductive filler with 20-60 wt% of polyurethane aqueous dispersion, performing ultrasonic treatment for 10-120 min, adding a curing agent, stirring at 300-3000 r/min, and adding a thickening agent to obtain piezoresistive coating liquid; pouring piezoresistive coating liquid into a liquid storage tank, enabling a yarn base material to penetrate through the liquid storage tank, and coating a wet coating on the surface of the yarn base material; placing the yarn base material coated with the wet coating on the surface at 100-150 ℃ for 5-60 s, winding at the speed of 0.5-30m/min, heating to 50-80 ℃, and drying for 0.5-5 h to obtain the piezoresistive yarn; the circular needle tubes at the upper and lower outlets of the liquid storage tank are 0.1-5 mm; the thickness of the wet coating is 0.01-0.5 mm; the viscosity of the piezoresistive coating liquid is 500-5000 cps; the apparent resistance value of the piezoresistive yarn is 200-. The preparation method provided by the invention is operated in a water-based system, the process is simple, the used materials are environment-friendly and pollution-free, the low-cost large-scale preparation is facilitated, and the obtained piezoresistive yarns are good in flexibility, high in piezoresistive sensitivity, and water-resistant and alcohol-resistant.

Description

Piezoresistive yarn preparation method and piezoresistive yarn prepared by same
Technical Field
The invention relates to the field of preparation of functional yarn coatings, in particular to a piezoresistive yarn preparation method and piezoresistive yarn prepared by the piezoresistive yarn preparation method.
Background
The resistance type touch sensor responds to the position and the size of an applied force by utilizing the change of the resistance value of the piezoresistive material in the sensing unit, and the piezoresistive material causes the change of an energy band when being applied with the stress, so that the resistance value is changed.
In the field of intelligent wearability, piezoresistive materials used by the resistive touch sensor can be yarns made of materials such as nylon, polyester, polyacrylonitrile and the like coated with piezoresistive coatings. The piezoresistive coating is prepared by dispersing micro-nano conductive particles or powder in a high polymer resin system, in the preparation process, most of carrier resin used in the conductive coating is single-component or double-component acrylate resin, organic silicon resin and the like, and the content of the conductive particles or powder used in the piezoresistive coating is higher, so that the problem that the alcohol resistance and the washing resistance of the yarn coated with the piezoresistive coating are poor is solved. In the preparation process, if the carrier resin is organic silicon resin, the formula of the organic silicon resin has the advantages of softness and skin friendliness, but the problems of high viscosity of a formula system, difficulty in uniform dispersion of conductive particles or powder, more bubbles and long-time high-temperature curing are solved; in the preparation process, when acrylate resin is used, the cured or dried piezoresistive coating has the problems of higher hardness, poor skin-friendly property, poor adhesion and poor piezoresistive sensitivity.
Disclosure of Invention
Based on this, in order to solve one of the above problems, the first aspect of the present invention provides a piezoresistive yarn manufacturing method, which has the following specific technical scheme:
a preparation method of piezoresistive yarns is characterized by comprising the following steps:
mixing a conductive filler with 20-60 wt% of polyurethane aqueous dispersion, then carrying out ultrasonic treatment for 10-120 min, adding a curing agent, stirring at a rotating speed of 300-3000 r/min for 30min-2h, and then adding a thickening agent to obtain piezoresistive coating liquid;
pouring the piezoresistive coating liquid into a liquid storage tank, and enabling the yarn substrate to penetrate through the liquid storage tank to obtain the yarn substrate coated with the wet coating;
placing the yarn base material coated with the wet coating on the surface at the temperature of 100-150 ℃ for 5-60 s, then winding the yarn base material coated with the wet coating on the surface at the speed of 0.5-30m/min, and then placing the yarn base material at the temperature of 50-80 ℃ for drying for 0.5-5 h to obtain the piezoresistive yarn;
the circular needle tubes at the upper and lower outlets of the liquid storage tank are 0.1-5 mm;
the thickness of the wet coating is 0.01-0.5 mm;
the viscosity of the piezoresistive coating liquid is 500-5000 cps;
the apparent resistance value of the piezoresistive yarn is 200-.
Further, the curing agent is one or more of di (propylene glycol) allyl ether acrylate, ethylene glycol dicyclopentenyl ether acrylate, di (propylene glycol) allyl ether methacrylate and ethylene glycol dicyclopentenyl ether methacrylate;
further, the mass of the curing agent is 0.3-5 wt% of the total mass of the polyurethane aqueous dispersion.
Further, the thickening agent is one or more of carboxymethyl cellulose, guar gum and hydrophobic modified polyurethane;
further, the mass of the thickening agent is 0.1-3 wt% of the total mass of the polyurethane aqueous dispersion.
Further, the conductive filler is one or more of conductive carbon black, graphite, conductive metal powder, graphene and carbon nanotubes.
Further, the particle diameters of the conductive carbon black, the graphite and the conductive metal powder are respectively and independently 0.5-100 μm, and the solid contents of the graphene and the carbon nano tube are respectively and independently 10-50 wt%.
Further, the yarn base material is one of nylon, polyester and polypropylene.
Further, the speed of the winding process is 0.5-30 m/min.
In a second aspect, the technical scheme also provides the piezoresistive yarn prepared by the preparation method.
In a third aspect, the present technical solution further provides a piezoresistive sensor, including a sensor body and an electrode, where the sensor body is woven by the piezoresistive yarn.
The preparation method is operated in a water-based system, has simple process, uses materials which are environment-friendly and pollution-free, and is beneficial to preparing the piezoresistive yarns with piezoresistive effect in a large scale at low cost; the piezoresistive yarn obtained by the invention has good flexibility, high piezoresistive sensitivity, and water and alcohol resistance. In addition, the piezoresistive yarn is prepared by using a 20-60 wt% polyurethane aqueous dispersion system, so that the piezoresistive yarn with excellent alcohol resistance and piezoresistive sensitivity can be obtained.
Drawings
FIG. 1 is a schematic microscopic view of a piezoresistive yarn prepared in example 1 of the present invention;
FIG. 2 is a schematic representation of a piezoresistive yarn made according to example 1 of the present invention;
FIG. 3 is a schematic diagram of the piezoresistive effect of piezoresistive yarn prepared in example 1 of the present invention in the pressure range of 0.5-20N;
fig. 4 is a schematic diagram of a wash water test sample of piezoresistive yarn prepared according to example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to embodiments thereof. It should be understood that the detailed description and specific examples, while indicating the scope of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In one aspect, in an embodiment of the present invention, a method for manufacturing piezoresistive yarns includes:
a method of making a piezoresistive yarn, the method comprising:
mixing a conductive filler with 20-60 wt% of polyurethane aqueous dispersion, performing ultrasonic treatment for 10-120 min, adding a curing agent, stirring at 300-3000 r/min, and adding a thickening agent to obtain piezoresistive coating liquid;
pouring the piezoresistive coating liquid into a liquid storage tank, enabling a yarn substrate to penetrate through the liquid storage tank, and coating a wet coating on the surface of the yarn substrate;
placing the yarn base material coated with the wet coating at 100-150 ℃ for surface drying for 5-60 s, winding at the speed of 0.5-30m/min, heating to 50-80 ℃, and drying for 0.5-5 h to obtain the piezoresistive yarn;
the circular needle tubes at the upper and lower outlets of the liquid storage tank are 0.1-5 mm;
the thickness of the wet coating is 0.01-0.5 mm;
the viscosity of the piezoresistive coating liquid is 500-5000 cps;
the apparent resistance value of the piezoresistive yarn is 200-.
In one embodiment, preferably, the apparent resistance value of the piezoresistive yarn is 1000-; further preferably, the apparent resistance value of the piezoresistive yarn is 2000-5000 omega;
the resistance value of the piezoresistive yarn obtained by the preparation method provided by the invention is controlled at 200-.
In one embodiment, the curing agent is one or more of di (propylene glycol) allyl ether acrylate, ethylene glycol dicyclopentenyl ether acrylate, di (propylene glycol) allyl ether methacrylate, and ethylene glycol dicyclopentenyl ether methacrylate; the curing agent is added, so that the washing water resistance and the alcohol resistance of the piezoresistive coating are improved, and the flexibility of the coating is not influenced.
In one embodiment, the mass of the curing agent is 0.3-5 wt% based on the total mass of the polyurethane aqueous dispersion; preferably, the mass of the curing agent is 0.5-4 wt% of the total mass of the polyurethane aqueous dispersion; more preferably, the mass of the curing agent is 1-3 wt% of the total mass of the polyurethane aqueous dispersion.
In one embodiment, the thickener is one or more of carboxymethyl cellulose, guar gum, and hydrophobically modified polyurethane;
in one embodiment, the mass of the thickening agent is 0.1-3 wt% of the total mass of the polyurethane aqueous dispersion;
in one embodiment, the conductive filler is one or more of conductive carbon black, graphite, conductive metal powder, graphene, carbon nanotubes; the content of the conductive filler is 10-150 wt% based on the total mass of the polyurethane aqueous dispersion; preferably, the content of the conductive filler is 20-120 wt% based on the total mass of the polyurethane aqueous dispersion.
In one embodiment, the conductive carbon black, the graphite and the conductive metal powder each independently have a particle size of 0.5 to 100 μm.
In one embodiment, the graphene is prepared for use as a graphene dispersion; the carbon nanotube is prepared to be used as a carbon nanotube dispersion liquid, and the solid contents of the graphene dispersion liquid and the carbon nanotube dispersion liquid are respectively and independently 10-50 wt%.
In one embodiment, the yarn substrate is one of nylon, polyester, and polypropylene.
In one embodiment, the winding speed is 0.5-30 m/min; preferably, the winding speed is 2-20 m/min; further preferably, the winding speed is 5-15 m/min;
according to the preparation method provided by the invention, the winding speed is too high, so that the piezoresistive coating is not completely dried, and continuous production is difficult.
In one embodiment, the viscosity of the piezoresistive coating liquid is 500-; preferably, the viscosity of the piezoresistive coating liquid is 1000-3000 cps; further preferably, the viscosity of the piezoresistive coating liquid is 1500-;
according to the preparation method provided by the invention, the proper thickener is added into the waterborne polyurethane formula system, the viscosity is controlled to be 500-5000cps, the piezoresistive wet coating can be uniformly spread when the yarn is coated, the coating liquid is not easy to gather, and the stability of the obtained piezoresistive yarn is greatly improved.
In a second aspect, the technical scheme also provides the piezoresistive yarn prepared by the preparation method.
In a third aspect, the present technical solution further provides a piezoresistive sensor, including a sensor body and an electrode, where the sensor body includes the piezoresistive yarn.
Embodiments of the present invention will be described in detail below with reference to specific examples.
Example 1:
a preparation method of piezoresistive yarns comprises the following specific steps:
adding conductive carbon black with the particle size of 100 mu m into 20 percent of polyurethane aqueous dispersion, wherein the weight of the conductive carbon black is 30 percent of that of the polyurethane aqueous dispersion, carrying out ultrasonic treatment for 30min, then adding di (propylene glycol) allyl ether acrylate with the dosage of 2 percent of that of the polyurethane aqueous dispersion, stirring for 30min at the rotating speed of 3000r/min, adding carboxymethyl cellulose with the dosage of 0.1 percent of that of the polyurethane aqueous dispersion in the process, and controlling the viscosity of a formula system to be 500cps to obtain piezoresistive coating liquid;
fixing a liquid storage tank on a bracket, pouring the prepared piezoresistive coating liquid into the liquid storage tank, wherein the upper outlet and the lower outlet of the liquid storage tank use circular needle tubes with the diameter of 0.1mm, the yarn uses 120D-2 strands of nylon yarn, and the thickness of the piezoresistive coating is 0.01 mm;
setting the temperature of the oven to 150 ℃, and quickly drying the yarn in the oven within 30 seconds after the yarn passes through the liquid storage tank;
winding the surface-dried yarn on a yarn drum, wherein the winding speed is controlled at 5 m/min;
and (3) placing the wound yarn in an oven at 50 ℃ for continuous drying for 5h to obtain the piezoresistive yarn with piezoresistive effect.
Example 2:
a preparation method of piezoresistive yarns comprises the following specific steps:
adding a graphene dispersion liquid with a solid content of 50% into a polyurethane aqueous dispersion liquid with a solid content of 40%, carrying out ultrasonic treatment for 10min, then adding di (propylene glycol) allyl ether acrylate with an amount of 2% of the weight of the polyurethane aqueous dispersion liquid, stirring for 2h at a rotating speed of 300r/min, adding 3% of hydrophobic modified polyurethane with an amount of 3% of the weight of the polyurethane aqueous dispersion liquid, and controlling the viscosity of a formula system to be 5000cps to obtain a piezoresistive coating liquid;
fixing a liquid storage tank on a bracket, pouring the prepared piezoresistive coating liquid into the liquid storage tank, wherein the upper outlet and the lower outlet of the liquid storage tank use circular needle tubes with the diameter of 0.5mm, the yarn uses 100D-5 strands of polyester yarn, and the thickness of the piezoresistive coating is 0.2 mm;
setting the temperature of the drying tunnel to be 100 ℃, and quickly drying the yarns in 60 seconds after the yarns pass through the liquid storage tank;
winding the surface-dried yarn on a yarn drum, wherein the winding speed is controlled at 30 m/min;
and (3) placing the wound yarn in an oven at 80 ℃ for continuous drying for 0.5h to obtain the piezoresistive yarn with piezoresistive effect.
Example 3:
a method for preparing piezoresistive yarns comprises the following specific steps:
adding conductive copper powder with the particle size of 10 mu m into 20% of solid polyurethane aqueous dispersion, carrying out ultrasonic treatment for 120min, then adding 3% of dipropylene glycol allyl ether methacrylate based on the weight of the polyurethane aqueous dispersion, stirring at the rotating speed of 1000r/min for 1h, adding guar gum based on 1% of the weight of the polyurethane aqueous dispersion in the process, controlling the viscosity of a formula system to be 2000cps, and obtaining piezoresistive coating liquid;
fixing a liquid storage tank on a bracket, pouring the prepared piezoresistive coating liquid into the liquid storage tank, wherein the upper outlet and the lower outlet of the liquid storage tank use circular needle tubes with the diameter of 0.5mm, the yarn uses 100D-5 strands of polyacrylonitrile yarn, and the thickness of the piezoresistive coating is 0.5 mm;
setting the temperature of the oven to 120 ℃, and quickly drying the yarn in the oven within 30 seconds after the yarn passes through the liquid storage tank;
winding the surface-dried yarn on a yarn drum, wherein the winding speed is controlled at 10 m/min;
and (3) placing the wound yarn in an oven at 60 ℃ to continuously dry for 2h, and finally obtaining the piezoresistive yarn with piezoresistive effect.
Example 4:
a preparation method of piezoresistive yarns comprises the following specific steps:
adding a carbon nanotube dispersion liquid with solid content of 10% into a polyurethane aqueous dispersion liquid with solid content of 60%, wherein the weight of the carbon nanotube dispersion liquid is 150% of that of the polyurethane aqueous dispersion liquid, carrying out ultrasonic treatment for 30min, then adding ethylene glycol dicyclopentenyl ether methacrylate with the dosage of 1% of that of the polyurethane aqueous dispersion liquid, stirring at the rotating speed of 800r/min for 1h, then adding hydrophobic modified polyurethane with the dosage of 0.5% of that of the polyurethane aqueous dispersion liquid, and controlling the viscosity of a formula system to be 3000cps to obtain a piezoresistive coating liquid;
fixing a liquid storage tank on a bracket, pouring the prepared piezoresistive coating liquid into the liquid storage tank, wherein the upper outlet and the lower outlet of the liquid storage tank use circular needle tubes with the diameter of 0.3mm, the yarn uses 120D-3 strands of nylon yarn, and the thickness of the piezoresistive coating is 0.1 mm;
the preparation method comprises the following steps of (1); the temperature of the oven is set to be 120 ℃, and the yarn passes through the liquid storage tank and then is quickly dried in the oven within 30 seconds;
winding the surface-dried yarn on a yarn drum, wherein the winding speed is controlled at 5 m/min;
after the preparation is finished, the wound yarn is placed in an oven at 60 ℃ for continuous drying for 2h, and finally the piezoresistive yarn with piezoresistive effect is obtained.
Comparative example 1:
the difference from example 1 is that the aqueous polyurethane dispersion is changed to a 20% aqueous polyacrylate dispersion.
Comparative example 2:
the difference from example 2 is that MDI (diphenylmethane diisocyanate), a common curing agent for polyurethane systems, is used in an amount of 2% by weight based on the weight of the aqueous polyurethane dispersion.
Comparative example 3:
the difference from example 2 is that the winding speed was controlled at 40 m/min.
Comparative example 4:
the difference from example 3 is that the viscosity of the piezoresistive coating layer coating liquid is controlled to 200cps after the thickener is added.
The above examples and comparative examples were subjected to the following performance tests:
performance test 1: the water wash test was performed by stitching piezoresistive yarns on a woven fabric, as shown in fig. 4, and performing one or more water washes according to AATCC-612013, after which the appearance of the piezoresistive coating was evaluated, with a no-break rating of 5, a very slight-break rating of 4, a slight-break rating of 3, a local crack rating of 2, and a coating-to-yarn peel rating of 1.
Performance test 2: and (4) alcohol resistance testing, namely immersing the piezoresistive yarns in 99% pure alcohol for 3min, and taking out to evaluate the integrity of the coating.
Performance test 3: and (3) testing dry rubbing fastness, namely sewing the piezoresistive yarns on the woven fabric, and testing the dry rubbing fastness of the piezoresistive yarns according to the test method of GB/T3920-2008.
Performance test 4: performing piezoresistive circulation test, namely sewing piezoresistive yarns on woven fabric in a cross shape, clamping the woven fabric in the upper and lower silica gel square blocks, and placing the woven fabric between the upper and lower pressing heads; the pre-pressurizing force is 1N, and the loading force value is 65N; the loading speed was 3mm/min and held for 10s, and the unloading speed was 3mm/min and held for 5 s. After a certain number of fatigue tests, the sample is taken down, placed for a period of time, the initial resistance of the sample is measured, then a 500g weight is placed on the sensing point, the resistance of the sensing point is measured, and finally the change rate of the resistance measured twice is calculated.
The test results of examples 1 to 5 and comparative examples 1 to 4 are shown in table 1 below.
Table 1:
Figure BDA0003564122930000101
Figure BDA0003564122930000111
from the comparison result of the test performances of the example 1 and the comparative example 1, when the polyurethane aqueous dispersion system with the concentration of 20-60 wt% is used for preparing the piezoresistive yarn, compared with the polyacrylate aqueous dispersion with the concentration of 20% in the comparative example 1, the piezoresistive yarn prepared by the preparation method disclosed by the invention can effectively improve the water resistance, the alcohol resistance, the piezoresistive sensitivity and the dry rubbing fastness, especially the dry rubbing fastness. From the comparison of the test performance of example 2 and comparative example 2, it can be seen that the preparation method of the present invention using di (propylene glycol) allyl ether acrylate as the curing agent can effectively improve the wash fastness, alcohol fastness, piezoresistive sensitivity and pliability, especially alcohol fastness, of the piezoresistive yarn prepared compared to the comparative example 2 using the common curing agent MDI (diphenylmethane diisocyanate) of polyurethane system. From the comparison result of the test performance of the example 2 and the comparative example 3, when the winding speed exceeds 30m/min, the prepared piezoresistive yarn has poor washing fastness, alcohol resistance, piezoresistive sensitivity and flexibility, and the yarn is easy to break during the preparation process, and the piezoresistive coating is not completely dried and is difficult to continuously produce. From the comparison result of the test performance of the example 2 and the comparative example 4, when the viscosity of the piezoresistive coating liquid is lower than 200cps, the prepared piezoresistive yarn has poor water resistance, alcohol resistance, piezoresistive sensitivity and flexibility, and the viscosity of the formula system is too low in the preparation process, the prepared piezoresistive yarn has a rough surface, the piezoresistive coating is difficult to spread uniformly, and the coating liquid is easy to gather and dry and then is distributed in a node shape.
In addition, as can be seen from the analysis of fig. 1 to 4, fig. 1 is a schematic microscopic view of the piezoresistive yarn prepared in example 1 of the present invention; as can be seen from the figure, the piezoresistive coating is uniformly distributed on the surface of the chemical fiber yarn, and the conductive filler is distributed on the piezoresistive coating in a nanoparticle shape; FIG. 3 is a schematic diagram of the piezoresistive effect of piezoresistive yarn produced in example 1 of the present invention in the 0.5-20N force region; from fig. 2, it can be seen that the piezoresistive yarn prepared by the present application has excellent and stable micro-force piezoresistive effect; fig. 4 is a schematic diagram of a water washing test sample of the piezoresistive yarn prepared in example 1 of the present invention, and it can be seen from fig. 4 that the piezoresistive yarn in the present application has excellent water washing resistance, and the flexibility of the piezoresistive yarn is not affected after water washing.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. A preparation method of piezoresistive yarns is characterized by comprising the following steps:
adding a conductive filler into 20-60 wt% of polyurethane aqueous dispersion, uniformly mixing, then carrying out ultrasonic treatment for 10-120 min, adding a curing agent, stirring at a rotating speed of 300-3000 r/min for 30min-2h, and then adding a thickening agent to obtain piezoresistive coating liquid;
pouring the piezoresistive coating liquid into a liquid storage tank, and enabling the yarn substrate to penetrate through the liquid storage tank to obtain the yarn substrate coated with the wet coating;
placing the yarn base material coated with the wet coating on the surface at the temperature of 100-150 ℃ for 5-60 s, then winding the yarn base material coated with the wet coating on the surface at the speed of 0.5-30m/min, and then placing the yarn base material at the temperature of 50-80 ℃ for drying for 0.5-5 h to obtain the piezoresistive yarn;
the circular needle tubes at the upper and lower outlets of the liquid storage tank are 0.1-5 mm;
the thickness of the wet coating is 0.01-0.5 mm;
the viscosity of the piezoresistive coating liquid is 500-5000 cps;
the apparent resistance value of the piezoresistive yarn is 200-.
2. The method of claim 1, wherein the curing agent is one or more of bis (propylene glycol) allyl ether acrylate, ethylene glycol dicyclopentenyl ether acrylate, bis (propylene glycol) allyl ether methacrylate, and ethylene glycol dicyclopentenyl ether methacrylate.
3. The method according to claim 1, wherein the curing agent is present in an amount of 0.3 to 5 wt% based on the total mass of the aqueous polyurethane dispersion.
4. The method of claim 1, wherein the thickener is one or more of carboxymethyl cellulose, guar gum, and hydrophobically modified polyurethane.
5. The method according to claim 1, wherein the thickener is present in an amount of 0.1 to 3 wt% based on the total mass of the aqueous polyurethane dispersion.
6. The preparation method according to claim 1, wherein the conductive filler is one or more of conductive carbon black, graphite, conductive metal powder, graphene, and carbon nanotubes; the content of the conductive filler is 10-150 wt% of the total mass of the polyurethane aqueous dispersion.
7. The method according to claim 6, wherein the particle diameters of the conductive carbon black, the graphite and the conductive metal powder are each independently 0.5 to 100 μm.
8. The method of claim 1, wherein the yarn substrate is one of nylon, polyester, and polypropylene.
9. Piezoresistive yarn produced according to the production method of any of claims 1 to 8.
10. A piezoresistive sensor comprising a sensor body and an electrode, wherein the sensor body comprises a piezoresistive yarn as claimed in claim 9.
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