CN114953669B - Electronic fabric with body temperature warning-unidirectional moisture conducting function and preparation method and application thereof - Google Patents

Electronic fabric with body temperature warning-unidirectional moisture conducting function and preparation method and application thereof Download PDF

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Publication number
CN114953669B
CN114953669B CN202210554359.8A CN202210554359A CN114953669B CN 114953669 B CN114953669 B CN 114953669B CN 202210554359 A CN202210554359 A CN 202210554359A CN 114953669 B CN114953669 B CN 114953669B
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sebs
fabric
layer
spinning
fiber fabric
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CN114953669A (en
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黄云鹏
董建成
彭义东
刘天西
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Jiangnan University
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Jiangnan University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D1/00—Garments
    • A41D1/002—Garments adapted to accommodate electronic equipment
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00—Materials specially adapted for outerwear
    • A41D31/02—Layered materials
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00—Materials specially adapted for outerwear
    • A41D31/04—Materials specially adapted for outerwear characterised by special function or use
    • A41D31/12—Hygroscopic; Water retaining
    • A41D31/125—Moisture handling or wicking function through layered materials
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00—Materials specially adapted for outerwear
    • A41D31/04—Materials specially adapted for outerwear characterised by special function or use
    • A41D31/24—Resistant to mechanical stress, e.g. pierce-proof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/103—Detecting, measuring or recording devices for testing the shape, pattern, colour, size or movement of the body or parts thereof, for diagnostic purposes
    • A61B5/11—Measuring movement of the entire body or parts thereof, e.g. head or hand tremor, mobility of a limb
    • A61B5/1118—Determining activity level
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
    • A61B5/25—Bioelectric electrodes therefor
    • A61B5/251—Means for maintaining electrode contact with the body
    • A61B5/256—Wearable electrodes, e.g. having straps or bands
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
    • A61B5/25—Bioelectric electrodes therefor
    • A61B5/263—Bioelectric electrodes therefor characterised by the electrode materials
    • A61B5/27—Conductive fabrics or textiles
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
    • A61B5/316—Modalities, i.e. specific diagnostic methods
    • A61B5/318—Heart-related electrical modalities, e.g. electrocardiography [ECG]
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
    • A61B5/316—Modalities, i.e. specific diagnostic methods
    • A61B5/389—Electromyography [EMG]
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0008—Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0036—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/08—Impregnating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/162—Cleaning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/164—Drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/56—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of cyclic compounds with one carbon-to-carbon double bond in the side chain
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4282—Addition polymers
    • D04H1/4291—Olefin series
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K11/00—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00
    • G01K11/12—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using changes in colour, translucency or reflectance
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K13/00—Thermometers specially adapted for specific purposes
    • G01K13/20—Clinical contact thermometers for use with humans or animals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0036—Heat treatment
    • B32B2038/0048—Annealing, relaxing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/20—All layers being fibrous or filamentary
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0223—Vinyl resin fibres
    • B32B2262/023—Aromatic vinyl resin, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/51—Elastic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/552—Fatigue strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/71—Resistive to light or to UV
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
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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
    • 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
    • D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups

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Abstract

The invention discloses an electronic fabric with body temperature warning-unidirectional moisture-conducting functions and a preparation method and application thereof, and belongs to the technical field of multifunctional intelligent fabric preparation. The SEBS is used as a base material, the SEBS is processed into the micro-nano fiber fabric with a multi-level pore structure by a multi-layer superposition spinning technology, a wetting gradient is constructed in the multi-layer fabric by utilizing selective plasma treatment, meanwhile, the hybrid carbon nanomaterial is used as a conductive substance, the thermochromic microcapsules are used as color-changing functional particles, and each layer of fiber fabric is respectively modified to prepare the high-elasticity functional electronic fabric with the functions of unidirectional moisture conduction and thermochromic of pore-wetting dual gradients. The electronic fabric obtained by the invention has good electric conductivity and body temperature warning function under the conditions of unidirectional moisture permeability and high stretching rate, and can be applied to the fields of flexible electrodes, wearable electronic devices, intelligent fabrics and the like.

Description

Electronic fabric with body temperature warning-unidirectional moisture conducting function and preparation method and application thereof
Technical Field
The invention belongs to the technical field of multifunctional intelligent fabric preparation, and particularly relates to an electronic fabric with a body temperature warning-unidirectional moisture-conducting function, and a preparation method and application thereof.
Background
In recent years, wearable electronic devices have received more and more attention, and stretchable electronic devices with flexibility, curved surface compliance and high elasticity greatly expand the application of traditional rigid electronic devices in the fields of motion sensing, health monitoring, soft robots and the like. As a core component of stretchable electronics, the development of high performance stretchable conductors has significant academic and market value.
Constructing the conductive layer on the elastically stretchable substrate material is an effective method of making the stretchable conductor. Common conductive materials mainly include metal nanomaterials such as silver nanowires, gold nanoplatelets, conductive polymers (e.g., PEDOT: PSS, poly-3-hexane thiophene), carbonaceous materials (e.g., graphene, carbon nanotubes, conductive carbon black, etc.). Although the metal nanomaterial and the conductive polymer have good conductivity, the metal nanomaterial and the conductive polymer have the defects of high price, poor processability and the like. In contrast, carbonaceous materials are low in cost, excellent in conductivity, and can be mass-produced. Meanwhile, the existing elastic stretchable conductors are composed of a dense film-like polymer and a composite material thereof which are airtight and moisture impermeable, and the defect that wearable electronic devices prepared from the elastic conductors are uncomfortable to wear for a long time is obvious, and skin health problems can be caused by long-term wear, such as the solvent-free fluorine-containing acrylate ion conductive elastomer disclosed in the invention patent CN113461871a, the stretchable conductive elastomer with a fold structure disclosed in the invention patent CN113808780a, and the ultrahigh toughness and high conductivity elastomer disclosed in the invention patent CN113789119 a.
Disclosure of Invention
Technical problems:
most of the existing flexible and stretchable conductors are air-impermeable and moisture-impermeable polymer films, and after the existing flexible and stretchable conductors are prepared into wearable electronic devices, the problem of long-time wearing comfort cannot be solved. In addition, polymer-based flexible conductors have difficulty maintaining stable, reversible conductive properties at large elongations. Therefore, solving the problem of air and moisture permeation of polymer conductors, and developing effective polymer conductivity enhancement strategies is a key problem to be solved in manufacturing wearable electronic products with excellent performance.
In addition to wearing comfort and electrical conductivity, wearable electronics are now evolving towards versatility and intelligence. The normal body temperature of the human body is about 36.5 ℃, the body temperature can rise after strenuous exercise, and researches show that if the human body runs for a medium and long distance, the body temperature can rise from 37.5 ℃ to 38.5 ℃, and if the human body is strenuous exercise with overload, the body temperature can rise to 39.5 ℃. The body temperature is too high for a long time without reducing the temperature, which can affect the normal physiological functions of the body, and even damage viscera and the like in serious cases. Therefore, it is also important that the wearable electronic device can realize the body temperature warning function.
The technical scheme is as follows:
in order to solve the problems, the invention uses a thermoplastic elastomer with high elasticity and low Young modulus, namely a polystyrene-ethylene-butylene-styrene segmented copolymer (SEBS), processes the SEBS into micro-nano fiber fabrics with a multi-level pore structure by a multi-layer superposition spinning technology, utilizes a selective plasma treatment technology to construct a wetting gradient in the multi-layer fabrics, simultaneously uses a hybrid carbon nano material as a conductive substance and thermochromic microcapsules as color-changing functional particles, respectively modifies each layer of fiber fabrics to prepare the high-elasticity functional fabrics with unidirectional moisture and thermal color-changing functions, and expands the application of the fabrics in the fields of flexible electrodes, wearable electronic devices, intelligent fabrics and the like.
The invention provides a preparation method of an electronic fabric with body temperature warning-unidirectional moisture-conducting functions, which comprises the following steps:
(1) Preparing a solution by taking thermoplastic elastomer polystyrene-ethylene-butylene-styrene block copolymer (SEBS) master batch as a raw material, adding lithium chloride into the solution to obtain SEBS spinning solution, then respectively adding poloxamer (F127) and Thermochromic Microcapsules (TMs), and uniformly mixing to obtain SEBS/F127 composite spinning solution and SEBS/TMs composite spinning solution;
(2) Carrying out electrostatic spinning on the SEBS spinning solution obtained in the step (1) to obtain a first layer of fiber fabric, taking the first layer of fiber fabric as a receiving substrate, and then superposing the SEBS/F127 composite spinning solution on the first layer of fiber fabric through electrostatic spinning to obtain a double-layer elastic fiber fabric;
(3) Annealing and cleaning the double-layer elastic fiber fabric obtained in the step (2), immersing the double-layer elastic fiber fabric in an ethanol dispersion liquid of carbon nanotubes/conductive carbon black (CNTs/CB), performing ultrasonic treatment and drying to obtain the conductive double-layer elastic fiber fabric;
(4) Further taking the conductive double-layer elastic fiber fabric in the step (3) as a receiving substrate, superposing SEBS/TMs composite spinning solution on the conductive double-layer elastic fiber fabric through air spinning, and annealing to obtain a multi-layer composite fiber fabric; and (3) carrying out single-sided selective treatment on the obtained multilayer composite fiber fabric by using plasma treatment to obtain the electronic fabric with the body temperature warning-unidirectional moisture conducting function.
In one embodiment of the present invention, in step (1), SEBS is a linear triblock copolymer having a polystyrene content of 20wt% to 30wt% and a shore hardness of 75A.
In one embodiment of the invention, in step (1), the thermochromic microcapsules have a colour change temperature of 35 ℃ and a colour change type of coloured and colourless.
In one embodiment of the present invention, in the step (1), the solvent for preparing the three spinning solutions is a chloroform/toluene mixed solvent, and the mass ratio of the two solvents is 90:10 to 70:30.
in one embodiment of the invention, in step (1), the solid content of the SEBS dope is formulated to be 10wt.% to 20wt.%.
In one embodiment of the invention, in the step (1), the proportion of lithium chloride in the prepared SEBS spinning solution to the SEBS is 0.1-1 wt%.
In one embodiment of the invention, in the step (1), the proportion of F127 in the prepared SEBS/F127 composite spinning solution is 5-30wt% of the SEBS.
In one embodiment of the invention, in the step (1), the proportion of TMs in the prepared SEBS/TMs composite spinning solution is 5-40 wt% of the SEBS.
In one embodiment of the present invention, the electrospinning parameters in step (2) are: the voltage is 15 kV-30 kV, the receiving distance is 10 cm-30 cm, the inner diameter of the needle head is 0.3 mm-1 mm, the rotating speed of the receiving roller is 70 rpm-140 rpm, the spinning speed is 5 mL/h-10 mL/h, the spinning temperature is 25-60 ℃, and the relative humidity is 20-60%.
In one embodiment of the present invention, the first layer of nonwoven fibrous web in step (2) has a thickness of 50 μm to 300 μm and the double layer fibrous web has a thickness of 100 μm to 500 μm.
In one embodiment of the invention, the annealing temperature of the double-layer elastic fiber fabric in the step (3) is 100-110 ℃, the annealing time is 20-120 min, and the cleaning solvent is absolute ethyl alcohol.
In one embodiment of the present invention, in the step (3), the concentration of carbon nanotubes/conductive carbon black (CNTs/CB) in the ethanol dispersion is 0.1 to 2wt%, and the mass ratio of CNTs to CB is 90: 10-10: 90.
in one embodiment of the present invention, the air pressure of the air spinning in the step (4) is 50kPa to 500kPa. Preferably 50-80kPa.
In one embodiment of the present invention, the spinning speed of the air spinning in the step (4) is 1mL/h to 5mL/h.
In one embodiment of the present invention, the jet head of the air spinning in the step (4) has an inner diameter of 0.25mm to 0.5mm and a receiving distance of 10cm to 30cm.
In one embodiment of the present invention, the multilayer nonwoven fabric produced by air spinning in step (4) has a thickness of 120 μm to 600 μm.
In one embodiment of the present invention, the annealing temperature of the fiber film obtained in the step (4) is 100 to 110 ℃ and the annealing time is 20 to 120 minutes.
In one embodiment of the invention, the exposed surface of the fabric in the step (4) is SEBS/TMs composite fiber, the selected plasma-treated gas is oxygen, and the oxygen flow is 0.1 Nl/min-1 Nl/min.
In one embodiment of the present invention, the power of the plasma treatment in the step (4) is 200W to 600W and the treatment time is 3min to 6min.
The invention is based on the method to prepare the electronic fabric with the body temperature warning-unidirectional moisture-conducting function.
The invention also provides application of the electronic fabric with the body temperature warning-unidirectional moisture-conducting function in the preparation of human body epidermis electronic devices, wearable medical equipment and intelligent fabrics which can be comfortably worn
The invention also provides application of the electronic fabric with the body temperature warning-unidirectional moisture-conducting function in preparing flexible strain sensing equipment.
The invention also provides application of the electronic fabric with the body temperature warning-unidirectional moisture-conducting function in preparing equipment for monitoring the physiological electric signals of the human body in real time.
The invention also provides application of the electronic fabric with the body temperature warning-unidirectional moisture-conducting function in preparing unidirectional moisture-conducting clothes.
The invention also provides application of the electronic fabric with the body temperature warning-unidirectional moisture-conducting function in preparing human body temperature warning equipment.
The invention relates to the following principle processes:
1) The SEBS has excellent stretchability, rebound resilience, weather resistance, ageing resistance and skin friendliness, and is a better flexible wearable electronic device substrate; meanwhile, the micro-nano fiber fabric prepared by the invention has the Young modulus close to that of human skin, can match the mechanical properties of the electronic fabric and the skin, and realizes accurate monitoring of human body activities.
2) The electrostatic spinning technology can spin common polymers into micro-nano continuous fiber/fiber non-woven fabrics, and can conveniently adjust the fiber diameter and the fabric thickness by regulating various spinning parameters (spinning solution composition, voltage, nozzle size, receiving distance and the like). According to the invention, the diameter uniformity of the SEBS can be effectively improved by adding the lithium chloride into the spinning solution, and the diameter of the composite fiber can be obviously reduced by blending the poloxamer and the SEBS.
3) According to the invention, the SEBS can be drawn into continuous fibers with smaller diameters by adopting the air spinning technology, and thermochromic microcapsules blended in the continuous fibers can be embedded in the fibers in the process of forming the fibers, so that the fibers are not easy to elute, and long-term use stability is realized.
4) The invention combines two spinning technologies to realize the layer-by-layer assembly of fiber membranes with different diameters and pores, and establishes a multi-stage pore canal structure with unidirectional water conveying capacity inside the micro-nano fiber fabric; meanwhile, the invention is inspired by the phenomenon of 'water diode', and a wetting gradient is constructed in the thickness direction of the fabric by utilizing a selective plasma treatment technology, so that water can be unidirectionally transmitted from a hydrophobic side to a hydrophilic side against gravity. The two mechanisms provide a basis for the efficient unidirectional moisture-conducting function of the electronic fabric.
5) According to the invention, the carbon nano tube and the conductive carbon black with low cost are used as conductive materials, and the conductive materials are hybridized and then adsorbed on the surface of the micro-nano fiber to be used as a conductive layer, so that the stable conductivity of the fabric under a large stretching rate can be endowed, and the strain sensing sensitivity and the detection interval of the electronic fabric can be remarkably improved.
The beneficial effects are that:
the preparation process is simple and easy to implement, and the used raw materials are low in price and easy to prepare in a large-scale and continuous mode.
The interface between layers of the multilayer electronic fabric prepared by the invention is firmly combined, and the multilayer electronic fabric can bear repeated stretching under large strain without detachment.
The electronic fabric prepared by the invention has stable conductivity under ultra-large stretching due to the carbon nano tube/carbon black hybridization conductive material, and can be used as a flexible electrode for human body movement and physiological electric signal detection.
According to the invention, the thermochromic microcapsules are introduced into the multifunctional electronic fabric, so that the thermochromic electronic fabric can perform color change early warning on the excessive human body temperature, remind people to take cooling measures in time, and effectively avoid damage to the human body caused by the excessive human body temperature when the thermochromic electronic fabric is applied to wearable electronic equipment.
The multifunctional electronic fabric prepared by the invention skillfully combines two moisture-conducting mechanisms, realizes the efficient combination of the unidirectional sweat-discharging function and the electronic fabric, and endows the flexible electronic device with excellent wearing comfort.
The electronic fabric with the body temperature warning-unidirectional moisture conducting function has wide application prospects in the fields of flexible electrodes, wearable electronic devices, intelligent fabrics and the like.
Drawings
Fig. 1 is a schematic structural diagram of an electronic fabric with body temperature warning-unidirectional moisture-conducting function and a physical photograph thereof.
Fig. 2 is a cross-sectional electron micrograph of the electronic textile with body temperature warning-unidirectional moisture-conducting function obtained in example 1.
FIG. 3 is an electron micrograph, fiber diameter distribution and fiber pore size distribution of the first layer (A, D, G) SEBS fibers, the second layer (B, E, H) SEBS/F127 fibers, and the third layer (C, F, I) SEBS/TMs fibers of the electronic fabric obtained in example 1.
Fig. 4 is a digital photograph of (a) stress strain curve, (B) strain sensing sensitivity under different stretching, (C) resistance signal of the finger under different bending angles, (D) resistance signal of the knee bending motion, (E) and its strain at 1000% of stretching of the obtained electronic fabric with body temperature warning-unidirectional moisture guiding function of example 1.
Fig. 5 shows the real-time detection of (a) electrocardiographic ECG, (B-C) myoelectric EMG physiological electrical signals by using the electronic fabric with body temperature warning-unidirectional moisture transfer function obtained in example 1 as a flexible electrode pair.
Fig. 6 is a thermochromic digital photograph of the electronic fabric with body temperature warning-unidirectional moisture-conducting function obtained in example 1 at different temperatures, (B) and its unidirectional moisture-conducting effect test.
Detailed Description
The invention will be further illustrated with reference to specific examples, which are to be understood as illustrative only and are not intended to limit the scope of the invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
Example 1 preparation of multifunctional electronic textile
(1) Respectively weighing 20G of SEBS master batch (KOTeng Co., trade name G1633), 20mg of lithium chloride, 102G of chloroform and 11G of toluene, respectively mixing the above materials with SEBS, and stirring in water bath at 60 ℃ for 3h until the SEBS master batch is completely dissolved to prepare SEBS spinning solution with 15wt% concentration; weighing 2g of poloxamer (Pluronic F127), adding into the 15wt% SEBS spinning solution, and stirring for 3 hours in a water bath at 60 ℃ to obtain SEBS/F127 spinning solution; 4g of thermochromic microcapsules (TMs for short, shenzhen eastern color-changing technology Co., ltd.) are weighed, 15wt% of SEBS spinning solution is added, and the mixture is stirred for 3 hours in a water bath at 60 ℃ to obtain the SEBS/TMs spinning solution.
(2) Transferring the SEBS spinning solution into a needle cylinder, and installing the needle cylinder into an electrostatic spinning machine for spinning to obtain a first layer of SEBS fibers; the spinning parameters are as follows: the voltage is 30kV, the receiving distance is 15cm, the inner diameter of a spray nozzle is 0.8mm, the rotating speed of a receiving roller is 140rpm, the spinning speed is 10mL/h, the spinning temperature is 25 ℃, and the relative humidity is 30%; the first layer of SEBS fabric had a thickness of 200 μm. Spinning the SEBS/F127 spinning solution by using the same spinning parameters after spinning the first layer as a receiving substrate, and collecting to obtain the double-layer SEBS composite fiber fabric, wherein the thickness of the fabric is 400 mu m.
(3) And (3) putting the double-layer composite SEBS fiber fabric into an oven for annealing at 105 ℃ for 60min, cleaning the double-layer composite SEBS fiber fabric with absolute ethyl alcohol after annealing, and drying the double-layer composite SEBS fiber fabric in the oven at 50 ℃. Weighing 0.25g of conductive carbon black, 0.75g of carbon nano tube and 0.2g of commercial dispersing agent (purchased from Nanjing pioneer nano material science and technology Co., ltd., product number 101112, product number XFZ 20), adding the three into 200g of ethanol, and processing in an 800W ultrasonic machine for 30min to obtain uniform and stable carbon nano tube/carbon black hybrid conductive material dispersion; immersing the annealed double-layer composite SEBS fiber fabric in the dispersion liquid, carrying out ultrasonic treatment for 30min, and drying in a 50 ℃ oven to obtain the conductive double-layer composite SEBS fiber fabric.
(4) Coating the double-layer composite SEBS fiber fabric subjected to the conductivity treatment on a receiving roller, and carrying out air spinning on SEBS/TMs spinning solution so as to composite the color-changing layer fiber with the conductive fabric; wherein, the air pressure adopted by the air spinning is 80kPa, the inner diameter of a spinning nozzle is 0.33mm, the receiving distance is 15cm, the spinning speed is 5mL/h, and the obtained three-layer composite electronic fabric is annealed in a drying oven at 105 ℃ for 20min.
Transferring the annealed composite electronic fabric into a plasma treatment instrument, exposing the SEBS/TMs side upwards to oxygen plasma, and performing single-sided selective plasma treatment on the fabric to finally obtain an electronic fabric product; wherein, the oxygen flow is 1Nl/min, the power of the plasma treatment instrument is 600W, and the treatment time is 4min.
And (3) the obtained electronic fabric. Performance testing is carried out:
the cross-sectional morphology and fiber diameter of the electronic textile prepared in this example were characterized using a scanning electron microscope.
As can be seen from the sectional electron micrograph of fig. 2, the electronic textile has a clear layered structure and good bonding between the fibrous layers.
As can be seen from the electron microscope image of fig. 3, the three layers of fibers have significant diameter differences, and the fiber pores have size gradients, which shows the multi-stage pore structure of the electronic fabric.
The tensile property of the electronic fabric is represented by adopting an electronic universal material tester, then the electronic fabric is used as a flexible strain sensor to detect the movement of a human joint, and the resistance change of the electronic fabric in the static-deformation process is measured by combining a digital source meter. The change of the resistance value is DeltaR/R 0 Wherein DeltaR is the variation of the resistance value of the fabric before and after stretching, R 0 Is the initial resistance of the fabric when unstretched. Sensitivity gf= (Δr/R) 0 ) Epsilon, where epsilon is the strain value.
As can be seen from fig. 4, the electronic fabric prepared in this example has a very large tensile strain value (epsilon >1000%, fig. 4E). When used in a strain sensor, it shows high sensitivity (GF > 14000) and can detect different angle bending of human fingers and knee bending motion signals in real time.
As can be seen from FIG. 5, the electronic textile prepared in this example can be used as a skin electrode for monitoring the Electrocardiosignals (ECG) of a human body and the electromyographic signals (EMG) of different actions in real time, and the bioelectric signals of the same body part are stable and repeatable, and the bioelectric signals conform to the biomedical signal characteristics (ECG: 0.01-5mV, EMG:0.1-5 mV).
As can be seen from FIG. 6, the electronic textile prepared in this example is sensitive to the skin temperature of the human body, and the color development difference is obvious at the body temperature of 35-40 ℃, so that the rapid color change can be realized within 5 seconds. At the same time, the electronic textile also exhibits excellent unidirectional moisture transport properties, i.e. water droplets can be transported from the hydrophobic side (conductive layer) against gravity to the hydrophilic side (thermochromic layer) within 2.5 seconds.
EXAMPLE 2 air spinning Process condition investigation
This embodiment differs from embodiment 1 in that:
the air pressure adopted by the air spinning is 50kPa, the inner diameter of a spinning nozzle is 0.33mm, the receiving distance is 15cm, the spinning speed is 5mL/h, and the obtained three-layer composite electronic fabric is annealed in a drying oven at 105 ℃ for 20min.
And (3) result comparison: after changing the air spinning pressure, the diameter of the obtained air spinning fiber was increased to 3.04. Mu.m, and the time required for unidirectional permeation of 50. Mu.L of water through the fabric was 5s in this example, and the moisture permeation effect was worse than in example 1.
EXAMPLE 3 investigation of plasma treatment conditions
This embodiment differs from embodiment 1 in that:
the fabric was subjected to single-sided selective plasma treatment with an oxygen flow of 0.5Nl/min, a plasma treatment apparatus power of 600W, and a treatment time of 4min.
And (3) result comparison: changing the oxygen flow rate of the plasma treatment will affect the surface treatment effect of the fabric, and the moisture permeability effect is worse than that of example 1, compared with the unidirectional moisture permeable electronic fabric obtained in example 1, the time required for 50 μl of water to pass through the fabric in one direction is 30 s.
Example 4 preparation of multifunctional electronic textile
This embodiment differs from embodiment 1 in that:
in the preparation of SEBS/TMs solution, two thermochromic microcapsules (TMs for short, shenzhen eastern color-changing technology Co., ltd.) with response temperature are selected, wherein TMs 2g at 30 ℃ and TMs 2g at 35 ℃ are simultaneously added into the SEBS solution with 15wt%, and the SEBS/TMs solution containing the two response temperatures TMs is obtained by stirring for 3 hours in a water bath with the temperature of 60 ℃. The same air spinning parameters as in example 1 were used to compound the third layer of color-changing fiber on the double layer fabric after the conductivity treatment. After annealing treatment and selective plasma treatment, the body temperature warning-one-way moisture-guiding electronic fabric with two response temperatures and color-changing intervals is obtained.
Comparative example 1
The preparation and annealing treatment of the double layer composite SEBS fiber fabric are the same as in example 1.
1g of conductive carbon black and 0.2g of commercial ethanol dispersing agent are weighed, added into 200g of ethanol, and treated in an 800W ultrasonic machine for 30min to obtain uniform and stable conductive carbon black dispersing liquid. Immersing the double-layer composite SEBS fiber fabric in the dispersion liquid, carrying out ultrasonic treatment for 30min, and drying in a 50 ℃ oven to obtain the double-layer composite SEBS fiber fabric treated by the single conductive material.
The third layer of color-changing fiber was compounded as in example 1.
The obtained electronic fabric is not subjected to selective plasma treatment and only contains a pore gradient and a single conductive material, compared with the electronic fabric with a pore-wetting dual gradient and a hybridized conductive material obtained in example 1, 50 mu L of water in the comparative example needs 42 seconds for unidirectional transmission of the fabric, the strain detection range is only 200%, and the comprehensive performance is poorer than that of example 1.
Comparative example 2
The formulation parameters and spinning parameters of the 15wt% SEBS solution were the same as in example 1. The SEBS/TMs solution and the carbon nanotube/carbon black hybrid conductive material dispersion were prepared as in example 1.
Immersing the single-layer SEBS fiber fabric in the conductive material dispersion liquid, carrying out ultrasonic treatment for 30min, and drying in a 50 ℃ oven to obtain the conductive single-layer SEBS fiber fabric. And taking the fabric as a receiving substrate, and carrying out air spinning on the SEBS/TMs spinning solution, so as to compound the color-changing layer fiber and the conductive fabric. The gas spinning parameters were the same as in example 1.
The selective plasma treatment process was the same as in example 1.
The resulting electronic fabric lacks color-changing properties and contains only a wet gradient, and the time required for 50. Mu.L of water to pass unidirectionally through the fabric for 60 seconds is inferior to that of example 1, compared to the electronic fabric having a pore-wet dual gradient obtained in example 1.

Claims (10)

1. The preparation method of the electronic fabric with the body temperature warning-unidirectional moisture conducting function is characterized by comprising the following steps of:
(1) Preparing a solution by taking SEBS master batches as raw materials, adding lithium chloride into the solution to obtain SEBS spinning solution, then respectively adding poloxamer F127 and thermochromic microcapsule TMs, and uniformly mixing to obtain SEBS/F127 composite spinning solution and SEBS/TMs composite spinning solution;
(2) Carrying out electrostatic spinning on the SEBS spinning solution obtained in the step (1) to obtain a first layer of fiber fabric, taking the first layer of fiber fabric as a receiving substrate, and continuously superposing the SEBS/F127 composite spinning solution on the first layer of fiber fabric through electrostatic spinning to obtain a double-layer elastic fiber fabric;
(3) The double-layer elastic fiber fabric obtained in the step (2) is immersed in ethanol dispersion liquid of carbon nano tube/conductive carbon black after annealing and cleaning, and is subjected to ultrasonic treatment and drying, so that the conductive double-layer elastic fiber fabric is obtained;
(4) Further taking the conductive double-layer elastic fiber fabric in the step (3) as a receiving substrate, superposing SEBS/TMs composite spinning solution on the conductive double-layer elastic fiber fabric through air spinning, and then carrying out annealing treatment to obtain a multi-layer composite fiber fabric; and then carrying out single-sided treatment on the obtained multilayer composite fiber fabric by using plasma treatment to obtain the electronic fabric with the body temperature warning-unidirectional moisture conducting function.
2. The method according to claim 1, wherein in the step (1), the solid content of the SEBS spinning solution is 10-20 wt%; the mass fraction of F127 in the SEBS/F127 composite spinning solution relative to the SEBS is 5-30wt%; the mass fraction of TMs in the SEBS/TMs composite spinning solution relative to the SEBS is 5-40 wt%.
3. The method according to claim 1, wherein in the step (1), the solvents of the three spinning solutions are mixed solvents of chloroform/toluene, and the mass ratio of the solvents is 90:10 to 70:30.
4. the method of claim 1, wherein in step (3), the concentration of carbon nanotubes/conductive carbon black in the ethanol dispersion of carbon nanotubes/conductive carbon black is 0.1wt% to 2wt%; wherein the mass ratio of the carbon nano tube to the conductive carbon black is 90: 10-10: 90.
5. the process according to claim 1, wherein the air spinning in step (4) is carried out at an air pressure of 50kPa to 500kPa.
6. The process according to claim 1, wherein the spinning speed of the air spinning in the step (4) is 1mL/h to 5mL/h.
7. The method of claim 1, wherein the exposed surface of the fabric in step (4) is SEBS/TMs composite fiber, the selected plasma-treated gas is oxygen, and the oxygen flow is 0.1Nl/min to 1Nl/min.
8. The method according to any one of claims 1 to 7, wherein the power of the plasma treatment in step (4) is 200W to 600W and the treatment time is 3min to 6min.
9. An electronic fabric with body temperature warning-unidirectional moisture-conducting function prepared by the method of any one of claims 1-8.
10. Use of the electronic textile with body temperature warning-unidirectional moisture transport function of claim 9 in the preparation of human body skin electronics, wearable medical devices and smart textiles that are comfortable to wear.
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