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WO2020076113A1 - Fibre conductrice et son procédé de fabrication - Google Patents

Fibre conductrice et son procédé de fabrication Download PDF

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Publication number
WO2020076113A1
WO2020076113A1 PCT/KR2019/013336 KR2019013336W WO2020076113A1 WO 2020076113 A1 WO2020076113 A1 WO 2020076113A1 KR 2019013336 W KR2019013336 W KR 2019013336W WO 2020076113 A1 WO2020076113 A1 WO 2020076113A1
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Prior art keywords
conductive
fiber
fibers
nanowire
nanowires
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Ceased
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English (en)
Korean (ko)
Inventor
박용해
김진권
김상호
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Flexio Co ltd
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Flexio Co ltd
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Priority claimed from KR1020190125596A external-priority patent/KR102272024B1/ko
Application filed by Flexio Co ltd filed Critical Flexio Co ltd
Publication of WO2020076113A1 publication Critical patent/WO2020076113A1/fr
Anticipated expiration legal-status Critical
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
    • D06C7/00—Heating or cooling textile fabrics
    • 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
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • 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

Definitions

  • the present invention relates to a conductive fiber having improved electrical properties and excellent mechanical properties and a method for manufacturing the same.
  • Natural or synthetic fibers have the advantage of being able to be fabricated in a variety of structures due to their weaving properties, but their direct use in the electrical and electronic fields is limited due to their low electrical conductivity. 2. Description of the Related Art Demand and necessity for conductive fibers having high electrical conductivity and being capable of being woven for use in electrically conductive fillers, displays, energy storage materials, and wearable devices are increasing.
  • textile-based electronic devices have textile solar cells, stretchable transistors, stretchable displays, external stimulus-type drug delivery, and biosensors due to advantages such as the possibility of stretching and weaving fibers, wide surface area, and ease of composition of composite materials.
  • gas sensors, light-regulating functional textiles, functional clothing, and functional products for the defense industry are particularly important.
  • Materials such as metals have excellent conductivity, but are hard to utilize as they are, although they can be manufactured in a fibrous form due to their hard and stiff properties. When materials such as carbon nanotubes or graphene are used alone, they are also difficult to manufacture with stretchable fibers.
  • the amount of filler when filling the inside of the fiber with a conductive filler such as silver nanoparticles and carbon nanotubes to form a conductive fiber, the amount of filler must be included at a threshold above which a percolation of the conductor is possible, so that the conductive fiber There is a problem that the cost increases in the manufacture of.
  • a conductive filler such as silver nanoparticles and carbon nanotubes
  • a method of coating a thin conductive metal layer on the surface of a fiber by electroless plating or electrolytic plating has been disclosed in Korean Patent Registration No. 0597466.
  • the initial surface coating state appears to be uniform, but due to the heterogeneous contact characteristics between the fiber and the thin metal layer, the binding strength is weak, and the metal plating layer is easily peeled off during bending or stretching of the fiber.
  • related characteristics such as electrical conductivity are significantly reduced due to loss or cracking.
  • wearable devices have limitations in areas where fiber properties with excellent mechanical stability are required due to the use environment in which mechanical shocks such as friction and wrinkles are applied.
  • the present invention is to provide a conductive fiber having low resistance of a hybrid type of a core-shell structure in which conductive nanowires are bonded to a surface of a natural or synthetic fiber substrate.
  • the present invention is to provide a conductive fiber having a mechanical surface stability that does not cause deformation or damage such as cracking of a surface conductive material due to stress such as bending of the conductive fiber, and a method of manufacturing the conductive fiber.
  • the present invention provides an ultrafine conductive fiber having a high specific surface area compared to other conductive fibers.
  • the conductive fiber according to the present invention uses a natural fiber or synthetic fiber as a fiber substrate, and has a core-shell double layer structure in which conductive nanowires are bonded to the fiber substrate surface.
  • the electrical resistance value of the conductive fiber may be 80 to 1 ⁇ / cm.
  • the conductive nanowires and the fiber substrate may be bound with a binder.
  • the binder may include both a hydrophobic component and a hydrophilic component.
  • the conductive nanowire and the fiber substrate may have the following surface properties of I) or II).
  • the conductive nanowire may be a nanowire that is hydrophilic or lipophilic.
  • the fiber substrate and the binder may be the same material.
  • the binder may be fibroin or a fibroin analog.
  • the conductive nanowire may be a metal nanowire.
  • the metal may be selected from one or more of silver, gold, platinum, copper, titanium, chromium, nickel, manganese, iron, zinc and aluminum.
  • the fiber substrate may be a refined silk fibroin fiber.
  • the nanowire on the surface of the fiber substrate may be in a sintered state by a method selected from one or more of heat treatment, chemical treatment, and optical treatment.
  • a protective layer or a metal layer may be further included on the nanowire layer on the surface of the fiber substrate.
  • the coverage that is the ratio of the area covered by the conductive nanowires in the total surface area of the fiber substrate may be 30 to 100%.
  • the present invention includes a fiber tissue comprising the conductive fibers described above.
  • Fiber tissue according to an embodiment of the present invention includes a fabric, a knitted fabric or a non-woven fabric.
  • the conductive fiber according to the present invention is formed of a core-shell structure in which conductive nanowires are bonded to the surface of the substrate based on natural or synthetic fibers, and the conductive fiber according to the present invention is a surface of a fiber substrate during mechanical friction or bending.
  • the nanowires bonded to the nanoparticles are stably bonded, and thus have advantages of good mechanical properties such as bending stability and low electrical resistance, and also have a high specific surface area based on the ultrafine fibers.
  • FIG. 1 is an SEM image of natural silk (FIG. 1 (a)) before the refining process of Preparation Example 2 and an SEM image of dSF fibers prepared according to the degumming method of Preparation Example 2 (FIG. 1 (b)).
  • FIG. 2 is an SEM image (FIG. 2 (a)) of a silk-silver nanowire hybrid conductive fiber prepared by performing a dip coating according to Example 1 once, and a high magnification SEM image of the surface of a silk-silver nanowire hybrid fiber ( 2 (b)).
  • Example 3 is a SEM image of a dSF-silver nanowire hybrid conductive fiber prepared by performing dip coating once according to the method of Example 2.
  • FIG. 4 is a view showing the role of the fibroin binder according to the surface properties of the silk and dSF fibers.
  • FIG. 6 is a SEM image of the surface of the fiber after the peeling test of the silk-nanowire hybrid conductive fiber (Silk / fibroin / AgNW-1) subjected to dipping (coating) once by the manufacturing method according to Example 1.
  • the conductive fiber according to the present invention is characterized by having a core-shell bilayer structure in which conductive nanowires are bonded to a natural or synthetic fiber surface, based on a natural fiber or synthetic fiber.
  • the electrical resistance value of the conductive fiber of the present invention may be 1 to 80 ⁇ / cm, specifically 1 to 40 ⁇ / cm, more specifically 1 to 20 ⁇ / cm, and more specifically 1 to 10 ⁇ / cm.
  • Natural fibers or synthetic fibers that serve as a base for conductive fibers according to the present invention are meant to be yan.
  • Synthetic fibers to be used are polyvinyl acetate (PVAc), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyethylene oxide (PEO), polymethyl methacrylate (PMMA), polyacrylic acid (PAA), Polycarbonate (PC), poly (m-phenylene isophthalamide) (PMIA), polyethylamine (PEI), PET, polytrimethylene tetraphthalate (PTT), polybutylene tetraphthalate (PBT), polysulfone (PSF), poly (etheretherketone) (PEEK), polystyrene (PS), polyvinylidene fluoride (PVDF), polyurethane, poly (vinyl butyral) resin (PVB), polyvinyl ester (PVE), polyferrocenyldimethylsilane (PFDMS), poly
  • natural fibers may include plant fibers such as cotton and flax, animal fibers such as silk (dog) and wool, and mineral fibers such as asbestos.
  • the fiber substrate may be a microfiber to general fiber having a small diameter of the fiber.
  • the thickness (diameter) of the fiber base material may be 0.1 to 50 ⁇ m, specifically, an ultrafine fiber thickness of 0.1 to 4 ⁇ m, an ultrafine fiber thickness of 3 to 10 ⁇ m, or a general fiber thickness of 10 to 50 ⁇ m, but is necessarily limited thereto. It does not work.
  • the fiber substrate and the conductive nanowire may be combined with a binder. That is, in one embodiment, the conductive fibers are natural fibers or synthetic fibers based on a fiber, and may have a core-shell double layer structure in which conductive nanowires are bonded to the surface of the fiber substrate by a binder.
  • a conductive fiber in which nanowires are bonded to a fiber substrate may be employed with a binder capable of enhancing the bond between the fiber substrate and nanowires, and the binder may include oligomeric or polymeric materials as natural or synthetic compounds.
  • the polymer may have a molecular weight of 50000 or less, 20000 or less, or 15000 or less, and a polymer satisfying the molecular weight may be cut-off through a dialysis method or the like.
  • nanowires can be combined, and when a dip coating method is employed, the binder can be mixed with a nanowire dip coating solution (nanowire dispersion) and used together.
  • the binder may include both hydrophilic and hydrophobic components.
  • the binder can increase the bonding strength between the conductive nanowire and the fiber substrate, and in particular, the binder containing both the hydrophilic component and the hydrophobic component is advantageous because the conductive nanowire can be uniformly and densely bonded to the fiber substrate.
  • the binder containing both the hydrophilic component and the hydrophobic component may be an amphiphilic polymer, a protein containing a hydrophilic block and a hydrophobic block, or a mixture thereof.
  • Amphiphilic polymers are polymers that have both a hydrophilicity and a hydrophobicity, and polyvinyl pyrrolidone (PVP), polyethylene oxide (PEO), and polyvinyl alcohol (polyvinyl alcohol, PVA), copolymers thereof, and hydrophilic blocks such as polyethylene oxide (PEO), perfluoromethylvinyl ether (PMVE), poly (N-isoacrylamide) (PNIPAM), etc.
  • Amphiphilic block copolymers such as propylene oxide (PPO), polybutylene oxide (PBO), polystyrene (PS), polymethyl methacrylate (PMMA), and the like, but are not limited thereto.
  • Proteins comprising hydrophilic and hydrophobic blocks can include simple proteins, complex proteins, inducing proteins, or mixtures thereof.
  • a hydrophilic block or a hydrophobic block in a protein includes not only a hydrophilic amino acid or a hydrophobic amino acid, but also a case where a certain region (peptide, for example, 4-50 amino acid length) is hydrophilic or hydrophobic by the sequence of amino acids.
  • hydrophilic amino acids include serine, threonine, tyrosine, cysteine, asparagine, glutamine
  • examples of hydrophobic amino acids include glycine, alanine, valine, leucine, isoleucine, methionine, proline, tenyllinine, and tryptophan.
  • the subscript means the number of repetitions of the amino acid or amino acid sequence.
  • sequence of the amino acids described above is only an example to help understanding a protein including a hydrophilic block and a hydrophobic block, and it goes without saying that the present invention cannot be limited by the type or specific sequence of the specific amino acid.
  • Fibroin or fibroin analogs may be employed as an embodiment of the binder.
  • the fibroin protein extracted from silk is not soluble in water, dilute acid, dilute alkali, etc., but as known, it is soluble in aqueous solutions such as lithium bromide, calcium chloride, calcium nitrate, thiocyanic acid and dichloroacetic acid.
  • Fibroin (dissolved fibroin) used as a binder according to an embodiment may be obtained by cut-off to a molecular weight of 100000 or less, or 60000 or less, 40000 or less, or 15000 or less using a dialysis process.
  • Fibroin or fibroin analog binders can be nano-wire-bonded to the fiber substrate, dried and irreversibly solidified by forming a beta sheet.
  • irreversible solidification solidification that does not re-dissolve
  • stable bonding is maintained even in a poor external environment and stability and physical properties of the conductive fiber can be improved.
  • the conductive nanowire and the fiber substrate may have the following surface properties of I) or II).
  • the hydrophilicity may have a water contact angle (static water contact angle) of less than 60 °, substantially 0 to 60 °, more substantially 0 to 50 °, and even more substantially 0 to 40 °.
  • the lipophilicity may also be referred to as hydrophobicity or water repellency, and the water contact angle may be 60 ° or more, substantially 60 to 180 °, more substantially 70 to 180 °, even more substantially 90 to 180 °.
  • the surface of the fiber substrate can be covered by the conductive nanowire with extremely high coverage by a binder containing both hydrophilic and hydrophobic components, and the conductive nanowire It is advantageous because the binding force between the wire and the fiber substrate can be greatly improved.
  • the binder containing both the hydrophilic component and the hydrophobic component has different surface properties (hydrophobicity provided by the binder) from the conductive nanowires to the conductive nanowires (eg, hydrophilic conductive nanowires) covering the surface of the fiber substrate.
  • the shell may have a multilayer structure of layer by layer of conductive nanowires.
  • the present invention does not exclude the case where the shell is a single layer of conductive nanowires.
  • the surface of a fibrous substrate can be converted from hydrophilic to lipophilic or lipophilic to hydrophilic by chemical or physical treatment.
  • a synthetic fiber substrate having lipophilicity may be converted to a hydrophilic surface by an atmospheric pressure plasma treatment.
  • the surface properties of the nanowires can be controlled through surface modification of a molecular layer having a functional group conforming to a desired surface characteristic, such as a hydrocarbon-based compound having a hydrophilic functional group such as glutamate or amine, on the surface of the fiber substrate.
  • surface properties may be controlled through surface treatment such as removing some or all of the surface components.
  • Conductive nanowires can include metal nanowires, conductive carbon nanowires (including carbon nanotubes) or mixtures thereof, and the metals of the conductive metal nanowires are silver, gold, platinum, copper, titanium, chromium, nickel , Manganese, iron, zinc, and one or more may be selected from aluminum, but is not limited thereto.
  • the nanowires of the present invention include silver nanowires. Silver nanowires or silver nanowire suspensions can be prepared from methods disclosed in Korean Patent Publication No. 2012-0010198.
  • the nanowires coupled to the fiber substrate include those in the range of 1 to 500 ⁇ m in length, specifically 1 to 100 ⁇ m, 5 to 100 nm in diameter, and specifically 10 to 50 nm, but the present invention provides the nanowires in the above range. It is not limited.
  • metals exhibit hydrophilicity
  • conductive carbons exhibit lipophilicity (hydrophobicity)
  • the surface properties of nanowires can be controlled from hydrophilic to lipophilic by surface treatment using a surfactant, etc., or by physical / chemical treatment.
  • the hydrophobic conductive carbon material may be surface-modified with a hydrophilic conductive carbon material by subjecting carbon nanowires (including carbon nanotubes) to a strong acid treatment or subcritical to supercritical treatment.
  • the surface properties of the conductive carbon material may be controlled by combining a hydrocarbon-based compound having a hydrophilic functional group on the surface of the carbon nanowire.
  • the metal nanowire may control the surface properties by modifying the surface of the nanowire with a hydrophilic or hydrophobic functional group.
  • Surface modifiers that provide hydrophilic or hydrophobic functional groups are simultaneously introduced during synthesis of nanowires to produce nanowires modified with the desired surface modifier, or introduced directly onto the surface of metal nanowires, or thiol groups on metal nanowire surfaces , Carboxyl groups, amine groups, aldehyde groups, ketone groups, peroxide groups, halogenated alkyl groups having 3 to 20 carbon atoms, ester groups, ether groups, epoxide groups, nitrile groups, carbonyl groups, and other functional groups.
  • the surface modifier may be an organic acid, an organic amine, a surfactant, or a polymer.
  • the surfactant may be any anionic surfactant, cationic surfactant, or amphoteric surfactant commonly used for surface modification of metals.
  • the anionic surfactant may be a hydrophilic portion, the hydrophilic portion is a carboxylic acid salt, a sulfate salt, a sulfonate salt, or a mixture thereof, and specifically, sodium laureth sulfate (Sodium Laureth Sulfate).
  • the cationic surfactant may be an amine salt containing a primary or tertiary amine, a quaternary ammonium salt, an onium compound, or a mixture thereof, and the quaternary ammonium salt is a nitrogen compound containing not only a chain-type alkyl but also a combination thereof.
  • the cyclic nitrogen compound may include a nitrogen heterocyclic compound, and the onium compound includes phosphonium, sulfonium salts, or mixtures thereof, and the nitrogen heterocyclic compound contains pyridinium salts, quinolium, imidazolium, or these. It may include a mixture of.
  • the cationic surfactant is an ester-containing quaternary ammonium salt (EQ) containing an ester, an amide group and an ester group in Quaternary Ammonium salts (amide), a pyridinium derivative (pyridinium derivatives), betaine derivatives, imidazolium derivatives, quinolinium derivatives, quinolinium derivatives, piperazinium derivatives and morpholinium derivatives, etc. It is not.
  • the polymer may be a water-soluble polymer commonly used for surface modification of metals or commonly used for liquid synthesis of metals in nanowire form.
  • the polymer may be a water-soluble polymer selected from one or more of polyvinylpyrrolidone, polyvinylalcohol polyarylamide, polyacrylic acid, and copolymers thereof. It is not limited.
  • the base fiber comprises silk or refined silk fibroin (fiber).
  • Silk is made of cocoons, raw silk, waste cocoons, raw silk waste, unreelable cocoons, silk fabric waste, and cotton ( bourette).
  • silk is a material that is composed of two different polymers, fibroin and sericin, in the form of sericin surrounding fibroin. The process of removing sericin from silk is called degumming.
  • degummed silk fibroin (dSF) where sericin is removed from silk through refining, dozens of strands of fibroin appear in several strands, and the fiber diameter is reduced to 30% to 50% before sericin removal.
  • the fiber properties are improved, such as fiber, elongation of the fiber.
  • the surface of the silk before refining has a rough surface due to sericin (FIG. 1A) and hydrophilic properties, while the sericin-removed dSF fiber has a smooth surface (FIG. 1B) while being lipophilic. (hydrophobic) properties.
  • the bonding strength is excellent, and the mechanical strength of the nanowire bonded to the surface is more excellent.
  • the conductive fiber according to the present invention includes sintered nanowires bonded to the surface of a fiber substrate by heat treatment, chemical treatment, or optical treatment.
  • the sintered conductive fiber has improved conductivity and mechanical properties.
  • the coverage (A nw / A t * 100 (%)) of the area (A nw ) covered by the conductive nanowires in the total surface area (A t ) of the fiber substrate is 30 to 100%, specifically May be 50 to 100%, more specifically 70 to 100%, even more specifically 85 to 100%, even more specifically 90 to 100%.
  • 100% coverage means that the surface area of the fiber substrate is all covered by the conductive nanowires.
  • the conductive fiber may contain 0.01 to 0.5 parts by weight of a binder based on 1 part by weight of the conductive nanowires, but the present invention is not limited thereto.
  • the conductive fiber may further include a protective layer or metal layer located on the formed nanowire layer on the surface of the fiber substrate.
  • the protective layer may be an insulating layer such as a polymer material, and the metal layer may include metal particles or metal nanowires (shell and heterogeneous metal nanowires).
  • the conductive fiber according to the present invention includes a conductive fiber in which nanowires of different nanowire types (materials) or sizes are bonded to a fiber substrate in a plurality of layers, and the conductive fiber includes nanowires of the same or different kinds. It can be obtained by a method such as performing a dip coating two or more times using a dip coating solution.
  • the present invention includes a fiber tissue comprising the conductive fibers described above.
  • the fiber tissue may include a fabric, a knitted fabric or a non-woven fabric.
  • the present invention may include an article comprising the above-described conductive fiber, the article is a textile solar cell, a stretchable transistor, a stretchable display, a biosensor, a gas sensor, a light-regulating functional textile, functional clothing, functional products for the defense industry, etc. It may be, but is not limited to this.
  • a dip-coating method of immersing a base fiber in a nanowire suspension solution is advantageous in terms of productivity, but the conductive fiber of the present invention is specially prepared through a dip coating method. It does not limit things.
  • the nanowire suspension solution used for deep coating may be prepared by a known method, and the nanowire aqueous suspension solution may include nanowires having an aqueous suspension of 0.01 to 10 w%, specifically 0.01 to 1 w%. .
  • the nanowire aqueous suspension solution (dip coating solution) may contain 0.0001 to 5w%, specifically 0.001 to 2w% of the binder.
  • Bombyx mori cocoons were heated at 100 ° C. for 30 minutes in 0.5 wt% Na 2 CO 3 aqueous solution to remove the gum and washed with deionized water three times for 20 minutes. After drying at room temperature overnight, the extracted silk was dissolved in a 9.0M LiBr aqueous solution at 60 ° C. The solution was centrifuged and dialyzed against deionized water for 3 days with a dialysis tubing cellulose membrane (molecular weight cut off (MWCO): 14000). The solution was diluted with deionized water to the desired concentration (1% by weight aqueous fibroin solution for Example 1).
  • MWCO molecular weight cut off
  • Sericin was removed by boiling 103 ⁇ m thick natural silk fibers in 0.5 wt% Na 2 CO 3 aqueous solution.
  • the silk fibers from which sericin was removed were washed with deionized water and dried to obtain refined silk fibroin (dSF) fibers having a thickness of 66 ⁇ m.
  • dSF refined silk fibroin
  • Figure 1 (a) is a SEM image of the natural silk before the refining process of Preparation Example 2
  • Figure 1 (b) is a SEM image of the dSF fiber prepared according to the degumming method of Preparation Example 2.
  • the surface of the natural silk before refining is a rough surface covered with sericin, but it can be confirmed that the dSF fiber produced according to Preparation Example 2 has a very smooth and uniform surface.
  • the natural silk fiber-silver nanowire hybrid fiber was obtained by repeating dip-coating the dried nanowire hybrid conductive fiber in a solution for a desired 5 minutes. When the coating was repeated three times, the same conditions as the one-coated conditions were repeated.
  • FIG. 2 is an SEM image (a) of a silk-silver nanowire hybrid conductive fiber prepared by performing a deep coating according to Example 1 once and an SEM image (b) of an enlarged surface of a silk-silver nanowire hybrid fiber. It can be seen from FIG. 2 (b) that the silver nanowire was strongly bonded to the curved portion of the silk fiber.
  • Table 1 shows the measured resistance values of the manufactured conductive fibers.
  • the resistance value shown is the value obtained by dividing the resistance value by the length after measuring the resistance with a multimeter.
  • the resistance value of the conductive fibers produced by one coating was 65 ⁇ / cm, and the resistance of the conductive fibers produced by three coatings was 11 ⁇ / cm.
  • DSF-silver nanowire hybrid conductive fibers were obtained by performing deep coating under the same conditions as in Example 1, except that the refined silk fibroin (dSF) fibers prepared in Preparation Example 2 were used instead of natural silk as the substrate.
  • dSF refined silk fibroin
  • FIG. 3 is an SEM image of dSF-silver nanowire hybrid fibers prepared by performing dip coating once according to the manufacturing method of Example 2.
  • dSF-silver nanowire hybrid fibers can be confirmed that the silver nanowires cover the surface of the dSF fibers so that the dSF fibers, which are substrates, are almost invisible even after only one dip coating based on the dSF fibers. 2, compared with the silk-silver nanowire hybrid fiber of FIG. 2, it can be seen that much more silver nanowire is tightly bonded to the dSF fiber substrate.
  • the resistance value of the conductive fibers produced by one coating was 29 ⁇ / cm, and the resistance of the conductive fibers produced by three coatings was 9 ⁇ / cm.
  • fibroin which acts as a binder, is bound to a fibrous substrate and then the hydrophilic block is converted to a ⁇ -sheet, but the lipophilic block is maintained, so dSF has a lipophilic surface property compared to silk having a hydrophilic surface property. It is presumed to be due to the better bonding with the fibers.
  • FIG. 5 is an SEM image of a silk-nanowire hybrid fiber prepared by the manufacturing method according to Comparative Example 1. Compared to the nanowire hybrid fibers prepared in Examples 1 and 2, it can be seen that silver nanowires are not only combined in a small amount, but also in a very weakly bonded state.
  • a dSF fiber-silver nanowire hybrid fiber was prepared by performing dip coating under the same conditions as in Example 1, except that the dSF fiber was used as the base fiber in a silver nanowire aqueous suspension solution, not a silver nanowire-fibrorin mixed solution.
  • the conductive fibers prepared from Examples 1 and 2 were heat treated at 150 ° C. for 20 minutes to obtain heat-treated silk-nanowire hybrid conductive fibers and dSF-nanowire hybrid conductive fibers. As shown in Table 2, the resistance of the heat-treated conductive fiber was reduced by about 10%.
  • a conductive fiber is attached on the adhesive tape of 3M company, and a peeling test for rapidly pulling the fiber is performed. After, by measuring the conductivity before and after the peeling test, the increased resistance (( ⁇ R) after the peeling test was confirmed by the resistance (R 0 ) reduction ratio ( ⁇ R / R 0 ) before the peeling test.
  • the silk-nanowire hybrid conductive fiber according to the present invention had a resistance reduction ratio ( ⁇ R / R 0 ) of 0.80 or less before and after the peeling test, and there was little change in resistance value.
  • Example 1 in three deep for a conductive fiber prepared by coating brought R 0, 6.1 ⁇ R of 11 ⁇ / cm, having a ⁇ R / R 0 value of 0.55, it performed three times in the Example 2, a dip coating in the case of the conductive fibers produced by bring the ⁇ R of R 0, 3.0 9 ⁇ / cm, it was found having a ⁇ R / R 0 value of only 0.33.
  • FIG. 6 is a SEM image of the surface of the fiber after the peeling test of the silk-nanowire hybrid conductive fiber (Silk / fibroin / AgNW-1), which was subjected to a single coating process in the manufacturing method according to Example 1. After the one-time coating process, it can be seen that the nanowires are stably bonded to the fibers after the peeling test.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

La présente invention concerne une fibre conductrice ayant des propriétés électriques améliorées et d'excellentes propriétés mécaniques, et son procédé de fabrication. La fibre conductrice selon la présente invention a une structure à double couche coeur-écorce dans laquelle une fibre naturelle ou synthétique est utilisée en tant que substrat et des nanofils conducteurs sont couplés à la surface de la fibre naturelle ou synthétique.
PCT/KR2019/013336 2018-10-12 2019-10-11 Fibre conductrice et son procédé de fabrication Ceased WO2020076113A1 (fr)

Applications Claiming Priority (4)

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KR10-2018-0121833 2018-10-12
KR20180121833 2018-10-12
KR1020190125596A KR102272024B1 (ko) 2018-10-12 2019-10-10 전도성 섬유 및 제조방법
KR10-2019-0125596 2019-10-10

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114657793A (zh) * 2022-03-22 2022-06-24 武汉纺织大学 基于铜纳米线的电热织物及其制备方法
CN114875508A (zh) * 2022-04-29 2022-08-09 上海旦芯悦灵脑智能科技有限公司 一种自发热柔性可穿戴纳米纤维材料的原位制备方法
CN114875660A (zh) * 2022-05-17 2022-08-09 厦门大学 一种介导金属纳米线直接吸裹的导电纺织布及其制备方法

Citations (5)

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