WO2017183463A1 - 導電性繊維構造物、電極部材および導電性繊維構造物の製造方法 - Google Patents
導電性繊維構造物、電極部材および導電性繊維構造物の製造方法 Download PDFInfo
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- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
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- A61B5/68—Arrangements of detecting, measuring or recording means, e.g. sensors, in relation to patient
- A61B5/6801—Arrangements of detecting, measuring or recording means, e.g. sensors, in relation to patient specially adapted to be attached to or worn on the body surface
- A61B5/6802—Sensor mounted on worn items
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- A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
- A61B5/25—Bioelectric electrodes therefor
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- A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
- A61B5/25—Bioelectric electrodes therefor
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- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
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- 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
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- 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
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
- D06M15/233—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene
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- 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
- D06M15/63—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing sulfur in the main chain, e.g. polysulfones
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- D06M23/08—Processes in which the treating agent is applied in powder or granular form
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
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- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
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- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
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- H01B1/20—Conductive material dispersed in non-conductive organic material
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- A61B2562/00—Details of sensors; Constructional details of sensor housings or probes; Accessories for sensors
- A61B2562/02—Details of sensors specially adapted for in-vivo measurements
- A61B2562/0209—Special features of electrodes classified in A61B5/24, A61B5/25, A61B5/283, A61B5/291, A61B5/296, A61B5/053
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- A61B2562/16—Details of sensor housings or probes; Details of structural supports for sensors
- A61B2562/164—Details of sensor housings or probes; Details of structural supports for sensors the sensor is mounted in or on a conformable substrate or carrier
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- A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
- A61B5/25—Bioelectric electrodes therefor
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Definitions
- the present invention relates to a conductive fiber structure in which a conductive resin containing a conductive polymer is included in the fiber structure. Specifically, the present invention relates to a conductive fiber structure, an electrode member, and a method for manufacturing a conductive fiber structure that can retain high conductivity even after repeated washing and can be applied to a biological electrode.
- the conductive fiber a fiber such as copper coated on the fiber surface, a fiber woven with carbon or a fine metal wire, and a conductive fiber formed of a conductive polymer in a string shape are known. These conductive fibers are used as various types of bioelectrodes used for measuring bioelectric signals such as brain waves, electrocardiograms, and electromyograms of human bodies and animals.
- the conductive materials such as metals and carbon used in the prior art have a problem that they are hydrophobic and hard, and have low suitability for use in contact with a body surface that is rich in moisture and flexible.
- a biological electrode is installed on the body surface, if the biological electrode is made of a hard and hydrophobic material, it is difficult to bring the biological electrode and the body surface into close contact with each other because they are in close contact with the body surface. It is necessary to use a conductive paste (jelly) that is electrically connected.
- a textile-shaped electrode having conductivity is considered effective as an electrode to be directly attached to the body surface of a living body without using a conductive paste or the like, and various proposals have been made. For example, it has been proposed to improve conductivity by combining a fabric electrode and a moisture-impermeable conductive material to suppress moisture evaporation of the fabric electrode (see Patent Document 1).
- PEDOT-PSS ((3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid)
- a conductive polymer fiber is produced by impregnating and / or adhering to a fiber, and the use of this conductive polymer fiber as a bioelectrode or an implantable electrode has been proposed (see Patent Document 2).
- the electrode portion of the fabric electrode disclosed in Patent Document 1 is a silicon rubber to which carbon black or silver powder, which is a conductive substance, is added, and when it is kept in close contact with the body surface for a long time, There is a problem that it cannot be worn comfortably because of a rash. Further, the technique of Patent Document 2 has a problem that the textile electrode is inferior in practical durability such as washing durability. Furthermore, the technology of Patent Document 3 does not take into consideration the particle diameter of the conductive polymer such as PEDOT-PSS to be used. PEDOT-PSS having a large particle diameter is a gap between single fibers of nanofibers and single fibers. However, the amount was supported on the surface of the single fiber.
- An object of the present invention is to provide a conductive fiber structure, an electrode member, and a method for manufacturing the conductive fiber structure that can be applied to a biological electrode.
- the conductive fiber structure of the present invention a conductive resin containing a conductive polymer is supported in the gap between the single fiber and the single fiber constituting the fiber structure, When the cross section in the thickness direction of the fiber structure is observed, the area ratio of the conductive resin existing in the region of 15 to 30 ⁇ m from the surface layer is 15% or more.
- the conductive high resin further contains a binder resin.
- the binder resin is an olefin resin in the above invention.
- the conductive fiber structure of the present invention is characterized in that, in the above invention, the main components of the conductive polymer are poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid.
- the conductive fiber structure of the present invention is characterized by having antibacterial properties in the above invention.
- the conductive fiber structure of the present invention is characterized in that, in the above invention, the antibacterial activity value is 3 or more according to the JIS L1902 (2015 version) fungus liquid absorption method.
- the conductive fiber structure of the present invention is characterized in that, in the above invention, the diameter of at least a part of single fibers constituting the fiber structure is 10 nm or more and 5000 nm or less.
- the conductive fiber structure of the present invention is characterized in that, in the above invention, the surface resistance after repeating washing 30 times according to JIS L0217 (2012 version) 103 method is 1 ⁇ 10 4 ⁇ or less.
- the electrode member of the present invention is characterized by using any one of the above-described conductive fiber structures used for acquiring a biological signal.
- a conductive resin containing a conductive polymer and having a dispersed particle diameter of less than 200 nm is supported in the gap between the single fibers constituting the fiber structure. It is characterized by that.
- a conductive resin containing a conductive polymer and having an average particle diameter of 20 nm or less is supported in the gap between the single fibers constituting the fiber structure and the single fibers. It is characterized by making it.
- the manufacturing method of the conductive fiber structure of this invention WHEREIN:
- the said conductive resin has as a main component the mixture of the said conductive polymer and binder resin.
- a conductive fiber structure having high-performance conductivity and flexibility using a textile base material and having excellent washing durability can be obtained. Further, it can be suitably used as a textile electrode member for obtaining a biological signal.
- FIG. 1 is a scanning probe microscope observation photograph of the conductive fiber structure of the present invention.
- a conductive resin containing a conductive polymer is a gap between a single fiber and a single fiber constituting the fiber structure.
- the area ratio of the conductive resin existing in the region of 15 to 30 ⁇ m from the surface layer is 15% or more. That is, in the present invention, the conductive resin is carried in the gap between the single fibers, but by impregnating to the deep part, it has high performance conductivity, flexibility, and excellent washing durability.
- a conductive fiber structure can be obtained. More preferably, the area ratio is 20% or more, and this is excellent in repeated washing durability. As an upper limit, the area ratio is preferably 30% from the viewpoint of flexibility.
- a conductive polymer is a compound for imparting conductivity to a conductive fiber structure.
- the conductive polymer is not particularly limited, and a conventionally known conductive polymer can be used. Specific examples thereof include polythiophene, polypyrrole, polyaniline, polyacetylene, polyphenylene vinylene, polynaphthalene, and the like. And derivatives thereof. These may be used alone or in combination of two or more. Among these, a conductive polymer including at least one thiophene ring in the molecule is preferable in that a molecule having high conductivity can be easily formed by including a thiophene ring in the molecule.
- the conductive polymer may form a complex with a dopant such as a polyanion.
- poly (3,4-disubstituted thiophene) is more preferable because it is extremely excellent in conductivity and chemical stability. Further, as poly (3,4-disubstituted thiophene), poly (3,4-dialkoxythiophene) or poly (3,4-alkylenedioxythiophene) is particularly preferred, and poly (3,4-ethylenedioxy) Thiophene) is most preferred.
- the conductive polymer is poly (3,4-disubstituted thiophene) or a complex of poly (3,4-disubstituted thiophene) and polyanion (dopant)
- the temperature is low and the time is short.
- a conductive composite material can be formed, and productivity is also excellent.
- the polyanion refers to a conductive polymer dopant.
- the dopant is not particularly limited, but a polyanion is preferable. Although it does not specifically limit as a poly anion,
- carboxylic acid polymers for example, polyacrylic acid, polymaleic acid, polymethacrylic acid, etc.
- sulfonic acid polymers for example, polystyrene sulfonic acid, polyvinyl sulfonic acid, polyisoprene Sulfonic acid etc.
- carboxylic acid polymers and sulfonic acid polymers are also copolymers of vinyl carboxylic acids and vinyl sulfonic acids with other polymerizable monomers such as aromatic vinyl compounds such as acrylates, styrene, vinyl naphthalene, etc. It may be.
- polystyrene sulfonic acid is particularly preferable.
- the conductive resin further contains a binder resin in addition to the conductive resin, and it is more preferable to use a conductive resin mainly composed of a mixture of (A) a conductive polymer and (B) a binder resin.
- the binder (B) contained in the conductive resin is preferably at least one selected from the group consisting of an olefin resin, a polyester resin, a polyurethane, an epoxy resin, and an acrylic resin.
- the olefin-based resin is particularly preferable because the compound constituting the conductive resin in the conductive fiber structure is brought into close contact with each other, and the conductivity is more reliably imparted to the fiber structure. Most preferred. ⁇ (B1) Olefin resin> (B1) The olefin-based resin is added for the purpose of bringing the compound constituting the conductive resin in the conductive fiber structure into close contact with each other and more reliably imparting conductivity to the fiber structure. (B1) The olefin resin is preferably (B2) a non-polar olefin resin from the viewpoint of flexibility and washing durability of the resulting fiber structure.
- “non-polar” means that the SP value is 6 to less than 10, preferably 7 to 9.
- the nonpolar olefin resin is not particularly limited as long as the SP value is less than 6 to 10.
- Nonpolar olefinic resins may be used alone or in combination of two or more.
- olefin resin examples include polyethylene, polypropylene, cycloolefin polymer (cyclic polyolefin), and polymers obtained by modifying them. In the conductive fiber structure, these may be used as (B1) olefin resin, or those obtained by modifying polyvinyl chloride, polystyrene or the like with olefin may be used as (B1) olefin resin. These may be used alone or in combination of two or more.
- olefin-based resin Commercially available products that can be used as the olefin-based resin include Hardren (Toyobo Co., Ltd.), Aptolock (Mitsubishi Chemical Co., Ltd.), Arrow Base (Unitika Ltd.), and the like.
- the content of the (B1) olefin resin is not particularly limited, but is 0.1 to 1000 parts by mass with respect to 100 parts by mass of the solid content of the (A) conductive polymer. Preferably, 5 to 500 parts by mass are more preferable.
- the amount is less than 0.1 parts by mass, the strength of the resulting fiber structure may be weakened.
- the amount exceeds 1000 parts by mass, the content of the conductive polymer (A) in the conductive fiber structure is relative. When it is used as an electrode member, sufficient conductivity may not be ensured. Further, when the strength of the fiber structure is weakened, the washing durability as a textile electrode may be inferior.
- the conductive resin may contain other components in addition to (A) the conductive polymer and (B) the binder resin.
- other components include (C) a conductivity improver, (D) a flexibility imparting agent, (E) a surfactant and / or a leveling agent, a crosslinking agent, a catalyst, and an antifoaming agent.
- a conductivity improver may be added to the conductive resin.
- the conductivity improver is not particularly limited. For example, a compound having a boiling point of 100 ° C. or higher and having two or more hydroxyl groups in the molecule, or a boiling point of 100 ° C. or higher and at least one sulfinyl group in the molecule.
- These (C) conductivity improvers may be used alone or in combination of two or more.
- Examples of the compound having a boiling point of 100 ° C. or more and having two or more hydroxyl groups in the molecule include ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, ⁇ -thiodiglycol, triethylene glycol, tripropylene glycol, 1 , 4-butanediol, 1,5-pentanediol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, catechol, cyclohexanediol, cyclohexanedimethanol, glycerin, erythritol, inmitol, lactitol, maltitol , Mannitol, sorbitol, xylitol, sucrose and the like. These may be used alone or in combination of two or more.
- Examples of the compound having a boiling point of 100 ° C. or higher and having at least one sulfinyl group in the molecule include dimethyl sulfoxide.
- Examples of the compound having a boiling point of 60 ° C. or more and having at least one carbonyl group in the molecule include acrylic acid, methacrylic acid, methanoic acid, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, octanoic acid and decane.
- Acid dodecanoic acid, benzoic acid, p-toluic acid, p-chlorobenzoic acid, p-nitrobenzoic acid, 1-naphthoic acid, 2-naphthoic acid, phthalic acid, isophthalic acid, oxalic acid, malonic acid, succinic acid, Examples include adipic acid, maleic acid, and fumaric acid. These may be used alone or in combination of two or more.
- Examples of the compound having a boiling point of 100 ° C. or more and having at least one amide group in the molecule include N, N-dimethylacetamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-ethylacetamide, N— Examples include phenyl-N-propylacetamide, benzamide and the like. These may be used alone or in combination of two or more.
- the conductive resin contains (C) a conductivity improver
- the content is not particularly limited, but is preferably 0.01 to 100,000 parts by weight with respect to 100 parts by weight of (A) the conductive polymer. 1 to 10000 parts by mass is more preferable.
- the content of the conductivity improver is less than 0.01 parts by mass, a sufficient conductivity improvement effect may not be obtained. If it exceeds 100000 parts by mass, the drying property of the fiber structure is poor. May be.
- a flexibility imparting agent may be added to the conductive resin.
- the flexibility-imparting agent is not particularly limited, and examples thereof include glycerol, sorbitol, polyglycerin, polyethylene glycol, polyethylene glycol-polypropylene glycol copolymer, and the like. These may be used alone or in combination of two or more.
- the conductive resin contains (D) a flexibility-imparting agent
- the content is not particularly limited, but (A) 10 to 10000 parts by mass is preferable with respect to 100 parts by mass of the conductive polymer, and 100 to 5000 parts by mass. Part is more preferred.
- a surfactant / leveling agent may be added to the conductive resin.
- one compound may correspond to both a surfactant and a leveling agent.
- the surfactant and the leveling agent may be used in combination.
- the surfactant is not particularly limited as long as it has an effect of improving leveling properties.
- Specific examples thereof include polyether-modified polydimethylsiloxane, polyether-modified siloxane, polyetherester-modified hydroxyl group-containing polydimethylsiloxane.
- Siloxane compounds such as polyether-modified acrylic group-containing polydimethylsiloxane, polyester-modified acrylic group-containing polydimethylsiloxane, perfluoropolydimethylsiloxane, perfluoropolyether-modified polydimethylsiloxane, perfluoropolyester-modified polydimethylsiloxane; Fluorine-containing organic compounds such as alkyl carboxylic acids and perfluoroalkyl polyoxyethylene ethanol; polyoxyethylene alkyl phenyl ethers, propylene oxides Polyether compounds such as olefin polymers and ethylene oxide polymers; carboxylic acids such as coconut oil fatty acid amine salts and gum rosin; castor oil sulfates, phosphate esters, alkyl ether sulfates, sorbitan fatty acid esters, sulfonate esters, succinates Ester compounds such as acid esters; sulfonate compounds such as
- the leveling agent is not particularly limited.
- polyether-modified polydimethylsiloxane polyether-modified siloxane, polyetherester-modified hydroxyl group-containing polydimethylsiloxane, polyether-modified acrylic group-containing polydimethylsiloxane, and polyester-modified acrylic group-containing polymer.
- Siloxane compounds such as dimethylsiloxane, perfluoropolydimethylsiloxane, perfluoropolyether-modified polydimethylsiloxane, and perfluoropolyester-modified polydimethylsiloxane; fluorine-containing organic compounds such as perfluoroalkylcarboxylic acid and perfluoroalkylpolyoxyethyleneethanol ; Polyether compounds such as polyoxyethylene alkylphenyl ether, propylene oxide polymer, ethylene oxide polymer Carboxylic acids such as coconut oil fatty acid amine salts and gum rosin; castor oil sulfate esters, phosphate esters, alkyl ether sulfates, sorbitan fatty acid esters, sulfonate esters, succinate esters and other ester compounds; alkylaryl sulfonate amine salts And sulfonate compounds such as dioctyl sodium sulfosuccinate
- the conductive fiber structure of the present invention is obtained by supporting a conductive resin mainly composed of a mixture of a conductive polymer and an olefin resin in a gap between a single fiber and a single fiber constituting the fiber structure.
- a conductive resin having a small particle diameter is used.
- the conductive resin is supported, it is preferably supported in the form of a dispersion or solution of the conductive resin.
- solvent there is a particular distinction between those that completely dissolve all components contained in the conductive resin (ie, “solvent”) and those that disperse insoluble components (ie, “dispersion medium”). Without being described as “solvent”.
- solvent will be described.
- the solvent is not particularly limited.
- water alcohols such as methanol, ethanol, 2-propanol, 1-propanol, and glycerin
- ethylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol
- Glycol ethers such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether
- glycol ether acetates such as ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate
- propylene glycol, di Propylene glycol, tripropylene Propylene glycols such as glycol; propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether,
- the solvent is preferably water or a mixture of water and an organic solvent.
- the content of water is not particularly limited, but is preferably 20 to 1,000,000 parts by mass with respect to 100 parts by mass of the solid content of the (A) conductive polymer, 200 to 500,000 parts by mass is more preferable.
- the water content is less than 20 parts by mass, the viscosity may increase and handling may be difficult.
- the content exceeds 1000000 parts by mass, the concentration of the conductive fiber structure becomes too low and the amount of liquid used increases. Sometimes.
- the conductive resin is supported on the fiber structure using a normal method such as a dipping method, a coating method, or a spray method, and the fiber structure supporting the conductive resin is heated to form the conductive fiber structure.
- a normal method such as a dipping method, a coating method, or a spray method
- the fiber structure supporting the conductive resin is heated to form the conductive fiber structure.
- the dipping method and the coating method are preferable because a large amount of the conductive resin can be carried in the gap between the single fibers constituting the fiber structure.
- the dispersed particle diameter of the conductive resin mainly composed of (A) the conductive polymer or (A) the conductive polymer and (B) the binder resin is preferably less than 200 nm. If the dispersed particle diameter of the conductive resin is 200 nm or more, the conductive resin is not easily supported in the gap between the single fibers of the fibers constituting the fiber structure, and is supported on the surface of the single fibers in large quantities, It peels easily and cannot maintain high conductivity after repeated washing.
- the dispersed particle size of the conductive resin is less than 200 nm, it is supported more on the surface of the single fiber and the gap between the single fiber and the single fiber, and is hardly peeled off by physical impact, and can maintain high conductivity after repeated washing. .
- the dispersed particle diameter is less than 200 nm is measured by filtering the conductive resin dispersed in the conductive resin dispersion with a syringe filter having a hole diameter of 0.2 ⁇ m. That is, if the conductive resin dispersed in the conductive resin dispersion passes through the syringe filter, it can be determined that the dispersed particle diameter is less than 200 nm.
- the average particle diameter of (A) conductive polymer or the conductive resin which has as a main component the mixture of (A) conductive polymer and (B) binder resin is 20 nm or less.
- the conductive resin is more supported by the surface of the single fiber and the gap between the single fiber and the single fiber, and is hardly peeled off by physical impact, and is more excellent in the high conductivity retention after repeated washing.
- the average particle diameter of the said conductive resin means the median diameter (D50) when measured by the dynamic light scattering method.
- a conductive resin containing (A) a conductive polymer or (A) a conductive polymer and (B) a binder resin is used, and the dispersed particle diameter is 200 nm or less, or the average particle diameter is By carrying 20 nm or less in the gap between the single fibers of the fiber constituting the fiber structure, the deep portion of the fiber structure can be impregnated with the conductive resin. Thereby, the conductive fiber structure excellent in repeated washing durability can be obtained.
- the main component is a mixture of a conductive polymer whose main components are poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid, and (B) an olefin-based resin as a binder resin (B).
- Denatron FB408B, Denatron TX401 manufactured by Nagase Chemtex Co., Ltd.
- Denatron TX401 manufactured by Nagase Chemtex Co., Ltd.
- the main component is a mixture of a conductive polymer whose main components are poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid, and (B) an olefin-based resin as a binder resin (B).
- Denatron FB408B, Denatron TX401 manufactured by Nagase Chemtex Co., Ltd.
- the like are commercially available as dispersions in which a conductive resin is dispersed in a solvent, and can
- a fiber structure containing a conductive resin and further added with glycerol, physiological saline, etc. can be suitably used.
- the fibrous structure is not limited to these.
- the form of the fiber constituting the fiber structure may be a monofilament yarn, a multifilament yarn, or a staple yarn.
- the shape of the irregular cross section having a high degree of irregularity is not particularly limited.
- the polymer that is the material of the fiber constituting the fiber structure is not particularly limited as long as it is a polymer that can be fiberized by a known method.
- Polyolefin fibers mainly composed of polyethylene, polypropylene, etc., chemical fibers such as rayon, acetate, etc.
- Fiber polymers and synthetic fiber polymers such as polyester and nylon, but are not limited thereto.
- the fineness of the fibers constituting the fiber structure is uniform and fine, and a thermoplastic polymer that can be composite-spun by melt spinning, particularly a fiber made of polyester.
- a thermoplastic polymer that can be composite-spun by melt spinning, particularly a fiber made of polyester.
- the polyester here refers to terephthalic acid as the main acid component, and alkylene glycol having 2 to 6 carbon atoms, that is, ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, Examples include polyesters having at least one glycol selected from ethylene glycol and tetramethylene glycol as a main glycol component, particularly preferably ethylene glycol.
- the polyester may be a polyester in which the acid component is a mixture of terephthalic acid and other difunctional carboxylic acids
- the glycol component may be a polyester in which the glycol is a mixture of other diol components.
- it may be a polyester in which the acid component is a mixture of terephthalic acid and another bifunctional carboxylic acid, and the glycol component is a mixture of the glycol and other diol components.
- Examples of other bifunctional carboxylic acids other than terephthalic acid used here include isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, adipic acid, sebacic acid, and 1,4-cyclohexanedicarboxylic acid.
- Examples thereof include aromatic, aliphatic and alicyclic bifunctional carboxylic acids such as acids.
- Examples of the diol compound other than the glycol include aromatic, aliphatic, and alicyclic diol compounds such as cyclohexane-1,4-dimethanol, neopentyl glycol, bisphenol A, and bisphenol S. .
- the polyester used as the fiber constituting the fiber structure may be synthesized by any method.
- terephthalic acid and ethylene glycol are usually esterified directly, or a lower alkyl ester of terephthalic acid such as dimethyl terephthalate is transesterified with ethylene glycol, or terephthalic acid is used.
- the first stage reaction of reacting ethylene oxide with ethylene oxide to produce a glycol ester of terephthalic acid and / or a low polymer thereof, and the reaction product of the first stage is heated under reduced pressure to give the desired It can be produced by a second stage reaction in which a polycondensation reaction is performed until the degree of polymerization is reached.
- the form of the fiber structure according to the present invention may be mesh, papermaking, woven fabric, knitted fabric, non-woven fabric, ribbon, string or the like.
- the fiber structure according to the present invention includes at least a multifilament yarn, and a conductive substance is supported on the surface of the single fiber constituting the multifilament yarn and the gap between the single fiber and the single fiber. This is a preferred embodiment.
- the fiber structure preferably includes a multifilament yarn composed of a plurality of single fibers.
- the fineness of the multifilament yarn is not particularly limited, it is preferably 30 dtex to 400 dtex from the viewpoint of utilizing the characteristics as a fiber structure.
- the mixing ratio of the multifilament yarn in the fiber structure is not particularly limited as long as it does not affect the performance, but a higher mixing ratio is preferable from the viewpoint of easily carrying the conductive resin and enhancing practical durability.
- the multifilament yarn to be used can be twisted, combined and crimped by a known method.
- the multifilament contained in the fiber structure contains a single fiber of 0.2 dtex or less.
- the fiber structure is desirably a fiber structure having a small fiber diameter, and preferably includes a single fiber of 0.2 dtex or less.
- a microfiber having a fiber diameter of about 5 ⁇ m is obtained at a fineness of 0.2 dtex. If the density of the polymer compound capable of forming the fiber is 0.2 dtex or less, the microfiber is a sufficiently fine fiber, and many gaps can be formed from the single fiber.
- a sea-island type composite fiber yarn composed of two types of polymers having different solubility is prepared, and one part of the sea-island type composite fiber is removed with a solvent to form an ultrafine fiber.
- a multifilament made of microfibers can be formed by increasing the number of island components.
- the number of constituents of the island component of the microfiber is related to the single fiber fineness or the presence or absence of the twisted yarn to the single fiber, but five or more, preferably 24 or more, More preferably, it is 50 or more. Furthermore, a denier mix is also included in the present invention. Moreover, the cross-sectional form of the entire multicomponent fiber is not limited to a round hole, but includes cross-sections of all known fibers such as a trilobal type, a tetralobal type, a T type, and a hollow type.
- a fabric woven using sea-island type composite fibers is treated by a method such as chemical peeling, physical peeling, dissolution removal, etc., and the constituent fibers are made into ultrafine fibers.
- a preferred embodiment is one in which a woven or knitted fabric is produced and fibers are entangled by water jet punching or the like.
- a polymer elastic material such as polyurethane is applied by means such as impregnation.
- a polymer elastic material such as polyurethane is applied by means such as impregnation.
- the fiber structure includes shrinkage treatment, shape fixing treatment, compression treatment, dyeing finishing treatment, oil application treatment, heat fixation treatment, solvent removal, shape fixing agent removal, combing treatment, and glossing treatment.
- Many treatments such as flat (roll) breath treatment and high-performance shortcut shearing treatment (raised napping) are carried out in appropriate combination at each place in each step, but as long as the performance as an electrode is not impaired It is not limited.
- the single fiber is a nanofiber having a single fiber diameter of 10 nm or more and 5000 nm or less, and is made from “Nanoalloy (registered trademark)” fiber.
- the multifilament yarn composed of nanofibers can be produced by a known composite spinning method.
- nanofiber multifilament yarns with small variations in fiber diameter can be used effectively, which is obtained by removing the composite fiber using the composite base exemplified in JP2013-185283A, but is limited to this. is not.
- the fabric weight of the conductive fiber structure of this invention is 50 g / m ⁇ 2 > or more and 300 g / m ⁇ 2 > or less.
- the basis weight is less than 50 g / m 2, since the dough is too thin, impregnation amount of the conductive resin is reduced, the basis weight exceeds 300 g / m 2, cause the wearing feeling too thick poor. More preferably, it is 100 g / m 2 or more and 250 g / m 2 or less.
- the conductive fiber structure of the present invention preferably has an antibacterial activity value of Staphylococcus aureus, which is a human resident bacterium, of 3 or more according to JIS L1902 (2015 version) bacterial liquid absorption method.
- the antibacterial activity value is less than 3, for example, when an electrode member using the conductive fiber structure of the present invention is attached to clothes, the growth of bacteria due to sweat cannot be suppressed, and the clothes after sweating remain as they are. If left unattended, bad smell is generated from clothes due to the propagation of bacteria.
- the electrode member using the conductive fiber structure having an antibacterial activity value of 3 or more the growth of bacteria due to sweat can be suppressed, and the generation of malodor can be suppressed.
- the conductive fiber structure of the present invention preferably has a surface resistance of 1 ⁇ 10 4 ⁇ or less after washing 30 times according to JIS L0217 (1995 edition) 103 method.
- the electrode member of the present invention comprises a fiber structure and a conductive resin, but can be washed at home.
- cleaning durability can be provided.
- the conductive fiber structure of the present invention When used as a bioelectrode, high ventilation is required to prevent adhesion and followability to the skin surface, flexibility and soft texture, swelling due to sweat on the skin surface, and blurring. Since the property is required, the shape of the fiber structure is preferably a woven fabric, a knitted fabric, or a nonwoven fabric.
- These fiber structures do not limit the execution of known methods, dyeing by means, functional processing, etc., as long as the performance as an electrode is not impaired.
- the surface physical processing such as brushing, calendering, embossing and water jet punching on the surface of the electrode member is not limited as long as the performance as an electrode is not impaired.
- the shape and size of the electrode member of the present invention are not particularly defined as long as a biological signal can be detected.
- a resin layer may be laminated on one side of the fiber structure containing the conductive resin.
- Favorable usage modes of the conductive fiber structure of the present invention include a mode in which an electrical signal can be obtained and / or an electrical signal can be applied by directly contacting a living body.
- An electrode member such as a cardiac potential, a myoelectric potential, and an electroencephalogram for obtaining an electrical signal from a living body, or an electrode member such as a low frequency, a high frequency, and an EMS that imparts electrical stimulation to the living body can be used.
- the structure is not limited to a fiber, a fabric, a film, a slit yarn, a non-woven fabric, a resin alone or a composite.
- an electrode In the case of an electrode, a form in which the electrode is used alone and / or in combination with the above-mentioned one in direct contact with the skin can be suitably used.
- the shape of the electrode alone is not limited to a circular diameter, a polygon, or the like.
- the size of the electrode may be a contact area for obtaining a desired biological signal, and is not limited.
- a general flat electrode may have a three-dimensional structure such as a loop shape in conjunction with movement, or may be inflated with air.
- the fiber structure When used in combination with other structures such as clothes as an electrode, the fiber structure can be attached to and detached from the clothes using buttons, hooks, magnets, and Velcro (registered trademark) together so that the electrical signal of the desired part can be acquired. It can be suitably used as a simple shape.
- the conductive fiber structure of the present invention can be used as a planar heating element, is excellent in flexibility and bending resistance, is lightweight, and can be reduced in thickness. Can be used.
- the conductive fiber structure of the present invention will be described in detail by way of examples.
- the conductive fiber structure of the present invention is not limited to these examples.
- the measured values in the examples and comparative examples were obtained by the following method.
- Conductive resin impregnated area ratio When observing a cross section in the thickness direction of the conductive fiber structure of the present invention, the ratio of the conductive resin existing in the region of 15 to 30 ⁇ m from the surface layer (conductive resin impregnated area) The ratio was determined as follows. Using an argon (Ar) ion beam processing apparatus, the conductive fiber structure was cut in the thickness direction to produce a thin film section of a cross section, which was used as a measurement sample. Using the scanning probe microscope (hereinafter referred to as SSRM), voltage was applied to the obtained measurement sample from the back side of the measurement sample, and the surface of the sample was connected using a conductive probe. The presence or absence of was observed.
- SSRM scanning probe microscope
- a 30 ⁇ m ⁇ 30 ⁇ m square region is set so that the highest portion of the surface layer portion of the fiber structure is in contact with the upper part of the visual field, as shown in a cross-sectional image of FIG.
- a 15 ⁇ m ⁇ 30 ⁇ m area 15 ⁇ m lower than the highest position of the surface layer part is set using an image processing software (GIMP 2.8 portable), the threshold value is set to 60, and 15 to 15 from the surface layer in the thickness direction of the conductive fiber structure The area ratio impregnated with the conductive resin in the 30 ⁇ m region was determined. At this time, the number of cross sections obtained by random sampling was measured at 20 locations.
- the fineness of the sea-island composite fibers constituting the fiber structure of the present invention is such that the easily soluble components are 99 by immersing the fabric in a 3% by weight aqueous solution of sodium hydroxide (75 ° C., bath ratio 1:30). After dissolution and removal of at least%, the yarn was disassembled, multifilaments made of ultrafine fibers were extracted, the mass of 1 m was measured, and calculated by multiplying by 10,000. This was repeated 10 times, and the value obtained by rounding off the second decimal place of the simple average value was defined as the fineness. For other fibers, the yarn was disassembled, the multifilament was extracted, the mass of 1 m was measured, and the fineness was calculated by multiplying it by 10,000. This was repeated 10 times, and the value obtained by rounding off the second decimal place of the simple average value was defined as the fineness.
- Dispersion Particle Diameter of Conductive Resin The conductive resin dispersed in the dispersion was filtered with a Miniart 0.2 ⁇ m syringe filter manufactured by Sartorius to determine whether the dispersed particle diameter of the conductive resin was less than 200 nm. .
- Average particle diameter of conductive resin (dynamic light scattering method) The average particle size is calculated by calculating the hydrodynamic diameter from the particle size distribution obtained by measuring a 50-fold diluted conductive resin in 49 g of water while stirring with a Nanotrac Wave series manufactured by Microtrac. It was.
- Adhesive tape for general use cut to a width of 25 mm and a length of 50 mm is affixed to a test piece of a 10 cm ⁇ 10 cm conductive fiber structure, and peeled off with a constant force. The presence or absence of peeling of the resin was visually observed. The thing without peeling was set as (circle) and the thing with peeling was set as x.
- the antibacterial property of the conductive fiber structure was measured according to the antibacterial test method (2015) bacterial solution absorption method of JIS L1902 textiles.
- the test strain was S. aureus.
- Example 1 75T-112F of an alkaline hot water soluble type polyester consisting of a copolymer of terephthalic acid and 5-sodiumsulfoisophthalic acid as an acid component of polyethylene terephthalate and sea component as polyester component (sea-island ratio 30%: 70%, island A circular knitted fabric was knitted with a smooth structure using 100T-136F polyester nanofiber mixed yarn in which nanofibers of several 127 islands / F) and 22T-24F high shrink yarn were mixed.
- Example 1 the cross-sectional photograph which used the conductive resin impregnation area ratio of the conductive fiber structure concerning Example 1 for evaluation in FIG. 1 is shown.
- the conductive layer is impregnated with a low resistance from the surface layer to 30 ⁇ m.
- Example 2 A conductive fiber structure was manufactured in the same manner as in Example 1 except that the dispersion containing the conductive resin was changed from “Denatron FB408B” to “Denatron TX401”. Table 1 shows the materials used and the properties of the resulting conductive fiber structure.
- Example 3 110T-118F polyester nanofiber blended yarn with high shrinkage yarn changed from 22T-24F to 33T-6F and nanofiber blended with 75T-112F (sea-island ratio 30%: 70%, 127 islands / F)
- the conductive fiber structure was manufactured in the same manner as in Example 1 except that the dyeing process was performed. Table 1 shows the materials used and the properties of the resulting conductive fiber structure.
- Example 4 A conductive fiber structure was produced by performing the same treatment as in Example 1 except that the fabric structure was changed from a knitted fabric to a plain woven fabric. Table 1 shows the characteristics of the materials used and the characteristics of the obtained conductive fiber structure.
- Example 5 The same treatment as in Example 1 except that the 22T-24F high-shrinkage yarn was not used and the polyester nanofiber single yarn of 75T-112F (sea-island ratio 30%: 70%, 127 islands / F) was used. To produce a conductive fiber structure. Table 1 shows the characteristics of the materials used and the characteristics of the obtained conductive fiber structure.
- Example 6 Without using 22T-24F high shrinkage yarn, 75T-112F (sea island ratio 30%: 70%, 127 islands / F) 100T-30F (sea island ratio 30%: 70%, 2048 islands / F)
- the conductive fiber structure was manufactured by carrying out the same treatment as in Example 1 except that the polyester nanofibers alone were changed. Table 1 shows the characteristics of the materials used and the characteristics of the obtained conductive fiber structure.
- Example 7 Without using 22T-24F high shrinkage yarn, 75T-112F (sea island ratio 30%: 70%, 127 islands / F) 120T-60F (sea island ratio 50%: 50%, 2048 islands / F)
- the conductive fiber structure was manufactured by carrying out the same treatment as in Example 1 except that the polyester nanofibers alone were changed. Table 1 shows the materials used and the properties of the resulting conductive fiber structure.
- Example 8 Example 1 except that the 22T-24F high-shrinkage yarn was not used and the polyester nanofiber single yarn having a triangular cross section of 75T-112F (sea island ratio 30%: 70%, 127 islands / F) was changed. The same treatment was performed to produce a conductive fiber structure. Table 1 shows the materials used and the properties of the resulting conductive fiber structure.
- Example 9 Without using 22T-24F high shrinkage yarn, 75T-112F (sea island ratio 30%: 70%, 127 islands / F) 66T-9F (sea island ratio 20%: 80%, 70 islands / F)
- the conductive fiber structure was manufactured by performing the same treatment as in Example 1 except that the fabric was changed to a microfiber fabric. Table 1 shows the materials used and the properties of the resulting conductive fiber structure.
- Example 10 4.2 dtex, 51mm island component is polyethylene terephthalate, sea component is a polymer array fiber (sea island ratio 57%: 43%, island number 16 islands) made of polystyrene, impregnated with polyurethane Then, wet coagulation was performed. The polyurethane content was 49% based on the mass of polyethylene terephthalate. This was soaked in trichlorethylene, and the polystyrene component was removed with a mangle to obtain ultrafine fibers having a single yarn fineness of 0.15 dtex. A nonwoven fabric subjected to napping and dyeing with buffing m / c was obtained.
- Example 1 “Denatron FB408B” (manufactured by Nagase ChemteX Corporation) as a conductive fiber structure was applied to the nonwoven fabric as the obtained fiber structure, and the drug application amount was 15 g by a known knife coating method. / M 2 was applied to obtain a conductive fiber structure. Table 1 shows the materials used and the properties of the resulting conductive fiber structure.
- Example 11 Circular knitted fabric using 100T-136F polyester nanofiber blended yarn with 75T-112F (sea island ratio 30%: 70%, 127 islands / F) nanofiber and 22T-24F high shrink yarn was knitted. Next, the fabric was dipped in a 3% by weight aqueous solution of sodium hydroxide (75 ° C., bath ratio 1:30) to remove easily soluble components, and a knitted fabric using mixed fibers of nanofibers and high shrinkage yarns was obtained.
- a polyurethane resin microporous membrane is laminated on the back surface of the obtained knitted fabric by a known method, and “DENATRON FB408B” (manufactured by Nagase ChemteX Corporation) is used as a dispersion containing a conductive resin on the surface.
- the conductive fiber structure was obtained by coating so that the amount of drug applied was 15 g / m 2 by a coating method. Table 1 shows the materials used and the properties of the resulting conductive fiber structure.
- Example 12 Except for changing the high shrinkage yarn from 22T-24F to 33T-6F and making it a polyester nanofiber mixed yarn with 75T-112F (sea-island ratio 30%: 70%, 127 islands / F) and dyeing The same treatment as in Example 11 was performed to obtain a conductive fiber structure. Table 1 shows the materials used and the properties of the resulting conductive fiber structure.
- Example 13 A conductive fiber structure was obtained by carrying out the same treatment as in Example 11 except that the fabric structure was changed from a knitted fabric to a plain woven fabric. Table 1 shows the materials used and the properties of the resulting conductive fiber structure.
- Example 14 A conductive fiber structure was obtained by carrying out the same treatment as in Example 11 except that the polyester nanofiber was changed to 75T-112F (sea / island ratio 30%: 70%, 127 islands / F). Table 1 shows the materials used and the properties of the resulting conductive fiber structure.
- Example 15 A conductive fiber structure was obtained by carrying out the same treatment as in Example 11 except that the polyester nanofiber was changed to 100T-30F (sea / island ratio 30%: 70%, 2048 islands / F). Table 1 shows the materials used and the properties of the resulting conductive fiber structure.
- Example 16 A conductive fiber structure was obtained by carrying out the same treatment as in Example 11 except that the polyester nanofiber was changed to 120T-60F (sea-island ratio 50%: 50%, 2048 islands / F). Table 1 shows the materials used and the properties of the resulting conductive fiber structure.
- Example 17 A conductive fiber structure was obtained by carrying out the same treatment as in Example 11 except that it was changed to a polyester nanofiber single yarn having a triangular cross-section of 75T-112F (sea-island ratio 30%: 70% 127 islands / F). .
- Table 1 shows the materials used and the properties of the resulting conductive fiber structure.
- Example 18 Example except that 22T-24F high-shrinkage yarn was not used and the circular knitted fabric obtained using 66T-9F (sea-island ratio 20%: 80%, 70 islands / F) microfiber was used. The same process as 11 was performed and the conductive fiber structure was obtained. Table 1 shows the materials used and the properties of the resulting conductive fiber structure.
- Example 19 A needle punched non-woven fabric formed using a polymer array fiber (sea island ratio 57%: 43%, island number 16 islands) consisting of 4.2 dtex, length 51 mm, island component polyethylene terephthalate, sea component polystyrene, polyurethane Was impregnated and wet coagulation was carried out. The polyurethane content was 49% based on the mass of polyethylene terephthalate. This was soaked in trichlorethylene, and the polystyrene component was removed with a mangle to obtain ultrafine fibers having a single yarn fineness of 0.15 dtex. A nonwoven fabric subjected to napping and dyeing with buffing m / c was obtained.
- Example 11 a polyurethane resin microporous film was laminated on the back surface of the obtained nonwoven fabric, and “Denatron FB408B” (manufactured by Nagase ChemteX Corporation) was used as a dispersion containing a conductive resin on the surface.
- the conductive fiber structure was obtained by coating so that the amount of drug applied was 20 g / m 2 by a coating method. Table 1 shows the materials used and the properties of the resulting conductive fiber structure.
- Example 20 Except having changed the polyester nanofiber of Example 5 into nylon nanofiber, the same process as Example 1 was performed and the conductive fiber structure was obtained. Table 1 shows the materials used and the properties of the resulting conductive fiber structure.
- Example 1 The same treatment as in Example 1 was performed except that the dispersion containing the conductive resin was changed from “Denatron FB408B” to “Seplatinida OC-AE401” (manufactured by Shin-Etsu Polymer Co., Ltd.) using an acrylic resin as a binder. Thus, a conductive fiber structure was manufactured. Table 1 shows the materials used and the properties of the resulting conductive fiber structure.
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Abstract
Description
また、特許文献2の技術は、テキスタイル電極としては洗濯耐久性などの実用耐久性に劣るという問題があった。
さらに特許文献3の技術は、使用するPEDOT−PSS等の導電性高分子の粒子径について何ら考慮されておらず、粒子径が大きいPEDOT−PSSは、ナノファイバー繊維の単繊維と単繊維の間隙に少なく、単繊維表面に多く担持されていた。したがって、ナノファイバー繊維の単繊維間隙の特性を十分に活かせず、テキスタイル電極としては洗濯耐久性など実用耐久性が十分なものではなかった。
本発明は、上記に鑑みてなされたものであって、繊維構造物と導電性樹脂の組み合わせにより、実用特性の高い導電性を有するとともに、高い洗濯耐久性および高い導電性を保持することで、生体電極にも適用が可能な導電性繊維構造物、電極部材および導電性繊維構造物の製造方法を提供することにある。
また、本発明の導電性樹脂構造物は、上記発明において、バインダ樹脂がオレフィン系樹脂である。
また、本発明の導電性繊維構造物は、上記発明において、前記導電性高分子の主成分が、ポリ(3,4−エチレンジオキシチオフェン)とポリスチレンスルホン酸であることを特徴とする。
また、本発明の導電性繊維構造物は、上記発明において、JIS L1902(2015年度版) 菌液吸収法にて、抗菌活性値が3以上であることを特徴とする。
また、本発明の導電性繊維構造物の製造方法は、導電性高分子を含み、分散粒子径200nm未満である導電性樹脂を、繊維構造物を構成する単繊維と単繊維の間隙に担持させることを特徴とする。
また、本発明の導電性繊維構造物の製造方法は、上記発明において、前記導電性樹脂が、前記導電性高分子とバインダ樹脂との混合物を主成分とする。
また、本発明の導電性繊維構造物の製造方法は、上記発明において、前記導電性樹脂が、前記導電性高分子とバインダ樹脂との混合物を主成分とする。
本発明の導電性繊維構造物は、導電性、柔軟性及び高洗濯耐久性の観点から、(A)導電性高分子を含む導電性樹脂が繊維構造物を構成する単繊維と単繊維の間隙に担持され、繊維構造物の厚み方向の断面を観察したときに、表層から15~30μmの領域に存在する導電性樹脂の面積比率が15%以上である。すなわち、本発明においては、導電性樹脂が単繊維と単繊維の間隙に担持されるが、深部にまで含浸させることにより、高性能な導電性と、柔軟性を有し、洗濯耐久性に優れた導電性繊維構造物が得られるものである。より好ましいのは上記面積比率が20%以上であり、これにより繰り返しの洗濯耐久性に優れる。上限としては、柔軟性の点から上記面積比率が30%で有ることが好ましい。
(A)導電性高分子は、導電性繊維構造物に導電性を付与するための配合物である。(A)導電性高分子としては特に限定されず、従来公知の導電性高分子を用いることができ、具体例としては、例えば、ポリチオフェン、ポリピロール、ポリアニリン、ポリアセチレン、ポリフェニレンビニレン、ポリナフタレン、及びこれらの誘導体が挙げられる。これらは単独で用いても良いし、2種以上を併用してもよい。中でも、チオフェン環を分子内に含むことで導電性が高い分子ができやすい点で、分子内にチオフェン環を少なくとも1つ含む導電性高分子が好ましい。(A)導電性高分子は、ポリ陰イオン等のドーパントと複合体を形成していてもよい。
導電性樹脂には上記導電性樹脂にさらにバインダ樹脂を含有することが好ましく、(A)導電性高分子と、(B)バインダ樹脂との混合物を主成分とする導電性樹脂とすることがより好ましい。
導電性樹脂に含まれる(B)バインダは、オレフィン系樹脂、ポリエステル系樹脂、ポリウレタン、エポキシ樹脂およびアクリル樹脂からなる群より選択される少なくとも1つであることが好ましい。(B)バインダ樹脂としては、導電性繊維構造物中の導電性樹脂を構成する配合物同士を密着させ、より確実に繊維構造物に導電性を付与する点から中でも(B1)オレフィン系樹脂がもっとも好ましい。
<(B1)オレフィン系樹脂>
(B1)オレフィン系樹脂は、導電性繊維構造物中の導電性樹脂を構成する配合物同士を密着させ、より確実に繊維構造物に導電性を付与する目的で添加されるものである。(B1)オレフィン系樹脂としては、得られる繊維構造物の柔軟性及び洗濯耐久性の観点から、(B2)非極性のオレフィン系樹脂であることが好ましい。ここで、本発明において、「非極性」とは、SP値が6~10未満、好ましくは7~9であることをいう。
導電性樹脂には、(C)導電性向上剤を添加しても良い。(C)導電性向上剤としては、特に限定されないが、例えば、沸点が100℃以上で分子内に2つ以上のヒドロキシル基を有する化合物、沸点が100℃以上で分子内に少なくとも1つのスルフィニル基を有する化合物、沸点が60℃以上で分子内に少なくとも1つのカルボニル基を有する化合物、沸点が100℃以上で分子内に少なくとも1つのアミド基を有する化合物等が挙げられる。これらの(C)導電性向上剤は、単独で用いても良いし、2種以上を併用しても良い。
導電性樹脂に(D)柔軟性付与剤を添加しても良い。(D)柔軟性付与剤としては、特に限定されないが、例えば、グリセロール、ソルビトール、ポリグリセリン、ポリエチレングリコール、ポリエチレングリコール‐ポリプロピレングリコールコポリマー等が挙げられる。これらは単独で用いても良いし、2種以上を併用しても良い。
導電性樹脂に(E)界面活性剤/レベリング剤を添加しても良い。なお、本発明の導電性繊維構造物においては、一の化合物が界面活性剤にもレベリング剤にも相当することがある。また、界面活性剤とレベリング剤とが異なる化合物の場合、界面活性剤とレベリング剤とを併用しても良い。
本発明の導電性繊維構造物は、導電性高分子とオレフィン系樹脂との混合物を主成分とする導電性樹脂を、繊維構造物を構成する単繊維と単繊維の間隙に担持させることにより得られるが、その際、担持させる導電性樹脂として、粒子径の小さいものを用いる。
なお、導電性樹脂を担持させるに際しては、導電性樹脂の分散液若しくは溶液の態様で担持させるのが好ましい。なお、本明細書においては、導電性樹脂に含まれる全ての成分を完全に溶解させるもの(即ち、「溶媒」)と、不溶成分を分散させるもの(即ち、「分散媒」)とは特に区別せずに、いずれも「溶媒」と記載する。以下溶媒について説明する。
上記溶媒としては、特に限定されず、例えば、水;メタノール、エタノール、2−プロパノール、1−プロパノール、グリセリン等のアルコール類;エチレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール等のエチレングリコール類;エチレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテル、エチレングリコールジエチルエーテル、ジエチレングリコールジメチルエーテル等のグリコールエーテル類;エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート等のグリコールエーテルアセテート類;プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール等のプロピレングリコール類;プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、プロピレングリコールジメチルエーテル、ジプロピレングリコールジメチルエーテル、プロピレングリコールジエチルエーテル、ジプロピレングリコールジエチルエーテル等のプロピレングリコールエーテル類;プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノエチルエーテルアセテート等のプロピレングリコールエーテルアセテート類;テトラヒドロフラン;アセトン;アセトニトリル等が挙げられる。これらの溶媒は単独で用いても良いし、2種類以上を併用しても良い。
導電性樹脂を、繊維構造物を構成する単繊維と単繊維の間隙に多く担持できる点から、浸漬法やコーティング法が好ましい。
(A)導電性高分子、あるいは(A)導電性高分子と(B)バインダ樹脂との混合物を主成分とする導電性樹脂の分散粒子径としては、200nm未満であることが好ましい。導電性樹脂の分散粒子径が200nm以上であれば、導電性樹脂は繊維構造物を構成する繊維の単繊維と単繊維の間隙に担持されにくく、単繊維の表面に多く担持され、物理衝撃で簡単に剥離し、繰り返し洗濯後の高い導電性が保持できない。導電性樹脂の分散粒子径が200nm未満であれば、単繊維の表面および単繊維と単繊維の間隙に多く担持され、物理衝撃で剥離することは少なく、繰り返し洗濯後の高い導電性が保持できる。
なお、上記導電性樹脂の平均粒子径は、動的光散乱法により測定したときのメジアン径(D50)をいう。
本発明の導電性繊維構造物において、繊維構造物を構成する繊維の形態は、モノフィラメント糸、マルチフィラメント糸、ステープル糸のいずれでもかまわず、繊維の断面形状については、丸断面、三角断面、その他、異形度が高い異形断面の形状でも特に限定されるものではない。
本発明の導電性繊維構造物の厚み方向の断面を観察したときに、表層から15~30μmの領域に存在する導電性樹脂の面積比率(導電性樹脂含浸面積比率)は以下のようにして求めた。
アルゴン(Ar)イオンビーム加工装置を用いて、導電性繊維構造物を厚み方向に切削して、断面の薄膜切片を作製し、測定用試料とした。得られた測定用試料を走査プローブ顕微鏡(Scanning Spreading Resistance Microscopy)(以下SSRMと称する)を用いて、測定用試料の裏側から電圧を印加し、導電性探針を用いて、試料の表層の導通の有無を観察した。観察した画像中、後述の図1の断面画像で示すように、繊維構造物の表層部の最も高い部分が視野上部に接するように30μm×30μmの正方形の領域を設定する。表層部の最も高い位置から15μm下部の15μm×30μmの領域を、画像処理ソフト(GIMP2.8portable)を用い、しきい値を60に設定し、導電性繊維構造物の厚み方向の表層から15~30μmの領域における導電性樹脂が含浸する面積比率を求めた。この時、観察する数は無作為抽出した横断面20箇所を測定した。20箇所で求めたそれぞれの面積比率の平均値を計算し、これを「導電性樹脂含浸面積比率」とした。
観察装置: Bruker AXS社Digital Instruments製
NanoScope Iva AFM
Dimension 3100ステージAFMシステム
+SSRMオプション
SSRM走査モード : コンタクトモードと拡がり抵抗の同時測定
SSRM探針(Tip): ダイヤモンドコートシリコンカンチレバー
探針品番: DDESP−FM(Bruker AXS社製)
Arイオンビーム加工装置:株式会社日立ハイテクノロジーズ製IM−4000
加速電圧3kV
本発明の繊維構造物を構成する海島型複合繊維の繊度は、布帛を水酸化ナトリウム3質量%水溶液(75℃、浴比1:30)に浸漬することで易溶解成分を99%以上溶解除去した後、糸を分解し、極細繊維からなるマルチフィラメントを抜き出し、この1mの質量を測定し、10000倍することで算出した。これを10回繰り返し、その単純平均値の小数点第2位を四捨五入した値を繊度とした。
その他の繊維については、糸を分解し、マルチフィラメントを抜き出し、この1mの質量を測定し、10000倍することで繊度を算出した。これを10回繰り返し、その単純平均値の小数点第2位を四捨五入した値を繊度とした。
繊維から抜き出したマルチフィラメントをエポキシ樹脂で包埋し、Reichert社製FC・4E型クライオセクショニングシステムで凍結し、ダイヤモンドナイフを具備したReichert−Nissei ultracut N(ウルトラミクロトーム)で切削した後、その切削面を株式会社キーエンス製VE−7800型走査型電子顕微鏡(SEM)にて、ナノファイバーは5000倍、マイクロファイバーは1000倍、その他は500倍で撮影した。得られた写真から無作為に選定した150本の極細繊維を抽出し、写真について画像処理ソフト(WINROOF)を用いて全ての外接円径(繊維径)を測定した。
(3)で測定した繊維径の平均繊維径および繊維径標準偏差を求め、下記式に基づき繊維径バラツキ(CV%(A):Coefficient of Variation)を算出した。以上の値は全て3ヶ所の各写真について測定を行い、3ヶ所の平均値とし、nm単位で小数点1桁目まで測定し、小数点1桁目を四捨五入するものである。
繊維径バラツキ(CV%(A))=(繊維径標準偏差/平均繊維径)×100
(3)の繊維径と同様の方法で、マルチフィラメントの断面を撮影し、その画像から、切断面に外接する真円の径を外接円径(繊維径)とし、さらに、内接する真円の径を内接円径として、異形度=外接円径÷内接円径から、小数点3桁目までを求め、小数点3桁目を四捨五入したものを異形度として求めた。この異形度を同一画像内で無作為に抽出した150本の極細繊維について測定し、その平均値および標準偏差から、下記式に基づき異形度バラツキ(CV%(B)(変動係数:Coefficient of Variation))を算出した。この異形度バラツキについては、小数点2桁目を四捨五入する。
異形度バラツキ(CV%(B))=(異形度の標準偏差/異形度の平均値)×100(%)
電極基布について、JIS L1096(一般織物試験方法)(1999)及びJIS L1018(ニット生地試験方法)(1999)の標準状態における単位面積あたりの目付けを測定した。
分散液に分散している導電性樹脂をSartorius社製Minisart0.2μmシリンジフィルターでろ過して、導電性樹脂の分散粒子径が200nm未満か否かを測定した。
49gの水に1gの導電性樹脂を攪拌しながら加えた50倍希釈の導電性樹脂をMicrotrac社製NanotracWaveシリーズで測定して求められた粒径分布から流体力学的径を算出して平均粒子径とした。
標準状態(20℃×65%RH)での導電性樹脂分散液塗布前後の試験布である繊維構造体の質量変化により導電性樹脂付着量を測定した。計算式は下記の通りである。
導電性樹脂付着量(g/m2)=
(加工後の試験布質量(g)−加工前の試験質質量(g))/試験布の分散液を塗布した面積(m2)
10cm×10cmの導電性繊維構造物を試験片として、高質発泡スチロールの上に乗せ、表面抵抗値(Ω)を、抵抗計(三菱アナリテック四探針抵抗計Loresta−AX MCP−T370)を用いて20℃、40%RH環境下で測定した。
10cm×10cmの導電性繊維構造物を試験片として、JIS L0217(1995)103法に準拠した方法で、30回繰り返し法による洗濯後の表面抵抗値を測定した。洗濯機は、全自動洗濯機(National NA−F50Z8)を使用した。
導電性繊維構造物の剛軟度は、JIS L 1096(織物および編物の生地試験方法)(1999)剛軟度A法(45°カンチレバー法)に準じて測定した。
幅25mm、長さ50mmに切断した一般用粘着テープを、10cm×10cmの導電性繊維構造物の試験片に貼り付け、一定の力で引き剥がし、導電性樹脂の剥離の有無を目視で観察した。剥離のない物を○、剥離がある物を×とした。
導電性を有する繊維構造物の抗菌性は、JIS L1902繊維製品の抗菌性試験方法(2015)菌液吸収法に準じて測定した。試験菌株は、黄色ブドウ球菌とした。
[実施例1]
島成分がポリエチレンテレフタレート、海成分がポリエステルの酸成分としてテレフタル酸と5−ナトリウムスルホイソフタル酸の共重合体からなるアルカリ熱水可溶型ポリエステルの75T−112F(海島比率30%:70%、島数127島/F)のナノファイバーと22T−24Fの高収縮糸を混繊した100T−136Fのポリエステルナノファイバー混繊糸を用いて、スムース組織で丸編物を製編した。次いで、布帛を水酸化ナトリウム3質量%水溶液(75℃、浴比1:30)に浸漬することで易溶解成分を除去し、ナノファイバーと高収縮糸の混繊糸使い編物を得た。得られた繊維構造物としての編物に、導電性樹脂を含む分散液として「デナトロンFB408B」(ナガセケムテックス株式会社製)を、既知のナイフコーティング法で薬剤塗布量が15g/m2になるように塗布し、120℃~130℃で加熱して導電性繊維構造物を得た。使用した材料および得られた導電性繊維構造物の特性を表1に示す。また、図1に実施例1にかかる導電性繊維構造物の導電性樹脂含浸面積比率を評価に用いた断面写真を示す。図1により、表層から30μmまで低抵抗、すなわち導電性樹脂が含浸されていることがわかる。
導電性樹脂を含む分散液を「デナトロンFB408B」から「デナトロンTX401」に変更した以外は、実施例1と同じ処理を行って導電性繊維構造物を製造した。使用した材料および得られた導電性繊維構造物の特性を表1に示す。
高収縮糸を22T−24Fから33T−6Fに変更し、ナノファイバーを75T−112F(海島比率30%:70%、島数127島/F)と混線した110T−118Fのポリエステルナノファイバー混繊糸とし、染色加工したこと以外は、実施例1と同じ処理を行って導電性繊維構造物を製造した。使用した材料および得られた導電性繊維構造物の特性を表1に示す。
布帛構造を編物から平織物に変更したこと以外は、実施例1と同じ処理を行って導電性繊維構造物を製造した。使用した材料の特性をおよび得られた導電性繊維構造物の特性を表1に示す。
22T−24Fの高収縮糸を使用せず、75T−112F(海島比率30%:70%、島数127島/F)のポリエステルナノファイバー単独糸に変更したこと以外は、実施例1と同じ処理を行って導電性繊維構造物を製造した。使用した材料の特性および得られた導電性繊維構造物の特性を表1に示す。
22T−24Fの高収縮糸を使用せず、75T−112F(海島比率30%:70%、島数127島/F)を100T−30F(海島比率30%:70%、島数2048島/F)のポリエステルナノファイバー単独糸に変更したこと以外は、実施例1と同じ処理を行って導電性繊維構造物を製造した。使用した材料の特性をおよび得られた導電性繊維構造物の特性を表1に示す。
22T−24Fの高収縮糸を使用せず、75T−112F(海島比率30%:70%、島数127島/F)を120T−60F(海島比率50%:50%、島数2048島/F)のポリエステルナノファイバー単独糸に変更したこと以外は、実施例1と同じ処理を行って導電性繊維構造物を製造した。使用した材料および得られた導電性繊維構造物の特性を表1に示す。
22T−24Fの高収縮糸を使用せず、75T−112F(海島比率30%:70%、島数127島/F)の三角断面のポリエステルナノファイバー単独糸に変更したこと以外は、実施例1と同じ処理を行って導電性繊維構造物を製造した。使用した材料および得られた導電性繊維構造物の特性を表1に示す。
22T−24Fの高収縮糸を使用せず、75T−112F(海島比率30%:70%、島数127島/F)を66T−9F(海島比率20%:80%、島数70島/F)のマイクロファイバーの織物に変更したこと以外は、実施例1と同じ処理を行って導電性繊維構造物を製造した。使用した材料および得られた導電性繊維構造物の特性を表1に示す。
4.2dtex、51mm島成分がポリエチレンテレフタレート、海成分がポリスチレンからなる高分子配列体繊維(海島比率 57%:43%、島数16島)を用いて形成したニードルパンチ不織布に、ポリウレタンを含浸付与し、湿式凝固を実施した。ポリウレタンの含有率はポリエチレンテレフタレートの質量に対し、49%であった。これをトリクロロエチレンに漬け、マングルで絞りポリスチレン成分を除去し、単糸繊度0.15dtexの極細繊維を得た。バフィングm/cにて立毛処理、染色加工を実施した不織布を得た。次いで、実施例1と同じく、得られた繊維構造物としての不織布に、導電性繊維構造物として「デナトロンFB408B」(ナガセケムテックス株式会社製)を、既知のナイフコーティング法で薬剤塗布量が15g/m2になるように塗布して導電性繊維構造物を得た。使用した材料および得られた導電性繊維構造物の特性を表1に示す。
75T−112F(海島比率30%:70%、島数127島/F)のナノファイバーと22T−24Fの高収縮糸を混繊した100T−136Fのポリエステルナノファイバー混繊糸を用いて、丸編物を製編した。次いで、布帛を水酸化ナトリウム3質量%水溶液(75℃、浴比1:30)に浸漬することで易溶解成分を除去し、ナノファイバーと高収縮糸の混繊糸使い編物を得た。得られた編物の裏面に、既知の方法でポリウレタン樹脂微多孔膜をラミネート加工し、表面に、導電性樹脂を含む分散液として「デナトロンFB408B」(ナガセケムテックス株式会社製)を、既知のナイフコーティング法で薬剤塗布量が15g/m2になるように塗布して導電性繊維構造物を得た。使用した材料および得られた導電性繊維構造物の特性を表1に示す。
高収縮糸を22T−24Fから33T−6Fに変更し、75T−112F(海島比率30%:70%、島数127島/F)とのポリエステルナノファイバー混繊糸とし、染色加工したこと以外は、実施例11と同じ処理を行って導電性繊維構造物を得た。使用した材料および得られた導電性繊維構造物の特性を表1に示す。
布帛構造を編物から平織物に変更したこと以外は、実施例11と同じ処理を行って導電性繊維構造物を得た。使用した材料および得られた導電性繊維構造物の特性を表1に示す。
75T−112F(海島比率30%:70%、島数127島/F)のポリエステルナノファイバー単独糸に変更したこと以外は、実施例11と同じ処理を行って導電性繊維構造物を得た。使用した材料および得られた導電性繊維構造物の特性を表1に示す。
100T−30F(海島比率30%:70%、島数2048島/F)のポリエステルナノファイバー単独糸に変更したこと以外は、実施例11と同じ処理を行って導電性繊維構造物を得た。使用した材料および得られた導電性繊維構造物の特性を表1に示す。
120T−60F(海島比率50%:50%、島数2048島/F)のポリエステルナノファイバー単独糸に変更したこと以外は、実施例11と同じ処理を行って導電性繊維構造物を得た。使用した材料および得られた導電性繊維構造物の特性を表1に示す。
75T−112F(海島比率30%:70% 島数127島/F)の三角断面のポリエステルナノファイバー単独糸に変更した以外は、実施例11と同じ処理を行って導電性繊維構造物を得た。使用した材料および得られた導電性繊維構造物の特性を表1に示す。
22T−24Fの高収縮糸を使用せず、66T−9F(海島比率20%:80%、島数70島/F)のマイクロファイバーを用いて得られた丸編物に変更した以外は、実施例11と同じ処理を行って導電性繊維構造物を得た。使用した材料および得られた導電性繊維構造物の特性を表1に示す。
4.2dtex、長さ51mm、島成分がポリエチレンテレフタレート、海成分がポリスチレンからなる高分子配列体繊維(海島比率57%:43%、島数16島)を用いて形成したニードルパンチ不織布に、ポリウレタンを含浸付与し、湿式凝固を実施した。ポリウレタンの含有率はポリエチレンテレフタレートの質量に対し、49%であった。これをトリクロロエチレンに漬け、マングルで絞りポリスチレン成分を除去し、単糸繊度0.15dtexの極細繊維を得た。バフィングm/cにて立毛処理、染色加工を実施した不織布を得た。実施例11と同様に、得られた不織布の裏面にポリウレタン樹脂微多孔膜をラミネート加工し、表面に導電性樹脂を含む分散液として「デナトロンFB408B」(ナガセケムテックス株式会社製)を既知のナイフコーティング法で薬剤塗布量が20g/m2になるように塗布して、導電性繊維構造物を得た。使用した材料および得られた導電性繊維構造物の特性を表1に示す。
実施例5のポリエステルナノファイバーをナイロンナノファイバーに変更した以外は、実施例1と同じ処理を行って導電性繊維構造物を得た。使用した材料および得られた導電性繊維構造物の特性を表1に示す。
導電性樹脂を含む分散液を「デナトロンFB408B」からバインダとしてアクリル系樹脂を使用している「セプルジーダOC−AE401」(信越ポリマー株式会社製)に変更した以外は、実施例1と同じ処理を行って導電性繊維構造物を製造した。使用した材料および得られた導電性繊維構造物の特性を表1に示す。
PETフィルムに、導電性樹脂を含む分散液として「デナトロンFB408B」(ナガセケムテックス株式会社製)を、既知のナイフコーティング法で薬剤塗布量が15g/m2になるように塗布して電極を得た。使用した材料および得られたフイルムの特性を表1に示す。
Claims (13)
- 導電性高分子を含む導電性樹脂が繊維構造物を構成する単繊維と単繊維の間隙に担持され、前記繊維構造物の厚み方向の断面を観察したときに、表層から15~30μmの領域に存在する前記導電性樹脂の面積比率が15%以上である導電性繊維構造物。
- 導電性樹脂がさらにバインダ樹脂を含む請求項1に記載の導電性繊維構造物。
- バインダ樹脂がオレフィン系樹脂である請求項2に記載の導電性繊維構造物。
- 前記導電性高分子の主成分が、ポリ(3,4−エチレンジオキシチオフェン)とポリスチレンスルホン酸であることを特徴とする請求項1~3のいずれかに記載の導電性繊維構造物。
- 抗菌性を有することを特徴とする請求項1~4のいずれかに記載の導電性繊維構造物。
- JIS L1902(2015年度版) 菌液吸収法にて、抗菌活性値が3以上であることを特徴とする請求項1~5のいずれかに記載の導電性繊維構造物。
- 前記繊維構造物を構成する単繊維の少なくとも一部の単糸繊維径が、10nm以上5000nm以下であることを特徴とする請求項1~6のいずれかに記載の導電性繊維構造物。
- JIS L0217(2012年度版)103法にて、30回洗濯を繰り返した後の表面抵抗が1×104Ω以下であることを特徴とする請求項1~7のいずれかに記載の導電性繊維構造物。
- 生体信号の取得に使用する、請求項1~8のいずれかに記載の導電性繊維構造物を用いることを特徴とする電極部材。
- 導電性高分子を含み、かつ分散粒子径が200nm未満である導電性樹脂を、繊維構造物を構成する単繊維と単繊維の間隙に担持させることを特徴とする導電性繊維構造物の製造方法。
- 前記導電性樹脂が、前記導電性高分子とバインダ樹脂との混合物を主成分とする請求項10に記載の導電性繊維構造物の製造方法。
- 導電性高分子を含み、かつ平均粒子径が20nm以下である導電性樹脂を、繊維構造物を構成する単繊維と単繊維の間隙に担持させることを特徴とする導電性繊維構造物の製造方法。
- 前記導電性樹脂が、前記導電性高分子とバインダ樹脂との混合物を主成分とする請求項12に記載の導電性繊維構造物の製造方法。
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019130833A1 (ja) * | 2017-12-27 | 2019-07-04 | アルプスアルパイン株式会社 | 導電材料、導電材、電極脚、および生体情報測定用電極 |
JP2020142014A (ja) * | 2019-03-08 | 2020-09-10 | 日東電工株式会社 | 電極及び生体センサ |
JP2022173125A (ja) * | 2021-05-07 | 2022-11-17 | 大立精準有限公司 | 導電性ポリマー材料及びその使用 |
WO2023181631A1 (ja) | 2022-03-24 | 2023-09-28 | 東レ株式会社 | 生体電極およびその製造方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4860155B2 (ja) | 2002-12-27 | 2012-01-25 | コーニンクレッカ フィリップス エレクトロニクス エヌ ヴィ | 電極構成 |
WO2013073673A1 (ja) | 2011-11-17 | 2013-05-23 | 日本電信電話株式会社 | 導電性高分子繊維、導電性高分子繊維の製造方法及び製造装置、生体電極、生体信号測定装置、体内埋め込み型電極、および生体信号測定装置 |
JP2013185283A (ja) | 2012-03-09 | 2013-09-19 | Toray Ind Inc | 複合口金および複合繊維の製造方法 |
JP2015140493A (ja) * | 2014-01-28 | 2015-08-03 | 東レ株式会社 | マルチフィラメント糸およびそれを用いた繊維構造物 |
WO2015115440A1 (ja) | 2014-01-28 | 2015-08-06 | 日本電信電話株式会社 | 電極部材および装置 |
US20160258110A1 (en) * | 2015-03-04 | 2016-09-08 | Umm AI-Qura University | Method of making conductive cotton using organic conductive polymer |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4975317A (en) * | 1987-08-03 | 1990-12-04 | Milliken Research Corporation | Electrically conductive textile materials and method for making same |
US5211810A (en) * | 1990-08-09 | 1993-05-18 | International Paper Company | Electrically conductive polymeric materials and related method of manufacture |
CA2127919A1 (en) * | 1993-09-03 | 1995-03-04 | Jessie Alvin Binkley | Process for producing ultrafine sized latexes |
US6228492B1 (en) * | 1997-09-23 | 2001-05-08 | Zipperling Kessler & Co. (Gmbh & Co.) | Preparation of fibers containing intrinsically conductive polymers |
EP1371697A3 (en) * | 2002-06-14 | 2004-01-02 | Rohm And Haas Company | Polymeric binders for inkjet inks |
AU2003903431A0 (en) * | 2003-07-03 | 2003-07-17 | Commonwealth Scientific And Industrial Research Organisation | Electroconductive textiles |
US20050095935A1 (en) | 2003-11-03 | 2005-05-05 | Mark Levine | Durable highly conductive synthetic fabric construction |
WO2007056557A1 (en) | 2005-11-08 | 2007-05-18 | North Carolina State University | Methods and devices for providing flexible electronics |
WO2007056556A2 (en) | 2005-11-08 | 2007-05-18 | Mycosol, Inc. | Polyethylene glycol conjugates of pyridinium and thiazolium compounds and methods of using the same |
CN101070672A (zh) * | 2006-05-12 | 2007-11-14 | 中国科学院化学研究所 | 一种超疏水导电纤维、织物及其制备方法和应用 |
CN101845753B (zh) | 2010-05-14 | 2012-06-06 | 苏州新纶超净技术有限公司 | 防静电/导电织物及其制作方法 |
CN104114373A (zh) * | 2011-12-20 | 2014-10-22 | 康涅狄格大学 | 通过喷墨印刷在导电织物上形成高分辨率图案及其对实际可穿戴显示器的应用 |
EP2879134A1 (en) * | 2012-07-24 | 2015-06-03 | Daicel Corporation | Conductive fiber-coated particle, curable composition and cured article derived from curable composition |
JP5984645B2 (ja) | 2012-11-30 | 2016-09-06 | 日本電信電話株式会社 | 感圧センサー、及び感圧センサー装置 |
CA2938025C (en) * | 2014-01-28 | 2021-11-16 | Nippon Telegraph And Telephone Corporation | Biosignal detecting garment |
-
2017
- 2017-03-30 US US16/094,220 patent/US10966656B2/en active Active
- 2017-03-30 EP EP17785805.7A patent/EP3447189B1/en active Active
- 2017-03-30 KR KR1020187032833A patent/KR102190599B1/ko active IP Right Grant
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- 2017-03-30 JP JP2017525992A patent/JP6963998B2/ja active Active
-
2018
- 2018-10-16 CL CL2018002952A patent/CL2018002952A1/es unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4860155B2 (ja) | 2002-12-27 | 2012-01-25 | コーニンクレッカ フィリップス エレクトロニクス エヌ ヴィ | 電極構成 |
WO2013073673A1 (ja) | 2011-11-17 | 2013-05-23 | 日本電信電話株式会社 | 導電性高分子繊維、導電性高分子繊維の製造方法及び製造装置、生体電極、生体信号測定装置、体内埋め込み型電極、および生体信号測定装置 |
JP2013185283A (ja) | 2012-03-09 | 2013-09-19 | Toray Ind Inc | 複合口金および複合繊維の製造方法 |
JP2015140493A (ja) * | 2014-01-28 | 2015-08-03 | 東レ株式会社 | マルチフィラメント糸およびそれを用いた繊維構造物 |
WO2015115440A1 (ja) | 2014-01-28 | 2015-08-06 | 日本電信電話株式会社 | 電極部材および装置 |
US20160258110A1 (en) * | 2015-03-04 | 2016-09-08 | Umm AI-Qura University | Method of making conductive cotton using organic conductive polymer |
Non-Patent Citations (1)
Title |
---|
See also references of EP3447189A4 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019130833A1 (ja) * | 2017-12-27 | 2019-07-04 | アルプスアルパイン株式会社 | 導電材料、導電材、電極脚、および生体情報測定用電極 |
JPWO2019130833A1 (ja) * | 2017-12-27 | 2020-10-22 | アルプスアルパイン株式会社 | 導電材料、導電材、電極脚、および生体情報測定用電極 |
JP2020142014A (ja) * | 2019-03-08 | 2020-09-10 | 日東電工株式会社 | 電極及び生体センサ |
JP2022173125A (ja) * | 2021-05-07 | 2022-11-17 | 大立精準有限公司 | 導電性ポリマー材料及びその使用 |
WO2023181631A1 (ja) | 2022-03-24 | 2023-09-28 | 東レ株式会社 | 生体電極およびその製造方法 |
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US10966656B2 (en) | 2021-04-06 |
CA3021276C (en) | 2020-09-15 |
EP3447189A4 (en) | 2019-12-18 |
TW201807290A (zh) | 2018-03-01 |
AU2017254146B2 (en) | 2020-04-30 |
CN109072540A (zh) | 2018-12-21 |
CL2018002952A1 (es) | 2019-02-22 |
CA3021276A1 (en) | 2017-10-26 |
EP3447189B1 (en) | 2024-02-28 |
EP3447189A1 (en) | 2019-02-27 |
JPWO2017183463A1 (ja) | 2019-02-21 |
TWI719183B (zh) | 2021-02-21 |
JP6963998B2 (ja) | 2021-11-10 |
US20190090810A1 (en) | 2019-03-28 |
KR20180132872A (ko) | 2018-12-12 |
AU2017254146A1 (en) | 2018-11-08 |
KR102190599B1 (ko) | 2020-12-14 |
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