WO2015115440A1 - 電極部材および装置 - Google Patents
電極部材および装置 Download PDFInfo
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- WO2015115440A1 WO2015115440A1 PCT/JP2015/052226 JP2015052226W WO2015115440A1 WO 2015115440 A1 WO2015115440 A1 WO 2015115440A1 JP 2015052226 W JP2015052226 W JP 2015052226W WO 2015115440 A1 WO2015115440 A1 WO 2015115440A1
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- fiber
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- electrode member
- conductive polymer
- fiber structure
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
- A61B5/25—Bioelectric electrodes therefor
- A61B5/279—Bioelectric electrodes therefor specially adapted for particular uses
- A61B5/28—Bioelectric electrodes therefor specially adapted for particular uses for electrocardiography [ECG]
- A61B5/282—Holders for multiple electrodes
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- 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
- A61B5/6804—Garments; Clothes
- A61B5/6805—Vests
Definitions
- the present invention relates to an electrode member made of a fiber structure and a conductive polymer, and an apparatus using the electrode member. Specifically, the present invention relates to a textile electrode member that can maintain high conductivity even after repeated washing and can be applied to a bioelectrode.
- materials made of highly conductive metals are generally used for electrode members because of their necessary characteristics.
- a thin metal layer is deposited on the film.
- flexible electrode base materials that can follow the shape of the base material on which the electrode is placed and pasted, such as increasing flexibility by making the metal itself into a fiber.
- conductive polymers are attracting attention as a material having both metal conductivity and organic polymer flexibility.
- a flexible electrode has been proposed in place of a metal electrode by combining a conductive polymer and a fiber structure.
- a flexible form has been used to follow an electrode-attached body.
- an electrode made of a metal material has some compatibility with a living body. Due to its lowness, electrodes using hydrogel are often used. However, such electrodes generally have low air permeability, and when they are in close contact with each other for a long time, the living body swells, rashes, and the like. Therefore, there is a high demand for an electrode having comfortable wearability.
- conductive textile electrodes are considered effective, 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).
- nanofibers are attracting attention as functional materials, and proposals have been made to take advantage of these properties. For example, proposals have been made to impart various functionalities by supporting a functional drug in the nanofiber single fiber gap (see Patent Document 4).
- nanofibers are used, but the proposed structure does not fully utilize the characteristics of the single fiber gap, and the textile electrode is inferior in practical durability such as washing durability.
- the present invention has been made in view of the above, and in order to create a practical electrode using a textile substrate, an electrode that can retain high conductivity even after repeated washing and can be applied to a biological electrode. It is to provide a member and an apparatus.
- the electrode member of the present invention is a fiber structure including a conductive polymer, and includes a surface of a single fiber constituting the fiber structure and / or a single fiber and a single fiber. A conductive polymer is supported in the gap between the fibers.
- the fiber structure includes at least a multifilament yarn, and the surface of the single fiber constituting the multifilament yarn and / or the gap between the single fiber and the single fiber is electrically conductive. It is characterized in that an active substance is supported.
- the electrode member of the present invention is characterized in that, in the above-described invention, the multifilament yarn constituting the fiber structure includes a single fiber of 0.2 dtex or less.
- the conductive polymer is dispersed in a solvent together with a binder, and a dispersion liquid in which the conductive polymer is dispersed is applied to the fiber structure.
- the conductive polymer is supported on the surface of the single fiber constituting the fiber structure and / or the gap between the single fiber and the single fiber.
- the electrode member of the present invention is characterized in that, in the above invention, the conductive polymer is a mixture of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid.
- the electrode member of the present invention is characterized in that, in the above-mentioned invention, a resin layer is laminated on one side of the fiber structure containing the conductive substance.
- the electrode member of the present invention is characterized in that, in the above invention, the surface resistance after repeating washing 20 times according to JIS L0217 (2012 version) 103 method is 1 ⁇ 10 6 ⁇ or less.
- the electrode member of the present invention is characterized in that in the above invention, it is laminated with a patch.
- the apparatus of the present invention is characterized by using the electrode member described above as at least a part of an electrode.
- a wearable sensoring material that has been difficult to deploy with conventional electrodes because an electrode member having a high conductive texture and excellent washing durability can be obtained using a textile as a base material.
- it can be suitably used for electrodes for biosignal sensing.
- FIG. 1 is a schematic view of a biological signal detection garment using an electrode member according to an embodiment of the present invention.
- the conductive polymer in a fiber structure containing a conductive polymer, is supported on the surface of the single fiber constituting the fiber structure and / or the gap between the single fiber and the single fiber.
- the conductive polymer mentioned here is not particularly limited as long as it is a resin having conductivity.
- a conductive resin paste in which carbon black, CNT (Carbon Nanotube), metal fine particles, and the like are contained in a low conductive resin, and a conductive polymer in which the resin itself has conductivity are preferably used.
- the conductive polymer is not particularly limited as long as it is a polymer exhibiting conductivity.
- acetylene-based, hetero 5-membered ring systems polypyrrole, poly (3-methylpyrrole), poly (3-ethyl) Pyrrole), poly (3-alkylpyrrole) such as poly (3-dodecylpyrrole); poly (3,4-dialkyl) such as poly (3,4-dimethylpyrrole), poly (3-methyl-4-dodecylpyrrole) Pyrrole); poly (N-alkylpyrrole) such as poly (N-methylpyrrole), poly (N-dodecylpyrrole); poly (N-methyl-3-methylpyrrole), poly (N-ethyl-3-dodecylpyrrole) ) Such as poly (N-alkyl-3-alkylpyrrole); pyrrole polymers such as poly (3-carboxypyrrole), polythiophene, poly (3-methyl), poly
- PVP polyparaphenylene vinylene
- Conductive polymers improve conductivity when used with dopants, including dopant ions such as chloride ions and bromide ions, and perchlorate ions.
- Phosphate ions such as tetrafluoroborate ion, hexafluoroarsenate ion, sulfate ion, nitrate ion, thiocyanate ion, hexafluorosilicate ion, phosphate ion, phenylphosphate ion, hexafluorophosphate ion, trifluoro Acetate ion, tosylate ion, ethylbenzenesulfonate ion, dodecylbenzenesulfone Alkyl benzene sulfonate ions such as acid ions, alkyl sulfonate ions such as methyl sulfonate ions and ethyl sulfonate ions, poly
- polypyrrole, poly3,4-ethylenedioxythiophene (PEDOT), polyaniline, polyparaphenylene vinylene (PPV), and the like are easy to be resinized and are preferably used as the conductive resin.
- the conductive polymer such as PEDOT / PSS is impregnated into the fiber structure by applying a dispersion liquid dispersed together with a binder in a solvent to the fiber structure.
- a binder By using a binder, it becomes easy to carry the conductive polymer on the fiber structure, and it is possible to suppress an increase in surface resistance after repeatedly washing the electrode member.
- the binder to be used may be a thermosetting resin or a thermoplastic resin.
- polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyimides; polyamide imides; polyamides such as polyamide 6, polyamide 6, 6, polyamide 12, and polyamide 11; polyvinylidene fluoride, polyvinyl fluoride, polytetrafluoroethylene Fluoropolymers such as ethylene tetrafluoroethylene copolymer and polychlorotrifluoroethylene; vinyl resins such as polyvinyl alcohol, polyvinyl ether, polyvinyl butyral, polyvinyl acetate, and polyvinyl chloride; epoxy resins; xylene resins; aramid resins; Polyurea; polyurea; melamine resin; phenol resin; polyether; acrylic resin and copolymers thereof.
- binders may be dissolved in an organic solvent, may be provided with a functional group such as a sulfonic acid group or a carboxylic acid group, may be formed into an aqueous solution, or may be dispersed in water such as emulsification.
- a functional group such as a sulfonic acid group or a carboxylic acid group
- aqueous solution or may be dispersed in water such as emulsification.
- water such as emulsification.
- the binder resins one or more of polyurethane, polyester, acrylic resin, polyamide, polyimide, epoxy resin, and polyimide silicone are preferable because they can be easily mixed.
- the solvent to be used is not limited as long as the conductive polymer and the binder are stably dispersed, but water or a mixed solution of water and alcohol can be preferably used.
- water or a mixed solution of water and alcohol can be preferably used.
- a polythiophene conductive polymer such as PEDOT / PSS
- a fiber structure containing a conductive polymer and further added with glycerol, physiological saline, etc. can be suitably used, but is not limited thereto. is not.
- known methods such as dipping method, coating method, spraying method, etc. for the precursors of these conductive polymers, conductive polymer solutions, emulsions, dispersions, etc. to the fiber structure, the fiber structure
- the conductive polymer can be supported on the surface of the single fiber constituting the metal and / or the gap between the single fiber and the single fiber.
- the form of the fiber constituting the fiber structure may be either a monofilament yarn or a multifilament yarn, and the cross-sectional shape of the fiber is a round cross-section, a triangular cross-section, etc.
- the shape of the cross section 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 in melt spinning, a thermoplastic polymer capable of composite spinning, particularly fibers made of polyester are particularly preferred.
- 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, preferably 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.
- 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.
- 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, but may be in any form according to the purpose of use and is not particularly limited.
- the electrode member of the present invention as a biological electrode, high breathability is required for the adhesion and followability to the skin surface, flexible and soft texture, swelling due to sweat on the skin surface, and suppression of blurring. Therefore, 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 fiber structure includes at least a multifilament yarn, and a conductive material is supported on the surface of the single fiber constituting the multifilament yarn and / or the gap between the single fiber and the single fiber. Is a preferred embodiment.
- the fiber structure preferably contains 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 the performance is not affected, 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.
- polyethylene terephthalate having a density of 1.38 g / cm 3 is a microfiber having a fiber diameter of about 5 ⁇ m 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.
- the gap formed by a plurality of single fibers that is, the portion where the conductive polymer is supported is re-differentiated, and the support property of the conductive polymer to the fiber structure is improved. Get higher. Moreover, even if the part capable of carrying the conductive polymer is re-differentiated due to the thin fiber diameter of the single fiber, the continuity of the conductive polymer is maintained, so that high conductivity can be expressed at the same time. .
- 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 island components of the microfiber is related to the single fiber fineness or the presence or absence of a 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 constituting the multifilament is more preferably a nanofiber having a fiber diameter of 0.01 to 0.0001 dtex, and the “nanoalloy (registered trademark)” fiber is used.
- Fiber structures including multifilament yarns composed of nanofibers produced by known methods, such as nanofiber staple yarn assemblies produced, monofilament yarn assemblies produced by electrospinning, etc. are suitably used it can.
- a multifilament yarn composed of nanofibers can be produced by a known composite spinning method or the like.
- nanofiber multifilament yarns with small variations in fiber diameter are effective in which composite fibers using composite bases exemplified in Japanese Patent No. 5472479 and Japanese Patent Application Laid-Open No. 2013-185283 (Fiber Research VESTA patent) are removed.
- the cross-sectional shape of the single fiber is not particularly limited, and may be a known cross-sectional shape such as a circle, a triangle, a flat shape, or a hollow shape.
- a cross section having a high degree of irregularity is a circumscribed circle and an inscribed circle of a different-diameter sectioned yarn
- a multifilament yarn having a higher ratio (the circumscribed circle / inscribed circle) has a higher degree of irregularity) can be suitably used.
- the thickness of the fiber structure used for the electrode member of the present invention is preferably 0.2 mm or more and 2.0 mm or less. If the thickness is less than 0.2 mm, the fabric is too thin and the basis weight becomes small, the amount of impregnation of the conductive polymer is reduced, and if the thickness exceeds 2.0 mm, it is too thick and the wear feeling is inferior. More preferably, it is 0.3 mm or more and 1.5 mm or less.
- the size of the electrode member is not particularly limited as long as a signal can be detected, but it is preferable that the length and width are 2 cm or more and 20 cm or less, respectively.
- the length and the width are 2.5 cm or more and 18 cm or less, respectively.
- a resin layer is preferably laminated on one side of a fiber structure containing a conductive polymer.
- the resin layer is preferably formed on the back surface of the electrode member in contact with the human skin surface.
- the humidity of the electrode member portion can be controlled, and stable conductivity can be expressed.
- by covering one surface of the electrode member with the resin layer it is possible to greatly suppress the durability of the electrode member, particularly the decrease in conductivity due to the dropping of the conductive polymer due to washing.
- the type and shape of the polymer constituting the resin layer are not limited as long as humidity control is possible, but a waterproof and moisture-permeable layer having insulating properties is preferable in terms of required characteristics as an electrode member.
- PTFE polytetrafluoroethylene
- hydrophilic polyester resin e.g., polytetrafluoroethylene
- hydrophilic elastomer such as polyurethane resin, a polyurethane resin microporous membrane, etc.
- the waterproof / moisture permeable layer is preferably one in which a polyurethane resin microporous film having stretchability is laminated and bonded by lamination from the viewpoint of following the fiber structure as a substrate.
- the electrode member of the present invention preferably has a surface resistance of 1 ⁇ 10 6 ⁇ or less after washing 20 times according to JIS L-0217 (2012) 103 method.
- the electrode member of the present invention comprises a fiber structure and a conductive polymer, but can be washed at home. As the number of single fibers constituting the fiber structure increases, voids composed of a plurality of single fibers, that is, portions where the conductive polymer is carried are re-differentiated to regenerate the conductive polymer into the fiber structure. It is believed that the supportability becomes high and high washing durability can be imparted.
- a sticking type electrode in combination with a patch utilizing the characteristics of a textile electrode, an apparatus using the electrode member of the present invention as at least a part of the electrode, etc. is mentioned.
- sensing devices As an example of an apparatus using the electrode member of the present invention, first, various sensing devices are exemplified, and an installation type, a portable type, a wearable type and the like are exemplified.
- sensing applications it can be applied to the measurement of heart rate, electrocardiogram waveform, respiratory rate, blood pressure, brain potential, myoelectric potential, etc., which is a sensing application obtained from the electrical signal of the living body, during daily health care, leisure, exercise Examples include, but are not limited to, remote management of health management, heart disease, high blood pressure, sleep apnea syndrome, and the like.
- devices that send electricity to the body include a low-frequency massager and a muscle stimulation muscle strengthening device.
- FIG. 1 is a schematic view of a biological signal detection garment 100 using the electrode member of the present invention.
- Two electrode members 101 (101 a, 101 b, 101 c) according to the present invention are arranged on the left and right side chests or the part in contact with the vicinity of the flank when wearing the clothing main body 104, and on the left and right sides of the clothing main body 104. The remaining one is disposed at a lower position away from the electrode member disposed in the vicinity of the chest or flank.
- Each electrode member 101 measures a biological signal, and the biological signal measured by the electrode member 101 is transmitted to the measuring device 102 via the wiring 103 (103a, 103b, 103c), and the biological signal transmitted to the measuring device 102 Is transmitted to a mobile terminal or personal computer after signal processing.
- the electrode member 101 of the present invention is used as a wearable electrode such as the biological signal detection garment 100 shown in FIG. 1, the biological signal can be stably detected.
- the electrode member of the present invention will be described in detail by way of examples.
- the electrode member 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.
- the sea-island type composite fiber dissolves and removes 99% or more of the readily soluble components by immersing the fabric in a 3% by weight aqueous solution of sodium hydroxide (75 ° C., bath ratio 1:30), then decomposes the yarn.
- the multifilament made of ultrafine fibers 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.
- the yarn was disassembled, the multifilament was extracted, the weight 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.
- Resin Adhesion Amount The resin adhesion amount was measured by a change in mass of the fiber structure as a test cloth before and after application of the conductive polymer dispersion in a standard state (20 ° C. ⁇ 65% RH). The calculation formula is as follows. Resin adhesion amount (g / m 2 ) (mass of test cloth after processing (g) ⁇ weight of test material before processing (g)) / area applied with dispersion of test cloth (m 2 )
- Example 1 75T-112F of alkaline hot water-soluble polyester consisting of a copolymer of terephthalic acid and 5-sodiumsulfoisophthalic acid as the 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 a 100T-136F polyester nanofiber mixed yarn in which nanofibers of several 127 islands / F) and 22T-24F high shrink yarn were mixed.
- 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 mixed solvent of water and ethanol water 44 wt%, ethanol 50 wt%), PEDOT / PSS 1.0 wt% as a conductive polymer, and acrylic thermosetting resin as a binder
- An electrode was obtained by applying a dispersion in which 5.0 wt% was dispersed by a known gravure coating method so that the drug application amount was 15 g / m 2 .
- the materials used and the properties of the resulting electrodes are shown in Tables 1 and 2.
- Example 2 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) Except for the above, the same treatment as in Example 1 was performed to produce an electrode. The materials used and the properties of the resulting electrodes are shown in Tables 1 and 2.
- Example 3 An electrode was manufactured by performing the same treatment as in Example 1 except that the fabric structure was changed from a knitted fabric to a plain fabric. The materials used and the properties of the resulting electrodes are shown in Tables 1 and 2.
- Example 4 The same treatment as in Example 1 except that 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 an electrode. The materials used and the properties of the resulting electrodes are shown in Tables 1 and 2.
- Example 5 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 electrode was manufactured by performing the same treatment as in Example 1 except that the polyester nanofibers alone were changed. The materials used and the properties of the resulting electrodes are shown in Tables 1 and 2.
- Example 6 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 electrode was manufactured by performing the same treatment as in Example 1 except that the polyester nanofibers alone were changed. The materials used and the properties of the resulting electrodes are shown in Tables 1 and 2.
- Example 7 Example 1 except that 22T-24F high-shrinkage yarn was not used and the yarn was changed to a polyester nanofiber single yarn having a triangular cross section of 75T-112F (sea-island ratio 30%: 70%, 127 islands / F). The same treatment was performed to produce an electrode. The materials used and the properties of the resulting electrodes are shown in Tables 1 and 2.
- Example 8 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 electrode was manufactured in the same manner as in Example 1 except that the fabric was changed to a microfiber fabric.
- the materials used and the properties of the resulting electrodes are shown in Tables 1 and 2.
- Example 9 4.2 dtex, 51 mm 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 2 a dispersion obtained by dispersing PEDOT / PSS as a conductive polymer and acrylic thermosetting resin as a binder in a mixed solvent of water and ethanol in a nonwoven fabric as the obtained fiber structure.
- the electrode was obtained by coating with a known gravure coating method so that the drug coating amount was 15 g / m 2 .
- the materials used and the properties of the resulting electrodes are shown in Tables 1 and 2.
- Example 10 Without using 22T-24F high shrinkage yarn, 75T-112F (sea-island ratio, 127 islands / F) is made into a polyester fiber fabric of 84T-36F (polyester fiber cloth for dyeing test, manufactured by Color Dye Co., Ltd.). Except for the change, the same process as in Example 1 was performed to manufacture an electrode. The materials used and the properties of the resulting electrodes are shown in Tables 1 and 2.
- Example 11 A circular knitted fabric was knitted using a mixed yarn obtained by mixing 56T-24F polyester fiber and polyurethane yarn. Subsequently, the yarn oil agent and dirt were removed by immersing the fabric in a mixed aqueous solution of sodium hydroxide 0.06 mass% and surfactant 0.05 mass% (80 ° C., bath ratio 1:30). A conductive polymer dispersion was applied to the obtained knitted fabric as a fiber structure in the same manner as in Example 1 to obtain an electrode. The materials used and the properties of the resulting electrodes are shown in Tables 1 and 2.
- Example 12 Circular knitted fabrics were knitted using 78T-24F nylon fiber single yarn. Subsequently, the yarn oil agent and dirt were removed by immersing the fabric in a mixed aqueous solution of sodium hydroxide 0.06 mass% and surfactant 0.05 mass% (80 ° C., bath ratio 1:30). A conductive polymer dispersion was applied to the obtained knitted fabric as a fiber structure in the same manner as in Example 1 to obtain an electrode. The materials used and the properties of the resulting electrodes are shown in Tables 1 and 2.
- Example 13 Circular knitted fabric using 100T-136F polyester nanofiber blended yarn blended 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.
- aqueous solution of sodium hydroxide 75 ° C., bath ratio 1:30
- a polyurethane resin microporous film is laminated on the back surface of the obtained knitted fabric by a known method, and on the surface, a mixed solvent of water and ethanol, PEDOT / PSS as a conductive polymer, and an acrylic thermosetting resin as a binder
- An electrode was obtained by applying a dispersion liquid in which the amount of the drug was applied by a known gravure coating method so that the drug application amount was 15 g / m 2 .
- the materials used and the properties of the resulting electrodes are shown in Tables 1 and 2.
- Example 14 Except that the high shrinkage yarn was changed from 22T-24F to 33T-6F, and a polyester nanofiber mixed yarn with 75T-112F (sea-island ratio 30%: 70%, 127 islands / F) was used. The same treatment as 13 was performed to obtain an electrode. The materials used and the properties of the resulting electrodes are shown in Tables 1 and 2.
- Example 15 An electrode was obtained by performing the same treatment as in Example 13 except that the fabric structure was changed from a knitted fabric to a plain fabric. The materials used and the properties of the resulting electrodes are shown in Tables 1 and 2.
- Example 16 An electrode was obtained by carrying out the same treatment as in Example 13, except that the polyester nanofiber was changed to 75T-112F (sea-island ratio 30%: 70%, 127 islands / F). The materials used and the properties of the resulting electrodes are shown in Tables 1 and 2.
- Example 17 An electrode was obtained by carrying out the same treatment as in Example 13, except that the polyester nanofiber was changed to 100T-30F (sea / island ratio 30%: 70%, 2048 islands / F). The materials used and the properties of the resulting electrodes are shown in Tables 1 and 2.
- Example 18 An electrode was obtained by carrying out the same treatment as in Example 13 except that the polyester nanofiber was changed to 120T-60F (sea-island ratio 50%: 50%, number of islands 2048 islands / F). The materials used and the properties of the resulting electrodes are shown in Tables 1 and 2.
- Example 19 An electrode was obtained by carrying out the same treatment as in Example 13 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). The materials used and the properties of the resulting electrodes are shown in Tables 1 and 2.
- Example 20 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 treatment as 13 was performed to obtain an electrode. The materials used and the properties of the resulting electrodes are shown in Tables 1 and 2.
- Example 21 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 13 In the same manner as in Example 13, a polyurethane resin microporous film was laminated on the back surface of the obtained nonwoven fabric, and a conductive polymer dispersion was applied to the surface to obtain an electrode.
- the materials used and the properties of the resulting electrodes are shown in Tables 1 and 2.
- Example 22 Using a polyester fiber fabric of 84T-36F (polyester fabric for dyeing test, Color dye Co., Ltd.), a polyurethane resin microporous membrane was laminated on the back surface of the fabric in the same manner as in Example 13, and the surface was electrically conductive. A conductive polymer dispersion was applied to obtain an electrode. The materials used and the properties of the resulting electrodes are shown in Tables 1 and 2.
- Example 23 A circular knitted fabric was knitted using a mixed yarn obtained by mixing 56T-24F polyester fiber and polyurethane yarn. Subsequently, the yarn oil agent and dirt were removed by immersing the fabric in a mixed aqueous solution of sodium hydroxide 0.06 mass% and surfactant 0.05 mass% (80 ° C., bath ratio 1:30). In the same manner as in Example 13, a polyurethane resin microporous film was laminated on the back surface of the obtained knitted fabric, and a conductive polymer dispersion was applied on the surface to obtain an electrode. The materials used and the properties of the resulting electrodes are shown in Tables 1 and 2.
- Example 24 Circular knitted fabrics were knitted using 78T-24F nylon fiber single yarn. Subsequently, the yarn oil agent and dirt were removed by immersing the fabric in a mixed aqueous solution of sodium hydroxide 0.06 mass% and surfactant 0.05 mass% (80 ° C., bath ratio 1:30). A polyurethane resin microporous film was laminated on the back surface of the obtained knitted fabric, and a conductive polymer dispersion was applied to the surface to obtain an electrode. The materials used and the properties of the resulting electrodes are shown in Tables 1 and 2.
- Example 25 An electrode was obtained by carrying out the same treatment as in Example 1 except that the conductive polymer was changed to a 5% polyaniline aqueous solution (manufactured by Aldrich). The materials used and the properties of the resulting electrodes are shown in Tables 1 and 2.
- Example 26 An electrode was obtained by carrying out the same treatment as in Example 1 except that the conductive polymer was changed to a polypyrrole 5% aqueous solution (manufactured by Aldrich). The materials used and the properties of the resulting electrodes are shown in Tables 1 and 2.
- Example 27 Except having changed the polyester nanofiber of Example 4 into nylon nanofiber, the same process as Example 1 was performed and the electrode was obtained. The materials used and the properties of the resulting electrodes are shown in Tables 1 and 2.
- Example 28 As an example of a device using the electrode member according to the present invention, 110T-34F of silver plated yarn “AGposs” manufactured by Mitsuji Fuji Textile Co., Ltd. is passed through a vinyl insulating tube, and is taken out from one end of the tube. The silver-plated thread coming out from one end was sewn and connected to the electrode of Example 1 cut to 3 cm square. A waterproof and moisture-permeable surgical sheet “Degaderm Smooth Film Roll” manufactured by 3M Healthcare Co., Ltd. was attached from the top to the surface on which the silver-plated thread is located, to create an electrocardiogram electrode.
- Example 29 As an example of a device using the electrode according to the present invention, as an electrode on the left chest and right chest on the inner side of a commercially available stretch-type sports inner, the electrode described in Example 1 cut to a length of 7 cm and a width of 5 cm with a sewing thread. Further, the electrode of Example 1 which was also cut into a vertical 5 cm length as an indifferent electrode (biological reference potential electrode) 5 cm below the left chest electrode was sewn with a sewing thread. Further, 110T-34F of silver plated yarn “AGposs” manufactured by Mitsufuji Textile Industry Co., Ltd. was used as the wiring, and the three electrodes were sewn to the inner side with a sewing needle so as not to contact each other.
- a waterproof seam tape “ ⁇ E-110” manufactured by Toray Cortex Co., Ltd. was pasted on the front and back of the wiring portion of the plated yarn to insulate the wiring portion.
- a wearable electrode inner capable of measuring an electrocardiogram at the time of wearing was prepared by connecting and attaching a signal detection device to the silver-plated thread drawn to the left clavicle.
- Example 2 A conductive polymer adhesive hydrogel was applied to a PET film by the same gravure coating method as in Example 1 so that the resin coating amount was 15 g / m 2 to obtain an electrode.
- the materials used and the properties of the resulting electrodes are shown in Tables 1 and 2.
Abstract
Description
使用するバインダとしては、熱硬化性樹脂であってもよいし、熱可塑性樹脂であってもよい。例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステル;ポリイミド;ポリアミドイミド;ポリアミド6、ポリアミド6,6、ポリアミド12、ポリアミド11等のポリアミド;ポリフッ化ビニリデン、ポリフッ化ビニル、ポリテトラフルオロエチレン、エチレンテトラフルオロエチレンコポリマー、ポリクロロトリフルオロエチレン等のフッ素樹脂;ポリビニルアルコール、ポリビニルエーテル、ポリビニルブチラール、ポリ酢酸ビニル、ポリ塩化ビニル等のビニル樹脂;エポキシ樹脂;キシレン樹脂;アラミド樹脂;ポリイミドシリコーン;ポリウレタン;ポリウレア;メラミン樹脂;フェノール樹脂;ポリエーテル;アクリル樹脂及びこれらの共重合体等が挙げられる。これらバインダは、有機溶剤に溶解されていてもよいし、スルホン酸基やカルボン酸基などの官能基が付与されて水溶液化されていてもよいし、乳化など水に分散されていてもよい。
バインダ樹脂の中でも、容易に混合できることから、ポリウレタン、ポリエステル、アクリル樹脂、ポリアミド、ポリイミド、エポキシ樹脂、ポリイミドシリコーンのいずれか1種以上が好ましい。
本発明の電極部材を生体電極として利用する場合、肌面への密着性・追随性の観点や、フレキシブルでソフト風合い、肌面の汗によるムレ、カブレの抑制のためには高い通気性が要求されることから、繊維構造物の形態は、織物、編物、不織布の形状が好ましい。
単繊維の断面形状も特に限定されず、丸、三角、扁平、中空など公知の断面形状でよい。特開2013-185283号公報に例示された複合口金を用いた多様な繊維断面形態、特に、異形度の高い断面(本発明で言う異形度とは、異径断面糸の外接円と内接円の比(外接円/内接円)が大きい方が、高い異形度を有する)のマルチフィラメント糸を好適に使用できる。
海島型複合繊維は、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。
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の重量を測定し、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。
得られ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)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。
前述した繊維径の平均繊維径および繊維径標準偏差を求め、下記式を基づき繊維径CV%(変動係数: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、小数点以下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
前述した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桁目以下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桁目以下は四捨五入する。
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(%)
標準状態(20℃×65%RH)での導電性高分子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樹脂付着量を測定した。計算式は下記の通りである。
樹脂付着量(g/m2)(加工後の試験布質量(g)-加工前の試験質重量(g))/試験布の分散液を塗布した面積(m2)
10cm×10cmの電極を試験片として、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の電極を試験片として、JIS L0217(2012)103法に準拠した方法で、20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。
電極の通気性は、JIS L 1096(織物および編物の生地試験方法)(1999)通気性A法(フラジール形法)に準じて測定した。
電極の剛軟度は、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。
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、水とエタノールの混合溶媒(水44wt%、エタノール50wt%)に、導電性高分子としてPEDOT/PSSを1.0wt%、バインダとしてアクリル系熱硬化性樹脂を5.0wt%を分散した分散液を、既知のグラビア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電極の特性を表1および表2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たこと以外は、実施例1と同じ処理を行って電極を製造した。使用した材料および得られた電極の特性を表1および表2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電極を製造した。使用した材料および得られた電極の特性を表1および表2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電極を製造した。使用した材料および得られた電極の特性を表1および表2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電極を製造した。使用した材料および得られた電極の特性を表1および表2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電極を製造した。使用した材料および得られた電極の特性を表1および表2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電極を製造した。使用した材料および得られた電極の特性を表1および表2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電極を製造した。使用した材料および得られた電極の特性を表1および表2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、水とエタノールの混合溶媒に、導電性高分子としてPEDOT/PSS、バインダとしてアクリル系熱硬化性樹脂を分散した分散液を、既知のグラビア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電極の特性を表1および表2に示す。
22T-24Fの高収縮糸を使用せず、75T-112F(海島比率、島数127島/F)を84T-36F(染色試験用ポリエステル繊維布 (株)色染社製)のポリエステルファイバー織物に変更した以外は、実施例1と同じ処理を行って電極を製造した。使用した材料および得られた電極の特性を表1および表2に示す。
56T-24Fのポリエステルファイバーとポリウレタン糸を混繊した混繊糸を用いて、丸編物を製編した。次いで、布帛を水酸化ナトリウム0.06質量%と界面活性剤0.05質量%の混合水溶液(80℃、浴比1:30)に浸漬することで原糸油剤や汚れを除去した。得られた繊維構造物としての編物に、実施例1と同様にして、導電性高分子の分散液を塗布して電極を得た。使用した材料および得られた電極の特性を表1および表2に示す。
78T-24Fのナイロンファイバー単独糸を用いて、丸編物を製編した。次いで、布帛を水酸化ナトリウム0.06質量%と界面活性剤0.05質量%の混合水溶液(80℃、浴比1:30)に浸漬することで原糸油剤や汚れを除去した。得られた繊維構造物としての編物に、実施例1と同様にして、導電性高分子の分散液を塗布して電極を得た。使用した材料および得られた電極の特性を表1および表2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、水とエタノールの混合溶媒に、導電性高分子としてPEDOT/PSS、バインダとしてアクリル系熱硬化性樹脂を分散した分散液を、既知のグラビア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電極の特性を表1および表2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たこと以外は、実施例13と同じ処理を行って電極を得た。使用した材料および得られた電極の特性を表1および表2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13と同じ処理を行って電極を得た。使用した材料および得られた電極の特性を表1および表2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13と同じ処理を行って電極を得た。使用した材料および得られた電極の特性を表1および表2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13と同じ処理を行って電極を得た。使用した材料および得られた電極の特性を表1および表2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13と同じ処理を行って電極を得た。使用した材料および得られた電極の特性を表1および表2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13と同じ処理を行って電極を得た。使用した材料および得られた電極の特性を表1および表2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13と同じ処理を行って電極を得た。使用した材料および得られた電極の特性を表1および表2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13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、表面に導電性高分子分散液を塗布して、電極を得た。使用した材料および得られた電極の特性を表1および表2に示す。
84T-36F(染色試験用ポリエステル繊維布 (株)色染社製)のポリエステルファイバー織物を用いて、実施例13と同様に、布帛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、表面に導電性高分子分散液を塗布して、電極を得た。使用した材料および得られた電極の特性を表1および表2に示す。
56T-24Fのポリエステルファイバーとポリウレタン糸を混繊した混繊糸を用いて、丸編物を製編した。次いで、布帛を水酸化ナトリウム0.06質量%と界面活性剤0.05質量%の混合水溶液(80℃、浴比1:30)に浸漬することで原糸油剤や汚れを除去した。実施例13と同様に、得られた編物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、表面に導電性高分子分散液を塗布して、電極を得た。使用した材料および得られた電極の特性を表1および表2に示す。
78T-24Fのナイロンファイバー単独糸を用いて、丸編物を製編した。次いで、布帛を水酸化ナトリウム0.06質量%と界面活性剤0.05質量%の混合水溶液(80℃、浴比1:30)に浸漬することで原糸油剤や汚れを除去した。得られた編物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、表面に導電性高分子分散液を塗布して、電極を得た。使用した材料および得られた電極の特性を表1および表2に示す。
導電性高分子としてポリアニリン5%水溶液(アルドリッチ製)に変更したこと以外は、実施例1と同じ処理を行って電極を得た。使用した材料および得られた電極の特性を表1および表2に示す。
導電性高分子としてポリピロール5%水溶液(アルドリッチ製)に変更したこと以外は、実施例1と同じ処理を行って電極を得た。使用した材料および得られた電極の特性を表1および表2に示す。
実施例4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電極を得た。使用した材料および得られた電極の特性を表1および表2に示す。
本発明にかかる電極部材を用いた機器の一例として、三ツ冨士繊維工業(株)製銀メッキ糸「AGposs」の110T-34Fをビニール絶縁系チューブの中に通し、該チューブの片端から出し、片端から出た該銀メッキ糸を3cm四方にカットした実施例1の電極に縫込み接続した。銀メッキ糸の位置する面に、スリーエムヘルスケア社製の防水透湿サージカルシート「デガダーム スムースフィルムロール」を上から貼り付け、心電図用の電極を作成した。
本発明にかかる電極を用いた機器の一例として、市販のストレッチ系スポーツインナーの内側の左側の胸部と右側の胸部に関電極として、タテ7cmヨコ5cmにカットした実施例1記載の電極を縫い糸で縫いつけ、更に、左側の胸部の電極の5cm下側に不関電極(生体基準電位電極)として、同じくタテ7cmヨコ5cmにカットした実施例1の電極を縫い糸で縫い付けた。更に、三ツ冨士繊維工業(株)製銀メッキ糸「AGposs」の110T-34Fを配線として、該3つの電極部分からそれぞれ左鎖骨部までお互いに接触しないよう縫い針でインナーに縫いつけ、該銀メッキ糸の配線部の表裏に、東レコーテックス(株)製の防水シームテープ「αE-110」を貼ることで配線部を絶縁被覆した。該左鎖骨部まで引いた銀メッキ糸に信号検出装置を接続して取り付けることで、着用時に心電図を測定することができるウエアブル電極インナーを作成した。
PETフィルムに、導電性高分子PEDOT/PSS(信越ポリマー社、SEP LYGIDA(登録商標))とアクリル樹脂を実施例1と同様に、既知のグラビア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電極の特性を表1および表2に示す。
PETフィルムに、導電性高分子粘着性ハイドロゲルを実施例1と同じ、既知のグラビアコーティング法で樹脂塗布量が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電極の特性を表1および表2に示す。
101 電極部材
102 測定装置
103 配線
104 衣料本体部
Claims (9)
- 導電性高分子を含む繊維構造物において、前記繊維構造物を構成する単繊維の表面および/または単繊維と単繊維の間隙に導電性高分子が担持されていることを特徴とする電極部材。
- 前記繊維構造物が少なくともマルチフィラメント糸を含んでなり、前記マルチフィラメント糸を構成する単繊維の表面および/または単繊維と単繊維の間隙に導電性物質が担持されていることを特徴とする請求項1に記載の電極部材。
- 前記繊維構造物を構成するマルチフィラメント糸は、0.2dtex以下の単繊維を含むこと特徴とする請求項1または2に記載の電極部材。
- 前記導電性高分子は、バインダとともに溶媒に分散され、前記導電性高分子が分散した分散液中を前記繊維構造物に塗布することにより、前記繊維構造物を構成する単繊維の表面および/または単繊維と単繊維の間隙に前記導電性高分子を担持させることを特徴とする請求項1~3のいずれかに記載の電極部材。
- 前記導電性高分子は、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との混合物であることを特徴とする請求項1~4のいずれかに記載の電極部材。
- 前記導電性物質を含む繊維構造物の片面に、樹脂層が積層されてなることを特徴とする請求項1~5のいずれかに記載の電極部材。
- JIS L0217(2012年度版)103法にて、20回洗濯を繰り返した後の表面抵抗が1×106Ω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電極部材。
- 貼付剤と積層することを特徴とする請求項1~7のいずれかに記載の電極部材。
- 請求項1~8のいずれかに記載の電極部材を少なくとも電極の一部として用いてなることを特徴とする装置。
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2015
- 2015-01-27 US US15/114,432 patent/US20160338645A1/en not_active Abandoned
- 2015-01-27 JP JP2015559953A patent/JP6454649B2/ja active Active
- 2015-01-27 EP EP15743324.4A patent/EP3100678A4/en not_active Ceased
- 2015-01-27 CA CA2938018A patent/CA2938018A1/en not_active Abandoned
- 2015-01-27 KR KR1020187034668A patent/KR20180130017A/ko active Search and Examination
- 2015-01-27 KR KR1020167019486A patent/KR20160114590A/ko active Application Filing
- 2015-01-27 WO PCT/JP2015/052226 patent/WO2015115440A1/ja active Application Filing
- 2015-01-27 CN CN201580006127.7A patent/CN105939659B/zh not_active Expired - Fee Related
- 2015-01-28 TW TW104102826A patent/TWI683402B/zh not_active IP Right Cessation
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2016
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Also Published As
Publication number | Publication date |
---|---|
JP6454649B2 (ja) | 2019-01-16 |
US20160338645A1 (en) | 2016-11-24 |
TW201546979A (zh) | 2015-12-16 |
EP3100678A4 (en) | 2017-09-20 |
CN105939659B (zh) | 2020-10-09 |
EP3100678A1 (en) | 2016-12-07 |
CN105939659A (zh) | 2016-09-14 |
KR20180130017A (ko) | 2018-12-05 |
KR20160114590A (ko) | 2016-10-05 |
CL2016001854A1 (es) | 2016-12-02 |
CA2938018A1 (en) | 2015-08-06 |
TWI683402B (zh) | 2020-01-21 |
JPWO2015115440A1 (ja) | 2017-03-23 |
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