WO2014123071A1 - Détecteur de signal biologique et procédé de détection de signal biologique - Google Patents

Détecteur de signal biologique et procédé de détection de signal biologique Download PDF

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Publication number
WO2014123071A1
WO2014123071A1 PCT/JP2014/052278 JP2014052278W WO2014123071A1 WO 2014123071 A1 WO2014123071 A1 WO 2014123071A1 JP 2014052278 W JP2014052278 W JP 2014052278W WO 2014123071 A1 WO2014123071 A1 WO 2014123071A1
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Prior art keywords
sensor
biological signal
signal detector
polymer
block copolymer
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PCT/JP2014/052278
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English (en)
Japanese (ja)
Inventor
幹也 松浦
基実 松島
活栄 高橋
和彦 淺原
貴弘 清水
友介 坂上
牧川　方昭
志麻 岡田
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株式会社クラレ
学校法人立命館
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Publication of WO2014123071A1 publication Critical patent/WO2014123071A1/fr

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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
    • A61B5/02—Detecting, measuring or recording pulse, heart rate, blood pressure or blood flow; Combined pulse/heart-rate/blood pressure determination; Evaluating a cardiovascular condition not otherwise provided for, e.g. using combinations of techniques provided for in this group with electrocardiography or electroauscultation; Heart catheters for measuring blood pressure
    • A61B5/024—Detecting, measuring or recording pulse rate or heart rate
    • A61B5/02444—Details of sensor
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B2560/00—Constructional details of operational features of apparatus; Accessories for medical measuring apparatus
    • A61B2560/04—Constructional details of apparatus
    • A61B2560/0406—Constructional details of apparatus specially shaped apparatus housings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • 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
    • A61B2562/0217—Electrolyte containing
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/08—Detecting, measuring or recording devices for evaluating the respiratory organs
    • A61B5/0803—Recording apparatus specially adapted therefor

Definitions

  • the present invention relates to a detection device that electrically detects a biological signal and a detection method of the biological signal using the detection device.
  • Patent Document 1 discloses a physiological function monitor garment for measuring a biological signal incorporating a respiratory sensor and a heart rate sensor.
  • Such a physiological function monitor garment is designed so that the conductive fibers are in direct contact with the skin of the subject, so that the action potential can be measured without using a conductive gel.
  • a physiological function monitor garment has a problem in that stable measurement is likely to be difficult because the contact resistance between the skin surface and the electrode is likely to change due to drying or sweating of the skin surface.
  • Patent Document 2 discloses a measuring device that can detect respiration and pulse by a piezoelectric film built in a belt that is wound around a torso of a human body.
  • This piezoelectric film material is made of fluororesin (polyvinylidene fluoride). From the viewpoint of environmental pollution caused by fluororesin and the burden on disposal facilities, it can be disposed of easily after use without any environmental pollution problems. There is a need for a method for detecting a biological signal using a material.
  • the present invention has been made to solve the above-described problem, and can detect a biological signal accurately without depending on the surface state of the skin surface, and can easily dispose of the biological signal after use.
  • An object is to provide a signal detection method.
  • the above object is achieved by sandwiching a polymer electrolyte membrane between a stretchable member having at least a cylindrical portion and a pair of electrode membranes made of a composition containing conductive particles and a resin.
  • a biological signal detector including a sensor, the biological signal detector having the sensor disposed on the inner surface of the cylindrical portion.
  • the shape of the main surface of the sensor is a circle or an ellipse.
  • a protective film is provided on at least one surface of the sensor.
  • the protective film is at least one selected from a polyethylene terephthalate film and a cloth made of cellulose fiber, nylon fiber, vinylon fiber, polyester fiber or rayon fiber.
  • the polymer electrolyte membrane and the resin are composed of a polymer block (S) in which an ion conductive group is introduced into a structural unit derived from an aromatic vinyl compound, and a structural unit derived from an unsaturated aliphatic hydrocarbon compound.
  • a block copolymer (Z) having a crystalline polymer block (T) is contained.
  • the elastic member is in close contact with the skin surface of the animal, and the sensor is elastically deformed by following the motion of the skin surface to detect the motion and generate an electrical signal.
  • Examples include those in which the electrical signal is generated by the sensor detecting movement of the skin surface accompanying heartbeat, pulse or respiration.
  • the present invention also relates to a biological signal detection method for measuring an electrical signal generated by elastic deformation of a sensor of the biological signal detector following the movement of the skin surface.
  • the biological signal detector of the present invention is capable of accurately detecting and measuring a biological signal without depending on the surface condition of the skin surface by being in close contact with the skin surface of an animal (preferably the human skin surface). It can. Further, since it does not contain a fluorine-based resin like a conventional piezoelectric film, there is no problem of environmental pollution after use and it can be easily disposed of.
  • the sensor of the biological signal detector is elastically deformed by following the movement of the skin surface accompanying the biological signal such as heartbeat, pulse, and respiration, and responds to this deformation.
  • a predetermined biological signal can be detected by measuring an electric signal having a predetermined potential.
  • FIG. 6 is a potential waveform diagram obtained during apnea in Example 1.
  • FIG. 6 is a potential waveform diagram obtained during respiration in Example 1.
  • FIG. 6 is a potential waveform diagram obtained in Example 2 and Comparative Example 1.
  • FIG. 6 is a potential waveform diagram obtained in Comparative Example 2.
  • the biological signal detector of the present invention includes an elastic member having at least a cylindrical portion, and a sensor in which a polymer electrolyte membrane is sandwiched between a pair of electrode membranes made of a composition containing conductive particles and a resin. Is provided. Moreover, the sensor is arrange
  • the biosignal detection tool 30 is configured such that the sensor 1 is disposed on the inner surface of a shirt that is an elastic member 20 having a cylindrical portion.
  • the stretchable member 20 having the cylindrical portion is made of a stretchable material, and the sensor 1 disposed on the inner surface of the biological signal detector 30 on the skin surface of the measurement target portion when the subject wears it. Is in close contact.
  • the sensor 1 follows the movement of the skin surface and elastically deforms to generate an electrical signal.
  • the electrical signal is output to the signal processing unit 20 installed together with the sensor 1 and amplified.
  • the signal processing unit 20 preferably includes a recording medium for recording the amplified electric signal.
  • the sensor 1 constituting the biological signal detector 30 of the present invention is a sensor that generates an electrical signal in accordance with elastic deformation.
  • the sensor 1 has a plate shape.
  • the plate shape means a shape suitable for preventing the elastic deformation of the sensor, and the ratio of thickness and (length or width) / thickness is not particularly limited. Including.
  • the thickness of the sensor 1 may or may not be constant, but is preferably constant from the viewpoint of productivity, and suppresses damage to the skin due to the use of the biological signal detector. From the viewpoint of doing so, it is preferable that the peripheral edge is thin.
  • “elastic deformation” includes all deformation due to compression, extension, bending, and the like.
  • a polymer electrolyte membrane made of a material that can be elastically deformed from a viewpoint of detecting a minute movement of the skin surface due to a pulse or the like and an energy saving viewpoint is an electrode film made of a pair of materials that can be elastically deformed.
  • a sandwiched sensor is preferred.
  • FIG. 2 and 3 are schematic cross-sectional views of the element structure of the sensor 1 used in the present invention.
  • the sensor 1 as shown in FIG. 2, a pair of electrode films 3a and 3b sandwich the polymer electrolyte membrane 2.
  • the sensor 1 may be provided with the electrode 4a and the protective film 5a in a layer form on the electrode film 3a, and the electrode 4b and the protective film 5b in a layer form on the electrode film 3b.
  • the polymer electrolyte membrane 2 used in the sensor 1 is a polymer block containing a structural unit derived from an aromatic vinyl compound and having an ion conductive group from the viewpoint of high signal strength and flexibility.
  • S (hereinafter simply referred to as “polymer block (S)”) and a polymer block (T) (hereinafter simply referred to as “polymer block (S)”) comprising an amorphous polymer containing a structural unit derived from an unsaturated hydrocarbon compound. It is preferable to contain a block copolymer (Z) having a polymer component (referred to as “polymer block (T)”).
  • the polymer block (S) is a polymer block (S 0 ) containing a structural unit derived from an aromatic vinyl compound and having no ion conductive group (hereinafter simply referred to as “polymer block (S 0 )”). ) Is introduced by introducing an ion conductive group into the aromatic ring.
  • the aromatic ring of the aromatic vinyl compound is preferably a carbocyclic aromatic ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, and a pyrene ring.
  • Examples of the monomer capable of forming the polymer block (S 0 ) include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 2,4-dimethylstyrene, 2,5 -Aromatic vinyl compounds such as dimethylstyrene, 3,5-dimethylstyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, vinylbiphenyl, vinylterphenyl, vinylnaphthalene, vinylanthracene, 4-phenoxystyrene, etc. Can be mentioned.
  • the ⁇ -position carbon ( ⁇ -carbon) of the aromatic ring in the aromatic vinyl compound may be a quaternary carbon.
  • the ⁇ -carbon is a quaternary carbon
  • examples of the substituent bonded to the ⁇ -carbon include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a sec-butyl group.
  • alkyl groups having 1 to 4 carbon atoms such as tert-butyl group; halogenated alkyl groups having 1 to 4 carbon atoms such as chloromethyl group, 2-chloroethyl group and 3-chloroethyl group; .
  • the aromatic vinyl compound having these substituents ⁇ -methylstyrene, ⁇ -methyl-4-methylstyrene, ⁇ -methyl-4-ethylstyrene, and 1,1-diphenylethylene are preferable.
  • Styrene, ⁇ -methyl styrene, 4-methyl styrene, 4-ethyl styrene, and vinyl biphenyl are more preferable from the viewpoint of easy introduction of ion conductive groups and high density of sulfonic acid groups.
  • the polymer block (S 0 ) may contain a structural unit derived from one or more other monomers other than the aromatic vinyl compound as long as the effects of the present invention are not impaired.
  • examples of such other monomers include butadiene, 1,3-pentadiene, isoprene, 1,3-hexadiene, 2,4-hexadiene, 2,3-dimethyl-1,3-butadiene, and 2-ethyl-1.
  • C4-C8 conjugated dienes such as 1,3-butadiene, 1,3-heptadiene; ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, 1-hexene, 2- Alkenes having 2 to 8 carbon atoms such as hexene, 1-heptene, 2-heptene, 1-octene and 2-octene; such as methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate (Meth) acrylic acid esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate; methyl vinyl ether, Vinyl ether such as source-butyl vinyl ether.
  • the copolymerization form of the aromatic vinyl compound and the other monomer is desirably random copolymerization.
  • the other monomer is preferably 10% by mass or less, and more preferably 5% by mass or less of the monomer capable of forming the polymer block (S 0 ).
  • Examples of the ion conductive group possessed by the polymer block (S) include a sulfonic acid group, a phosphoric acid group, and a carboxylic acid group, and among these, a sulfonic acid group is preferable.
  • the introduction amount of the ion conductive group is not particularly limited, but from the viewpoint of the handling property of the block copolymer (Z), the solubility in a solvent, the ion conductivity, and the performance of the obtained sensor, the polymer block (S)
  • the ratio of the ion conductive group to the aromatic ring constituting the ring (hereinafter referred to as “ion conductive group introduction rate”) is preferably in the range of 10 to 100 mol%, more preferably in the range of 20 to 80 mol%, and 30 to 60 mol%. The range of is more preferable.
  • the ion conductive group introduction rate is lower than 10 mol%, the ion conductivity becomes insufficient, and the performance of the obtained sensor is lowered, which is not preferable.
  • the polymer block (T) which is a constituent component of the block copolymer (Z) is an amorphous polymer block containing a structural unit derived from an unsaturated hydrocarbon compound.
  • amorphous can be confirmed by measuring the dynamic viscoelasticity of the block copolymer (Z) and confirming that there is no change in the storage elastic modulus derived from the crystalline olefin polymer.
  • the monomer capable of forming the polymer block (T) is not particularly limited as long as it is an unsaturated hydrocarbon compound having a polymerizable carbon-carbon double bond, but is preferably a chain unsaturated hydrocarbon compound, for example, Carbon number such as ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, 1-heptene, 2-heptene, 1-octene, 2-octene 2-8 olefins; butadiene, 1,3-pentadiene, isoprene, 1,3-hexadiene, 2,4-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, Examples thereof include conjugated diene compounds having 4 to 8 carbon atoms such as 1,3-heptadiene.
  • any of them may be used for polymerization.
  • a 1,2-bond may be used.
  • 4-bonds may be mixed.
  • the monomers capable of forming the polymer block (T) may be used alone or in combination of two or more. When using 2 or more types together, it is preferable that the arrangement
  • the polymer block (T) may contain a structural unit derived from another monomer within the range not impairing the effects of the present invention, in addition to the monomer.
  • examples of such other monomers include aromatic vinyl compounds such as styrene and vinyl naphthalene; halogen-containing vinyl compounds such as vinyl chloride; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl pivalate. And vinyl ethers such as methyl vinyl ether and isobutyl vinyl ether.
  • the arrangement of the structural units forming the polymer block (T) is preferably random.
  • the structural unit derived from the other monomer is preferably 5% by mass or less of the polymer block (T).
  • the block copolymer (Z) has at least one polymer block (S) and one polymer block (T).
  • S polymer block
  • T polymer block
  • their structures type of monomer constituting, degree of polymerization, type of ion conductive group, introduction ratio, etc.
  • a polymerization degree, etc. may mutually be the same, and may differ.
  • an ST type diblock copolymer (S and T are polymer blocks ( S) represents a polymer block (T), the same applies hereinafter), a STS type triblock copolymer, a TST type triblock copolymer, a STS type triblock copolymer.
  • examples thereof include a block copolymer or a mixture of a TST type triblock copolymer and a ST type diblock copolymer.
  • these block copolymers may be used alone or in combination of two or more.
  • the mass ratio of the total amount of the polymer block (S) and the total amount of the polymer block (T) is preferably in the range of 15:85 to 85:15, and 20: It is more preferably 80 to 80:20, and further preferably 25:75 to 75:25.
  • the ratio of the polymer block (S) in the block copolymer (Z) is less than 15% by mass, the output of the sensor decreases, which is not preferable.
  • flexibility of a sensor is lost when the ratio of the polymer block (S) in a block copolymer (Z) exceeds 85 mass%, it is unpreferable.
  • the block copolymer (Z) forming the polymer electrolyte membrane 2 configured in the biological signal detector 30 of the present invention is a block copolymer comprising a polymer block (S 0 ) and a polymer block (T). After producing (Z 0 ), a method of introducing an ion conductive group into the polymer block (S 0 ) can be used.
  • the mass ratio of the total amount of the polymer block (S 0 ) and the polymer block (T) is preferably in the range of 10:90 to 80:20, and 15:85 More preferably, it is ⁇ 75: 25, and further preferably 20:80 to 70:30.
  • the ratio of the polymer block (S 0 ) in the block copolymer (Z 0 ) is less than 10% by mass, the output of the sensor decreases, which is not preferable.
  • the ratio of the polymer block (S 0 ) in the block copolymer (Z 0 ) exceeds 80% by mass, the flexibility of the sensor is lost, which is not preferable.
  • the proportion of such block copolymer (Z 0) in the polymer block (S 0) of the total amount and the weight ratio and the polymer block of the polymer total weight of the block (T) (S 0) is, 1 H -Can be determined by NMR.
  • the production method of the block copolymer (Z 0 ) is appropriately selected from radical polymerization method, anion polymerization method, cationic polymerization method, coordination polymerization method, etc. depending on the kind of monomer constituting, molecular weight, etc.
  • the radical polymerization method, the anionic polymerization method, and the cationic polymerization method are preferably selected from the viewpoint of practical ease.
  • a so-called living polymerization method is preferable from the viewpoint of molecular weight, molecular weight distribution, and the like, and specifically, a living radical polymerization method, a living anion polymerization method, and a living cation polymerization method are preferable.
  • the polymer block (S 0 ) is styrene, ⁇ -methylstyrene, t-
  • a method for producing a block copolymer (Z 0 ) formed from an aromatic vinyl compound such as butylstyrene and having a polymer block (T) formed from a conjugated diene or isobutene will be described.
  • a living anionic polymerization method or a living cationic polymerization method from the viewpoint of industrial ease, molecular weight, molecular weight distribution, polymer block (S 0 ), ease of bonding with the polymer block (T), and the like.
  • the following specific synthesis examples are shown.
  • the method for producing the block copolymer (Z 0 ) by living anionic polymerization is as follows: (1) In the presence of an anionic polymerization initiator in a nonpolar solvent such as cyclohexane, at a temperature of 20 to 100 ° C., aromatic There is a method in which a vinyl compound, a conjugated diene, and an aromatic vinyl compound are sequentially polymerized to obtain an S 0 -TS 0 type block copolymer (Z 0 ).
  • a coupling agent such as phenyl benzoate after sequential polymerization of an aromatic vinyl compound and a conjugated diene in a nonpolar solvent such as cyclohexane in the presence of an anionic polymerization initiator at a temperature of 20 to 100 ° C.
  • a nonpolar solvent such as cyclohexane
  • an anionic polymerization initiator at a temperature of 20 to 100 ° C.
  • t-butylstyrene, styrene, and conjugated diene are sequentially added one or more times in a desired order in the presence of an anionic polymerization initiator in a nonpolar solvent such as cyclohexane at a temperature of 20 to 100 ° C.
  • a method of adding and obtaining a block copolymer (Z 0 ) composed of three or more kinds of polymer blocks is employed.
  • the unsaturated bond When an unsaturated hydrocarbon compound having a plurality of carbon-carbon double bonds (unsaturated bonds) is used as the monomer for forming the polymer block (T), the unsaturated bond usually remains after polymerization. is doing. In this case, some or all of the remaining unsaturated bonds may be converted to saturated bonds by a known hydrogenation reaction.
  • the hydrogenation rate of the carbon-carbon double bond can be calculated by a commonly used method such as 1 H-NMR measurement.
  • the hydrogenation rate of the carbon-carbon double bond is preferably 50 mol% or more, and more preferably 80 mol% or more.
  • the number average molecular weight of the block copolymer (Z) is difficult to measure after the ion conductive group is introduced, the number average molecular weight of the block copolymer (Z 0 ) before introduction of the sulfonic acid group may be used as an index.
  • the number average molecular weight of the block copolymer (Z 0 ) is preferably in the range of 3000 to 300,000, and more preferably in the range of 10,000 to 200,000.
  • the number average molecular weight of the block copolymer (Z 0 ) is smaller than 3000, it is not preferable because the mechanical strength of the polymer electrolyte membrane is inferior. When it is larger than 300000, the solubility in a solvent is lowered. Therefore, it is not preferable.
  • a sulfonic acid group in the block copolymer (Z 0) typically it is reacted with sulfonating agent to be described later with block copolymer (Z 0) in the presence or absence of a solvent. If a solvent is used, usually, after preparing a solution or suspension of the block copolymer (Z 0), added to and mixed with sulfonating agent.
  • sulfuric acid As the sulfonating agent, sulfuric acid; a mixed system of sulfuric acid and an aliphatic acid anhydride; a chlorosulfonic acid; a mixed system of chlorosulfonic acid and trimethylsilyl chloride; a sulfur trioxide; a mixed system of sulfur trioxide and triethyl phosphate;
  • aromatic organic sulfonic acids represented by 2,4,6-trimethylbenzenesulfonic acid.
  • organic solvent to be used include halogenated hydrocarbons such as methylene chloride, linear aliphatic hydrocarbons such as hexane, cyclic aliphatic hydrocarbons such as cyclohexane, and the like. You may select and use suitably.
  • the polymer electrolyte membrane 2 is preferably composed only of the block copolymer (Z). However, as long as the effects of the present invention are not impaired, other resins, softeners, water, organic solvents, and various additives are added as optional components. You may contain.
  • the method for producing the polymer electrolyte membrane 2 is not particularly limited.
  • a solution or suspension of the block copolymer (Z) and, if necessary, the block copolymer (Z) prepared by mixing the above-mentioned optional components with an appropriate solvent is placed on a plate such as glass.
  • the polymer electrolyte membrane 2 can be obtained by removing the solvent after being cast into a film, applied using a coater or applicator, or printed using a screen printer or the like.
  • Solvents include halogenated hydrocarbons such as dichloromethane; aromatic hydrocarbons such as toluene, xylene, benzene, isopropylbenzene, and diisopropylbenzene; aliphatic hydrocarbons such as hexane, heptane, and cyclohexane; ethers such as tetrahydrofuran; methanol, ethanol , Alcohols such as 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 1-hexanol; or a mixed solvent thereof, and a mixed solvent of an aromatic hydrocarbon and an alcohol is preferable.
  • halogenated hydrocarbons such as dichloromethane
  • aromatic hydrocarbons such as toluene, xylene, benzene, isopropylbenzene, and diisopropylbenzene
  • aliphatic hydrocarbons such as hexane, hept
  • a block copolymer (Z) it is preferable that it is 20 times or less of a block copolymer (Z).
  • the conditions for removing the solvent are not particularly limited as long as the block copolymer (Z) is not decomposed. For example, a method of drying with hot air in the range of 60 to 140 ° C .; a method of drying under normal pressure in the range of 10 to 30 ° C., and further drying with hot air in the range of 60 to 140 ° C.
  • a method of drying under normal pressure in the range of 10 to 30 ° C. and further drying under normal pressure at 80 to 120 ° C. is preferable.
  • the block copolymer (Z) may be molded by compression molding, roll molding, extrusion molding, injection molding, or the like to form the polymer electrolyte membrane 2.
  • the electrode film 3 a and the electrode film 3 b used for the sensor 1 are insulated by the polymer electrolyte film 2.
  • the electrode film 3a and the electrode film 3b are made of a composition containing conductive particles and a resin, and the composition is preferably formed by dispersing conductive particles in a matrix made of a resin.
  • the electrode film 3a and the electrode film 3b are preferably flexible because they do not hinder elastic deformation of the polymer electrolyte membrane 2.
  • it is preferable that the interface between the electrode film 3 a and the electrode film 3 b and the polymer electrolyte membrane 2 does not peel off due to the elastic deformation of the sensor 1.
  • the resin contained in the composition forming the electrode film 3a and the electrode film 3b contains the block copolymer (Z).
  • the block copolymer (Z) that can be used for the polymer electrolyte membrane 2 and the electrode membranes 3a and 3b is composed of repeating units, ratio of polymer blocks, arrangement of polymer blocks, number average molecular weight, ion conduction
  • the kind of the ionic group, the ion conductive group introduction rate and the like may be the same or different.
  • Examples of the conductive particles used for the electrode film 3a and the electrode film 3b include metals such as gold, silver, copper, platinum, aluminum, and nickel; ruthenium oxide (RuO 2 ), titanium oxide (TiO 2 ), and tin oxide (SnO 2 ).
  • Metal oxides such as iridium dioxide (IrO 2 ), tantalum oxide (Ta 2 O 5 ) and indium-tin composite oxide (ITO); metal sulfides such as zinc sulfide (ZnS); carbon black (eg, Ketjen Black (registered trademark, etc.), conductive carbon such as carbon nanotubes; particles made of conductive polymer such as polyacetylene, polypyrrole, polythiophene, and the like. From the viewpoint of easy handling, conductive carbon is preferable. These may be used individually by 1 type, or may use multiple types together.
  • the electric double layer is formed at the interface between the resin and the conductive particles contained in the composition forming the electrode film 3a and the electrode film 3b, and the strength and stability of the signal intensity of the sensor 1 are increased. Therefore, if there are many interfaces between the resin and the conductive particles, the signal strength is improved and the value of the signal strength is stabilized when the working portion of the sensor 1 is deformed.
  • the ratio of the resin and the conductive particles contained in the composition forming the electrode film 3a and the electrode film 3b is preferably 1: 1 to 10: 1, more preferably 2: 1 to 7: 1. preferable.
  • the ratio of the conductive particles is too low, the signal intensity is lowered because the formation of the electric double layer is insufficient.
  • the ratio of the conductive particles is too high, the conductivity of the electrode film 3a and the electrode film 3b is improved and the formation of the electric double layer is inhibited, so that the signal intensity is lowered.
  • the molding method for forming the electrode film 3a and the electrode film 3b is the same as the method for preparing the polymer electrolyte membrane 2 except that the conductive particles are dispersed.
  • Examples of the method for forming the electrode film 3a and the electrode film 3b on both surfaces of the polymer electrolyte membrane 2 include a method of bonding by vacuum deposition of metals, sputtering, electroplating, chemical plating, etc .; including electrode materials A method of applying ink; a method of press-bonding and welding a separately produced electrode, and the like. Among them, a method of applying an ink containing an electrode material is preferable from the viewpoint of workability and versatility.
  • the two joined bodies are bonded to each other by polymer electrolyte membranes, thereby forming a polymer electrolyte membrane having two layers.
  • Two electrode films 3a and 3b may be bonded to both sides of the two.
  • the material and thickness of the two-layer polymer electrolyte membrane 2 may be the same or different.
  • the method of bonding the two bonded bodies is preferably thermocompression bonding.
  • the electrode film 3a and the electrode film 3b may be formed on one side of the protective film 5a and the protective film 5b described later, and the polymer electrolyte membrane 2 may be formed on the electrode film.
  • the collector electrode 4a on the surface of the electrode film 3a and the collector electrode 4b on the surface of the electrode film 3b as shown in FIG.
  • the collector electrode 4a and the collector electrode 4b include metal foils and metal thin films such as gold, silver, copper, platinum, and aluminum; metal powders such as gold, silver, nickel, or carbon powder, carbon nanotubes, and carbon fibers.
  • metal foils and metal thin films such as gold, silver, copper, platinum, and aluminum
  • metal powders such as gold, silver, nickel, or carbon powder, carbon nanotubes, and carbon fibers.
  • examples thereof include a molded body composed of carbon fine powder and a binder resin.
  • the collector electrode 4a and the collector electrode 4b are film-shaped molded bodies made of metal powder and a binder resin.
  • the collection of the electrical signal is excellent by providing the collector electrode 4a and the collector electrode 4b having higher conductivity than the electrode film on the surfaces of the electrode film 3a and the electrode film 3b.
  • the thickness of the collector electrode 4a and the collector electrode 4b is preferably in the range of 0.01 to 200 ⁇ m, more preferably in the range of 0.05 to 100 ⁇ m, and still more preferably in the range of 0.1 to 20 ⁇ m.
  • the thickness of the collector electrode 4a and the collector electrode 4b is 0.01 nm or less, film formation tends to be difficult, and when the thickness exceeds 200 ⁇ m, the flexibility of the collector electrode 4a and the collector electrode 4b tends to decrease.
  • Examples of a method for forming the collecting electrode 4a and the collecting electrode 4b on the electrode film 3a and the electrode film 3b include a method of bonding by a vacuum deposition method of metals, a sputtering method, electroplating, a chemical plating method, etc.
  • bonding and welding the electrode produced separately, etc. are mentioned,
  • coating the ink containing an electrode material is especially preferable from a viewpoint of workability and versatility.
  • two joined bodies in which the collecting electrode 4a and the collecting electrode 4b, the electrode film 3a and the electrode film 3b, and the polymer electrolyte membrane 2 are sequentially formed on one surface of the protective film 5a and the protective film 5b described later are manufactured.
  • the polymer electrolyte membranes of the joined body may be bonded together by thermocompression bonding or the like.
  • the sensor may be provided with a protective film on at least one surface from the viewpoint of suppressing damage associated with contact with the skin. Further, in order to physically protect the polymer electrolyte membrane 2, as well as the electrode membrane 3a and the electrode membrane 3b, as shown in FIG. 3, a protective membrane 5a and a protective membrane covering the polymer electrolyte membrane 2, the electrode membrane 3a and the electrode membrane 3b are provided. It is preferable to provide the film 5b.
  • the protective film 5 a and the protective film 5 b also function as a support for the sensor 1.
  • Examples of the protective film 5a and protective film 5b include polyethylene terephthalate film, polyethylene naphthalate film, polyolefin film, polyurethane film, polyvinyl chloride film, polymer film such as elastomer film; aramid fiber, cellulose fiber, nylon fiber, vinylon fiber, A fabric (woven fabric or non-woven fabric) made of fibers such as polyester fiber, polyolefin fiber, rayon fiber, etc. can be used as appropriate.
  • a polyethylene terephthalate film and at least one selected from fabrics made of cellulose fibers (such as cotton), nylon fibers, vinylon fibers, polyester fibers or rayon fibers may be used. It is preferred.
  • the thickness of the protective film 5a and the protective film 5b is preferably in the range of 5 to 350 ⁇ m, more preferably 7.5 to 300 ⁇ m, and most preferably 10 to 200 ⁇ m. If the protective film 5a and the protective film 5b are too thin, the thickness tends to be non-uniform, and if it is too thick, the flexibility of the sensor 1 tends to be impaired.
  • the protective film 5a and the protective film 5b are formed by, for example, further sandwiching a joined body in which the polymer electrolyte membrane 2 is sandwiched between a pair of the electrode film 3a and the electrode film 3b with the protective film 5a and the protective film 5b, and bonding them by thermocompression bonding or the like. It can be formed by combining them. Further, two joined bodies in which the electrode film 3a, the electrode film 3b, and the polymer electrolyte membrane 2 are sequentially laminated on one surface of the protective film 5a and the protective film 5b are produced, and the polymer electrolyte membranes of the two joined bodies are formed. You may stick together by thermocompression bonding.
  • the stretchable member 10 used in the biological signal detector 30 of the present invention includes a tubular portion, and by inserting a measurement object so as to stretch the tubular portion, the inner surface of the tubular portion due to the stretchability of the tubular portion. Adheres closely to the skin surface to be measured. It is important that the sensor 1 disposed on the inner surface side of the cylindrical portion is in close contact with the skin surface at the measurement target site, and it is preferable to design the inner diameter of the cylindrical portion to be narrower than the thickness of the measurement target. .
  • the material of the elastic member is not particularly limited as long as it is an elastic material capable of forming a strong elongation, but from the viewpoint of air permeability, a fabric made of fibers is preferable, such as polyester-based, nylon-based, etc. A knitted or woven fabric material of synthetic fiber and polyurethane or polyolefin elastic fiber is preferably used. Further, the shape of the stretchable member is preferably a belt or a garment shape. In the case of a garment shape, for example, a commercially available sports shirt is preferably used.
  • the shape of the main surface of the sensor 1 used in the biological signal detector 30 of the present invention is preferably a shape having a curve from the viewpoint of suppressing damage to the skin due to contact with the sensor 1, for example, a circle; an ellipse; Examples include a shape in which a corner of a polygon such as a quadrangle, hexagon, or octagon is curved, and a shape including only a curve such as a circle or an ellipse is more preferable.
  • the biological signal detector 30 of the present invention may be used by electrically connecting a device for amplifying and recording the generated electrical signal, but the signal processing for amplifying and recording the electrical signal integrated with the sensor 1 It is preferable to provide the part 20.
  • the signal processing unit 20 includes a measurement device for amplifying the electric signal output from the sensor 1.
  • the measuring device is usually composed of a differential amplifier, a non-inverting amplifier, a low-pass filter, an A / D (digital analog) converter, and a recording medium.
  • the recording medium for example, a rewritable and detachable recording device such as a USB memory or an SD card is used.
  • the signal processing unit 20 preferably includes a portable power source such as a lithium battery.
  • the test subject passes a part to be measured, for example, a torso, an arm, or the like, inside the cylindrical part of the biological signal detector. From the viewpoint of fixing the object to be measured to the cylindrical part due to the elasticity of the elastic member 10, it is extremely preferable that the diameter of the cylindrical part is designed to be smaller than the part to be measured.
  • the sensor 1 is disposed on the inner surface of the cylindrical portion, and the sensor 1 is in close contact with the skin surface. Therefore, when the sensor 1 follows the movement of the skin surface, the sensor 1 can be elastically deformed to detect the movement.
  • the sensor 1 arranged on the biological signal detector 30 When the sensor 1 arranged on the biological signal detector 30 is elastically deformed, an electric signal corresponding to the elastic deformation is continuously generated.
  • the potential of the electrical signal generated when the biological signal detector 30 is bent in a certain direction is a positive value
  • the potential of the electrical signal when bent in the opposite direction is a negative value.
  • the sensor 1 of the biological signal detector 30 when detecting respiration, it is preferable to install the sensor 1 of the biological signal detector 30 so as to be located near the lungs on the chest or the back, and so that it is located near the lungs on the back. It is more preferable to install in the.
  • An example of detection of a biological signal in which an electrical signal generated by elastic deformation of the sensor of the biological signal detector of the present invention by following the movement of the skin surface is shown.
  • detection of a biological signal motion by measuring a potential (action potential) of an electric signal generated in the body accompanying a biological signal is shown as a comparative example.
  • the number average molecular weight of the poly ⁇ -methylstyrene after polymerization for 5 hours was measured by GPC and found to be 6400 in terms of polystyrene.
  • 27 g of butadiene was added, and after stirring for 30 minutes, 1703 g of cyclohexane was added.
  • the number average molecular weight (GPC measurement, polystyrene conversion) of the polybutadiene block (b1) was 3,640.
  • 303 g of butadiene was added, and polymerization was performed for 2 hours while raising the temperature to 60 ° C.
  • the number average molecular weight (GPC measurement, polystyrene conversion) of the obtained triblock copolymer was 74000, the 1,2-bond amount determined from 1 H-NMR measurement was 43.9%, and the number of ⁇ -methylstyrene units. The content was 28% by mass. In addition, it was found by composition analysis by 1 H-NMR spectrum measurement that ⁇ -methylstyrene was not substantially copolymerized in the polybutadiene block.
  • block copolymer (Z 0 -1) The poly- ⁇ -methylstyrene-b-hydrogenated polybutadiene-b-poly ⁇ -methylstyrene type triblock copolymer (hereinafter referred to as block copolymer (Z 0 -1)) Called).
  • the hydrogenation rate of the obtained block copolymer (Z 0 -1) was calculated by 1 H-NMR spectrum measurement and found to be 99.6%.
  • block copolymer (Z-1) The sulfonation rate of the benzene ring of the ⁇ -methylstyrene unit in the obtained block copolymer (Z-1) was 50 mol% from 1 H-NMR analysis.
  • the storage elastic modulus of the obtained block copolymer (Z-1) was measured. Based on the fact that there was no change in the storage elastic modulus at 80 to 100 ° C. derived from the crystallized olefin polymer, the polymer block (T) was judged to be amorphous.
  • the electrode dispersion liquid is printed on the collector electrode of a soft film (thickness 200 ⁇ m) provided with a collector electrode (thickness 10 ⁇ m) with a commercially available silver paste, and then dried at 80 ° C. The process was repeated to form a layered electrode film having a thickness of 100 ⁇ m.
  • Example 1 The biological signal detector of the embodiment shown in FIG. 1 was produced using the sensor produced in Reference Example 3. That is, the sensor 1a and the signal processing unit 20 are integrally configured, and a commercially available sports shirt (compression SS manufactured by Under Armor Co.) is used as the elastic member 10, and the sensor 1a is disposed so as to be positioned near the heart of the chest. A biological signal detector 30a was obtained. The biological signal detector 30a was worn by a subject, and the heartbeat during apnea and the heartbeat and respiration during breathing were detected by the biological signal detector 30a. The indoor humidity at the time of measurement was 35%.
  • the electrical signal output from the sensor 1a is amplified and filtered by a measurement circuit including a differential amplifier, a non-inverting amplifier, and a low-pass filter, and then mounted on PC (Smart Projects), which is a general-purpose microcomputer board.
  • AD conversion was performed via the A / D port.
  • the potential of the electric signal after AD conversion was recorded on a microSD card mounted on PC, and analyzed by a personal computer (PC) after the measurement was completed.
  • the signal amplification factor was 72 dB, the pass frequency band was 0 to 10 Hz, and the sampling frequency was 200 Hz.
  • FIG. 4 shows the potential waveform during apnea. From the graph, it can be seen that the heartbeat of the subject is clearly observed.
  • FIG. 5 shows a potential waveform diagram during respiration. From FIG. 5, it was confirmed that both heartbeat and respiration signals were observed. The portion indicating breathing is surrounded by a dotted line. By analyzing the obtained potential waveform diagram, the heartbeat and respiration signals can be separated from each other. Therefore, it is possible to detect the heartbeat and respiration using the biological signal detector 30a.
  • Example 2 The sensor 1a produced in Reference Example 3 was measured in the same manner as in Example 1 except that the sensor 1a was positioned near the left lung on the back, and measurement was performed for 30 seconds with apnea and then for 30 seconds while breathing. . The indoor humidity at the time of measurement was 35%.
  • the obtained potential waveform diagram is shown in FIG. 6 (described as “biological signal detector (back bending sensor)” in the figure).
  • Comparative Example 1 A subject was allowed to wear a shirt in which conductive fibers (manufactured by Textronics Inc .: 20 mm long ⁇ 20 mm wide) were placed on a commercially available sports shirt (compression SS, manufactured by Under Armor, Inc.) so as to be positioned near the heart of the chest. At this time, the skin surface near the heart of the chest was moistened with physiological saline. In this state, action potential was measured for 30 seconds with apnea and then for 30 seconds while breathing. The indoor humidity at the time of measurement was 35%.
  • the action potential is amplified and filtered by a measurement circuit including a differential amplifier, a non-inverting amplifier, and a low-pass filter, and then installed in an chicken (SmartS Projects) which is a general-purpose microcomputer board.
  • AD conversion was performed via The potential of the electric signal after AD conversion was recorded on a microSD card mounted on chicken, and analyzed with a PC after the measurement was completed.
  • the signal amplification factor was 60 dB
  • the pass frequency band was 10 to 100 Hz
  • the sampling frequency was 200 Hz.
  • the obtained potential waveform diagram is shown in FIG. 6 (described as “electrocardiogram” in the figure).
  • Example 2 heartbeat is not detected and only respiration is detected.
  • Comparative Example 1 respiration is not observed and heartbeat is not detected. It can be seen that it has been detected.
  • Comparative Example 2 Heartbeat was detected in the same manner as in Comparative Example 1 except that the skin surface near the heart of the chest was not moistened. The obtained potential waveform diagram is shown in FIG. The obtained potential waveform diagram was irregular, and it was determined that an accurate heartbeat could not be detected. From the results of Comparative Example 1 and Comparative Example 2, it was confirmed that the measured value of the action potential associated with the heartbeat is likely to change due to drying of the skin surface or perspiration, so that stable measurement is difficult.
  • Example 3 (Observation of effects on skin by long-term test) After five biological subjects were worn with the biological signal detector 30a and conducted normal life for 24 hours, the surface of the skin that the sensor 1a was in contact with was observed. .
  • Example 4 (Observation of effects on skin by long-term test) Except for using the sensor 1b instead of the sensor 1a, the same five subjects as in Example 3 wear the biological signal detector 30b produced by the same method as that of the biological signal detector 30a so that a normal life can be obtained. After the time, when the surface of the skin that the sensor 1b was in contact with was observed, no flushing was observed on the skin of all five people.
  • Example 5 (Observation of effects on skin by long-term test) Except for using the sensor 1c in place of the sensor 1a, the same five subjects as in Example 3 were allowed to wear the biological signal detector 30c produced by the same method as the biological signal detector 30a, and the normal life could be improved. After the time, when the surface of the skin that the sensor 1c was in contact with was observed, no flushing was observed on the skin of all five people.
  • the biological signal detector of the present invention closely contacts the skin surface and the sensor, and the sensor elastically deforms following the movement of the skin surface accompanying the biological signal such as heartbeat, pulse, respiration, etc., and responds to this elastic deformation.
  • a predetermined biological signal is detected by generating an electrical signal.
  • Such a biological signal detector can detect biological signals such as heartbeat, pulse, respiration, etc. under daily life and exercise conditions without depending on the state of the skin surface to be measured, and always measures in real time. It can be used as a detector.
  • SYMBOLS 1 is a sensor
  • 2 is a polymer electrolyte membrane
  • 3a and 3b are electrode films
  • 4a and 4b are collector electrodes
  • 5a and 5b are protective films
  • 10 is an elastic member
  • 20 is a signal processing part
  • 30 is a biological signal detector It is.

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Abstract

L'invention concerne un détecteur de signal biologique qui peut détecter précisément un signal biologique d'une manière qui n'est pas dépendante de la condition de la surface de peau dans une région de mesure, et qui est facilement éliminé après utilisation. Le détecteur de signal biologique comprend un élément extensible ayant une partie cylindrique, et un capteur (1) fabriqué en prenant en sandwich une membrane d'électrolyte polymère (2) entre une paire de films d'électrode (3a) et (3b) comprenant une composition contenant des particules conductrices et une résine. Le capteur (1) est agencé à l'intérieur de la partie cylindrique.
PCT/JP2014/052278 2013-02-07 2014-01-31 Détecteur de signal biologique et procédé de détection de signal biologique WO2014123071A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007336790A (ja) * 2006-06-19 2007-12-27 Kuraray Co Ltd 高分子電気化学素子
WO2009096419A1 (fr) * 2008-01-28 2009-08-06 Kuraray Co., Ltd. Capteur souple de déformation
WO2012039425A1 (fr) * 2010-09-24 2012-03-29 株式会社クラレ Pâte et transducteur polymère contenant un film de revêtement constitué de ladite pâte et servant de film d'électrolyte ou de films d'électrodes
WO2012066056A1 (fr) * 2010-11-17 2012-05-24 Smart Solutions Technologies, S.L. Capteur permettant l'acquisition de signaux physiologiques

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007336790A (ja) * 2006-06-19 2007-12-27 Kuraray Co Ltd 高分子電気化学素子
WO2009096419A1 (fr) * 2008-01-28 2009-08-06 Kuraray Co., Ltd. Capteur souple de déformation
WO2012039425A1 (fr) * 2010-09-24 2012-03-29 株式会社クラレ Pâte et transducteur polymère contenant un film de revêtement constitué de ladite pâte et servant de film d'électrolyte ou de films d'électrodes
WO2012066056A1 (fr) * 2010-11-17 2012-05-24 Smart Solutions Technologies, S.L. Capteur permettant l'acquisition de signaux physiologiques

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* Cited by examiner, † Cited by third party
Title
"Junan Keiryo na Polymer Sensor no Shutten ni Tsuite", NEWS RELEASE 2010 NEN, 19 November 2010 (2010-11-19), KURARAY CO., LTD., Retrieved from the Internet <URL:http://www.kuraray.co.jp/release/2010/101119.html> [retrieved on 20140312] *
KAZUHIKO ASAHARA: "Dai 26 Kai Techno Festa ''Development of a flexible bending sensor 'Polymer Sensor'", FINE CERAMICS REPORT, vol. 30, no. 2, 20 April 2012 (2012-04-20), pages 66 - 68 *

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