WO2014123072A1

WO2014123072A1 - Muscular motion detector and muscular motion detection method

Info

Publication number: WO2014123072A1
Application number: PCT/JP2014/052279
Authority: WO
Inventors: 基実松島; 幹也松浦; 活栄高橋; 和彦淺原; 友介坂上; 牧川　方昭; 志麻岡田
Original assignee: 株式会社クラレ; 学校法人立命館
Priority date: 2013-02-07
Filing date: 2014-01-31
Publication date: 2014-08-14

Abstract

Provided is a muscular motion detector that imposes little burden on the test subject during monitoring of muscular motion, that has exceptional ease of operation and accuracy of detection, and that may be disposed of by a simple process subsequent to use. The muscular motion detector (10) has a sensor (5) of panel form, produced by sandwiching a polymer electrolyte membrane (1) between a pair of electrode films (2a) and (2b) comprising a composition containing conductive particles and a resin, to one outside surface of which a contact adhesion means (6) is applied.

Description

Muscle motion detector and muscle motion detection method

The present invention relates to a detector that electrically detects muscle movement and a method for detecting muscle movement using the detector.

For the purpose of health management, etc., it has been studied to detect and monitor muscle movements associated with chewing, swallowing, and toothpaste.

As a method for detecting muscle movement, a method of measuring the potential (action potential) of an electric signal generated in the body accompanying muscle movement is known. For example, a muscle activity monitoring system (see Patent Document 1) that detects muscular movement associated with mastication and toothbrushing by measuring action potentials and records changes over time, and a method of detecting and monitoring muscular movement associated with swallowing (patented) Document 2) is known. In these methods, the action potential is measured by an electrode attached to the skin surface located near the muscle to be measured.

However, the action potential that can be measured with an electrode attached to the skin surface is very weak, and varies depending on the wetness of the skin surface, the thickness of the stratum corneum, the presence or absence of body hair, and so on, so that accurate measurement is difficult. Therefore, in order to reduce the contact resistance between the electrode and the skin surface, it is necessary to perform treatments such as shaving the hair on the skin surface or washing the skin surface with absorbent cotton soaked in alcohol, which is a burden on the subject. Also, workability is low.

On the other hand, as another method for detecting muscular movement, a method is known in which pressure generated with muscular movement is converted into an electrical signal using a piezoelectric film and measured. For example, a method is shown in which a piezo-electric film is attached to the subject's larynx, lower jaw, or the like to detect muscular movement associated with swallowing (see Non-Patent Document 1). Also, a method is known in which a mouthpiece to which a piezoelectric film is attached is attached to the mouth to detect muscle movement associated with a toothpaste (see Non-Patent Document 2). However, only a fluororesin (polyvinylidene fluoride) is known as a material for piezoelectric films in practical use, and there is a problem of environmental pollution after use from the viewpoint of environmental pollution and load on disposal facilities. There is a need for a method for detecting muscle movement using a material that can be easily discarded.

JP 2010-137015 A JP 2005-304890 A

The present invention has been made in order to solve the above-described problems. When monitoring muscle exercise, the burden on the subject is small, the workability is excellent, and the detection can be accurately performed, and the disposal process after use. An object of the present invention is to provide a simple muscle motion detector and a muscle motion detection method.

According to the present invention, the object is to provide at least one outer surface of a plate-shaped 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. This is achieved by providing a muscular motion detector having an adhesive means.

As a preferred embodiment of the muscle movement detector of the present invention,
The shape of the main surface of the sensor is circular or elliptical;
The adhesive means has an in-plane cut;
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. Containing a block copolymer (Z) having a crystalline polymer block (T);
The adhesive means is in contact with the skin surface of the animal, and the sensor elastically deforms following the movement of the skin surface to detect the movement and generate an electrical signal;
The electrical signal is generated when the sensor detects the movement of the skin surface due to muscle movement associated with mastication, swallowing, or toothbrushing;

The present invention also relates to a muscle motion detection method for measuring an electrical signal generated by elastic deformation of a sensor of the muscle motion detection tool by following the movement of the skin surface.

The muscle movement detector of the present invention is brought into close contact with the skin surface of an animal (preferably the skin surface of a human body) via an adhesive means, so that it does not depend on the surface state of the skin surface, and the movement of muscle (muscle movement). ) Can be detected accurately. 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.

According to the muscle motion detection method of the present invention, the sensor of the muscle motion detector is elastically deformed by following the movement of the skin surface, and an electric signal having a potential corresponding to the elastic deformation is measured. The predetermined muscle movement can be detected.

It is a schematic cross section which shows one Embodiment of the muscle exercise | movement detector of this invention. It is a schematic cross section which shows another embodiment of the muscle exercise | movement detector of this invention. It is a schematic diagram which shows the muscular motion detector of this invention which attached | subjected the some adhesion means. It is a schematic diagram which shows the muscular motion detector of this invention which attached | subjected the some adhesion means. It is a schematic diagram which shows the muscular movement detection tool of this invention which attached | subjected the adhesion means which has an incision in a surface. It is a schematic diagram which shows the muscular movement detection tool of this invention which attached | subjected the adhesion means which has an incision in a surface. It is a schematic plan view which shows the shape of the adhesion means of the muscle exercise | movement detector Z produced in the reference example 3. FIG. It is a model side view which shows the shape of the adhesion | attachment means of the muscle exercise | movement detector Z produced in the reference example 3. FIG. It is a figure which shows the usage pattern of the muscle movement detector of this invention. It is a figure which compares the electric potential waveform obtained in Example 1 and Comparative Example 1. FIG. 6 is a diagram showing a potential waveform obtained in Example 2. FIG. FIG. 6 is a diagram for comparing potential waveforms obtained in Example 3-1 and Comparative Example 2-1. It is a figure which compares the potential waveform obtained in Example 3-2 and Comparative Example 2-2. It is a figure which compares the electric potential waveform obtained in Example 3-3 and Comparative Example 2-3. It is a figure which compares the electric potential waveform obtained in Example 3-4 and Comparative Example 2-4.

Hereinafter, embodiments of the muscle motion detector of the present invention will be described in detail. In addition, this invention is not limited by embodiment described below.

The muscle movement detector of the present invention has an adhesive means attached to at least one outer surface of a plate-like sensor. In this plate-shaped sensor, a polymer electrolyte membrane is sandwiched between a pair of electrode membranes made of a composition containing conductive particles and a resin. An embodiment of the muscle movement detector will be described in detail with reference to FIG.

The muscle movement detector 10 includes a plate-like sensor 5 that is elastically deformed and converted into an electric signal in accordance with the movement of the skin surface due to muscle movement, and an adhesive means 6 attached to at least one outer surface of the sensor 5. . The muscle motion detector 10 of the present invention is attached to the skin surface of the subject by the adhesive means 6, and the sensor 5 is elastically deformed along with the movement of the skin surface accompanying the muscle motion, and the electric potential of the electric potential according to the deformation amount. Generate a signal. Such an electrical signal is measured by a known measuring instrument.

The sensor 5 constituting the muscular motion detector 10 is a sensor that generates an electrical signal in accordance with elastic deformation. The sensor 5 has a plate shape. Here, the plate shape means a suitable shape so as not to hinder the elastic deformation of the sensor and the arrangement of the adhesive means, and the ratio of thickness and (length or width) / thickness is not particularly limited, and is a film shape. Including sheet form. In addition, the thickness of the sensor 5 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 muscle motion detector. From the viewpoint of doing so, it is preferable that the peripheral edge is thin. In this specification, “elastic deformation” includes all deformation due to compression, extension, bending, and the like.

The sensor 5 includes an electrode made of a material that can elastically deform a polymer electrolyte membrane made of a material that can be elastically deformed from the viewpoint of detecting minute muscular movements such as mastication, swallowing, and toothbrushing, and energy saving. A sensor sandwiched between membranes is preferred.

A sensor 5 shown in FIG. 1 has an element structure in which a polymer electrolyte membrane 1 is sandwiched between a pair of

electrode films

2a and 2b. Further, as shown in FIG. 2, the sensor 5 may include a collector electrode 3a and a protective film 4a on the electrode film 2a in layers, and a collector electrode 3b and a protective film 4b on the electrode film 2b. .

Hereinafter, the sensor 5 shown in FIGS. 1 and 2 in which the polymer electrolyte membrane 1 is sandwiched between the pair of

electrode films

2a and 2b will be described.

The polymer electrolyte membrane 1 used for the sensor 5 is a polymer block containing a structural unit derived from an aromatic vinyl compound and containing 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 an amorphous polymer containing a structural unit derived from an unsaturated hydrocarbon compound). It is preferable to consist of a block copolymer (Z) having “polymer block (T)” as a constituent component.

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.

Further, the α-position carbon (α-carbon) of the aromatic ring in the aromatic vinyl compound may be a quaternary carbon. When the α-carbon is a quaternary carbon, examples of the substituent bonded to the α-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. And 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; . As the aromatic vinyl compound having these substituents, α-methylstyrene, α-methyl-4-methylstyrene, α-methyl-4-ethylstyrene, and 1,1-diphenylethylene are preferable.

From the viewpoint of introducing an ion conductive group into the aromatic ring of the polymer block (S ₀ ), there is no functional group on the aromatic ring of the aromatic vinyl compound that inhibits the reaction for introducing the ion conductive group. desirable. For example, if hydrogen on the aromatic ring of styrene (particularly hydrogen at the 4-position) is substituted with an alkyl group (particularly an alkyl group having 3 or more carbon atoms) or the like, it may be difficult to introduce an ion conductive group. It is preferable that the aromatic ring is not substituted with another functional group, or is substituted with a substituent capable of introducing an ion conductive group itself, such as an aryl group. Styrene, α-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. When 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. Here, “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. When the monomer has a plurality of polymerizable carbon-carbon double bonds, any of them may be used for polymerization. For example, in the case of a conjugated diene compound, it may be a 1,2-bond. 1,4-bond may be used, or these may be mixed.

The said monomer which can form a polymer block (T) may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types together, it is preferable that the arrangement | sequence of the structural unit which comprises a polymer block (T) is random.

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. In this case, 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). In the case of having a plurality of polymer blocks (S), their structures (type of monomer constituting, degree of polymerization, type of ion conductive group, introduction ratio, etc.) may be the same or different. May be. Moreover, when it has two or more polymer blocks (T), those structures (a kind of monomer to comprise, a polymerization degree, etc.) may mutually be the same, and may differ.

As an example of the arrangement of the polymer block (S) and the polymer block (T) in the block copolymer (Z), 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. In the polymer electrolyte membrane 1 configured in the sensor 5 used in the present invention, these block copolymers may be used alone or in combination of two or more.

In the block copolymer (Z), 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. When 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. Moreover, since the softness | 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 1 configured in the sensor 5 used in the present invention is a block copolymer (Z) composed of a polymer block (S ₀ ) and a polymer block (T). ₀ ) can be used, and a method of introducing an ion conductive group into the polymer block (S ₀ ) can be used.

In the block copolymer (Z ₀ ), 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. When 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. Moreover, when 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, or the cationic polymerization method is preferably selected from the viewpoint of practical ease. In particular, 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.

As a specific example of the method for producing a block copolymer (Z ₀ ) comprising a polymer block (S ₀ ) and a polymer block (T), the polymer block (S ₀ ) is styrene, α-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. In this case, it is preferable to produce by 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.

As a method for producing the block copolymer (Z ₀ ) by living anionic polymerization, the following methods (1) to (4) are employed.

(1) the presence of an anionic polymerization initiator in a nonpolar solvent such as cyclohexane, at a temperature of 20 ~ 100 ° C., an aromatic vinyl compound, a conjugated diene, by sequential polymerization of an aromatic vinyl compound S ₀ -T- An S ₀ type block copolymer (Z ₀ ) is obtained.

(2) 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. Is added to obtain a S ₀ -T—S ₀ type block copolymer (Z ₀ ).

(3) In the presence of an organolithium compound as an anionic polymerization initiator in a nonpolar solvent such as cyclohexane, in the presence of a polar compound having a concentration of 0.1 to 10% by mass, at a temperature of −30 to 30 ° C., 5 to After polymerizing an aromatic vinyl compound having a concentration of 50% by mass and polymerizing a conjugated diene to the resulting living polymer, a coupling agent such as phenyl benzoate is added to form a S ₀ -TS ₀ type block copolymer. The coalescence (Z ₀ ) is obtained.

(4) t-butylstyrene, styrene, and conjugated diene are sequentially added one or more times in the 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 block copolymer (Z ₀ ) comprising three or more types of polymer blocks is obtained.

As a method for producing the block copolymer (Z ₀ ) by living cationic polymerization, (5) using a bifunctional cationic polymerization initiator at −78 ° C. in a mixed solvent of halogenated hydrocarbon and hydrocarbon, A method in which isobutene is cationically polymerized in the presence of a Lewis acid and then an aromatic vinyl compound such as styrene is polymerized to obtain a S ₀ -TS ₀ type block copolymer (Z ₀ ) (Macromol. Chem., Macromol. Symp. 32, 119 (1990).

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. ing. 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, for example, 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.

Since 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 the introduction of the sulfonic acid group may be used as an index. . In that case, the number average molecular weight of the block copolymer (Z ₀ ) is preferably in the range of 3000 to 300000, and more preferably in the range of 10,000 to 200000. When 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.

Next, a method for producing a block copolymer (Z) by introducing a sulfonic acid group into the block copolymer (Z ₀ ) will be described. A known method can be used to introduce the ion conductive group.

Hereinafter, a case where a sulfonic acid group is introduced as an ion conductive group will be described.

When introducing 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.

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; Examples thereof include aromatic organic sulfonic acids represented by 2,4,6-trimethylbenzenesulfonic acid. Examples of the 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 1 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.

There is no particular limitation on the method for producing the polymer electrolyte membrane 1. For example, 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 1 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.

Although there is no restriction | limiting in particular in the usage-amount of a solvent, 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. (especially 80 to 120 ° C.); 10 A method of drying under normal pressure in the range of -30 ° C and further drying under reduced pressure in the range of 25-40 ° C; after drying under normal pressure in the range of 10-30 ° C, further 60-140 ° C Examples thereof include a method of drying under normal pressure in the range of (especially 80 to 120 ° C.).

From the viewpoint of film forming properties, 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.

Alternatively, 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 1.

The electrode film 2 a and the electrode film 2 b used for the sensor 5 are insulated by the polymer electrolyte film 1. The electrode film 2a and the electrode film 2b 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 2a and the electrode film 2b are preferably flexible because they do not hinder elastic deformation of the polymer electrolyte membrane 1. Moreover, it is preferable that the interface of the electrode film 2a and the electrode film 2b, and the polymer electrolyte membrane 1 does not peel with the elastic deformation of the sensor 5. Furthermore, for example, when detecting a muscular movement associated with a toothpaste or the like, it is preferable that an electrical signal is continuously transmitted not only at the moment of elastic deformation but also during the elastic deformation state. From the above viewpoint, it is preferable that the resin contained in the composition forming the electrode film 2a and the electrode film 2b is made of a block copolymer (Z).

The holding time of the electric signal when the elastically deformed state is held for a certain period varies depending on the size of the sensor 5, and the larger the area of the sensor 5, the more the electric signal can be generated. The area of the sensor 5 needs to be an appropriate size that can bend as a whole with respect to the movement of the skin surface associated with muscle exercise, and is appropriately selected depending on the detection target.

The block copolymer (Z) that can be used for the polymer electrolyte membrane 1 and the

electrode membranes

2a and 2b is composed of repeating units, ratio of polymer blocks, arrangement of polymer blocks, number average molecular weight, ion conduction. The kind of the functional 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 2a and the electrode film 2b 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.

An electric double layer is formed at the interface between the resin and the conductive particles contained in the composition forming the electrode film 2a and the electrode film 2b, and the strength and stability of the electric signal emitted from the sensor 5 is 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 action portion of the sensor 5 is deformed. From this viewpoint, the ratio of the resin to the conductive particles in the composition forming the electrode film 2a and the electrode film 2b is preferably 1: 1 to 10: 1, more preferably 2: 1 to 7: 1. When the amount of the conductive particles added to the resin is too small, the signal strength decreases because the electric double layer is not sufficiently formed. On the other hand, when the amount of the conductive particles added to the resin is too large, the conductivity of the electrode film 2a and the electrode film 2b 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 2a and the electrode film 2b is the same as the method for preparing the polymer electrolyte membrane 1 except that the conductive particles are dispersed.

As a method of forming the electrode film 2a and the electrode film 2b on both surfaces of the polymer electrolyte membrane 1, for example, a method of bonding by vacuum deposition method of metals, sputtering method, electroplating, chemical plating method, etc. The method of apply | coating the ink containing, the method of crimping | bonding and welding the electrode produced separately, etc. are mentioned, Especially the method of apply | coating the ink containing an electrode material from a viewpoint of workability and versatility is preferable.

Further, after forming the

electrode film

2a or 2b on one surface of the polymer electrolyte membrane 1 to form a joined body, 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

2a and 2b may be bonded to both sides of one. The material and thickness of the two-layer polymer electrolyte membrane 1 may be the same or different. The method of bonding the two bonded bodies is preferably thermocompression bonding. Alternatively, the electrode film 2a and the electrode film 2b may be formed on one surface of the protective film 4a and the protective film 4b described later, and the polymer electrolyte membrane 1 may be formed on the electrode film.

In order to reduce the surface resistance of the electrode film 2a and the electrode film 2b, a collector electrode 3a is formed on the surface of the upper electrode film 2a and a collector electrode 3b is formed on the surface of the lower electrode film 2b as shown in FIG. preferable. Examples of the collector electrode 3a and the collector electrode 3b include metal foils and metal thin films such as gold, silver, copper, platinum, and aluminum; metal powders such as gold, silver, and nickel; carbon powders, carbon nanotubes, and carbon fibers. Examples thereof include a molded body composed of carbon fine powder and a binder resin. Among these, from the viewpoint of flexibility, a film-like molded body made of a metal powder and a binder resin is preferable.

When the electrode film 2a and the electrode film 2b are used, the electrical signal can be easily taken out by providing the collector electrode 3a and the collector electrode 3b having higher conductivity than the electrode film on the surfaces of the electrode film 2a and the electrode film 2b. This is preferable. The thickness of the collector electrode 3a and the collector electrode 3b is preferably in the range of 0.01 to 200 μm, more preferably in the range of 0.05 to 100 μm, and still more preferably in the range of 0.1 to 20 μm. When the thickness of the collecting electrode 3a and the collecting electrode 3b is less than 0.01 nm, film formation becomes difficult, and when the thickness exceeds 200 μm, the flexibility of the collecting electrode 3a and the collecting electrode 3b decreases.

Examples of a method for forming the collecting electrode 3a and the collecting electrode 3b on the electrode film 2a and the electrode film 2b include a method of bonding by a vacuum deposition method of metal, sputtering method, electroplating, chemical plating method, etc. The method of apply | coating the ink containing this, the method of crimping | bonding and welding the electrode produced separately, etc. are mentioned, The method of apply | coating the ink containing an electrode material is especially preferable from a viewpoint of workability and versatility. In addition, two joined bodies in which the collector electrode 3a and the collector electrode 3b, the electrode film 2a and the electrode film 2b, and the polymer electrolyte membrane 1 are sequentially formed on one surface of the protective film 4a and the protective film 4b described later are manufactured. The polymer electrolyte membranes of the joined body may be bonded together by thermocompression bonding or the like.

In order to physically protect the polymer electrolyte membrane 1, and the electrode membrane 2a and the electrode membrane 2b, as shown in FIG. 2, the protective membrane 4a and the protective membrane 4b covering the polymer electrolyte membrane 1, the electrode membrane 2a and the electrode membrane 2b Is preferably provided. The protective film 4 a and the protective film 4 b also function as a support for the sensor 5. Examples of the protective film 4a and protective film 4b 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 cloth (woven cloth or non-woven cloth) made of fibers such as polyester fiber, polyolefin fiber, rayon fiber, or the like can be used as appropriate.

The thickness of the protective film 4a and the protective film 4b is preferably in the range of 5 to 350 μm, more preferably 7.5 to 300 μm, and most preferably 10 to 200 μm. If the protective film 4a and the protective film 4b are too thin, the thickness tends to be non-uniform, and if it is too thick, the flexibility of the sensor 5 tends to be impaired.

The protective film 4a and the protective film 4b are formed by, for example, further sandwiching a joined body in which the polymer electrolyte membrane 1 is sandwiched between the pair of

electrode films

2a and 2b with the protective film 4a and the protective film 4b. It can be formed by bonding. Further, two joined bodies in which the electrode film 2a, the electrode film 2b, and the polymer electrolyte membrane 1 are sequentially laminated on one side of the protective film 4a and the protective film 4b are manufactured, and the polymer electrolyte membranes of the two joined bodies are formed. You may stick together by thermocompression bonding.

The adhesive means 6 is a means for fixing the sensor 5 to the subject's skin surface. The adhesive means 6 is disposed on one of the plate-like outer surfaces of the sensor 5. Examples of the adhesive means 6 include an adhesive, or an adhesive tape having an adhesive layer made of an adhesive and a base material layer. As the pressure-sensitive adhesive, known pressure-sensitive adhesives such as rubber-based pressure-sensitive adhesives, acrylic pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives and the like can be used. From the viewpoint of high adhesiveness, high moisture permeability, and low skin irritation, an adhesive tape having an adhesive layer made of a medical adhesive and a base material layer is preferred. For example, a double-sided adhesive tape for skin application manufactured by Sumitomo 3M Limited, specifically, product numbers 1524, 1504XL, 1510, 1522, 1509, and the like can be used.

The thickness of the adhesive layer made of an adhesive in the adhesive tape is preferably in the range of 5 to 500 μm, more preferably 15 to 250 μm, and most preferably 30 to 100 μm. When the thickness of the adhesive layer is 5 μm or less, the adhesion force between the skin surface and the muscle motion detector 10 is reduced, and the muscle motion detector 10 is easily peeled off from the skin surface. The follow-up performance of the muscle movement detector 10 with respect to the above is reduced.

The adhesive means 6 preferably increases the contact area with the skin surface from the viewpoint of attaching the entire outer surface of the sensor 5 to the skin surface. When the contact area between the adhesive means 6 and the skin surface is smaller than the area of the outer surface of the sensor 5, the followability of the sensor 5 with respect to the movement of the skin surface decreases, and furthermore, the skin surface and the muscle motion detector 10 are in close contact with each other. The force is reduced, and the muscle motion detector 10 is easily peeled off from the skin surface.

The adhesive means 6 is disposed on the outer surface of the sensor 5 in order to fix the sensor 5 to the skin surface. An adhesive may be applied as the adhesive means 6 on the sensor 5, or a double-sided tape may be attached. In this case, the sensor 5 is attached to the skin surface such that the adhesive means 6 is positioned between the sensor 5 and the skin surface. Alternatively, an adhesive tape larger than the sensor 5 may be used as the adhesive means 6 so as to cover the outer surface of the sensor 5. In this case, the sensor 5 is attached to the skin surface so that the sensor 5 is positioned between the adhesive means 6 and the skin surface.

The shape of the main surface of the muscle motion detector 10 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 end of the muscle motion detector 10, for example, circular; oval; Examples include a shape in which each vertex 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. Further, from the viewpoint of suppressing the maceration of the skin due to sweating or insensitive vaporization on the skin surface at the affixed site, a ventilation hole may be provided in the muscle movement detector 10 to improve the moisture permeability of the affixed site. However, as the size of the vent hole increases and the number increases, the effective area resulting from the signal generation of the muscle movement detector 10 decreases, and the resistance of the

electrode films

2a and 2b and the

collector electrodes

3a and 3b also increases. The shape, size, and quantity of the vent holes need to be appropriately selected according to the detection target.

In the muscle movement detector 10 of the present invention, a plurality of adhesive means 6 are attached to the outer surface of the sensor 5 from the viewpoint of suppressing the sense of tension associated with the movement of the skin surface and enhancing the sensor's followability and increasing the sensitivity of the sensor. Is preferred. 3 and 4 are schematic views showing an example in which a plurality of adhesive means 6 are attached to the outer surface of the sensor 5. For the same purpose, it is also preferable to attach an adhesive means 6 having a cut 7 in the surface to the outer surface of the sensor 5. 5 and 6 are schematic views showing an example in which an adhesive means 6 having a cut 7 in the surface is attached to the outer surface of the sensor 5.

When the muscle movement detector 10 is elastically deformed, an electric signal corresponding to the curvature of the bending deformation is continuously generated. Here, when the potential when the muscle motion detector 10 is bent in one direction is a positive value, the potential when bent in the opposite direction is a negative value.

In the muscle movement detection method of the present invention, the muscle movement detector 10 is affixed to the skin surface of the subject via the adhesive means, and the sensor 5 is elastically deformed in accordance with the movement of the skin surface accompanying the muscle movement, so that A predetermined muscular motion is detected by measuring an electrical signal having a potential corresponding to the amount of deformation generated in the measuring instrument. When the muscle movement detector 10 is attached to the skin surface, it is not necessary to perform pretreatment such as hair removal and washing on the skin surface.

Hereinafter, the present invention will be described in detail with reference to examples, but the scope of the present invention is not limited to these examples.

The sensor 5 included in the muscle motion detector 10 of the present invention shows an example of muscle motion detection in which an electrical signal generated by elastic deformation by following the movement of the skin surface is shown. As a comparative example, the detection of muscle movement by measuring the potential (action potential) of an electric signal generated in FIG.

The measurement methods and measurement conditions for various analyzes used in the reference examples are shown below.

(1) Derived from the α-methylstyrene content (% by mass) of the block copolymer (Z ₀ ), the hydrogenation rate of the polymer block (T), and the α-methylstyrene in the block copolymer (Z) The content (mol%) of the sulfonic acid group with respect to the structural unit was calculated. Using a nuclear magnetic resonance apparatus (JNM-LA400) manufactured by JEOL Ltd., it was calculated from ¹ H-NMR spectrum measured using deuterated chloroform alone or a mixture of deuterated tetrahydrofuran and deuterated methanol (mass ratio 80:20) as a solvent. .

(2) Measurement of number average molecular weight Gel permeation chromatography (GPC) was measured under the following conditions, and calculated in terms of standard polystyrene.
Instrument: Gel permeation chromatograph (HLC-8020) manufactured by Tosoh Corporation
Column: Tosoh TSK-GEL SuperMultipore HZ-M 4.6 mm (ID) × 15.0 cm (L) connected in series Guard column: TSK guard column SuperMP (HZ) -M 4.6 mm (ID) × 2.0 cm (L) )
Eluent: Tetrahydrofuran, flow rate 1.0 ml / min Calibration curve: prepared using standard polystyrene Detection method: differential refractive index (RI)

(3) Measurement of storage elastic modulus Using a wide-range dynamic viscoelasticity measuring device (“DVE-V4FT Rheospectr” manufactured by Rheology), in a tensile mode (frequency: 11 Hz), the rate of temperature increase was 3 ° C./min. The temperature was raised from −80 ° C. to 250 ° C., and the storage elastic modulus (E ′), loss elastic modulus (E ″) and loss tangent (tan δ) were measured.

(Reference Example 1: Synthesis of block copolymer (Z ₀ -1) comprising poly α-methylstyrene and hydrogenated polybutadiene)
After sufficiently replacing the pressure vessel equipped with a stirrer with nitrogen, 172 g, 258.1 g, 28.8 g and 5.9 g of α-methylstyrene, cyclohexane, n-hexane and tetrahydrofuran, which had been sufficiently dehydrated, were added. Subsequently, 17.5 ml of sec-butyl lithium (1.3 M, cyclohexane solution) was added, and polymerization was performed at −10 ° C. for 5 hours. The number average molecular weight of the poly α-methylstyrene after polymerization for 5 hours was measured by GPC and found to be 6400 in terms of polystyrene. Next, 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 3640. Next, 303 g of butadiene was added, and polymerization was performed for 2 hours while raising the temperature to 60 ° C. Further, 27.0 ml of α, α′-dichloro-p-xylene (0.3 M, toluene solution) was added to the polymerization solution in the pressure vessel, and the mixture was stirred at 60 ° C. for 1 hour to conduct a coupling reaction. A triblock copolymer of (α-methylstyrene) -polybutadiene-poly (α-methylstyrene) type was synthesized.

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 α-methylstyrene units was. The content was 28% by mass. In addition, it was found by composition analysis by ¹ H-NMR spectrum measurement that α-methylstyrene was not substantially copolymerized in the polybutadiene block.

Next, a cyclohexane solution of such a triblock copolymer was prepared and charged into a pressure-resistant vessel that had been sufficiently substituted with nitrogen, and then at 80 ° C. in a hydrogen atmosphere using a Ni / Al Ziegler-type hydrogenation catalyst. A hydrogenation reaction was conducted for 5 hours to obtain a poly α-methylstyrene-b-hydrogenated polybutadiene-b-polyα-methylstyrene type triblock copolymer (hereinafter referred to as a block copolymer (Z ₀ -1)). Obtained. 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%.

(Reference Example 2: Synthesis of block copolymer (Z-1))
100 g of the block copolymer (Z ₀ -1) obtained in Reference Example 1 was vacuum-dried in a glass reaction vessel equipped with a stirrer for 1 hour and then purged with nitrogen. And stirred for 2 hours to dissolve. After dissolution, a sulfating reagent obtained by reacting 21.0 ml of acetic anhydride and 9.34 ml of sulfuric acid at 0 ° C. in 41.8 ml of methylene chloride was gradually added dropwise over 20 minutes. After stirring at 25 ° C. for 7 hours, the polymer solution was poured into 2 L of distilled water while stirring to coagulate and precipitate the polymer. The precipitated solid was washed with distilled water at 90 ° C. for 30 minutes and then filtered. This washing and filtration operation was repeated until there was no change in the pH of the washing water, and the polymer collected by filtration at the end was vacuum dried to obtain a block copolymer (Z) (hereinafter referred to as block copolymer (Z- 1)). The sulfonation rate of the benzene ring of the α-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.

(Reference Example 3: Production of muscle movement detector)
(1) An electrolyte solution was prepared by dissolving 50 g of the block copolymer (Z-1) obtained in Reference Example 2 in 200 g of a diisopropylbenzene / 1-hexanol mixed solvent (mass ratio 8/2). On the other hand, 4.4 g of ketjen black was further added to 250 g of the electrolyte solution prepared in the same manner, and mixed using a homogenizer to obtain an electrode dispersion.

(2) Printing the electrode dispersion using a screen printer on the

collector electrodes

3a and 3b of an elastomer film (thickness 200 μm) provided with

collector electrodes

3a and 3b (thickness 10 μm) with a commercially available silver paste Then, the step of drying at 80 ° C. was repeated to form

layered electrode films

2 a and 2 b having a film thickness of 100 μm.

(3) After the electrolyte solution is printed on the

electrode films

2a and 2b formed by the operation of (2) using a screen printing machine, the step of drying at 100 ° C. is repeated to obtain a polymer electrolyte having a film thickness of 15 μm. A layer composed of the membrane 1 was formed, and a joined body in which the collector electrode / electrode membrane / polymer electrolyte membrane were joined in this order was obtained.

(4) The two bonded bodies obtained by the operation of (3) above are superposed so that the polymer electrolyte membranes are in contact with each other, and pressure-bonded at 100 ° C. and 0.5 MPa for 5 minutes to thereby produce a block copolymer (Z— A sensor 5 having 1) as a polymer electrolyte membrane 1 was obtained. The sensor 5 includes a sensor (referred to as sensor X) whose main surface has a rectangular shape (20 mm long × 2 mm wide) and a rectangular shape (two parallel lines with 18 mm and two halves with a radius of 1 mm). A sensor (referred to as sensor Y) that is a circle) was produced.

(5) A double-sided medical tape (manufactured by Sumitomo 3M Limited: MSD-S-1524, thickness 0.06 mm) is formed as the adhesive means 6 on one surface of the sensor X obtained by the operation of (4). As a result, a muscle motion detector 10 (referred to as muscle motion detector X) was obtained (FIG. 2).

Similarly, a medical double-sided tape (manufactured by Sumitomo 3M Co., Ltd .: MSD-S-1524, thickness 0.06 mm) is formed as the adhesive means 6 on one surface of the sensor Y obtained by the operation (4). As a result, a muscle motion detector 10 (referred to as muscle motion detector Y) was obtained. Similarly, adhesive means 6 (double-sided tape (manufactured by Sumitomo 3M Limited: MSD-) provided with notches 7 at intervals of 5 mm as shown in the schematic plan view of FIG. 7 and the schematic side view of FIG. S-1524 (thickness 0.06 mm)) was formed to obtain a muscle motion detector 10 (referred to as muscle motion detector Z).

(Example 1)
Using the muscle motion detector X produced in Reference Example 3, muscle motion associated with mastication was detected. As a detection method, as shown in FIG. 9, the muscle motion detector 10 is attached to the skin surface of the lower jaw of the subject 30, and the muscle motion that occurs when the subject 30 bites the gum is output from the muscle motion detector 10. Detected as the electric signal potential.

The potential of the electrical signal output from the muscle movement detector 10 is detected by the

lead wires

21a and 21b connected to the collecting electrode 3a and the collecting electrode 3b, and the measuring instrument 22 (Keyence Corporation data logger: NR600), AD After the conversion, measurement was performed with a personal computer (PC) 20 connected via the USB cable 23. The pass frequency band was 0 to 10 Hz, and the sampling frequency was 1 kHz.

(Comparative Example 1)
In parallel with Example 1, the action potential generated along with muscle exercise was measured. The action potential was measured from a plate electrode (manufactured by Nihon Kohden Co., Ltd .: silver-silver chloride electrode) with a ground electrode attached to the earlobe and attached to the skin surface near the masseter of the masseter muscle. In attaching the plate electrode, the skin surface was washed with absorbent cotton soaked in alcohol, and then the electrolyte paste was packed evenly on the plate electrode and applied to the skin surface and fixed. Furthermore, the measurement was started after being left for about 10 minutes until the skin surface and the electrode became compatible. The generated action potential is detected by a measuring instrument (Keyence Co., Ltd. data logger: NR600) via a low-pass filter, AD converted, and then by a personal computer (PC) connected to the measuring instrument via a USB cable. It was measured. The pass frequency band was 10 to 500 Hz, and the sampling frequency was 1 kHz.

FIG. 10 shows a comparison of potential waveforms obtained in Example 1 and Comparative Example 1. From the potential waveform diagram obtained in Comparative Example 1 (described as “electromyogram” in the figure), the generation and stop of an electrical signal are repeated at regular intervals. It is thought that it was detected. On the other hand, the potential waveform diagram obtained in Example 1 (described as “muscle movement detector (mandibular affixation)” in the figure) fluctuates at the same cycle as the potential waveform diagram of Comparative Example 1, and thus the present invention. It was shown that it is possible to detect the muscular movement associated with the masticatory movement using the muscular movement detector.

(Example 2)
Using the muscle motion detector X produced in Reference Example 3, muscle motion associated with swallowing was detected. As a detection method, muscle movement detector X is attached to the subject's laryngeal protuberance (throat buddha) and mandibular skin surface, and the muscle movement associated with swallowing is detected using the protocol (5 seconds rest → 1 swallowing) x 5 sets of protocol. did. The electric signal potential output from the muscle movement detector X is amplified and filtered by a measurement circuit including a differential amplifier, a non-inverting amplifier, and a low-pass filter, and a measuring instrument (AD board manufactured by Contec: AIO-). 160802AY-USB), and AD conversion was performed, and measurement was performed using a PC connected to a measuring instrument via a USB cable. The signal amplification factor was 60 dB, the pass frequency band was 0 to 10 Hz, and the sampling frequency was 1 kHz.

FIG. 11 shows the potential waveform obtained in Example 2. Potential waveform diagrams obtained from the muscle movement detector X placed on the laryngeal protuberance and mandibular skin surface (in the figure, "muscle movement detector (laryngeal protuberance sticking)", "muscle movement detector (mandibular sticking), respectively) The peak observed from the above is consistent with the timing and frequency of swallowing by the subject's self-report, so that the muscle movement accompanying swallowing movement can be detected using the muscle movement detector of the present invention. It was shown that.

(Example 3)
Using the muscle motion detector X produced in Reference Example 3, muscle motion associated with toothbrushing was detected. Generally, three types of toothbrushing are known: clenching (operation for tightening teeth), tapping (operation for dynamically engaging teeth), and gliding (operation for engaging upper and lower teeth). As a detection method, the muscle movement detector X was attached to the skin surface on the laryngeal protuberance and the lower jaw of the subject, and the muscle movement accompanying the toothpaste was detected in the following experimental protocol examples 3-1 to 3-3. The measurement method of the potential output from the muscle motion detector X in Examples 3-1 to 3-4 is the same as that in Example 2.

Example 3-1
A muscle movement was detected in which a series of actions such as “keeping a rest for 5 seconds and then continuing the clenching action for 5 seconds” was repeated three times.

(Example 3-2)
A muscle motion was detected in which a series of actions such as “keeping a tapping action for 5 seconds after keeping calm for 5 seconds” was repeated three times.

(Example 3-3)
A muscle motion was detected in which a series of actions such as “keeping rest for 5 seconds and then continue the gliding action for 5 seconds” was repeated three times.

(Example 3-4)
A muscle motion was detected in which a series of operations such as “keeping a rest for 10 seconds and then performing a clenching operation continuously for 10 seconds” was repeated twice.

(Comparative Example 2)
For comparison with Example 3, the following Comparative Examples 2-1 to 2-4 were performed.

(Comparative Example 2-1)
As a comparison with Example 3-1, in parallel with Example 3-1, the action potential generated along with muscle exercise was measured. The action potential was measured from a plate electrode (manufactured by Nihon Kohden Co., Ltd .: silver-silver chloride electrode) with a ground electrode attached to the earlobe and attached to the skin surface near the masseter of the masseter muscle. In attaching the plate electrode, the skin surface to be measured was washed with absorbent cotton soaked in alcohol, and then the electrolyte paste was packed uniformly on the plate electrode and applied to the skin surface and fixed. Furthermore, the measurement was started after being left for about 10 minutes until the skin surface and the electrode became compatible. The action potential of the generated electric signal is amplified and filtered by a measuring circuit composed of a differential amplifier, a non-inverting amplifier, and a low-pass filter, and detected by a measuring instrument (AD board manufactured by Contec: AIO-160802AY-USB). After AD conversion, measurement was performed using a PC connected to a measuring instrument via a USB cable. The signal amplification factor was 60 dB, the pass frequency band was 10 to 500 Hz, and the sampling frequency was 1 kHz.

(Comparative Example 2-2)
As a comparison with Example 3-2, the action potential generated with muscle exercise was measured in parallel with Example 3-2. The action potential is measured in the same manner as in Comparative Example 2-1.

(Comparative Example 2-3)
As a comparison with Example 3-3, the action potential generated with muscle exercise was measured in parallel with Example 3-2. The action potential is measured in the same manner as in Comparative Example 2-1.

FIG. 12 shows potential waveform diagrams obtained from Example 3-1 and Comparative Example 2-1. Among the potential waveform diagrams obtained from Example 3-1, a potential waveform diagram obtained from the muscle motion detector X placed on the skin surface of the laryngeal protuberance (in the figure, “muscle motion detector (laryngeal protuberance affixed)) ”), A clear potential waveform associated with the clenching motion was not confirmed, but a potential waveform diagram obtained from the muscle motion detector X placed on the skin surface on the lower jaw (“ muscle motion detector ”in the figure) (Described as “mandibular part affixed”) varies in the same cycle as the potential waveform obtained from Comparative Example 2-1 (indicated as “electromyogram” in the figure), and the potential is maintained during the clenching period. From this fact, it was shown that the muscle movement associated with the clenching exercise can be detected using the muscle movement detector of the present invention.

A graph showing the potential waveforms obtained in Example 3-2 and Comparative Example 2-2 is shown in FIG. From FIG. 13, potential waveform diagrams obtained from the muscle motion detector X placed on the laryngeal protuberance and mandibular skin surface in Example 3-2 (in the figure, “muscle motion detector (laryngeal protuberance sticking)”, "Muscle movement detector (mandibular portion affixed)" is described in the same period as the potential waveform diagram (described as "electromyogram" in the figure) obtained from Comparative Example 2-2, It has been shown that it is possible to detect muscle movement accompanying tapping exercise using the muscle movement detector of the present invention.

FIG. 14 shows potential waveform diagrams obtained from Example 3-3 and Comparative Example 2-3. FIG. 14 shows potential waveforms obtained from the laryngeal protuberance and the muscle movement detector X placed on the skin surface of the lower jaw (in the figure, “muscle movement detector (laryngeal protuberance sticking)”, “muscle movement detector ( Since the potential waveform diagram obtained from Comparative Example 2-3 (described as “electromyogram” in the figure) fluctuates in the same cycle, the detection of muscle movement of the present invention It was shown that the muscle movement accompanying gliding movement can be detected using the tool.

(Comparative Example 2-4)
As a comparison with Example 3-4, in parallel with Example 3-4, the pressure generated with the muscle exercise was measured using a piezoelectric element. A piezoelectric element (manufactured by Tokyo Sensor Co., Ltd .: DTI-028K / L) having a polyvinylidene fluoride film (length 16 mm x width 4 mm, thickness 28 mm) is attached to the skin surface of the subject's lower jaw, and the potential output from the piezoelectric element is It was measured. Here, the method for measuring the potential is the same as the method for measuring the potential output from the muscle exercise detector in the second and third embodiments described above except that the output potential is not amplified.

FIG. 15 shows potential waveform diagrams obtained in Example 3-4 and Comparative Example 2-4. From FIG. 15, the potential waveform diagram obtained from Comparative Example 2-4 (in the drawing, described as “piezoelectric element (mandible portion))” shows the instantaneous potential at the start P of the clenching operation and the release Q of the clenching operation. It was confirmed that the muscle movement during the clenching operation cannot be detected continuously because the potential is quickly reduced. On the other hand, the potential waveform diagram obtained from Example 3-4 (in the figure, described as “muscle movement detector (mandible part attachment))” shows the muscles from the start P of the clenching operation to the release Q of the clenching operation. It was confirmed that motion can be detected continuously.

Example 4
(Observation of effects on skin by long-term test)
After attaching the muscle movement detector X to the skin surface of the laryngeal protuberance of five subjects and conducting normal life for 24 hours, the surface of the skin that the muscle movement detector X was in contact with was observed. At the portion where the end of the motion detector X was in contact, a sticking mark that was flushed by three people was observed.

(Example 5)
(Observation of effects on skin by long-term test)
The muscle motion detector Y was attached to the skin surface of the laryngeal protuberance of the same five subjects as in Example 4, and after performing normal life for 24 hours, the surface of the skin that the muscle motion detector Y was in contact with was observed. As a result of observation, no sticking marks were observed in all five people.

(Example 6)
(Evaluation of wearing feeling of muscle movement detector by long-term test)
The muscle movement detector Z was affixed to the skin surface of the laryngeal protuberance of the same five subjects as in Example 4, and after conducting a normal life for 24 hours, an interview regarding the feeling of wearing the muscle movement detectors X and Z was conducted. It was. As a result, all the five people felt that the muscle movement detector X felt skin tension in the state of being affixed to the skin, but when the muscle movement detector Z was affixed, four out of five people It was evaluated that the feeling of wearing was good without feeling the tension described above.

The muscle movement detection device of the present invention is an instrument that elastically deforms in response to the movement of the skin surface and transmits an electrical signal to detect muscle movement, and can be used for measurement and monitoring of oral functions such as mastication, swallowing, and toothpaste. .

1 is a polymer electrolyte membrane, 2a and 2b are electrode membranes, 3a and 3b are collecting electrodes, 4a and 4b are protective films, 5 is a sensor, 6 is an adhesive means, 7 is a notch, 10 is a muscle motion detector, and 20 PC, 21a, 21b are lead wires, 22 is a measuring instrument, 23 is a USB cable, and 30 is a subject.

Claims

An adhesive means is attached to at least one outer surface of a plate-shaped 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. Muscular movement detector.
The muscle motion detector according to claim 1, wherein the shape of the main surface of the sensor is a circle or an ellipse.
The muscle movement detector according to claim 1, wherein the adhesive means has a cut in the surface.
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. The muscle movement detector according to claim 1, comprising a block copolymer (Z) having a crystalline polymer block (T).
The adhesive means is for contacting the skin surface of an animal, and the sensor elastically deforms following the movement of the skin surface to detect the movement and generate an electrical signal. The muscle movement detector according to 1.
6. The muscle movement detector according to claim 5, wherein the electrical signal is generated when the sensor detects a movement of the skin surface due to muscle movement associated with mastication, swallowing or tooth-gearing.
A method for detecting muscle movement, wherein the sensor of the muscle movement detector according to any one of claims 1 to 6 measures an electrical signal generated by elastic deformation by following the movement of the skin surface.