WO2019058739A1

WO2019058739A1 - Electrode sheet, electrode sheet manufacturing method, biological signal acquiring device, and biological signal acquiring method

Info

Publication number: WO2019058739A1
Application number: PCT/JP2018/027324
Authority: WO
Inventors: 徹平荒木; 毅関谷; 秀輔吉本; 隆文植村; 岩瀬　雅之; 暁生吉田; 秀樹佐竹; 田中　秀典
Original assignee: 国立大学法人大阪大学; 日本メクトロン株式会社; 株式会社カネカ
Priority date: 2017-09-19
Filing date: 2018-07-20
Publication date: 2019-03-28
Also published as: JP2019051236A

Abstract

Provided are: an electrode sheet in which changes in characteristics during a period of prolonged storage after being manufactured or while being distributed and at the time of use are small, and which enables a biological signal to be easily acquired; a method for manufacturing the electrode sheet; a biological signal acquiring device that includes the electrode sheet; and a biological signal acquiring method in which the biological signal acquiring device is used. An electrode sheet (1) comprises: a sheet-shaped elastic base (10); at least two elastic lead-out wires (11); at least two elastic electrodes (12); and adhesive parts (15). The at least two elastic electrodes (12) are located on at least one main surface of the elastic base (10). The adhesive parts (15) each contact and cover at least part of a surface of each of the at least two elastic electrodes (12) on the opposite side from the surface of the elastic electrode (12) facing the sheet-shaped elastic base (10). At least one of the at least two elastic lead-out wires (11) is connected to each of the at least two elastic electrodes (12). The adhesive parts (15) are composed of a non-gel material that is elastic and electrically conductive.

Description

ELECTRODE SHEET, METHOD FOR MANUFACTURING ELECTRODE SHEET, BIOLOGICAL SIGNAL ACQUIRING DEVICE, AND BIOLOGICAL SIGNAL ACQUIRING METHOD

The present invention relates to an electrode sheet, a method of manufacturing an electrode sheet, a biological signal acquisition apparatus, and a biological signal acquisition method.

In recent years, with the rise of healthcare-oriented in the whole society, the reduction of increasing medical expenses, and the use of big data for the Internet of Things (IOT) society, the weak environment represented by brain waves etc. in various environments There is a growing social need to acquire useful biosignals.

For example, when acquiring an electroencephalogram as a biomedical signal, a simplified electroencephalograph in which an electrode and a measuring instrument are integrated is known. In this simple type electroencephalograph, an electroencephalogram is acquired by measuring for a long time using a hard electrode. Therefore, the burden on the patient could not be ignored.
Then, the electroencephalograph which aimed at reduction of the burden on a patient is proposed by using the resin sheet which can be stuck on a forehead and has elasticity (for example, refer to patent documents 1).

JP, 2013-121489, A

According to the electroencephalograph disclosed in Patent Document 1, affixing the three electrodes provided on the resin sheet to the forehead of the subject alleviates the burden on the patient or subject in long-time measurement. Can. Further, by forming each electrode with an adhesive conductive gel, it is possible to easily acquire an electroencephalogram simply by attaching it to the forehead of the subject.

However, the gel retains water and an organic solvent in the gel state. Therefore, in the resin sheet which has been left to stand for a long time, the moisture and the organic solvent of the adhesive conductive gel are evaporated, and the function as the adhesive conductive gel is lowered. As a result, there is a possibility that characteristic changes may be caused to affect the detection accuracy of the biological signal.

It is also conceivable to apply a medical hydrogel paste to each electrode, using each electrode as a metal electrode. However, the medical hydrogel paste has a low viscosity, and it takes time and effort to apply each electrode properly. Moreover, the medical hydrogel paste after use may remain on the skin.

The present invention is an electrode sheet capable of easily acquiring a biomedical signal with little change in characteristics during long-term storage or use during production or distribution, a method of manufacturing the electrode sheet, a biomedical signal acquiring device including the above electrode sheet, And it aims at providing the living body signal acquisition method using the living body signal acquisition device concerned.

(1) The present invention comprises a sheet-like stretchable base material, two or more stretchable lead wires, two or more stretchable electrodes, and an adhesive part, and at least one of the stretchable base materials. Two or more of the stretchable electrodes are positioned on the main surface, and the adhesive portion is a surface opposite to the surface on the stretchable substrate side of the stretchable electrode for each of the two or more stretchable electrodes And at least a part of the two or more stretchable wiring lines is connected to one or more of the two or more stretchable electrodes, and the adhesion portion is stretchable and conductive. The present invention relates to an electrode sheet made of a non-gel material having elasticity.

(2) Moreover, it is preferable that the said non-gel material contains an adhesive resin and an electrically-conductive material.

(3) Moreover, it is preferable that the said electroconductive material contains an electroconductive polymer and / or electroconductive fine particles.

(4) Moreover, it is preferable that the said electroconductive material contains the said electroconductive fine particle.

(5) Moreover, it is preferable that the relative value of the volume resistivity of the thickness direction of the said adhesion part with respect to the volume resistivity of the surface direction of the said adhesion part is 0.5 or less.

(6) Moreover, it is preferable that the said adhesion part coats at least one part of the main surface of the said elastic base material.

(7) Moreover, it is preferable that the electrode sheet further comprises an elastic cover made of an insulating material and covering the elastic lead-out wire.

(8) Moreover, it is preferable that the said adhesion part coat | covers at least one part of the main surface of the said elastic cover at least.

(9) Moreover, it is preferable that the said adhesion part spaces apart between each of the part which coats the said elastic electrode, and the part which covers another.

(10) Moreover, it is preferable that the part which coats the said elastic electrode and the part which coats the said adhesion part are one-sided.

(11) Further, the present invention is a method for producing the electrode sheet according to the above (1), wherein the stretchable electrode is disposed on at least one main surface of the stretchable substrate, and The present invention relates to a method of manufacturing an electrode sheet including connection of each stretchable lead wire to each of the stretchable electrodes and formation of the adhesive portion.

(12) Moreover, it is preferable to form the said adhesion part by the transcription | transfer of the adhesion layer which consists of a printing method, a coating method, or the said non-gel material.

(13) Further, the present invention relates to a biological signal acquiring apparatus including the electrode sheet according to any one of (1) to (11) above.

(14) Further, it is preferable that the biological signal acquisition device further includes an analysis device that acquires biological signal data transmitted from the electrode sheet via the Internet or a local network, and analyzes the state of the biological body.

(15) Further, the present invention relates to a biological signal acquisition method using the biological signal acquisition device described in the above (13) or (14).

According to the present invention, there is little change in characteristics during long-term storage or use during production or distribution, and an electrode sheet capable of easily acquiring a biosignal, a method of manufacturing the electrode sheet, and biosignal acquisition comprising the aforementioned electrode sheet An apparatus and a biological signal acquisition method using the biological signal acquisition apparatus can be provided.

It is a top view showing an electrode sheet concerning a 1st embodiment of the present invention. It is the sectional view on the AA line of FIG. It is the top view which removed the adhesion part of the electrode sheet of 1st Embodiment. It is a top view which shows the usage example of the electrode sheet of 1st Embodiment. It is a top view which shows the electrode sheet concerning a 2nd embodiment of the present invention. FIG. 6 is a cross-sectional view taken along the line BB in FIG. 5; It is a top view which shows the electrode sheet which concerns on 3rd Embodiment of this invention. FIG. 8 is a cross-sectional view taken along the line CC in FIG. 7; It is a top view which shows arrangement | positioning of a rectangular part, a projecting piece part, and a string-like part in an elastic base material.

Hereinafter, an electrode sheet, a method of manufacturing an electrode sheet, a biological signal acquisition apparatus, and a biological signal acquisition method according to each embodiment of the present invention will be described with reference to the drawings.
The biological signal acquisition apparatus according to each embodiment of the present invention is an apparatus that acquires a biological signal from a living body and examines the state of the living body. The biological signal acquisition device includes an electrode sheet and an analysis device.

Since the electrode sheet has elasticity as a whole, it follows the surface shape of the object to be measured and adheres well to the surface of the object to be measured. The object to be measured is not particularly limited, and may be organic or inorganic, and may be living or non-living. The electrode sheet is preferably used for acquiring a biosignal. Further, the electrode sheet is particularly preferably attached to the forehead of a human body and used for acquiring an electroencephalogram. In this case, the electrode sheet is curved following the curved surface shape of the forehead and adheres well to the forehead and adheres well. As a result, an electroencephalogram is effectively acquired by the electrode sheet.

The analyzer is connected to the electrode sheet wirelessly or by wire. The analysis device is, for example, a cloud server, a local server, etc., and acquires biological signal data such as brain waves transmitted from the electrode sheet via the Internet or a local network (including communication between terminals) to obtain the state of the living body Analyze The analysis device accumulates data of a plurality of biological signals transmitted in the past, and estimates the state of a living body based on the data of the accumulated plurality of biological signals with respect to newly acquired biological signal data (AI (Artificial Intelligence) ) May have a function.

First Embodiment
The electrode sheet 1, the method of manufacturing the electrode sheet 1, the biological signal acquisition apparatus, and the biological signal acquisition method according to the first embodiment will be described with reference to FIGS. 1 to 4.
The electrode sheet 1 according to the present embodiment is, as shown in FIGS. 1 to 3, a stretchable base 10, a stretchable lead wire 11, a stretchable electrode 12, a stretchable cover 13, and a film base 14. And an adhesive unit 15.

The stretchable substrate 10 is formed in a sheet shape, for example, by an estramer material represented by a urethane-based estramer or a stretchable fabric. The elastomer material is not particularly limited, and various materials such as polyester elastomers, styrene elastomers, polyolefin elastomers, polyamide elastomers and urethane elastomers can be adopted. Such a stretchable base material 10 has stretchability that extends in the in-plane direction by an external force. The stretchable substrate 10 essentially includes the rectangular portion 101, and optionally includes the projecting portion 102 and the string-like portion 103.
The rectangular portion 101 is formed in a rectangular shape in plan view.
The rectangular portion 101, the projecting portion 102, and the string-like portion 103 are preferably arranged on the stretchable base 10 as shown in FIG.

The projecting portion 102 is integrally formed with the rectangular portion 101. The projecting portion 102 projects from one side of the rectangular portion 101 in the out-of-plane direction. The projecting portion 102 is connectable to a wireless device (not shown) that transmits a biological signal to the analysis device 2 wirelessly.

The cord-like portion 103 is integrally formed with the rectangular portion 101. One end of the string-like portion 103 is connected to one of the sides of the rectangular portion 101 that is adjacent to the side connected to the protrusion 102.

The material of the stretchable lead-out wiring is not particularly limited as long as it is a material having both the desired stretchability and conductivity. Typically, the stretchable lead-out wire 11 is formed of a conductive material in which conductive particles are dispersed and blended in a resin material (resin binder). As the resin material, in terms of stretchability, an elastomeric material used as a material of the stretchable substrate 10 is preferable. The stretchable lead-out lines 11 are disposed so as to overlap on at least one main surface of the stretchable base material 10. The stretchable lead wire 11 is formed in a straight line so as to cross over the stretchable substrate 10. Specifically, the stretchable lead-out wire 11 is formed to cross the main surface from the projecting portion 102 to the rectangular portion 101. In the present embodiment, eight stretchable lead wires 11 are provided, and one stretchable lead wire 11 is extended to the string-like portion 103. In addition, the stretchable lead wire 11 has a very low Young's modulus (for example, 100 MPa or less, more preferably 10 MPa or less) in the conductive material itself, and the stretching movement of the stretchable substrate 10 in the in-plane direction It develops following behavior. The stretchable lead wire 11 may be formed by, for example, a printing method.

The stretchable electrode 12 is formed of, for example, a conductive material in which conductive particles are dispersed in a thermoplastic resin (resin binder). As the resin binder, an elastomeric material used as a material of the stretchable substrate 10 is preferable in terms of stretchability. The shape of the stretchable electrode 12 is not particularly limited. Preferably, the stretchable electrode 12 is formed on the stretchable substrate 10 in a circular shape or a substantially circular shape in plan view. Although one stretchable electrode 12 is not particularly limited area when viewed in plan, typically preferably 0.1 mm ² or more 100,000 mm ² or less, more preferably 1 mm ² or more 10000 mm ² or less, 10 mm ² or more 1000 mm ² The following are particularly preferred. In addition, two or more stretchable electrodes 12 are positioned on at least one main surface of the stretchable substrate 10. In the present embodiment, four stretchable electrodes 12 are positioned at one end of the rectangular portion 101 on the same plane (on one principal surface) with the stretchable lead wire 11 interposed therebetween, and the other end Three are located. In addition, the stretchable electrodes 12 are positioned so as not to overlap with each other along the extension direction of the stretchable lead-out wires 11. Furthermore, one stretchable electrode 12 is positioned at the other end of the string portion 103. One or more of the two or more stretchable lead wires 11 are connected to each of the stretchable electrodes 12. In the present embodiment, one stretchable lead wire 11 is connected to each of the stretchable electrodes 12. The stretchable electrode 12 has a low Young's modulus (for example, 100 MPa or less, more preferably 10 MPa or less) similarly to the stretchable lead wire 11 and exhibits high followability to the movement of the stretchable substrate 10. The stretchable electrode 12 may be formed by printing together with the formation of the stretchable lead wire 11, for example.

The stretchable cover 13 is formed of, for example, an elastomeric material or a stretchable fabric. The elastomer material is not particularly limited, and various materials such as polyester elastomers, styrene elastomers, polyolefin elastomers, polyamide elastomers and urethane elastomers can be adopted. When the adhesive portion 15 is formed by the printing method, a sheet made of an elastomeric material is preferable as the elastic cover 13 because the composition for forming the adhesive portion 15 hardly penetrates into the elastic cover 13 or the like.

The thickness of the stretchable cover is not particularly limited. The film thickness of the stretchable cover 13 is preferably 0.001 mm or more and 10 mm or less, more preferably 0.005 mm or more and 1 mm or less from the viewpoint of achieving both good handling of the electrode sheet 1 and low manufacturing cost of the electrode sheet 1 0.01 mm or more and 0.1 mm or less are more preferable.

The stretchable cover 13 is superimposed on the stretchable lead wire 11. In the present embodiment, the stretchable cover 13 is formed so as to overlap on one main surface of the stretchable base 10 beyond the formation position of the stretchable lead-out wire 11. Specifically, the stretchable cover 13 is formed to overlap with one of the main surfaces of the rectangular portion 101 and the string-like portion 103. In addition, the stretchable cover 13 is disposed so as to overlap a part of the film base 14 described later. The stretchable cover 13 has a recessed portion 131 having a diameter smaller than that of the stretchable electrode 12 at a position overlapping the stretchable electrode 12. Thereby, in the recess 131, one main surface of the stretchable electrode 12 is exposed as the bottom surface.

The film base 14 is formed of an insulating material different from the stretchable cover 13. The film substrate 14 is formed in accordance with the shape of the main surface of the projecting portion 102, and is superimposed on the main surface of the stretchable lead wire 11 and the projecting portion 102. The film substrate 14 is preferably formed of a material having higher in-plane rigidity than the stretchable substrate 10. Thereby, the film base 14 suppresses the disconnection of the stretchable lead-out wire 11. Moreover, since the film base 14 is provided with appropriate stiffness, it is possible to improve the handling when connecting the analysis device 2 and the electrode sheet 1.

The adhesive portion 15 is formed of a non-gel material having stretchability and conductivity. The adhesion portion 15 is formed of, for example, a non-gel material containing a resin having both adhesiveness and conductivity, or a non-gel material containing an adhesive resin and a conductive material. Here, the conductive material is not limited to a material which itself has conductivity, and may be a material which can impart conductivity to a non-gel material by being mixed with the non-gel material.
The non-gel material which comprises the adhesion part 15 contains an electroconductive polymer and / or electroconductive microparticles as an electroconductive material. The adhesive unit 15 contacts at least a part of the surface of the stretchable electrode 12 opposite to the stretchable substrate 10 side, as shown in FIG. 3, for each of the two or more stretchable electrodes 12. It is preferred to coat. In the present embodiment, as shown in FIG. 2, the adhesive portion 15 covers the stretchable electrode 12 exposed by being superimposed on each of the seven stretchable electrodes 12 positioned on the rectangular portion 101. Do. That is, the adhesive portion 15 closes the concave portion 131 by being filled in each of the seven concave portions 131 and covers the stretchable electrode 12. The recess 131 is defined by an inner side surface which is an end surface of the stretchable cover 13 and a bottom surface which is a surface of the stretchable electrode 12. The adhesive portion 15 protrudes with respect to one main surface of the stretchable cover 13 in the height direction which is the thickness direction D2 of the stretchable substrate 10. Further, in the present embodiment, the adhesive portion 15 covers a part of the main surface of the stretchable cover 13 along the outer periphery of the recess 131.

The above electrode sheet 1 is used as follows. Here, a case where the measurement object is the living body L and an electroencephalogram as a biological signal is acquired from the forehead F of the living body L will be described.
First, one principal surface side of the rectangular portion 101 of the stretchable base 10 faces the forehead F of the living body L. Next, the electrode sheet 1 is aligned such that the adhesive unit 15 is located at a position on the forehead F of the living body L at which an electroencephalogram is acquired. The electrode sheet 1 is brought close to the forehead F in the aligned state as described above. The electrode sheet 1 is attached to the forehead F by bringing all the adhesive portions 15 into contact with the forehead F. The stretchable base material 10, the stretchable lead wire 11, and the stretchable electrode 12 expand and contract in accordance with the curvature of the forehead F, whereby the electrode sheet 1 adheres to the forehead F as shown in FIG.

The stretchable electrode 12 disposed on the string-like portion 103 is attached to the earlobe E of the living body L. Thereby, the stretchable electrode 12 disposed on the string-like portion 103 acquires the reference potential of the living body L. Each of the seven stretchable electrodes 12 located on the rectangular portion 101 acquires an electroencephalogram via the adhesive portion 15. The stretchable lead-out wire 11 transmits the acquired electroencephalogram to the analysis device 2.

Next, a method of manufacturing the electrode sheet 1 according to the present embodiment will be described.
First, the stretchable electrode 12 is disposed on one main surface of the stretchable substrate 10. Further, the stretchable lead wire 11 is disposed in a state of being connected to the stretchable electrode 12.

Next, the film base 14 is disposed so as to overlap the stretchable lead wire 11 and a part of one main surface of the projecting portion 102. The stretchable cover 13 is formed on the stretchable lead wire 11, a part of one main surface of the rectangular part 101, a part of one main surface of the string-like part 103, and a part of one main surface of the stretchable cover 13. It is arranged in piles.

Next, the adhesive portion 15 is formed at the position of the recess 131 on the rectangular portion 101. The adhesive portion 15 is formed by, for example, printing, coating, or transfer of an adhesive layer made of a non-gel material.

As a printing method, a method of using a liquid composition for forming the adhesion part 15 such as a screen printing method or an inkjet printing method as an ink is preferable. Screen printing is preferable as a printing method because stable printing is easy.

The coating method may, for example, be a bar coating method, a slit coating method, a die coating method, a blade coating method, a roll coating method or a dip coating method. As a coating method, a bar coating method and a blade coating method are preferable, and a blade coating method is more preferable, because this method is a method suitable in consideration of the viscoelasticity of a typical composition used for forming the adhesive portion 15. In the coating method, if necessary, the application of the composition for forming the adhesive portion 15 is carried out through a mask that has an opening at the position where the adhesive portion 15 is formed and covers the area where the adhesive portion 15 is not formed. It takes place.

Formation of the adhesion part 15 by transfer of the adhesion layer which consists of non-gel materials is performed as follows. First, an adhesive layer made of a non-gel material having a predetermined shape corresponding to the shape of the adhesive portion 15 is formed on the release film, and then the adhesive layer is formed at a predetermined position including the position on the stretchable electrode 12 The adhesive portion 15 is formed by transferring and then peeling the release film from the adhesive layer.
Although the method of forming an adhesive layer on a release film is not specifically limited, It is preferable to form an adhesive layer by the above-mentioned printing method and a coating method. In addition, on the release film, the coating film which consists of a composition for adhesion part 15 formation may be hardened, and an adhesion layer may be formed.

More specifically, after a coating film made of a composition for forming the adhesive portion 15 or an adhesive layer is formed at the position of the concave portion 131 by the above method, the coating film or the adhesive layer may be formed, if necessary. The adhesive part 15 which has adhesiveness is formed by removing a solvent from this or hardening the said coating film and adhesive layer.

The degree of freedom in processing when forming the adhesive part 15 is high, and in view of the adhesive part 15 having a desired shape with good dimensions and positional accuracy, a coating is formed using a curable liquid composition, Preferred is a method of curing the film. That is, it is preferable that the adhesion part 15 consists of hardened | cured material of a liquid curable composition. The curing method is appropriately selected according to the components contained in the composition, and may be heat curing, photo curing, or moisture curing.

The film thickness of the adhesion part 15 is not specifically limited. For example, when the film thickness of the adhesion portion 15 is preferably 50 μm or less, more preferably 40 μm or less, particularly preferably 30 μm or less, the resistance value in the thickness direction of the adhesion portion 15 can be reduced, and biosignals of higher quality Easy to get In addition, the thinner the film thickness of the adhesive portion 15, the less the peeling residue of the adhesive portion 15 on the surface of the object to be measured occurs when peeling the sheet electrode 1 from the object to be measured, which is preferable. Furthermore, since the adhesion part 15 can be formed with the composition for adhesion part 15 formation of a small amount as the film thickness of the adhesion part 15 is thin, it is preferable at the point which can manufacture the electrode sheet 1 at low cost.
The lower limit of the film thickness of the adhesive portion 15 is not particularly limited, but for example, 5 μm or more is preferable and 10 μm or more is more preferable because the adhesive portion 15 having a uniform film thickness can be stably formed easily.

According to the electrode sheet 1 of the first embodiment, the method of manufacturing the electrode sheet 1, the biological signal acquiring apparatus, and the biological signal acquiring method described above, the following effects can be obtained.

(I) The electrode sheet 1 was configured to include a sheet-like stretchable base material 10, two or more stretchable lead wires 11, two or more stretchable electrodes 12, and an adhesive part 15. Then, two or more stretchable electrodes 12 are positioned on at least one main surface of the stretchable substrate 10, and the adhesive portion 15 stretches the stretchable electrode 12 for each of the two or more stretchable electrodes 12. At least a part of the surface opposite to the surface on the side of the porous substrate 10 was in contact and coated. Further, one or more of the two or more stretchable lead wires 11 are connected to each of the two or more stretchable electrodes 12, and the adhesive portion 15 is formed of a non-gel material having stretchability and conductivity. did. Thereby, at the time of use or long-term storage of electrode sheet 1, a functional fall of adhesion part 15 can be controlled. Moreover, since it can attach more easily to a head compared with a headgear type | mold electrode when using for acquisition of the brain wave of the electrode sheet 1, a biosignal can be acquired simply.

(II) The non-gel material was made to contain the adhesive resin and the conductive material. Thereby, the type and amount of use of the adhesive resin and the conductive material can be adjusted independently, and the adhesiveness and conductivity of the adhesion part 15 made of the non-gel material can be adjusted independently. In addition, since the adhesive resin does not have to have conductivity and the conductive material does not need to have adhesiveness, the material options for the adhesive resin and the conductive material are particularly wide.

(III) The conductive material contains a conductive polymer and / or conductive particles. Thereby, uniform conductivity with little unevenness can be easily imparted to the adhesion portion 15.

(IV) The electrode sheet 1 was further configured to include the stretchable cover 13 made of an insulating material and covering the stretchable lead wire 11. Thereby, since the stretchable lead-out wire 11 contacts the measurement object (typically, the living body L) through the stretchable cover 13, each of the stretchable lead-out wires 11 shorts with the other stretchable lead-out wires 11 Can be suppressed. Therefore, the quality of the signal acquired from the measurement object can be made higher.

(V) At least a part of the main surface of the stretchable cover 13 of the adhesive portion 15 is covered. Thereby, the exposed surface of the adhesion part 15 can be expanded, and the contact area of the adhesion part 15 to a measurement object (typically, the living body L) can be expanded. Therefore, peeling of the electrode sheet 1 from the measurement target can be suppressed.

Second Embodiment
An electrode sheet 1A according to a second embodiment, a method of manufacturing the electrode sheet 1A, a biological signal acquisition apparatus, and a biological signal acquisition method will be described with reference to FIGS. 5 and 6. In the description of the second embodiment, the same components will be assigned the same reference numerals, and the description thereof will be omitted or simplified.
In the electrode sheet 1A and the biological signal acquiring apparatus according to the second embodiment, as shown in FIGS. 5 and 6, the adhesive portion 15A is disposed so as to overlap the entire main surface of the stretchable cover 13 and stretchable. It differs from the first embodiment in that each of the portions covering the electrode 12 and the portion covering the other are separated.
About the manufacturing method of electrode sheet 1A concerning a 2nd embodiment, and a living body signal acquisition method, since only the formation field of adhesion part 15A differs from a 1st embodiment, explanation is omitted.

According to the above-described electrode sheet 1A, the method of manufacturing the electrode sheet 1A, the biological signal acquiring apparatus, and the biological signal acquiring method according to the second embodiment, the following effects can be obtained.

(VI) The adhesive portion 15A is configured to be separated between each of the portions covering the stretchable electrode 12 and the portion covering the other. As a result, since each of the stretchable electrodes 12 can be prevented from being short-circuited with the other stretchable electrodes 12, it is possible to obtain a biosignal of higher quality.

Third Embodiment
An electrode sheet 1B, a method of manufacturing the electrode sheet 1B, a biological signal acquisition apparatus, and a biological signal acquisition method according to a third embodiment of the present invention will be described with reference to FIGS. 7 and 8. In the description of the third embodiment, the same components will be assigned the same reference numerals, and the description thereof will be omitted or simplified.
In the electrode sheet 1B and the biological signal acquiring apparatus according to the third embodiment, as shown in FIGS. 7 and 8, the adhesive portion 15B has a portion covering the stretchable electrode 12 and a portion covering the other. The second embodiment differs from the first and second embodiments in terms of points. Further, in the electrode sheet 1B and the biological signal acquiring apparatus according to the third embodiment, the non-gel material constituting the adhesive portion 15B necessarily includes conductive fine particles as a conductive material in the first embodiment and the second embodiment. It is different. A particle material having an aspect ratio (average major axis length / average minor axis length) of 50 or less is defined as conductive fine particles.
The average major axis length and the average minor axis length are obtained by processing an image obtained by microscopically observing conductive particles with commercially available image analysis software, and determining the major axis length and the minor axis length for each of 10 or more particles The value can be obtained as the number average length from the obtained values.
Here, the longest distance in the distance between any two points on the outer periphery of the particle in the electron microscope image is taken as the long axis length. In the electron microscope image, the longest width among the widths of particles in the direction perpendicular to the direction of the long axis length is taken as the short axis length.
In the case of flake-like plate-like particles, the average major axis length and the average minor axis length are determined based on the shape of the main surface. That is, the thickness of the plate-like particles is not used as the minor axis length.
Further, the particle size of the conductive fine particles is not particularly limited as long as the particle size is generally recognized as fine particles. Typically, the particle size of the conductive fine particles is preferably 500 μm or less, more preferably 300 μm or less, and particularly preferably 100 μm or less as a volume average particle size.

Since the conductive fine particles are contained as the conductive material, the adhesion part 15B has anisotropic conductivity. The reason why such anisotropic conductivity is developed is not clear, but is considered to be due to the aggregation of the conductive fine particles in the adhesion part 15B. In particular, when the adhesive portion 15B is formed by screen printing, since the adhesive portion 15B is formed while the shearing force in the thickness direction of the adhesive portion 15B is applied, the thickness direction of the adhesive portion 15B of the aggregate of conductive fine particles The conductive path oriented in the thickness direction of the adhesive portion 15B is likely to be formed by the orientation of

Specifically, the adhesive portion 15B has a high resistance value in the in-plane direction D1 and a low resistance value in the thickness direction D2. For example, in the adhesive portion 15B, the relative value of the volume low efficiency in the thickness direction D2 to the volume low efficiency in the in-plane direction D1 is preferably 0.5 or less, more preferably 0.3 or less, particularly preferably 0. It is formed to be less than or equal to one.
About the manufacturing method of electrode sheet 1B concerning a 3rd embodiment, and a living body signal acquisition method, since only the formation field of adhesion part 15B differs from a 1st embodiment and a 2nd embodiment, explanation is omitted.

According to the above-described electrode sheet 1B according to the third embodiment, the method of manufacturing the electrode sheet 1B, the biological signal acquiring apparatus, and the biological signal acquiring method, the following effects can be obtained.

(VII) The conductive material contained conductive particles. As a result, it is possible to impart to the adhesive portion 15B good anisotropic conductivity in the thickness direction, and in the in-plane direction, which is difficult to conduct. Therefore, even if the adhesive portion 15 is disposed so as to overlap the plurality of stretchable electrodes 12, a short circuit of the stretchable electrode 12 can be suppressed, and the area to which the adhesive portion 15B is exposed is expanded to measure the electrode sheet 1B Peeling from an object (typically, the living body L) can be prevented.

(VIII) In the adhesive portion 15B, the portion covering the stretchable electrode 12 and the portion covering the other were on one side. Thereby, the area of adhesion part 15B which contacts a measurement object can be expanded, and the sticking nature of electrode sheet 1B can be improved.

[Composition for forming adhesive part]
As a material of the adhesion part 15, as mentioned above, for example, a material in which a conductive material is dispersed in an adhesive resin may be used, or a resin having both conductivity and adhesion may be used.
The material of the adhesive portion 15 is an adhesive resin, because various characteristics such as adhesiveness, mechanical characteristics, conductivity and the like can be easily adjusted by appropriately changing the type and amount of the adhesive resin and the conductive material. Materials in which the conductive material is dispersed are preferred.

Specifically, the adhesive portion 15 is preferably made of a cured product of a composition containing a polyoxyalkylene polymer (A) and a conductive material (B).
Hereinafter, the components contained in the composition used for formation of adhesion part 15 are explained.

(Polyoxyalkylene polymer (A))
Examples of the main chain skeleton of the polyoxyalkylene polymer (A) include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene- Although a polyoxybutylene copolymer etc. can be used, it is preferable that it is a polyoxypropylene type polymer.

The polyoxyalkylene polymer essentially consists of the formula (2):
-R ² -O- (2)
(Wherein, R ² is a linear or branched alkylene group having 1 to 14 carbon atoms)
It is preferable that it is a polymer which has a repeating unit represented by
The alkylene group as R ² described in the formula (2) may be linear or branched. The carbon atom number of the alkylene group as R ² is 1 or more and 14 or less, preferably 2 or more and 4 or less.

There is no limitation in particular as a repeating unit represented by Formula (2), For example, the repeating unit etc. which are shown below are mentioned.

The main chain skeleton of the polyoxyalkylene polymer (A) may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units.
As a polyoxyalkylene polymer having a main chain skeleton consisting of repeating units represented by the above formula (2), a propylene oxide polymer is mainly contained because it is amorphous and has a relatively low viscosity. Preferred is a polyoxypropylene polymer, and particularly preferred is a polyoxypropylene polymer whose main chain is composed of only oxypropylene units (—CH ₂ CH (CH ₃ ) C—O—).

The synthesis method of the polyoxyalkylene polymer (A) is not particularly limited.
The polyoxyalkylene polymer (A) is, for example, a polymerization method using an alkali catalyst such as KOH, a complex obtained by reacting an organoaluminum compound shown in JP-A-61-215623 and a porphyrin. JP-B-46-27250, JP-B-59-15336, U.S. Pat. No. 3,278,457, U.S. Pat. No. 3,278,458, U.S. Pat. No. 3,278,459, U.S. Pat. No. 3,427,256, U.S. Pat. JP-A-11-060722 discloses a polymerization method using a complex metal cyanide complex catalyst as disclosed in US Pat. No. 3,427,335 and the like, a polymerization method using a catalyst composed of a polyphosphazene salt as disclosed in JP-A-10-273512. Touch consisting of the indicated phosphazene compounds Polymerization method using thereof.

The molecular chain constituting the polyoxyalkylene polymer (A) may be linear or may have a branch.
The number average molecular weight of the polyoxyalkylene polymer (A) is not particularly limited as long as the object of the present invention is not impaired.
The number average molecular weight of the polyoxyalkylene polymer (A) is preferably 3,000 or more, more preferably 3,000 to 100,000, still more preferably 3,000 to 50, as the polystyrene-equivalent molecular weight measured by GPC. 1,000 or less is particularly preferable, and 3,000 to 30,000 is most preferable.

When the number average molecular weight is too low, it may be difficult to form the adhesive portion 15 having excellent stretchability using a composition containing the polyoxyalkylene polymer (A).
When the number average molecular weight is too large, it may be necessary to devise a method of forming the adhesive portion 15 due to the high viscosity of the polyoxyalkylene polymer (A).

The molecular weight distribution of the polyoxyalkylene polymer (A) is not particularly limited, but is preferably narrow, preferably less than 2.00, more preferably 1.60 or less, and particularly preferably 1.40 or less.
If the molecular weight distribution is too broad, it may be necessary to devise a method of forming the adhesive portion 15 due to the high viscosity of the polyoxyalkylene polymer (A).

The polyoxyalkylene polymer (A) has a formula (1):
-CH ₂ -C (R ¹ ) = CH ₂ (1)
(In the formula, R ¹ is a hydrogen atom or a substituent represented by a hydrocarbon group having 1 to 20 carbon atoms) (hereinafter sometimes referred to as an alkenyl group)
It is preferable to have one or more functional groups represented by 1 in the molecule.
As R ¹ , a hydrogen atom or a methyl group is preferable from the viewpoint of the reactivity of the functional group represented by Formula (1).

The number of alkenyl groups represented by the formula (1) possessed by the polyoxyalkylene polymer (A) is preferably at least one in average in one molecule of the polyoxyalkylene polymer (A), The number is preferably 5 or more, more preferably 1 or more and 3 or less, and particularly preferably 1 or more and 2 or less.

When the number of alkenyl groups represented by the formula (1) in one molecule of the polyoxyalkylene polymer (A) is too small, the curability of the composition containing the polyoxyalkylene polymer (A) is somewhat inferior There is a case.
In addition, when the number of alkenyl groups represented by the formula (1) contained in one molecule is too large, in a cured product formed using a composition containing a polyoxyalkylene polymer (A), In some cases, a network structure is formed, and it is difficult to form a cured product with good tackiness.

(Conductive material (B))
It is preferable that the composition used for formation of the adhesion part 15 contains a conductive material (B) with a polyoxyalkylene type polymer (A).
The conductive material (B) is not limited to a material generally recognized as having conductivity, and if it is a material that can impart conductivity to the adhesion portion 15 when it is blended in the adhesion portion 15 It is not particularly limited. The conductive material (B) may be an organic material or an inorganic material.

The form of the conductive material (B) is not particularly limited. As described above, in view of anisotropic conductivity, the conductive material (B) is preferably conductive fine particles. As described above, a particle material having an aspect ratio (average major axis length / average minor axis length) of 50 or less is used as conductive fine particles. Typically, the particle size of the conductive fine particles is preferably 500 μm or less, more preferably 300 μm or less, and particularly preferably 100 μm or less as a volume average particle size.

As the material of the conductive material (B), inorganic materials such as metals are preferable in terms of low cost and easy availability, and excellent in chemical and physical stability.
On the other hand, it is not necessary to consider the problem of metal allergy etc. when the dispersibility in the adhesive part 15, the dispersion stability, etc. are good, and the sheet-like electrode 1 is used by sticking on the skin of a living body. From the point of view, non-metallic inorganic materials are preferred.

As the inorganic material, for example, a conductive carbon material can be used. Although some carbon materials contain a small amount of organic groups, carbon materials which do not contain organic groups in the main skeleton are described as inorganic materials in the present specification.
Such carbon materials include carbon black, carbon fibers, graphite and carbon nanomaterials.

Among carbon materials, a nanocarbon material is preferable because it is easy to lower the volume resistivity of the adhesive portion 15 to a desired extent with a small amount of use.
The nanocarbon material is preferably at least one selected from the group consisting of carbon nanotubes, carbon nanohorns, graphene, nanographite, fullerenes, and carbon nanocoils. Among these, carbon nanotubes are preferable from the viewpoints of easy availability and easy formation of the adhesive portion 15 having low volume resistivity and excellent conductivity.

Moreover, as an inorganic material, metal powder and metal fiber can be used, for example.

As the metal powder, for example, a metal fine powder having an average particle diameter of 100 μm or less, preferably 50 μm or less, which is manufactured by an atomizing method, is preferable.
As a metal fiber, metal nano fiber material represented by silver nanowire etc. is preferable.
For example, 200 nm or less is preferable and, as for the fiber diameter of metal nanowire, 10 nm or more and 100 nm or less are more preferable. 5 micrometers or more and 100 micrometers or less are preferable, and, as for the fiber length of metal nanowire, 10 micrometers or more and 50 micrometers or less are more preferable.

As for the fiber length of the metal fiber, the average major axis length is preferably 1 μm to 1000 μm, and more preferably 5 μm to 500 μm.
The metal fiber having such an average major axis length is easy to prepare and obtain, easily forms a conductive path, and easily reduces the volume resistivity of the adhesive portion 15 to a desired value even with a small amount of use.
The average minor axis length of the metal fibers is preferably 1 nm or more and 1000 nm or less, and more preferably 5 nm or more and 500 nm or less.
The metal fiber having such an average minor axis length is easily dispersed in the composition used for forming the adhesive portion 15, and the conductive path is easily formed well, and the volume of the adhesive portion 15 is used even with a small amount of use. It is easy to lower the resistivity to a desired value.

The aspect ratio (average major axis length / average minor axis length) of the metal fibers is preferably 100 or more and 1,000 or less in view of the easiness of formation of the conductive path in the adhesive portion 15.

The metal composition of the metal powder and the metal fiber is not particularly limited.
The material of the metal powder and the metal fiber may contain two or more metal elements, and may contain a metal oxide, a metal salt, a carbon-based conductive material, and the like together with the metal.
Examples of metals preferred as the metal powder or metal fiber material include gold, platinum, silver, palladium, neodymium, iron, cobalt, copper, tin, zinc and nickel, and two or more metals selected therefrom Alloy etc. are mentioned.
Among them, silver is preferable in terms of high conductivity and easy processing. With regard to the material of metal nanofibers, silver is preferable also from the viewpoint that mass production by wet synthesis is easy. Also, metal powder or metal fiber may be plated or deposited using a material different from those materials. It may be coated by

For example, as a method of producing metal nanowires, as a method of producing silver nanowires, for example, (Sun, Y. et al. “Uniform Silver Nanowires Synthesis by Reducing AgNO ₃ with Ethylene Glycol in the Presence of Seeds and Poly (Vinyl Pyrrolidone) ", (2002) Chem. Mater. 14, 4736-4745), for example, the method of reducing silver nitrate in ethylene glycol in the presence of polyvinylpyrrolidone and the like.
Moreover, as a synthesis method of the silver nanowire which has the above-mentioned average major axis length and average minor axis length, for example, Nano Research 2014, 7, 236-245. And J. Mater. Chem. A, 2014, 2, 6326 to 6330.

Organic materials include conductive polymers. The conductive polymer is not particularly limited, and polyacetylene, polythiophene, poly (3,4-ethylenedioxythiophene) (hereinafter also referred to as PEDOT), poly (p-phenylene), polyfluorene, poly (p-phenylene) Vinylene), polyethylene vinylene, polypyrrole, polyaniline and the like.
Among these, PEDOT is preferable in terms of high conductivity and excellent stability. However, the composition used for formation of adhesion part 15 may contain two or more types of polymers as a conductive polymer.

When the conductive material (B) is an organic material, it is preferable that the conductive material (B) contains a dopant together with the conductive polymer, since it is easy to form the adhesive portion 15 exhibiting desired conductivity. The dopant is a component that enhances the conductivity of the conductive material (B).

The type of dopant is not particularly limited as long as the conductivity of the conductive polymer can be enhanced. For example, preferable dopants for PEDOT include polystyrene sulfonic acid (hereinafter also described as PSS), polyvinyl sulfonic acid, perchlorate, sulfonic acid and the like.
Among these dopants, PSS is preferable from the viewpoint of easy availability and easy formation of the adhesive portion 15 exhibiting desired conductivity.
Hereinafter, the combination of PEDOT and PSS as the conductive material (B) will also be described as PEDOT / PSS.

It does not specifically limit as a manufacturing method of PEDOT / PSS, A chemical polymerization method, an electrolytic polymerization method, the gas phase polymerization method is mentioned.

The weight ratio of the conductive polymer to the dopant in the conductive material (B) is preferably 1: 0.5 to 1: 5, more preferably 1: 1 to 1: 3 as conductive polymer: dopant.

The method of mixing the electrically-conductive material (B) demonstrated above with a polyoxyalkylene type polymer (A) will not be specifically limited if the adhesion part 15 which shows desired electroconductivity can be formed using the composition containing these.

For example, after mixing the dispersion liquid of a conductive material (B) with a polyoxyalkylene type polymer (A), the method of distilling off the dispersion medium derived from a dispersion liquid from a composition is mentioned.
The type of dispersion medium is not particularly limited, and water, alcohol, monomethyl formamide, dimethyl sulfoxide and the like can be mentioned. Among them, from the viewpoint of compatibility with the polyoxyalkylene polymer (A), an alcohol is preferable as the dispersion medium, 2-propanol and ethanol are more preferable, and a mixed solvent of 2-propanol and ethanol is more preferable.
The above-mentioned alcohol is particularly preferable as a dispersion medium when PEDOT is used as the conductive material (B).

The composition may contain a metal salt as conductive particles. The metal salt is not particularly limited as long as it is a salt compound comprising a metal cation and an anion, and may be an inorganic metal salt or an organic metal salt, and an inorganic metal salt is preferable.

Examples of the metal cation constituting the metal salt include sodium ion, potassium ion, magnesium ion, calcium ion, barium ion, manganese ion, iron ion, copper ion, silver ion, zinc ion, aluminum ion and the like. When these metal ions can have multiple ion valences, the ion valence of the metal ions is not particularly limited.

Specific examples of the anion constituting the metal salt include chloride ion, bromide ion, iodide ion, fluoride ion, sulfate ion, sulfite ion, hydrogen sulfate ion, phosphate ion, nitrate ion, carbonate ion, and carbonate ion. Inorganic anions such as hydrogen ion, acetate ion, formate ion, propionate ion, butyrate ion, valerate ion, isovalerate ion, lactate ion, oxalate ion, trichloroacetate ion, dichloroacetate ion, monochloroacetate ion, tricarbonate ion Organic anions such as fluoroacetate ion, difluoroacetate ion, monofluoroacetate ion, benzoate ion, salicylate ion, methanesulfonate ion, ethanesulfonate ion, trifluoromethanesulfonate ion, benzenesulfonate ion, and toluenesulfonate ion But It is.

A metal salt such as a metal chloride, a metal bromide, a metal iodide, or a metal fluoride can be obtained as the metal salt because it is easy to obtain a signal such as a biological signal stably and favorably by using the sheet-like electrode 1 having the adhesion part 15 Metal halide compounds are preferred, metal chlorides and metal bromides are more preferred, and metal chlorides are particularly preferred.
As metal chlorides, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, iron (III) chloride, iron (II) chloride, copper (II) chloride, copper (I) chloride, silver (I) chloride, and chloride Examples thereof include zinc and the like, sodium chloride, potassium chloride and silver (I) chloride are preferable, and silver chloride is more preferable.

When the viscosity of the polyoxyalkylene polymer (A) is low or when the viscosity is lowered by adding a small amount of organic solvent to the polyoxyalkylene polymer (A), the polyoxyalkylene polymer ( Polyoxyalkylene by mixing A) and the solid conductive material (B) or the dispersion liquid of the conductive material (B) by a kneading apparatus such as a Huber type Marler, two rolls, three rolls, etc. The conductive material (B) can also be dispersed in the base polymer (A).
After the dispersion treatment of the conductive material (B), water and an organic solvent are preferably distilled off from the composition.

The content of the conductive material (B) in the composition used to form the adhesive portion 15 is not particularly limited as long as it has the desired conductivity and can form the adhesive portion 15 having the desired adhesiveness.
The amount of the conductive material (B) used is appropriately set in consideration of the conductivity of the adhesive portion 15 to be formed.
The content of the conductive material (B) in the composition is typically preferably 3 parts by mass or more with respect to 100 parts by mass of the polyoxyalkylene polymer (A).
The content of the conductive material (B) in the composition is 10 parts by mass even if it is 5 parts by mass or more or 8 parts by mass or more with respect to 100 parts by mass of the polyoxyalkylene polymer (A) It may be more than.
Moreover, 200 mass parts or less are preferable with respect to 100 mass parts of polyoxyalkylene type polymers (A) in content of a conductive material (B) in a composition, 150 mass parts or less are more preferable, and 100 mass parts or less Is more preferable, 50 parts by mass or less is particularly preferable, and 20 parts by mass or less is the most preferable.

When the conductive material (B) is a metal powder or metal fiber, the content of the conductive material (B) is 3 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the polyoxyalkylene polymer (A) Preferably, 3 parts by mass or more and 150 parts by mass or less are more preferable, 3 parts by mass or more and 100 parts by mass or less are particularly preferable, and 3 parts by mass or more and 20 parts by mass or less are most preferable.
By using the conductive material (B) in an amount within this range, it is easy to balance the desired volume resistivity of the adhesive portion 15 with the desired adhesiveness.

When the conductive material (B) is a conductive polymer, or a combination of a conductive polymer and a dopant, the content of the conductive material (B) is 3 with respect to 100 parts by mass of the polyoxyalkylene polymer (A). The mass part is preferably 100 parts by mass or less, more preferably 3 parts by mass to 50 parts by mass, and particularly preferably 3 parts by mass to 20 parts by mass.
By using the amount of the conductive polymer or the combination of the conductive polymer and the dopant in such an amount, it is easy to balance the desired conductivity of the adhesive part 15 with the desired adhesiveness.

When the conductive material (B) is a metal salt, the content of the conductive material (B) is preferably 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass of the polyoxyalkylene polymer (A), 0.1 parts by mass or more and 8 parts by mass or less are more preferable, and 1 parts by mass or more and 7 parts by mass or less are particularly preferable.
If the amount of metal salt used as the conductive material (B) is within such a range, the viscosity of the composition can be easily controlled within an easy-to-handle range, and the non-brittle adhesion portion 15 can be easily formed.

(Silicone compound (C))
It is preferable that the composition used for formation of the adhesion part 15 contains a silicone compound (C) with the above-mentioned polyoxyalkylene type polymer (A) and a conductive material (B).
As the silicone compound (C), a compound having 1 or more and 10 or less hydrosilyl groups in the molecule is used. The hydrosilyl group means a group having a Si-H bond.
The hydrosilyl group contained in the silicone compound (C) reacts with the alkenyl group represented by the formula (1) contained in the polyoxyalkylene polymer. By such reaction, a cured product having properties suitable as the adhesive portion 15 is formed.

In the present specification, when two hydrogen atoms (H) are bonded to the same silicon atom (Si), it is calculated as two hydrosilyl groups. The number of hydrosilyl groups is preferably 2 or more and 8 or less.
By using the silicone compound (C) having the number of hydrosilyl groups within the above range, it is easy to form the adhesive portion 15 having both good strength and good stretchability.

There are no particular limitations on the chemical structure of the silicone compound (C) other than the hydrosilyl group. The number average molecular weight of the compound (C) calculated from the SiH group value obtained by titration is preferably 400 or more and 3,000 or less, and more preferably 500 or more and 2,000 or less.
When using a silicone compound (C) having a number average molecular weight within this range, it is easy to obtain a cured product having desirable characteristics as the adhesive part 15 in a short time while suppressing volatilization of the silicone compound (C) at the time of curing. .

The silicone compounds (C) may be used alone or in combination of two or more. The silicone compound (C) is preferably one which is well compatible with the polyoxyalkylene polymer (A). From the viewpoint of availability of raw materials and compatibility with the polyoxyalkylene polymer (A), organohydrogensiloxane modified with an organic group is exemplified as a suitable silicone compound (C). Typical examples of organohydrogensiloxanes have the following formula:

It is a compound represented by

The value of c + d in the above formula is not particularly limited, but is preferably 2 or more and 50 or less. R ³ is a hydrocarbon group having 2 to 20 carbon atoms in its main chain.
The silicone compound (C) represented by the above formula can be obtained by modifying unmodified methyl hydrogen silicone to introduce R ³ . Unmodified methyl hydrogen silicone corresponds to a compound in which R ³ is all H, and issued by CMC Co., Ltd. (1990.1.31) “Market prospect of silicone-manufacturer strategy and application development-” As described, it is used as a raw material for various modified silicones.
Examples of the organic compound for introducing R ³ include α-olefin, styrene, α-methylstyrene, allyl alkyl ether, allyl alkyl ester, allyl phenyl ether, allyl phenyl ester and the like.
The number of hydrosilyl groups in the molecule after modification can be adjusted by the amount of the above-mentioned organic compound added for modification.

The ratio of the amount of polyoxyalkylene polymer (A) to the amount of silicone compound (C) in the composition used to form adhesion portion 15 is relative to the total amount of alkenyl groups derived from polyoxyalkylene polymer (A). And the total amount of hydrosilyl groups derived from the silicone compound (C). The magnitude of the total amount of hydrosilyl groups per mole of total alkenyl groups determines the degree of crosslinking density after curing.
The total amount of hydrosilyl groups possessed by the silicone compound (C) per mol of the total amount of alkenyl groups possessed by the polyoxyalkylene polymer (A) is preferably from the viewpoint of easily forming the adhesive portion 15 having desirable mechanical properties. Is 0.1 mol or more and 2.0 mol or less, more preferably 0.4 mol or more and 1.5 mol or less.

(Hydrosilylation catalyst (D))
The composition used to form the adhesive portion 15 preferably contains a hydrosilylation catalyst (D) together with the polyoxyalkylene polymer (A), the conductive material (B), and the silicone compound (C) described above. .

The hydrosilylation catalyst (D) is not particularly limited as long as it promotes the hydrosilylation reaction between the alkenyl group of the polyoxyalkylene polymer (A) and the hydrosilyl group of the silicone compound (C). It can be suitably selected from the various catalysts for hydrosilylation reaction used.

Specific examples of the hydrosilylation catalyst (D) include chloroplatinic acid, platinum-vinylsiloxane complex (eg, platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex and platinum -1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane complex), platinum-olefin complex (eg, Pt ₁ (ViMe ₂ SiOSiMe ₂ Vi) _m , Pt [(MeViSiO) ] ₄ ] _n (However, l, m and n show a positive integer and Vi is a vinyl group.) Etc. are illustrated.

Among these, from the viewpoint of the activity of the catalyst, a platinum complex catalyst not containing a conjugate base of a strong acid as a ligand is preferred, a platinum-vinylsiloxane complex is more preferred, and platinum-1,3-divinyl-1,1. Particularly preferred is a 3,3,3-tetramethyldisiloxane complex or a platinum-1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane complex.

Although the amount of the hydrosilylation catalyst (D) is not particularly limited, it is preferably 10 ⁻⁸ mol or more and 10 ⁻¹ mol or less with respect to 1 mol in total of alkenyl groups contained in the polyoxyalkylene polymer (A). More preferably, it is 10 ^-6 mol or more and 10 ^-2 mol or less.
Within the above range, it is easy to achieve appropriate curing speed, stable curability, necessary pot life of the composition, and the like.

(Storage stabilizer)
When a silicone compound (C) and a hydrosilylation catalyst are added to the composition used to form the adhesion part 15, as a storage stabilizer, a compound containing an aliphatic unsaturated bond, an organophosphorus compound, an organosulfur compound, It is preferable to add nitrogen-containing compounds, tin compounds, organic peroxides and the like to the composition.

The storage stabilizer suppresses the conversion of the hydrosilyl group (Si-H group) in the silicone compound (C) to the Si-OH group (due to long standing and moisture contamination), and the coating pot life Can be improved. The compounding amount of the storage stabilizer is preferably 10 ⁻⁶ to 10 ⁻¹ mol with respect to ¹ mol in total of hydrosilyl groups contained in the curable composition due to the silicone compound (C).

(Polyethylene glycol)
The composition used to form the adhesive portion 15 preferably also contains polyethylene glycol. For example, polyethylene glycol. -S. Hsiao et al. , J. Mater. Chem. 2008, 18, 5948 report improvement in conductivity of conductive materials such as PEDOT / PSS by the addition of high boiling point organic compounds such as dimethyl sulfoxide and ethylene glycol.
As understood from this, by blending polyethylene glycol (PEG) having a high boiling point with the composition used for forming the adhesive portion 15, the adhesive portion 15 having excellent conductivity can be easily formed.

The molecular weight of PEG is preferably 1000 or less. When the molecular weight of PEG is too large, PEG may be difficult to be compatible with the polyoxyalkylene polymer (A), and it may be difficult to obtain a desired effect on reduction of volume resistivity.

As addition amount of PEG, 1 mass part or more and 100 mass parts or less are preferable with respect to 100 mass parts of polyoxyalkylene type polymer (A).
By making the polyoxyalkylene polymer (A) compatible with PEG by using PEG in an amount within this range, the conductivity of the adhesive part 15 is enhanced while the adhesive part 15 having desired adhesiveness is obtained. Easy to form.

(Other materials)
The composition used for formation of adhesion part 15 may contain various ingredients in the range which does not inhibit the object of the present invention other than the above-mentioned ingredient.
For example, although the effect by the hydrosilylation reaction was described above, when the composition does not contain the silicone compound (C) or the hydrosilylation catalyst (D), a general photopolymerization initiator is blended in the composition, and the above formula The alkenyl groups represented by (1) may be reacted with each other to form the adhesive portion 15 by photocuring.

Furthermore, in addition to the components described above, the composition used to form the adhesive portion 15 may be, for example, a surfactant, an antioxidant, an ultraviolet light absorber, a pigment, a dye, a plasticizer, and a thixotropic agent, From the above, additives which are blended in various resin compositions can be blended.

(Method of forming adhesive part)
The formation method of the adhesion part 15 is not specifically limited. Typically, the above-mentioned composition is formed into a film having a desired thickness, and then the obtained film is cured to form the adhesion part 15.
The curing method is not particularly limited, and may be appropriately selected depending on the components of the composition.
For example, the composition comprises a polyoxyalkylene polymer (A) represented by the aforementioned formula (1), a conductive material (B), a silicone compound (C) having a hydrosilyl group, and a hydrosilylation catalyst ( When D) is included, as curing conditions, heating at 40 ° C. to 180 ° C. for 1 minute to 180 minutes is exemplified.
If more complete curing is desired, it may be further left for several days at 40 ° C. to 80 ° C.

[Examples 1 to 3 and Comparative Example 1]
Next, an electrode sheet and a biological signal acquiring apparatus according to each embodiment of the present invention will be described by the following examples and comparative examples. The scope of the present invention is not limited at all by the examples shown below.

In the example and the comparative example, the configurations of the adhesive portions were respectively changed and compared. Also, an electroencephalogram was acquired as a biosignal.

Synthesis Example 1
A polypropylene glycol is used as an initiator, propylene oxide is polymerized using a zinc hexacyanocobaltate glyme complex catalyst, and a number average molecular weight is about 28,500 (using a Tosoh HLC-8120 GPC as a liquid delivery system, the column is a Tosoh TSK-GEL Using H type, the solvent was the polystyrene conversion molecular weight measured using THF, and obtained polypropylene oxide.
A methanol solution of 1.2 times equivalent of NaOMe was added to the hydroxyl group of the hydroxyl group-terminated polypropylene oxide, methanol was distilled off, and allyl chloride was further added to convert the terminal hydroxyl group to an allyl group.
After mixing and stirring 300 parts by mass of n-hexane and 300 parts by mass of water with respect to 100 parts by mass of the unpurified allyl-terminated polypropylene oxide obtained, the water is removed by centrifugation and the obtained hexane solution is further mixed with water After 300 parts by mass were mixed and stirred, water was removed again by centrifugation, and then hexane was removed by evaporation under reduced pressure.
Thus, a polyoxypropylene polymer (A1-1) having a number average molecular weight of about 28,500 and an allyl group at the end was obtained.

Synthesis Example 2
A polyoxypropylene polymer (A1-2) having a number average molecular weight of 7,000 and having an allyl group at one end was obtained in the same manner as in Synthesis Example 1 except that butanol was used as the initiator.

Synthesis Example 3
In the presence of a platinum catalyst, 0.6 equivalent of α-methylstyrene, which is the total amount of hydrosilyl groups, is added to methylhydrogensilicone represented by the following chemical formula (3) (wherein, x is an average of 5), 1 A silicone compound (C-1) having an average of two hydrosilyl groups in the molecule was obtained. The hydrosilyl group content of this silicone compound was 2.5 mmol / g.

Synthesis Example 4
0.5 g of silver (Aldrich, flake-like, particle size 10 μm) and 6 g of a solution of iron chloride (III) at a concentration of 274 mol / L (40% iron chloride (III) solution manufactured by Wako Pure Chemical Industries, Ltd.) Mixed) and stirred for 15 minutes. Silver chloride (I) formed after stirring was washed with water and ethanol, and then dried at 100 ° C. for 10 minutes to obtain 0.67 g of silver chloride (I) (E-1).

Example 1
PEDOT / PSS (B-1) (Orgacon manufactured by Agfa) is added to a solution of 2-propanol and ethanol at a ratio of 98/2 (wt / wt) to a concentration of 1 wt%, using ultrasound PEDOT / PSS (B-1) was dispersed.
PEDOT / PSS (B-1) is a total of 100 parts by mass of 83.8 parts by mass of the polyoxypropylene polymer (A1-1) and 16.2 parts by mass of the polyoxypropylene polymer (A1-2) 500 parts by mass of the dispersed solution (containing 5 parts by mass of PEDOT / PSS (B-1)) was added and stirred.
In PEDT / PSS (B-1), PEDOT: PSS (mass ratio) was 1: 2.5.
After stirring, 2-propanol and ethanol were removed at 80 ° C. by an evaporator to obtain a mixture of polyoxypropylene polymer and PEDOT / PSS (B-1).

In the obtained mixture, 2.0 parts by weight of dimethyl silicone (KF-96-100 cs manufactured by Shin-Etsu Chemical Co., Ltd.) as a defoamer with respect to 100 parts by mass of the polyoxypropylene polymer (A1-1 and A1-2) And 1.0 parts by mass of dimethyl maleate were added.
After the mixture was added to the disposable cup, platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (3 mass% platinum isopropanol solution) (D-1) was used as a platinum catalyst (D). After adding 1000 μL per 100 parts by mass of the polyoxypropylene polymer (A1-1 and A1-2), and adding 2.5 parts by mass of the silicone compound (C-1), the mixture in the cup is spatula The mixture was stirred for 5 minutes to obtain a composition for forming an adhesive part.

Using the obtained composition, a pressure-sensitive adhesive portion was formed by a screen printing method and a method of transferring a pressure-sensitive adhesive layer on a release film, and it was confirmed whether a sheet-like electrode having the configuration shown in FIG.
In addition, hardening of the coating film formed of the screen-printing method was performed on the conditions heated at 40 degreeC for 24 hours following heating for 5 minutes at 120 degreeC. In addition, the adhesive layer on the release film is formed by heating the coating film at 120 ° C. for 5 minutes and then at 40 ° C. for 24 hours after forming the coating film consisting of the composition on the release film by the screen printing method. did.
As a result of the above-mentioned confirmation test, using the above composition, the adhesion part of the desired shape and film thickness (26 μm) is formed by screen printing method or the method of transferring the adhesion layer on the release film. The sheet-like electrode of the configuration shown in 1 was able to be manufactured.

Moreover, the sheet-like electrode of the structure shown by FIG.1, FIG5 and FIG.7 was manufactured by forming the adhesion part with a film thickness of 26 micrometers by the screen-printing method.
Note that the formed adhesive section, the volume resistivity in the thickness direction (R ^A, [Omega] cm), a volume resistivity in-plane direction (R ^B, [Omega] cm) and was measured. The measurement results are shown in Table 1.
When the obtained sheet-like electrode was attached to the forehead of the subject and impedance measurement was performed, the impedance measurement result of the sheet-like electrode having the configuration shown in FIG. 1 and FIG. Met. On the other hand, when using the sheet-like electrode having the configuration shown in FIG. 7, it was difficult to measure the electroencephalogram well.
In the sheet-like electrode of the structure shown by FIG. 7, the substantially whole surface of the sheet-like electrode is coat | covered with the adhesion part. Since the conductivity anisotropy of the adhesive portion formed using the composition obtained in Example 1 is not so large, a short circuit occurs between a plurality of electrodes in the sheet-like electrode having the configuration shown in FIG. It is thought that it was difficult to measure brain waves well.

Furthermore, after measuring the impedance, the sheet-like electrode was peeled off from the forehead of the subject, and the presence or absence of adhesion of the adhesive portion to the skin after peeling was visually confirmed. As a result, adhesion of the adhesion part to the skin after peeling of the sheet electrode was not confirmed.

Example 2
In place of the dispersion in 2-propanol and ethanol containing PEDOT / PSS (B-1), 6.9 parts by mass of silver chloride (I) (E-1) obtained in Synthesis Example 4 is added to the composition A composition for pressure-sensitive adhesive layer formation was obtained in the same manner as in Example 1 except for the above.

Using the obtained composition, a pressure-sensitive adhesive portion was formed by a screen printing method and a method of transferring a pressure-sensitive adhesive layer on a release film, and it was confirmed whether a sheet-like electrode having the configuration shown in FIG.
In addition, hardening of the coating film formed of the screen-printing method was performed on the conditions heated at 40 degreeC for 24 hours following heating for 5 minutes at 120 degreeC. In addition, the adhesive layer on the release film is formed by heating the coating film at 120 ° C. for 5 minutes and then at 40 ° C. for 24 hours after forming the coating film consisting of the composition on the release film by the screen printing method. did.
As a result of the above-mentioned confirmation test, using the above composition, the adhesion part of the desired shape and film thickness (25 μm) is formed by screen printing method or the method of transferring the adhesion layer on the release film. The sheet-like electrode of the configuration shown in 1 was able to be manufactured.

Moreover, the sheet-like electrode of the structure shown by FIG.1, FIG.5 and FIG.7 was manufactured by forming the adhesion part with a film thickness of 25 micrometers by the screen-printing method.
Note that the formed adhesive section, the volume resistivity in the thickness direction (R ^A, [Omega] cm), a volume resistivity in-plane direction (R ^B, [Omega] cm) and was measured. The measurement results are shown in Table 1.
When the obtained sheet-like electrode is attached to the forehead of a subject and electroencephalogram measurement is performed, the electroencephalogram can be measured favorably even when using the sheet-like electrode having the configuration shown in any of FIG. 1, FIG. 5 and FIG. The
In the sheet-like electrode of the structure shown by FIG. 7, the substantially whole surface of the sheet-like electrode is coat | covered with the adhesion part. Since the adhesion part formed using the composition obtained in Example 2 exhibits high anisotropic conductivity, even when the sheet-like electrode having the configuration shown in FIG. 7 is used, a short circuit occurs between a plurality of electrodes. It is considered that EEG could be measured well.

Furthermore, after measurement of the electroencephalogram, the sheet-like electrode was peeled off from the forehead of the subject, and the presence or absence of adhesion of the adhesive portion to the skin after peeling was visually confirmed. As a result, adhesion of the adhesion part to the skin after peeling of the sheet electrode was not confirmed.

[Example 3]
A composition for forming a pressure-sensitive adhesive layer was obtained in the same manner as in Example 1 except that 6.9 parts by mass of silver chloride (I) (E-1) obtained in Synthesis Example 4 was added to the composition. .

Moreover, the sheet-like electrode of the structure shown by FIG.1, FIG5 and FIG.7 was manufactured by forming the adhesion part with a film thickness of 26 micrometers by the screen-printing method.
Note that the formed adhesive section, the volume resistivity in the thickness direction (R ^A, [Omega] cm), a volume resistivity in-plane direction (R ^B, [Omega] cm) and was measured. The measurement results are shown in Table 1.
When the obtained sheet-like electrode is attached to the forehead of a subject and electroencephalogram measurement is performed, the electroencephalogram can be measured favorably even when using the sheet-like electrode having the configuration shown in any of FIG. 1, FIG. 5 and FIG. The
In the sheet-like electrode of the structure shown by FIG. 7, the substantially whole surface of the sheet-like electrode is coat | covered with the adhesion part. Since the adhesion part formed using the composition obtained in Example 2 exhibits high anisotropic conductivity, even when the sheet-like electrode having the configuration shown in FIG. 7 is used, a short circuit occurs between a plurality of electrodes. It is considered that EEG could be measured well.

Comparative Example 1
In the comparative example 1, the commercially available medical hydrogel paste was used as a material of the adhesion part. It was not possible to apply a screen printing method or a method of transferring an adhesive layer on a release film as a method of forming an adhesive part to such a hydrogel paste.

Further, by applying a hydrogel paste with a finger, an adhesive portion with a film thickness of 20 μm was formed, and a sheet-like electrode having a configuration shown in FIG. 1 was produced.
Note that the formed adhesive section, the volume resistivity in the thickness direction (R ^A, [Omega] cm), a volume resistivity in-plane direction (R ^B, [Omega] cm) and was measured. The measurement results are shown in Table 1.
The obtained sheet-like electrode was attached to the forehead of a subject and electroencephalogram measurement was performed. By using the sheet-like electrode having the configuration shown in FIG. 1, the electroencephalogram could be measured favorably.

Furthermore, after measurement of the electroencephalogram, the sheet-like electrode was peeled off from the forehead of the subject, and the presence or absence of adhesion of the adhesive portion to the skin after peeling was visually confirmed. As a result, adhesion of the adhesion part to the skin after peeling of the sheet electrode was confirmed.

Although the preferred embodiments of the electrode sheet, the electrode sheet manufacturing method, the biological signal acquisition apparatus, and the biological signal acquisition method of the present invention have been described above, the present invention is not limited to the above-described embodiments. Appropriate changes are possible.

In the above embodiments, in

Embodiments

1 and 2, the conductive material is preferably at least one of a conductive polymer and conductive particles. In the third embodiment, the conductive material preferably contains at least conductive particles. Further, in the electrode sheet and the biological signal acquiring apparatus according to the third embodiment, the stretchable cover 13 may not be provided because the resistance value of the adhesion section 15B in the in-plane direction D1 is high. That is, the adhesive portion 15 may be disposed on one main surface of the stretchable electrode 12, the stretchable lead wire 11, and the stretchable base material 10.

In the embodiment, the stretchable electrode 12 and the stretchable lead wire 11 may be formed on both main surfaces of the stretchable substrate 10. In addition, the stretchable electrode 12 and the stretchable lead-out wire 11 may be formed on different main surfaces of the stretchable substrate 10. In this case, the adhesive portion 15 may be disposed on the main surface of the stretchable electrode 12 and the stretchable substrate 10.

Moreover, in the said embodiment, although the brain wave was demonstrated as an example as a biosignal,

electrode sheet

1, 1A, 1B may acquire other biosignals, such as a pulse.

Moreover, although the example which forms

adhesion part

15, 15A, 15B by the printing method was shown in the said embodiment, it is not restrict | limited to this. For example, the

adhesive portions

15, 15A, 15B may be formed by a coating method or transfer of an adhesive layer made of a non-gel material.

Moreover, in the said embodiment, although each of the elastic electrode 12 is coat | covered with

adhesion part

15, 15A, 15B, it is not restrict | limited to this. The

adhesive parts

15, 15A, 15B may cover at least one stretchable electrode 12 as long as the

electrode sheets

1, 1A, 1B can be attached to the object to be measured. For example, the

adhesive portions

15, 15A, 15B may cover one, preferably two or more stretchable electrodes 12.

Moreover, in the said embodiment, the electrode sheet 1 may be comprised so that isolation | separation (separating) is possible in two or more parts by in-plane direction D1. At this time, it is preferable that the electrode sheet 1 has at least one stretchable electrode 12 and each stretchable lead-out wire 11 connected to the stretchable electrode 12 at each separated portion. As described above, by making the electrode sheet 1 separable, it is possible to flexibly change the sticking position of the stretchable electrode 12 according to the acquisition position of the biological signal, so that versatility of the electrode sheet 1 can be obtained. Can be improved.

1, 1A, 1B electrode sheet 10 stretchable base material 11 stretchable lead wire 12 stretchable electrode 13

stretchable cover

15, 15A, 15B adhesive portion

Claims

A sheet-like stretchable base material, two or more stretchable lead wires, two or more stretchable electrodes, and an adhesive part;
Two or more of the stretchable electrodes are located on at least one major surface of the stretchable substrate,
The adhesive unit contacts and covers at least a part of the surface of the stretchable electrode opposite to the stretchable substrate side of at least one stretchable electrode,
One or more of two or more stretchable lead wires are connected to each of the two or more stretchable electrodes,
The electrode sheet which the said adhesion part consists of a non-gel material which has elasticity and electroconductivity.
The electrode sheet according to claim 1, wherein the non-gel material comprises a tacky resin and a conductive material.
The electrode sheet according to claim 2, wherein the conductive material contains a conductive polymer and / or conductive particles.
The electrode sheet according to claim 3, wherein the conductive material contains the conductive particles.
5. The electrode sheet according to claim 4, wherein the relative value of the volume resistivity in the thickness direction of the adhesive portion to the volume resistivity in the in-plane direction of the adhesive portion is 0.5 or less.
The electrode sheet according to claim 4 or 5, wherein the adhesive portion further covers at least a part of the main surface of the stretchable substrate.
The electrode sheet according to any one of claims 1 to 6, further comprising an elastic cover made of an insulating material and covering the elastic lead-out wire.
The electrode sheet according to claim 7, wherein the adhesive portion covers at least a part of the main surface of the stretchable cover.
The electrode sheet according to any one of claims 1 to 8, wherein the adhesive portion is separated between each of the portions covering the stretchable electrode and a portion covering the other.
The electrode sheet according to any one of claims 4 to 6, wherein the adhesion part has a part covering the stretchable electrode and a part covering the other.
A method of manufacturing the electrode sheet according to claim 1, wherein
Arrangement of the stretchable electrode on at least one major surface of the stretchable substrate;
Connection of the stretchable lead-out wire to each of the stretchable electrodes;
Formation of the adhesive portion;
Method of producing an electrode sheet comprising:
The method for producing an electrode sheet according to claim 11, wherein the adhesive portion is formed by a printing method, a coating method, or transfer of an adhesive layer made of a non-gel material.
The biological signal acquisition apparatus provided with the said electrode sheet as described in any one of Claims 1-11.
The biological signal acquisition apparatus according to claim 13, further comprising an analysis device that acquires the data of the biological signal transmitted from the electrode sheet via the Internet or a local network, and analyzes the state of the living body.
A biological signal acquisition method using the biological signal acquisition apparatus according to claim 13 or 14.