JP2019051236A - Electrode sheet, manufacturing method for electrode sheet, biological signal acquisition device, and biological signal acquisition method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrode sheet which can easily acquire a biological signal with little change in characteristics during long-term storage or use after production or distribution, a method for manufacturing the electrode sheet, a biological signal acquisition device provided with the above-mentioned electrode sheet, and To provide a biological signal acquisition method using the biological signal acquisition device. SOLUTION: An electrode sheet 1 includes a sheet-shaped elastic base material, two or more elastic drawer wirings 11, two or more elastic electrodes, and an adhesive portion 15, and is made of an elastic base material. Two or more elastic electrodes are located on at least one main surface, and the adhesive portion 15 is located on a surface opposite to the surface of the elastic electrode on the elastic substrate side for each of the two or more elastic electrodes. At least a part is contacted and covered, and one or more of two or more elastic lead wiring 11s are connected to each of the two or more elastic electrodes, and the adhesive portion 15 is elastic and conductive. Consists of a non-gel material having. [Selection diagram] Fig. 1

Description

  The present invention relates to an electrode sheet, a method for manufacturing the electrode sheet, a biological signal acquisition device, and a biological signal acquisition method.

  In recent years, the weakness represented by brain waves, etc. in various environments against the backdrop of rising health care orientation in society as a whole, reduction of increasing medical costs, and the use of big data for IOT (Internet of Things) society There is a growing social need for acquiring vital biosignals.

For example, when acquiring an electroencephalogram as a biological signal, a simple electroencephalograph in which an electrode and a measuring instrument are integrated is known. In this simple electroencephalograph, an electroencephalogram is acquired by performing a long-time measurement using a hard electrode. Therefore, the burden on the patient could not be ignored.
Then, the electroencephalograph which aimed at the 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 patent document 1).

JP 2013-121489 A

  According to the electroencephalograph disclosed in Patent Document 1, it is possible to alleviate the burden on the patient and the subject in long-time measurement by pasting the three electrodes provided on the resin sheet on the forehead portion of the subject. Can do. Further, by configuring each electrode with an adhesive conductive gel, it is possible to easily acquire an electroencephalogram simply by pasting it on the forehead portion of the subject.

  However, the gel retains moisture and an organic solvent in the gel state. Therefore, in the resin sheet left for a long time, the moisture and organic solvent of the adhesive conductive gel evaporate, and the function as the adhesive conductive gel is lowered. As a result, there is a possibility that a characteristic change that may affect the detection accuracy of the biological signal is caused.

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

  The present invention provides an electrode sheet that can easily acquire a biological signal after long-term storage during use or at the time of manufacture or at the time of use and can easily acquire a biological signal, a method for manufacturing the electrode sheet, a biological signal acquisition device including the electrode sheet, And it aims at providing the biosignal acquisition method using the said biosignal acquisition apparatus.

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

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

  (3) Moreover, it is preferable that the said electrically-conductive material contains a conductive polymer and / or conductive fine particle.

  (4) Moreover, it is preferable that the said electrically-conductive material contains the said electroconductive fine particles.

  (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 in-plane direction of the said adhesion part is 0.5 or less.

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

  (7) Moreover, it is preferable that an electrode sheet is further provided with the elastic cover which consists of an insulating material and coat | covers the said elastic | stretch extraction wiring.

  (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 separates between each of the part which coat | covers the said elastic electrode, and the part which coat | covers others.

  (10) Moreover, as for the said adhesion part, it is preferable that the part which coat | covers the said elastic electrode and the part which coat | covers others are one surface shape.

  (11) Moreover, this invention is a method of manufacturing the electrode sheet according to (1) above, wherein the stretchable electrode is disposed on at least one main surface of the stretchable substrate, and The present invention relates to a method for manufacturing an electrode sheet comprising: connection of stretchable lead wires 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 transfer of the printing method, the coating method, or the adhesion layer which consists of the said non-gel material.

  (13) Moreover, this invention relates to a biosignal acquisition apparatus provided with the said electrode sheet in any one of said (1) thru | or (11).

  (14) Moreover, 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 a biological state.

  (15) Moreover, this invention relates to the biosignal acquisition method using the said biosignal acquisition apparatus as described in said (13) or (14).

  According to the present invention, there is little change in characteristics during long-term storage or use after production or distribution, and an electrode sheet that can easily obtain a biosignal, a method for producing the electrode sheet, and a biosignal acquisition provided with the electrode sheet described above. An apparatus and a biological signal acquisition method using the biological signal acquisition apparatus can be provided.

It is a top view which shows the electrode sheet which concerns on 1st Embodiment of this 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 which concerns on 2nd Embodiment of this invention. FIG. 6 is a sectional view taken along line B-B in FIG. 5. It is a top view which shows the electrode sheet which concerns on 3rd Embodiment of this invention. It is CC sectional view taken on the line of FIG. It is a top view which shows arrangement | positioning of a rectangular part, a protrusion piece part, and a string-like part in an elastic base material.

Hereinafter, an electrode sheet, an electrode sheet manufacturing method, a biological signal acquisition device, 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 inspects the state of the living body. The biological signal acquisition device includes an electrode sheet and an analysis device.

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

  The analysis device is connected to the electrode sheet wirelessly or by wire. The analysis device is, for example, a cloud server or a local server, and acquires biological signal data such as an electroencephalogram transmitted from the electrode sheet via the Internet or a local network (including inter-terminal communication) to obtain a biological state. Is analyzed. The analysis apparatus accumulates data of a plurality of biological signals transmitted in the past, and AI (Artificial Intelligence) that estimates the state of the living body based on the data of the plurality of accumulated biological signals for newly acquired biological signal data ) May have a function.

[First Embodiment]
The electrode sheet 1, the manufacturing method of the electrode sheet 1, the biological signal acquisition device, and the biological signal acquisition method according to the first embodiment will be described with reference to FIGS.
As shown in FIGS. 1 to 3, the electrode sheet 1 according to the present embodiment includes a stretchable base material 10, a stretchable lead wire 11, a stretchable electrode 12, a stretchable cover 13, and a film base material 14. And an adhesive portion 15.

The stretchable base material 10 is formed into a sheet shape from, for example, an elastomer material typified by a urethane elastomer or a stretchable fabric. It does not specifically limit as an elastomer material, Various materials, such as a polyester elastomer, a styrene-type elastomer, a polyolefin-type elastomer, a polyamide-type elastomer, a urethane-type elastomer, are employable. Such a stretchable base material 10 has stretchability that extends in an in-plane direction by an external force. The stretchable base material 10 includes a rectangular portion 101 as an essential component, and optionally includes a protruding piece portion 102 and a string-like portion 103.
The rectangular portion 101 is formed in a rectangular shape in plan view.
The rectangular portion 101, the projecting piece portion 102, and the string-like portion 103 are preferably arranged in the stretchable base material 10 as shown in FIG.

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

  The string portion 103 is formed integrally with the rectangular portion 101. One end of the string portion 103 is connected to a side adjacent to the side connected to the protruding piece portion 102 among the sides of the rectangular portion 101.

  The material of the stretchable lead-out wiring is not particularly limited as long as the material has both desired stretchability and conductivity. Typically, the stretchable lead 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, an elastomer material used as the material of the stretchable substrate 10 is preferable from the viewpoint of stretchability. The stretchable lead wire 11 is 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 wire 11 is formed so as to cross the main surface from the protruding piece portion 102 to the rectangular portion 101. In the present embodiment, eight elastic lead wires 11 are provided, and one extends to the string portion 103. Further, the stretchable lead wire 11 has a very low Young's modulus (for example, 100 MPa or less, more preferably 10 MPa or less), and the conductive material itself is capable of stretching in the in-plane direction of the stretchable substrate 10. The following behavior is expressed. The stretchable lead wire 11 can 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 elastomer material used as the material of the stretchable base material 10 is preferable from the viewpoint 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. The area of one stretchable electrode 12 in plan view is not particularly limited, but is typically 0.1 mm 2 or more and 100000 mm 2 or less, more preferably 1 mm 2 or more and 10000 mm 2 or less, and particularly preferably 10 mm 2 or more and 1000 mm 2 or less. 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 main surface) with the stretchable lead wire 11 interposed therebetween, and at the other end. Three are located. The stretchable electrodes 12 are positioned so as not to overlap each other along the extending direction of the stretchable lead wires 11. Further, one elastic electrode 12 is positioned at the other end of the string-like 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 stretchable electrode 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 can be formed by, for example, a printing method together with the formation of the stretchable lead wire 11.

  The stretchable cover 13 is made of, for example, an elastomer material or a stretchable fabric. It does not specifically limit as an elastomer material, Various materials, such as a polyester elastomer, a styrene-type elastomer, a polyolefin-type elastomer, a polyamide-type elastomer, a urethane-type elastomer, are employable. When the adhesive portion 15 is formed by the printing method, since the penetration of the composition for forming the adhesive portion 15 into the stretchable cover 13 is difficult to occur, a sheet made of an elastomer material is preferable as the stretchable cover 13.

  The film thickness of the elastic 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, and more preferably 0.005 mm or more and 1 mm or less, from the viewpoint of good handleability of the electrode sheet 1 and compatibility between the electrode sheet 1 and low manufacturing costs. More preferably, it is 0.01 mm or more and 0.1 mm or less.

  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 the one main surface of the stretchable base material 10 beyond the position where the stretchable lead wiring 11 is formed. Specifically, the stretchable cover 13 is formed so as to overlap one main surface of the rectangular portion 101 and the string-like portion 103. Moreover, the elastic cover 13 is arrange | positioned so that it may overlap with a part of film base material 14 mentioned later. The stretchable cover 13 has a recess 131 having a diameter smaller than the diameter of the stretchable electrode 12 at a position overlapping the stretchable electrode 12. Thereby, in the recessed part 131, one main surface of the elastic electrode 12 is exposed as a bottom face.

  The film base 14 is formed of an insulating material different from the stretchable cover 13. The film base material 14 is formed in accordance with the shape of the main surface of the projecting piece portion 102, and is superposed on one main surface of the stretchable lead wire 11 and the projecting piece 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 material 14 suppresses that the elastic | stretch leader line 11 is disconnected. Moreover, since the film base material 14 is provided with an appropriate stiffness, it is possible to improve the handleability when connecting the analysis device 2 and the electrode sheet 1.

The adhesion part 15 is formed with the non-gel material which has a stretching property and electroconductivity. The adhesive portion 15 is formed of, for example, a non-gel material including a resin having both adhesiveness and conductivity, or a non-gel material including an adhesive resin and a conductive material. Here, the conductive material itself is not limited to a material having conductivity, and may be a material that can impart conductivity to the non-gel material by being blended with the non-gel material.
The non-gel material constituting the adhesive portion 15 includes a conductive polymer and / or conductive fine particles as a conductive material. As shown in FIG. 3, the adhesive portion 15 contacts at least a part of the surface of the stretchable electrode 12 opposite to the stretchable substrate 10 side of each of the two or more stretchable electrodes 12. It is preferable to coat. In this embodiment, as shown in FIG. 2, the adhesive portion 15 covers the exposed elastic electrode 12 by being positioned on each of the seven elastic electrodes 12 positioned on the rectangular portion 101. To do. That is, the adhesive portion 15 fills the inside of each of the seven recesses 131 to close the recess 131 and cover the stretchable electrode 12. The recess 131 is defined by an inner surface that is an end surface of the stretchable cover 13 and a bottom surface that is the surface of the stretchable electrode 12. The adhesive portion 15 protrudes from one main surface of the stretchable cover 13 in the height direction that is the thickness direction D2 of the stretchable base material 10. 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 a brain wave is acquired as a biological signal from the forehead F of the living body L will be described.
First, one main surface side of the rectangular portion 101 of the stretchable base material 10 is opposed to the forehead F of the living body L. Next, the electrode sheet 1 is aligned so that the adhesive portion 15 is located at the position where the brain waves are acquired in the forehead F of the living body L. The electrode sheet 1 is brought close to the forehead F while being aligned as described above. The electrode sheet 1 is affixed to the forehead F when all the adhesive portions 15 come 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 is in close contact with 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 arranged on the string-like portion 103 acquires the reference potential of the living body L. Each of the seven stretchable electrodes 12 positioned on the rectangular part 101 acquires an electroencephalogram via the adhesive part 15. The stretchable lead wire 11 transmits the acquired electroencephalogram toward the analysis device 2.

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

  Next, the film base material 14 is disposed so as to overlap a part of one main surface of the stretchable lead wire 11 and the protruding piece portion 102. The stretchable cover 13 is formed on the stretchable lead wire 11, a part of one principal surface of the rectangular portion 101, a part of one principal surface of the string-like portion 103, and a part of one principal surface of the stretchable cover 13. Arranged in layers.

  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, a printing method, a coating method, or a transfer of an adhesive layer made of a non-gel material.

  As the printing method, a method using a liquid composition for forming the adhesive portion 15 as an ink, such as a screen printing method or an ink jet printing method, is preferable. A screen printing method is preferred as a printing method because stable printing is easy.

  Examples of the coating method include a bar coating method, a slit coating method, a die coating method, a blade coating method, a roll coating method, and a dip coating method. Since it is a method suitable in consideration of the viscoelasticity of a typical composition used for forming the adhesive portion 15, the bar coating method and the blade coating method are preferable, and the blade coating method is more preferable. In the coating method, if necessary, the composition for forming the adhesive portion 15 is applied through a mask having an opening where the adhesive portion 15 is formed and covering the place where the adhesive portion 15 is not formed. Done.

Formation of the adhesion part 15 by transfer of the adhesion layer which consists of non-gel materials is performed as follows. First, after forming an adhesive layer made of a non-gel material having a predetermined shape corresponding to the shape of the adhesive portion 15 on the release film, the adhesive layer is placed at a predetermined position including a position on the stretchable electrode 12. The adhesive part 15 is formed by transferring and then peeling the release film from the adhesive layer.
The method for forming the adhesive layer on the release film is not particularly limited, but it is preferable to form the adhesive layer by the aforementioned printing method or coating method. In addition, you may harden the coating film which consists of a composition for adhesion part 15 formation on a release film, and may form an adhesion layer.

  More specifically, after a coating film or a pressure-sensitive adhesive layer formed from the composition for forming the pressure-sensitive adhesive portion 15 is formed at the position of the recess 131 by the above method, the coating film or the pressure-sensitive adhesive layer is formed as necessary. The adhesive portion 15 having adhesiveness is formed by removing the solvent from the substrate or curing the coating film or the adhesive layer.

  The degree of freedom of processing when forming the adhesive portion 15 is high, and the adhesive portion 15 having a desired shape is good in terms of dimensions and position accuracy, after forming a coating film using a curable liquid composition, A method of curing the film is preferred. 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 thermosetting, photocuring, or moisture curing.

The film thickness of the adhesion part 15 is not specifically limited. For example, when the thickness of the adhesive portion 15 is preferably 50 μm or less, more preferably 40 μm or less, and particularly preferably 30 μm or less, the resistance value in the thickness direction of the adhesive portion 15 can be reduced, and a higher quality biological signal can be obtained. Easy to get. Further, the thinner the adhesive portion 15 is, the less likely that the adhesive portion 15 is not peeled off from the surface of the measurement object when the sheet-like electrode 1 is peeled from the measurement object. Furthermore, since the adhesion part 15 can be formed with a small amount of the composition for forming the adhesion part 15 as the film thickness of the adhesion part 15 is thin, it is preferable in that the electrode sheet 1 can be manufactured at low cost.
Although the minimum of the film thickness of the adhesion part 15 is not specifically limited, For example, since it is easy to form the adhesion part 15 with a uniform film thickness stably, 5 micrometers or more are preferable and 10 micrometers or more are more preferable.

  According to the electrode sheet 1, the manufacturing method of the electrode sheet 1, the biological signal acquisition device, and the biological signal acquisition method of the first embodiment described above, the following effects are obtained.

(I) The electrode sheet 1 includes a sheet-like stretchable substrate 10, two or more stretchable lead wires 11, two or more stretchable electrodes 12, and an adhesive portion 15. Then, two or more stretchable electrodes 12 are positioned on at least one main surface of the stretchable base material 10, and the stretchable electrodes 12 are stretched on the adhesive portion 15 for each of the two or more stretchable electrodes 12. At least a part of the surface opposite to the surface on the conductive substrate 10 side was contacted 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 made of a non-gel material having stretchability and conductivity. did. Thereby, the functional fall of the adhesion part 15 can be suppressed at the time of use of the electrode sheet 1 or long-term storage. Moreover, when using it for acquisition of the electroencephalogram of the electrode sheet 1, since it can be easily attached to the head as compared with the headgear type electrode, a biological signal can be easily acquired.

(II) The non-gel material includes an adhesive resin and a conductive material. Thereby, the kind and the usage-amount of adhesive resin and a conductive material can be adjusted independently, respectively, and the adhesiveness and electroconductivity of the adhesion part 15 which consist of non-gel materials can be adjusted independently, respectively. In addition, since the adhesive resin does not need to have conductivity and the conductive material does not need to have adhesiveness, there are a wide range of material options for each of the adhesive resin and the conductive material.

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

(IV) The electrode sheet 1 was further configured to include an elastic cover 13 made of an insulating material and covering the elastic lead wire 11. As a result, the stretchable lead wires 11 come into contact with the measurement object (typically the living body L) via the stretchable cover 13, so that each of the stretchable lead wires 11 is short-circuited with the other stretchable lead wires 11. This can be suppressed. Therefore, the quality of the signal acquired from the measurement object can be improved.

(V) About the adhesion part 15, at least one part of the main surface of the elastic cover 13 was coat | covered. Thereby, the exposed surface of the adhesion part 15 can be expanded, and the contact area of the adhesion part 15 to a measuring object (typically living body L) can be expanded. Therefore, peeling of the electrode sheet 1 from the measurement object can be suppressed.

[Second Embodiment]
An electrode sheet 1A according to a second embodiment, a method for manufacturing the electrode sheet 1A, a biological signal acquisition device, and a biological signal acquisition method will be described with reference to FIGS. In the description of the second embodiment, the same constituent elements are denoted by the same reference numerals, and the description thereof is omitted or simplified.
As shown in FIGS. 5 and 6, the electrode sheet 1 </ b> A and the biological signal acquisition device according to the second embodiment are arranged such that the adhesive portion 15 </ b> A is placed over the entire main surface of the stretchable cover 13 and stretchable. The difference from the first embodiment is that each of the portions covering the electrode 12 is separated from the portion covering the other.
About the manufacturing method and biological signal acquisition method of 1 A of electrode sheets which concern on 2nd Embodiment, since only the formation area of 15 A of adhesion parts differs from 1st Embodiment, description is abbreviate | omitted.

  According to the electrode sheet 1A, the manufacturing method of the electrode sheet 1A, the biological signal acquisition device, and the biological signal acquisition method according to the second embodiment described above, the following effects are obtained.

(VI) The adhesive portion 15A was configured such that each of the portions covering the stretchable electrode 12 and the portions covering the other were separated. Thereby, each of the stretchable electrodes 12 can be prevented from being short-circuited with the other stretchable electrodes 12, so that a higher quality biological signal can be obtained.

[Third Embodiment]
An electrode sheet 1B, an electrode sheet 1B manufacturing method, a biological signal acquisition device, and a biological signal acquisition method according to a third embodiment of the present invention will be described with reference to FIGS. In the description of the third embodiment, the same constituent elements are denoted by the same reference numerals, and the description thereof is omitted or simplified.
As shown in FIGS. 7 and 8, the electrode sheet 1 </ b> B and the biological signal acquisition device according to the third embodiment are such that the part where the adhesive part 15 </ b> B covers the stretchable electrode 12 and the part which covers the other are in one plane. This is different from the first and second embodiments. In addition, in the electrode sheet 1B and the biological signal acquisition device according to the third embodiment, the non-gel material constituting the adhesive portion 15B necessarily includes conductive fine particles as a conductive material, and the first embodiment and the second embodiment. Different. A particulate 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 average minor axis length are obtained by processing images obtained by observing conductive particles under a microscope using commercially available image analysis software, and obtaining the major axis length and minor axis length for each of ten or more particles. The number average length can be obtained from the obtained value.
Here, the longest distance among the distances between any two points on the outer periphery of the particle in the electron microscope image is defined as the long axis length. In the electron microscope image, the longest width of the particle widths in the direction perpendicular to the long axis length direction is defined as the short axis length.
For 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. In other words, the thickness of the plate-like particles is not used as the short axis length.
The particle diameter of the conductive fine particles is not particularly limited as long as it is generally recognized as a fine particle. Typically, the particle diameter 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 diameter.

  Since the conductive fine particles are included as the conductive material, the adhesive portion 15B has anisotropic conductivity. The reason why such anisotropic conductivity develops is not clear, but is thought to be due to aggregation of the conductive fine particles in the adhesive portion 15B. In particular, when the adhesive portion 15B is formed by screen printing, since the adhesive portion 15B is formed while a 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 is formed. With this orientation, a conductive path oriented in the thickness direction of the adhesive portion 15B is easily formed.

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 with respect 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 1 or less.
About the manufacturing method and biological signal acquisition method of the electrode sheet 1B which concern on 3rd Embodiment, since only the formation area of the adhesion part 15B differs from 1st Embodiment and 2nd Embodiment, description is abbreviate | omitted.

  According to the electrode sheet 1B, the manufacturing method of the electrode sheet 1B, the biological signal acquisition device, and the biological signal acquisition method according to the third embodiment described above, the following effects are obtained.

(VII) The conductive material contains conductive fine particles. As a result, anisotropic conductivity can be imparted to the adhesive portion 15B in such a manner that it can be energized well in the thickness direction and hardly energized in the in-plane direction. Therefore, even if the adhesive part 15 is arranged so as to overlap the plurality of elastic electrodes 12, the elastic electrode 12 can be prevented from being short-circuited, and the measurement area of the electrode sheet 1B can be increased by increasing the exposed area of the adhesive part 15B. Detachment from an object (typically the living body L) can be prevented.

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

[Composition for forming adhesive part]
As described above, the material of the adhesive portion 15 may be, for example, a material in which a conductive material is dispersed in an adhesive resin, or may be a resin having both conductivity and adhesiveness.
The material of the adhesive portion 15 is made of an adhesive resin because various properties such as adhesiveness, mechanical properties, and conductivity can be easily adjusted by appropriately changing the type and amount of the adhesive resin and the conductive material. A material in which a conductive material is dispersed is preferable.

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 forming the adhesive portion 15 will be described.

(Polyoxyalkylene polymer (A))
Examples of the main chain skeleton of the polyoxyalkylene polymer (A) include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene- A polyoxybutylene copolymer or the like can be used, but a polyoxypropylene polymer is preferable.

The polyoxyalkylene polymer essentially has the formula (2):
-R ² -O- ⁽²⁾
(In the formula, 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 these.
The alkylene group as R ² described in Formula (2) may be linear or branched. The number of carbon atoms of the alkylene group as R ² is 1 or more and 14 or less, and 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 consist of only one type of repeating unit or may consist of two or more types of repeating units.
As the polyoxyalkylene polymer having a main chain skeleton composed of the repeating unit represented by the above formula (2), the propylene oxide polymer is a main component because it is amorphous or has a relatively low viscosity. The polyoxypropylene polymer is preferably a polyoxypropylene polymer in which the main chain is composed only of oxypropylene units (—CH ₂ CH (CH ₃ ) C—O—).

The method for synthesizing 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, or a complex obtained by reacting an organoaluminum compound and porphyrin as disclosed in JP-A-61-215623. Polymerization method using transition metal compound-porphyrin complex catalyst, Japanese Patent Publication No. 46-27250, Japanese Patent Publication No. 59-15336, US Pat. No. 3,278,457, US Pat. No. 3,278,458, US Pat. No. 3,278,459, US Pat. No. 3,427,256, US Pat. No. 3,427,334, In the polymerization method using a double metal cyanide complex catalyst shown in each publication such as US Pat. No. 3,427,335, the polymerization method using a catalyst comprising a polyphosphazene salt shown in JP-A-10-273512, and JP-A-11-060722 Touch composed of the indicated phosphazene compounds Polymerization method using thereof.

The molecular chain constituting the polyoxyalkylene polymer (A) may be linear or branched.
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, more preferably 3,000 to 50, as the molecular weight in terms of polystyrene measured by GPC. Is particularly preferably 3,000 or less and most preferably 3,000 or more and 30,000 or less.

If the number average molecular weight is too small, it may be difficult to form the adhesive portion 15 having excellent stretchability using the composition containing the polyoxyalkylene polymer (A).
When the number average molecular weight is excessive, the polyoxyalkylene polymer (A) may have a high viscosity, and thus there may be a need to devise a method for forming the adhesive portion 15.

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 wide, the polyoxyalkylene polymer (A) may have a high viscosity, and thus the device for forming the adhesive portion 15 may need to be devised.

The polyoxyalkylene polymer (A) has the formula (1):
—CH ₂ —C (R ¹ ) ═CH ₂ (1)
(Wherein R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms) (hereinafter sometimes referred to as an alkenyl group)
It is preferable to have at least one functional group represented by
R ¹ is preferably a hydrogen atom or a methyl group from the viewpoint of the reactivity of the functional group represented by the formula (1).

  The number of alkenyl groups represented by the formula (1) of the polyoxyalkylene polymer (A) is preferably at least one on average in one molecule of the polyoxyalkylene polymer (A). One or more and five or less are more preferable, one or more and three or less are more preferable, and one or more and two or less are especially preferable.

When the number of alkenyl groups represented by formula (1) in one molecule of polyoxyalkylene polymer (A) is too small, the curability of the composition containing polyoxyalkylene polymer (A) is slightly inferior. There is a case.
Further, if the number of alkenyl groups represented by formula (1) contained in one molecule is too large, in a cured product formed using a composition containing a polyoxyalkylene polymer (A), A network structure may be formed, and it may be difficult to form a cured product having good adhesion.

(Conductive material (B))
The composition used for forming the adhesive portion 15 preferably contains the conductive material (B) together with the polyoxyalkylene polymer (A).
The conductive material (B) is not limited to a material generally recognized as having conductivity, and may be any material that can impart conductivity to the adhesive portion 15 when blended in the adhesive portion 15. There is no particular limitation. 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, from the viewpoint of anisotropic conductivity, the conductive material (B) is preferably conductive fine particles. As described above, a particulate material having an aspect ratio (average major axis length / average minor axis length) of 50 or less is defined as conductive fine particles. Typically, the particle diameter 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 diameter.

In general, the conductive material (B) is preferably an inorganic material such as a metal because it is inexpensive and easily available, and is excellent in chemical and physical stability.
On the other hand, when the dispersibility and dispersion stability in the adhesive part 15 are good, and when the sheet-like electrode 1 is used by being attached to a biological skin, there is no need to consider the problem of metal allergy. In terms of points, non-metallic inorganic materials are preferred.

As the inorganic material, for example, a conductive carbon material can be used. Note that some carbon materials contain a small amount of organic groups, but carbon materials that do not contain organic groups in the main skeleton are described as inorganic materials in this specification.
Examples of the carbon material include carbon black, carbon fiber, graphite, and carbon nanomaterial.

Among carbon materials, a nanocarbon material is preferable because it can be easily reduced to a desired level by reducing the volume resistivity of the adhesive portion 15 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, nanographites, fullerenes, and carbon nanocoils. Among these, carbon nanotubes are preferable because they are easily available and easily form the adhesive portion 15 having a low volume resistivity and excellent conductivity.

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

As the metal powder, for example, metal fine powder produced by an atomizing method and having an average particle diameter of 100 μm or less, preferably 50 μm or less is preferable.
As the metal fibers, metal nanofiber materials represented by silver nanowires and the like are preferable.
For example, the fiber diameter of the metal nanowire is preferably 200 nm or less, and more preferably 10 nm or more and 100 nm or less. The fiber length of the metal nanowire is preferably 5 μm or more and 100 μm or less, and more preferably 10 μm or more and 50 μm or less.

Regarding the fiber length of the metal fiber, the average major axis length is preferably 1 μm or more and 1000 μm or less, and more preferably 5 μm or more and 500 μm or less.
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.
Regarding the fiber length of the metal fiber, the average minor axis length 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 well in the composition used for forming the adhesive portion 15, easily forms a conductive path, and the volume of the adhesive portion 15 even when used in a small amount. 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 fiber is preferably 100 or more and 1000 or less from the viewpoint of easy formation of a conductive path in the adhesive portion 15.

The metal composition of the metal powder or metal fiber is not particularly limited.
The material of the metal powder or the metal fiber may contain two or more kinds of metal elements, and may contain a metal oxide, a metal salt, a carbon-based conductive substance, and the like together with the metal.
Examples of the metal preferable as the material of the metal powder and the metal fiber include gold, platinum, silver, palladium, neodymium, iron, cobalt, copper, tin, zinc, nickel, and two or more kinds of metals selected from these. An alloy etc. are mentioned.
Among these, silver is preferable because it has high conductivity and is easy to process. As for the material of the metal nanofiber, silver is preferable from the viewpoint that mass production by wet synthesis is easy. Also, a method such as plating or vapor deposition of metal powder or metal fiber using a material different from those materials. May be coated.

For example, as a method for producing a metal nanowire, a method for producing a silver nanowire is, for example, (Sun, Y. et al. “Uniform Silver Now Synthesis by Reducing AgNO ₃ with Ethylene in the Pres-of-the-Price. Pyrrolidene) ", (2002) Chem. Mater. 14, 4736-4745), and a method for reducing silver nitrate in ethylene glycol in the presence of polyvinylpyrrolidone.
Moreover, as a synthesis | combining 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.A. Mater. Chem. A, 2014, 2, 6326 to 6330, and the like.

Examples of the organic material include a conductive polymer. 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, and polyaniline.
Among these, PEDOT is preferable because of high conductivity and excellent stability. However, the composition used for formation of the 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 because the adhesive portion 15 exhibiting desired conductivity is easily formed. The dopant is a component that enhances the conductivity of the conductive material (B).

The kind of dopant is not particularly limited as long as the conductivity of the conductive polymer can be enhanced. For example, preferred dopants for PEDOT include polystyrene sulfonic acid (hereinafter also referred to as PSS), polyvinyl sulfonic acid, perchlorate, and sulfonic acid.
Among these dopants, PSS is preferable because it is easily available and easily forms the adhesive portion 15 exhibiting desired conductivity.
Hereinafter, the combination of PEDOT and PSS as the conductive material (B) is also referred to as PEDOT / PSS.

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

  In the conductive material (B), the mass ratio of the conductive polymer to the dopant is preferably 1: 0.5 to 1: 5, more preferably 1: 1 to 1: 3 as a conductive polymer: dopant.

  The method for mixing the conductive material (B) described above with the polyoxyalkylene polymer (A) is not particularly limited as long as the adhesive portion 15 exhibiting desired conductivity can be formed using a composition containing them.

For example, after mixing the dispersion liquid of a conductive material (B) with a polyoxyalkylene type polymer (A), the method of distilling the dispersion medium derived from a dispersion liquid from a composition is mentioned.
The type of the dispersion medium is not particularly limited, and examples thereof include water, alcohol, monomethylformamide, and dimethyl sulfoxide. Among these, from the viewpoint of compatibility with the polyoxyalkylene polymer (A), the dispersion medium is preferably alcohol, more preferably 2-propanol or ethanol, and even more preferably a mixed solvent of 2-propanol and ethanol.
The above 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 fine particles. The metal salt is not particularly limited as long as it is a salt compound composed of a metal cation and an anion, and may be an inorganic metal salt or an organic metal salt, and an inorganic metal salt is preferred.

  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 and aluminum ion. When these metal ions can have a plurality of ionic valences, the ionic valence of the metal ions is not particularly limited.

  Specific examples of anions constituting the metal salt include chloride ions, bromide ions, iodide ions, fluoride ions, sulfate ions, sulfite ions, hydrogen sulfate ions, phosphate ions, nitrate ions, carbonate ions, and carbonate ions. Inorganic anions such as hydrogen ions, acetate ions, formate ions, propionate ions, butyrate ions, valerate ions, isovalerate ions, lactate ions, oxalate ions, trichloroacetate ions, dichloroacetate ions, monochloroacetate ions, 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 Raised It is.

Since it is easy to acquire a signal such as a biological signal stably and satisfactorily using the sheet-like electrode 1 provided with the adhesive portion 15, examples of the metal salt include metal chloride, metal bromide, metal iodide, and metal fluoride. Metal halides are preferred, metal chlorides and metal bromides are more preferred, and metal chlorides are particularly preferred.
Metal chlorides include 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 Zinc etc. are mentioned, Sodium chloride, potassium chloride, and silver chloride (I) are preferred, and silver chloride is more preferred.

When the viscosity of the polyoxyalkylene polymer (A) is low, or when the viscosity is lowered by adding a small amount of an organic solvent to the polyoxyalkylene polymer (A), the polyoxyalkylene polymer (A) A) and a solid conductive material (B) or a dispersion of the conductive material (B) are mixed by a kneader such as a Hoover-type Mahler, a two-roller, a three-roller, etc. The conductive material (B) can also be dispersed in the polymer (A).
It is preferable that water and an organic solvent are distilled off from the composition after the dispersion treatment of the conductive material (B).

The content of the conductive material (B) in the composition used for forming the adhesive part 15 is not particularly limited as long as the adhesive part 15 having the desired conductivity and the desired adhesiveness can be formed.
The usage-amount of electroconductive material (B) is suitably set in consideration of the electroconductivity of the adhesion part 15 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 may be 5 parts by mass or more, 8 parts by mass or more with respect to 100 parts by mass of the polyoxyalkylene polymer (A). It may be the above.
In addition, the content of the conductive material (B) in the composition is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, and 100 parts by mass or less with respect to 100 parts by mass of the polyoxyalkylene polymer (A). Is more preferably 50 parts by mass or less, and most preferably 20 parts by mass or less.

When the conductive material (B) is 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). It is preferably 3 parts by mass or more and 150 parts by mass or less, more preferably 3 parts by mass or more and 100 parts by mass or less, and most preferably 3 parts by mass or more and 20 parts by mass or less.
By using the amount of the conductive material (B) in such a range, it is easy to balance the desired volume resistivity of the adhesive portion 15 and 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). It is preferably no less than 100 parts by mass and no greater than 3 parts by mass and no greater than 50 parts by mass, and particularly preferably no less than 3 parts by mass and no greater than 20 parts by mass.
By using the amount of the conductive polymer in such a range, or a combination of the conductive polymer and the dopant, it is easy to balance the desired conductivity of the adhesive portion 15 and 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 or more and 10 parts by mass or less with respect to 100 parts by mass of the polyoxyalkylene polymer (A). The amount is more preferably 0.1 parts by mass or more and 8 parts by mass or less, and particularly preferably 1 part by mass or more and 7 parts by mass or less.
When the amount of the metal salt used as the conductive material (B) is within such a range, it is easy to control the viscosity of the composition within an appropriate range that is easy to handle, and it is easy to form the adhesive portion 15 that is not brittle.

(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 to 10 hydrosilyl groups in the molecule is used. The hydrosilyl group means a group having a Si—H bond.
The hydrosilyl group possessed by the silicone compound (C) reacts with the alkenyl group represented by the formula (1) possessed by the polyoxyalkylene polymer. By this reaction, a cured product having suitable properties 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 a number of hydrosilyl groups within such a range, it is easy to form the adhesive portion 15 having both good strength and good stretchability.

The chemical structure of the silicone compound (C) other than the hydrosilyl group is not particularly limited. 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, more preferably 500 or more and 2,000 or less.
When the silicone compound (C) having a number average molecular weight within such a range is used, it is easy to obtain a cured product having preferable characteristics as the adhesive portion 15 in a short time while suppressing the volatilization of the silicone compound (C) during curing. .

で表される化合物である。 A silicone compound (C) may be used independently and may be used together 2 or more types. The silicone compound (C) is preferably compatible with the polyoxyalkylene polymer (A). From the viewpoint of easy availability of raw materials and compatibility with the polyoxyalkylene polymer (A), examples of suitable silicone compounds (C) include organohydrogensiloxanes modified with organic groups. A typical example of an organohydrogensiloxane has the following formula:

It is a compound represented by these.

In the above formula, the value of c + d 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 the main chain.
The silicone compound (C) represented by the above formula can be obtained by modifying an unmodified methyl hydrogen silicone and introducing R ³ . Unmodified methylhydrogen silicone corresponds to a compound in which R ³ is all H, and is also described in “Silicon Market Outlook-Manufacturer Strategy and Application Development-” issued by CMC Co., Ltd. (1990.1.31). 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 organic compound added for modification.

The ratio of the amount of the polyoxyalkylene polymer (A) to the silicone compound (C) in the composition used for forming the adhesive portion 15 is based on the total amount of alkenyl groups derived from the polyoxyalkylene polymer (A). , Expressed by the total amount of hydrosilyl groups derived from the silicone compound (C). The level of the crosslinking density after curing is determined by the size of the total amount of hydrosilyl groups per 1 mol of the total amount of alkenyl groups.
From the viewpoint of easily forming the adhesive part 15 having desirable mechanical properties, the total amount of hydrosilyl groups of the silicone compound (C) per 1 mol of the total amount of alkenyl groups of the polyoxyalkylene polymer (A) is preferably 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 for forming the adhesive portion 15 preferably contains a hydrosilylation catalyst (D) together with the aforementioned polyoxyalkylene polymer (A), conductive material (B), and silicone compound (C). .

  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). Can be appropriately selected from the various catalysts for hydrosilylation used.

Specific examples of the hydrosilylation catalyst (D) include chloroplatinic acid, platinum-vinylsiloxane complexes (for example, platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complexes and platinum). -1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane complex), platinum-olefin complexes (for example, Pt _l (ViMe ₂ SiOSiMe ₂ Vi) _m , Pt [(MeViSiO ₄ ] _n (wherein l, m, and n are positive integers, and Vi is a vinyl group)) and the like.

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

The amount of the hydrosilylation catalyst (D) is not particularly limited, but is preferably 10 ⁻⁸ mol or more and 10 ⁻¹ mol or less with respect to 1 mol of the total amount of alkenyl groups of the polyoxyalkylene polymer (A), More preferably, it is 10 ⁻⁶ mol or more and 10 ⁻² mol or less.
If it is in the said range, it will become easy to achieve appropriate hardening rate, stable sclerosis | hardenability, ensuring of the pot life required of a composition, etc.

(Storage stabilizer)
When the silicone compound (C) and the hydrosilylation catalyst are added to the composition used for forming the adhesive portion 15, the storage stabilizer includes a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, It is preferable to add a nitrogen-containing compound, a tin-based compound, an organic peroxide, and the like to the composition.

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

(Polyethylene glycol)
It is also preferable that the composition used for forming the adhesive portion 15 contains polyethylene glycol. For example, polyethylene glycol. -S. Hsiao et al. , J. et al. Mater. Chem. In 2008, 18, 5948, it is reported that the conductivity of a conductive material such as PEDOT / PSS is improved by the addition of a high boiling point organic compound such as dimethyl sulfoxide or ethylene glycol.
As can be seen from this, the adhesive part 15 having excellent conductivity can be easily formed by blending polyethylene glycol (PEG) having a high boiling point with the composition used for forming the adhesive part 15.

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

The amount of PEG added is preferably 1 part by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the polyoxyalkylene polymer (A).
By using the amount of PEG in such a range, the polyoxyalkylene polymer (A) is compatible with PEG, thereby increasing the conductivity of the adhesive portion 15 and providing the adhesive portion 15 having the desired adhesiveness. Easy to form.

(Other materials)
The composition used for forming the adhesive portion 15 may contain various components in addition to the above components as long as the object of the present invention is not impaired.
For example, the effect of the hydrosilylation reaction has been described above. When the composition does not contain the silicone compound (C) or the hydrosilylation catalyst (D), a general photopolymerization initiator is added to the composition, 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 for forming the adhesive portion 15 includes a surfactant, an antioxidant, an ultraviolet absorber, a pigment, a dye, a plasticizer, and a thixotropic agent. Accordingly, additives that are blended in various resin compositions can be blended.

(Formation method of adhesive part)
The formation method of the adhesion part 15 is not specifically limited. Typically, the adhesive portion 15 is formed by forming the above-described composition into a desired film thickness and then curing the obtained film.
The curing method is not particularly limited, and is appropriately selected according to the components of the composition.
For example, the composition comprises a polyoxyalkylene polymer (A) represented by the above formula (1), a conductive material (B), a silicone compound (C) having a hydrosilyl group, a hydrosilylation catalyst ( D), the curing conditions include heating at 40 ° C. to 180 ° C. for 1 minute to 180 minutes.
When it is desired to complete the curing, it may be further allowed to stand at 40 ° C. or higher and 80 ° C. or lower for several days.

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

  In Examples and Comparative Examples, the configurations of the adhesive portions were changed and compared. Moreover, the electroencephalogram was acquired as a biological signal.

[Synthesis Example 1]
Polypropylene glycol is used as an initiator, propylene oxide is polymerized using a zinc hexacyanocobaltate glyme complex catalyst, and a number average molecular weight of about 28,500 (Tosoh's HLC-8120GPC is used as the liquid feeding system, and the column is Tosoh's TSK-GEL. The H type was used, and the solvent was a polypropylene oxide having a molecular weight in terms of polystyrene measured using THF.
A 1.2-fold equivalent of a methanol solution of NaOMe with respect to the hydroxyl group of the hydroxyl group-terminated polypropylene oxide was added to distill off the methanol, and allyl chloride was further added to convert the terminal hydroxyl group into 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 obtained unpurified allyl-terminated polypropylene oxide, water was removed by centrifugation, and water was further added to the resulting hexane solution. 300 parts by mass were mixed and stirred, and after removing water again by centrifugation, hexane was removed by vacuum devolatilization.
As described above, a polyoxypropylene polymer (A1-1) having a number average molecular weight of about 28,500 having 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 having one end of an allyl group was obtained in the same manner as in Synthesis Example 1 except that butanol was used as an initiator.

[Synthesis Example 3]
In the presence of a platinum catalyst, 0.6 equivalent of α-methylstyrene of the total hydrosilyl group amount is added to methyl hydrogen silicone represented by the following chemical formula (3) (wherein x is an average of 5), 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]
Using 0.5 g of silver (Aldrich, flaky, particle size 10 μm) and 6 g of an aqueous solution of iron (III) chloride with a concentration of 274 mol / L (40% iron (III) chloride solution manufactured by Wako Pure Chemical Industries, Ltd.) Prepared) and stirred for 15 minutes. The silver chloride (I) produced 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) was added to a solution having a ratio of 2-propanol and ethanol of 98/2 (wt / wt) to a concentration of 1 wt%, and ultrasonic waves were used. PEDOT / PSS (B-1) was dispersed.
For 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), PEDOT / PSS (B-1) is 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. with an evaporator to obtain a mixture of a polyoxypropylene polymer and PEDOT / PSS (B-1).

To the obtained mixture, dimethyl silicone (KF-96-100cs manufactured by Shin-Etsu Chemical Co., Ltd.) as a defoaming agent was added in an amount of 2.0 parts by weight based on 100 parts by weight of the polyoxypropylene polymer (A1-1 and A1-2). Then, 1.0 part by mass of dimethyl maleate was added.
After adding the mixture to the disposable cup, platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (3 mass% platinum isopropanol solution) (D-1) is used as the platinum catalyst (D). After adding 1000 microliters with respect to 100 mass parts of polyoxypropylene-type polymers (A1-1 and A1-2) and adding 2.5 mass parts of silicone compounds (C-1), the mixture in a cup is made a spatula. Was stirred for 5 minutes to obtain a composition for forming an adhesive part.

Using the obtained composition, an adhesive part was formed by a screen printing method and a method of transferring an adhesive layer on a release film, and it was confirmed whether or not a sheet-like electrode having the configuration shown in FIG. 1 could be formed.
The coating film formed by the screen printing method was cured under the condition of heating at 120 ° C. for 5 minutes followed by heating at 40 ° C. for 24 hours. The pressure-sensitive adhesive layer on the release film is formed by forming a coating film made of the composition on the release film by screen printing, and then heating the coating film at 120 ° C. for 5 minutes, followed by heating at 40 ° C. for 24 hours. did.
As a result of the above confirmation test, an adhesive part having a desired shape and film thickness (26 μm) is formed using the above composition by either a screen printing method or a method of transferring an adhesive layer on a release film. The sheet-like electrode having the configuration shown in FIG.

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 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 subject's forehead and impedance measurement was performed, the impedance measurement result of the sheet-like electrode having the configuration shown in FIGS. 1 and 5 is a level at which electroencephalogram measurement can be satisfactorily performed. Met. On the other hand, when the sheet-like electrode having the configuration shown in FIG. 7 is used, it is difficult to measure the electroencephalogram well.
In the sheet-like electrode having the configuration shown in FIG. 7, substantially the entire surface of the sheet-like electrode is covered with the adhesive portion. Since the conductivity anisotropy of the adhesive part 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 the electroencephalogram well.

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

[Example 2]
Change to a dispersion in 2-propanol and ethanol containing PEDOT / PSS (B-1), and add 6.9 parts by mass of silver chloride (I) (E-1) obtained in Synthesis Example 4 to the composition. Otherwise, a composition for forming an adhesive layer was obtained in the same manner as in Example 1.

Using the obtained composition, an adhesive part was formed by a screen printing method and a method of transferring an adhesive layer on a release film, and it was confirmed whether or not a sheet-like electrode having the configuration shown in FIG. 1 could be formed.
The coating film formed by the screen printing method was cured under the condition of heating at 120 ° C. for 5 minutes followed by heating at 40 ° C. for 24 hours. The pressure-sensitive adhesive layer on the release film is formed by forming a coating film made of the composition on the release film by screen printing, and then heating the coating film at 120 ° C. for 5 minutes, followed by heating at 40 ° C. for 24 hours. did.
As a result of the above confirmation test, an adhesive part having a desired shape and film thickness (25 μm) was formed by using the above composition by either a screen printing method or a method of transferring an adhesive layer on a release film. The sheet-like electrode having the configuration shown in FIG.

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 was attached to the subject's forehead and the electroencephalogram was measured, the electroencephalogram could be satisfactorily measured even when the sheet-like electrode having the configuration shown in any of FIGS. 1, 5, and 7 was used. It was.
In the sheet-like electrode having the configuration shown in FIG. 7, substantially the entire surface of the sheet-like electrode is covered with the adhesive portion. Since the adhesive 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 thought that the electroencephalogram could be measured well.

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

Example 3
A composition for forming an 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. .

Using the obtained composition, an adhesive part was formed by a screen printing method and a method of transferring an adhesive layer on a release film, and it was confirmed whether or not a sheet-like electrode having the configuration shown in FIG. 1 could be formed.
The coating film formed by the screen printing method was cured under the condition of heating at 120 ° C. for 5 minutes followed by heating at 40 ° C. for 24 hours. The pressure-sensitive adhesive layer on the release film is formed by forming a coating film made of the composition on the release film by screen printing, and then heating the coating film at 120 ° C. for 5 minutes, followed by heating at 40 ° C. for 24 hours. did.
As a result of the above confirmation test, an adhesive part having a desired shape and film thickness (26 μm) is formed using the above composition by either a screen printing method or a method of transferring an adhesive layer on a release film. The sheet-like electrode having the configuration shown in FIG.

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 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 subject's forehead and the electroencephalogram was measured, the electroencephalogram could be satisfactorily measured even when the sheet-like electrode having the configuration shown in any of FIGS. 1, 5, and 7 was used. It was.
In the sheet-like electrode having the configuration shown in FIG. 7, substantially the entire surface of the sheet-like electrode is covered with the adhesive portion. Since the adhesive 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 thought that the electroencephalogram could be measured well.

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

[Comparative Example 1]
In Comparative Example 1, a commercially available medical hydrogel paste was used as the material for the adhesive part. For such a hydrogel paste, a screen printing method or a method of transferring an adhesive layer on a release film cannot be applied as a method for forming an adhesive part.

Moreover, the adhesive part with a film thickness of 20 micrometers was formed by stroking hydrogel paste with a finger | toe, and the sheet-like electrode of the structure shown by FIG. 1 was manufactured.
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 subject's forehead and electroencephalogram measurement was performed, the electroencephalogram could be satisfactorily measured by using the sheet-like electrode having the configuration shown in FIG.

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

  As described above, the preferred embodiments of the electrode sheet, the electrode sheet manufacturing method, the biological signal acquisition device, and the biological signal acquisition method of the present invention have been described, but the present invention is not limited to the above-described embodiments. Changes can be made as appropriate.

  In the above embodiment, in Embodiments 1 and 2, the conductive material is preferably at least one of a conductive polymer and conductive fine particles. In Embodiment 3, the conductive material preferably includes at least conductive fine particles. Further, in the electrode sheet and the biological signal acquisition device according to Embodiment 3, the stretchable cover 13 may not be provided because the resistance value in the in-plane direction D1 of the adhesive portion 15B 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 above-described 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 wire 11 may be formed on different main surfaces of the stretchable substrate 10. In this case, you may make it arrange | position the adhesion part 15 on one main surface of the elastic electrode 12 and the elastic base material 10. FIG.

  Moreover, in the said embodiment, although the electroencephalogram was demonstrated to an example as a biological signal, the electrode sheets 1, 1A, and 1B may acquire other biological signals, such as a pulse.

  Moreover, in the said embodiment, although the example which forms the adhesion parts 15, 15A, and 15B by the printing method was shown, 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. As long as the electrode sheets 1, 1 </ b> A, 1 </ b> B can be attached to the measurement object, the adhesive portions 15, 15 </ b> A, 15 </ b> B may cover at least one stretchable electrode 12. For example, the adhesive portions 15, 15 </ b> A, 15 </ b> B 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 (separation) can be carried out into two or more parts by the in-plane direction D1. At this time, it is preferable that the electrode sheet 1 has at least one stretchable electrode 12 and each stretched lead wire 11 connected to the stretchable electrode 12 in each separated portion. In this way, by making the electrode sheet 1 separable, the attachment position of the stretchable electrode 12 can be flexibly changed in accordance with the acquisition position of the biological signal. Can be improved.

1, 1A, 1B Electrode sheet 10 Stretchable substrate 11 Stretchable lead wire 12 Stretchable electrode 13 Stretchable cover 15, 15A, 15B Adhesive part

Claims (15)

A sheet-like stretchable base material, two or more stretchable lead wires, two or more stretchable electrodes, and an adhesive portion,
Two or more stretchable electrodes are located on at least one main surface of the stretchable substrate,
The adhesive portion covers 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 elastic lead wires are connected to each of the two or more elastic electrodes,
An electrode sheet in which the adhesive portion is made of a non-gel material having stretchability and conductivity.   The electrode sheet according to claim 1, wherein the non-gel material includes an adhesive resin and a conductive material.   The electrode sheet according to claim 2, wherein the conductive material includes a conductive polymer and / or conductive fine particles.   The electrode sheet according to claim 3, wherein the conductive material contains the conductive fine particles.   The electrode sheet according to claim 4, wherein a relative value of the volume resistivity in the thickness direction of the adhesive portion with respect 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 a main surface of the stretchable base material.   The electrode sheet according to claim 1, further comprising a stretchable cover made of an insulating material and covering the stretchable lead wiring.   The electrode sheet according to claim 7, wherein the adhesive portion covers at least a part of a main surface of the stretchable cover.   The electrode sheet according to any one of claims 1 to 8, wherein the adhesive portion is separated from each of the portions covering the stretchable electrode and the portion covering the other.   The electrode sheet according to any one of claims 4 to 6, wherein the adhesive portion has a single surface portion covering the stretchable electrode and a portion covering the other. A method for producing the electrode sheet according to claim 1,
Arrangement of the stretchable electrode on at least one main surface of the stretchable substrate;
Connection of the stretchable lead wires to each of the stretchable electrodes;
Forming the adhesive portion;
An electrode sheet manufacturing method 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.   A biological signal acquisition apparatus comprising the electrode sheet according to any one of claims 1 to 11.   The biological signal acquisition device according to claim 13, further comprising 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.   The biosignal acquisition method using the said biosignal acquisition apparatus of Claim 13 or 14.

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