WO2023013358A1

WO2023013358A1 - Electrode device and brain wave measuring device

Info

Publication number: WO2023013358A1
Application number: PCT/JP2022/026924
Authority: WO
Inventors: 慈厚尾野; 雄眞北添
Original assignee: 住友ベークライト株式会社
Priority date: 2021-08-03
Filing date: 2022-07-07
Publication date: 2023-02-09

Abstract

This electrode device is a reference electrode (40) that is worn on the external ear to acquire a biopotential, and has a worn part (70) that is worn on the recessed shape of the external ear and a biopotential acquisition unit (46) that is provided on the mounting part (70), is brought into contact with the external ear, and is formed from an electric conductive material.

Description

Electrode device and electroencephalogram measurement device

The present invention relates to an electrode device for acquiring biopotentials and an electroencephalogram measurement device having such an electrode device.

A technology is known that observes biological signals emitted from the human body, such as heartbeats and electroencephalograms, and evaluates the state of human health.

As such a technology, for example, there is a technology to clip a clip-shaped electrode to the ear (outer ear). In addition, US Pat. No. 6,200,001 discloses an ear device comprising an ear canal portion having an ear canal electrode configured to be placed in a person's ear canal.

Patent No. 6852162

By the way, the above technology has various problems. For example, the technique of clipping electrodes in the ear sometimes causes pain and discomfort due to the clipping. In addition, some people hesitate to wear the device because of the appearance of the device when they wear it. Furthermore, there is a problem that there are many parts protruding from the ends of the ears and on the front and back, and it is likely to become a cause of detachment due to catching. The technique of Patent Document 1 has a configuration for inserting into the external auditory canal, and there is a problem that it is difficult to wear.

The present invention has been made in view of such a situation, and aims to provide a technology that makes it easy to attach an electrode device that acquires a biopotential to the ear and makes it less likely to cause discomfort such as pain.

According to the present invention, the following techniques are provided.
[1]
An electrode device that is attached to the outer ear and acquires a biopotential,
a mounting portion to be mounted in the concave shape of the outer ear;
The electrode device, comprising: a biopotential acquisition section that is provided in the attachment section and that is a portion that contacts the outer ear and is made of a conductive material.
[2]
The electrode device according to [1], wherein the mounting part has a turbinate mounting part that is fitted into the turbinate vessel of the outer ear.
[3]
The electrode device according to [2], wherein the turbinate attachment section includes the biopotential acquisition section.
[4]
The electrode device according to any one of [1] to [3], wherein the attachment part has a fossa navicular attachment part that is fitted into the fossa navicularis of the external ear.
[5]
The electrode device according to [4], wherein the scaphoid attachment part has the biopotential acquisition part.
[6]
The electrode device according to any one of [1] to [5], wherein the attachment part has an auricle hole attachment part that is fitted into the auricle hole of the outer ear.
[7]
The electrode device according to [6], wherein the auricular hole attachment section has the biopotential acquisition section.
[8]
The wearing part has a helix-wearing part to be worn on the helix of the outer ear,
The ear ring mounting part
a helix fitting portion having a C-shaped opening at the tip and into which the helix is fitted;
a first extending portion extending from one end of the helix fitting portion;
a second extending portion extending from the other tip of the helix fitting portion;
has
The first extending portion has a protrusion projecting in the direction of the second extending portion at a position extended by a predetermined length,
The electrode device according to [1], wherein the projection is provided with the biopotential acquisition section.
[9]
The mounting part is
a mounting portion main body made of a resin material;
The electrode device according to any one of [1] to [8], including the biopotential acquisition section provided in the attachment section main body.
[10]
The electrode device according to [9], wherein the biopotential acquisition section is provided by coating the surface of the mounting section main body with silver paste as the conductive material.
[11]
The electrode device according to [9] or [10], wherein the entire mounting portion main body is made of a conductive material.
[12]
The electrode device according to any one of [9] to [11], wherein the mounting portion main body is made of an elastic material.
[13]
The electrode device according to [12], wherein the elastic material comprises a silicone resin.
[14]
The electrode device according to any one of [9] to [13], which has a signal extracting portion provided in the attachment portion main body and extracting the acquired biopotential to the outside.
[15]
The electrode device according to [14], further comprising a conductive member that electrically connects the biopotential acquisition section and the signal extraction section through the attachment section main body.
[16]
An electroencephalogram measurement apparatus having the electrode device according to any one of [1] to [15] as a reference electrode for electroencephalogram measurement.

According to the present invention, it is possible to provide a technology that makes it easy to attach an electrode device that acquires a biopotential to an ear and that makes it difficult to cause discomfort such as pain.

1 is a schematic diagram showing an electroencephalogram detection system with an electroencephalogram measuring device attached to the head according to the first embodiment; FIG. 1 is a schematic diagram showing an electroencephalogram detection system with an electroencephalogram measuring device attached to the head according to the first embodiment; FIG. 1 is a front view of an electroencephalogram detection electrode according to a first embodiment; FIG. 1 is a plan view of an electroencephalogram detection electrode according to a first embodiment; FIG. 4 is an enlarged view of a partial area X1 of FIG. 3 according to the first embodiment; FIG. 5 is a cross-sectional view taken along line X2-X2 of FIG. 4 according to the first embodiment; FIG. 5 is a diagram showing another example of the X2-X2 cross-sectional view of FIG. 4 according to the first embodiment; FIG. 1 is a perspective view of a reference electrode according to a first embodiment; FIG. 3 is an exploded perspective view of a reference electrode according to the first embodiment; FIG. 5A and 5B are five views of the reference electrode according to the first embodiment; FIG. 4 is a cross-sectional view of a reference electrode according to the first embodiment; FIG. FIG. 10 is a diagram showing a state in which the reference electrode according to the second embodiment is attached to the outer ear; FIG. 5 is a perspective view of a reference electrode according to a second embodiment; 5A and 5B are five views of a reference electrode according to a second embodiment; FIG. FIG. 12 is a diagram showing a state in which the reference electrode according to the third embodiment is attached to the outer ear; FIG. 11 is a perspective view of a reference electrode according to a third embodiment; FIG. 11 is a perspective view of a reference electrode according to a third embodiment; It is a five-sided view of the reference electrode according to the third embodiment. FIG. 14 is a diagram showing a state in which the reference electrode according to the fourth embodiment is attached to the outer ear; FIG. 11 is a perspective view of a reference electrode according to a fourth embodiment; It is a five-sided view of the reference electrode according to the fourth embodiment.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described with reference to the drawings.
This embodiment will exemplify an electroencephalogram detection system that performs electroencephalogram measurement by attaching an electrode device that acquires a biopotential to the ear. Also, in the electroencephalogram detection system, an example of using it as a reference electrode when detecting electroencephalograms in the head will be described.
In addition to electroencephalogram signals, biopotentials include, for example, electrocardiogram signals, electrodermal reflection signals, electromyogram signals, and electrooculogram signals, and may be used as electrodes for directly acquiring them, or as reference electrodes. may be used.

<<First Embodiment>>
<Outline of electroencephalogram measurement device 10>
1 and 2 are schematic diagrams showing the electroencephalogram detection system 1 with the electroencephalogram measuring device 10 attached to the head 99 of a person. FIG. 1 is a front view of a person wearing an electroencephalogram measuring device 10. FIG. FIG. 2 is a side view of a person wearing the electroencephalogram measuring device 10. FIG. The electroencephalogram detection system 1 includes an electroencephalogram measurement device 10 and an electroencephalogram display device 20 .

The electroencephalogram measurement device 10 is attached to a person's head 99 and detects electroencephalograms as potential fluctuations from the living body, and outputs the detected electroencephalograms to the electroencephalogram display device 20 . The electroencephalogram display device 20 acquires electroencephalograms detected by the electroencephalogram measurement device 10, displays them on a monitor, stores data, and performs well-known electroencephalogram analysis processing (measurement processing).

<Schematic structure of electroencephalogram measurement device 10>
As shown in FIGS. 1 and 2, the electroencephalogram measurement apparatus 10 includes a rubber-like elastic band member 11 that is worn following the shape of a human head 99, and a reference electrode 40 that is attached to the outer ear 80. , and a mounting portion 50 for connecting the reference electrode 40 and the band member 11 .

Here, the reference electrode 40 is configured to be attached to both ears, but may be configured to be attached to only one ear. With such a configuration, it is possible to prevent the both ends of the band member 11 from being lifted from the head 99 and prevent appropriate electroencephalogram measurement from occurring, and to acquire the reference potential at the outer ear 80 . As a result, stable electroencephalogram measurement can be realized.

A plurality of elastic protrusions 12 integrally formed with the band member 11 are provided on one surface of the band member 11 (here, the band inner surface 11a on the head 99 side). At least the tip portion of the protrusion 12 constitutes an electrode portion 13 made of a conductive member.

At both ends of the band member 11 in the longitudinal direction, there are provided a reference electrode 40 attached to the outer ear 80 , a mounting portion 50 attached to the band member 11 , and a portion extending between the reference electrode 40 and the mounting portion 50 . A cable portion 60 connected to the band member 11 is also provided. A female snap button electrode 49 is provided at one end of the cable portion 60 and attached to the male snap button electrode 48 of the reference electrode 40 (see FIG. 8, for example).

The cable section 60 transmits the reference potential to the electroencephalogram display device 20 and may be directly connected to the electroencephalogram display device 20 without going through the band member 11 .

In this embodiment, the reference electrode 40 has a function of acquiring a reference potential and a function of supporting the band member 11 to follow the head 99 . In other words, it is possible to prevent the both ends of the band member 11 from being lifted from the head 99 and thus preventing appropriate electroencephalogram measurement.

<System overview configuration of electroencephalogram display device 20>
The electroencephalogram measurement device 10 is provided with connectors, electronic components, etc., and is connected to the electroencephalogram display device 20 . The electroencephalogram measurement device 10 and the electroencephalogram display device 20 may be configured integrally. Also, the electroencephalogram display device 20 may be composed of a smart device (smart phone, tablet terminal) and a predetermined application functioning therewith. In this case, the electroencephalogram measurement device 10 has a communication function of wirelessly transmitting detected electroencephalograms.

The electroencephalogram display device 20 has, for example, a control section, a storage section, a user IF, an output section, and an electroencephalogram processing data processing section. These include arithmetic units such as CPUs, memories such as ROMs and RAMs, storage devices such as HDDs and SSDs, monitors, communication IFs, etc., and are capable of using electroencephalograms obtained from the electroencephalogram measuring apparatus 10 according to a predetermined program. Convert to data format and perform well-known electroencephalogram analysis functions.

<Specific Configuration of Electroencephalogram Measurement Device 10>
Regarding the specific structure of the electroencephalogram measurement device 10, the structures of the band member 11 and the electrode section 13 will be described first, and then the structures of the attachment section 50 and the reference electrode 40 will be described.

<Band member 11>
FIG. 3 is a front view of the band member 11. FIG. 4 is a plan view of the band member 11. FIG. Here, the band member 11, which was curved in FIG. 1, is shown in a flat state. In the explanation of each figure, for the sake of convenience, the thickness direction of the band member 11 is the Z direction (the upward direction is +Z), the longitudinal direction of the rectangular shape is the X direction (the right direction is +X), and the lateral direction is the Y direction. (The depth direction is +Y). Further, the back side (+Y side) will be described as the front side, and the near side (−Y side) as the rear side.

<Shape of band member 11>
The band member 11 is a plate-like body with a predetermined thickness t. Specifically, the band member 11 has a strip-like rectangular shape when viewed from above (plan view).
A thickness t of the band member 11 is, for example, 0.1 mm to 30 mm.
The longitudinal length L1 of the rectangular shape is, for example, 20 cm to 65 cm.
The length L2 of the rectangular shape in the lateral direction is, for example, 0.5 cm to 5 cm.
Note that the shape of the band member 11 is not limited to a strip-like rectangular shape. For example, an elongated elliptical shape may be used instead of a rectangular shape. Moreover, the thickness t of the band member 11 is not limited to a constant value, and the thickness may be partially thinned or thickened. In any case, the band member 11 follows the shape of the head 99 when the electroencephalogram measuring device 10 is worn on the head 99 .

<Arrangement of Projection 12>
A plurality of projecting portions 12 are provided integrally with the band member 11 on one surface of the band member 11 (band inner surface 11a on the head 99 side). For example, as shown in the plan view of FIG. 4, the plurality of protrusions 12 are arranged in a row at a predetermined pitch P when viewed from above. The pitch P of the protrusions 12 (that is, the electrode portions 13) is, for example, 1 mm to 20 mm. The pitch P is determined from the viewpoint of the number of electrode units 13 required for brain wave detection and the followability of the band member 11 to the head 99 .

<Shape of protrusion 12>
5 and 6 show views of the protrusion 12 viewed from the front side (rear side). FIG. 5 is a diagram showing one protrusion 12 by enlarging the region X1 in the front view of FIG. 6 is a cross-sectional view taken along line X2-X2 in FIG. 4, and is also a cross-sectional view of the protrusion 12 in FIG.

The protrusion 12 is formed integrally with the band member 11 so as to protrude from one surface of the band member 11 (in this case, the band inner surface 11a). An attachment portion 50 is attached to the surface on which the protrusion 12 is not provided (here, the band outer surface 11b).
The height h1 of the triangular pyramid projection 12 is, for example, 0.5 mm to 20 mm, preferably 3 mm to 15 mm, and more preferably 4 mm to 10 mm.

As a specific shape of the triangular pyramid that the protrusion 12 exhibits, for example, as shown in FIG. Yes, they are oriented. Here, the vertices of the isosceles triangle are on one side (the front side (+Y side) in the drawing) in the short direction of the rectangular shape, and the base is on the other side (the rear side (−Y side) in the drawing). In the illustrated example, the apex of the triangular pyramid (that is, the tip of the protrusion 12) is located at the center of gravity of the isosceles triangle when viewed from above. In other words, the protruding portion 12 is oriented such that the front side (+Y side) is gentle and the rear side (−Y side) is steep. In the present embodiment, "the direction of the projection 12" means "the direction in which the vertices of the isosceles triangle face".

When the electroencephalogram measurement device 10 is attached to the head 99, the protruding portion 12 is applied to the head 99 from the gentle side (+Y side), so that the subject does not feel discomfort (pain, etc.) and the hair is removed. The electroencephalogram measurement device 10 can be attached smoothly with little resistance from the outside.

<Shape and Material of Electrode Portion 13>
An electrode portion 13 made of a conductive member is provided at least at the tip of the protrusion 12 so as to cover the surface of the protrusion 12 . Here, the electrode portion 13 is provided on the surface of the projection 12 within a predetermined height h2 from the apex of the triangular pyramid.
The predetermined height h2 at which the electrode portion 13 is formed is, for example, 1 mm to 10 mm, depending on the height h1 of the projection portion 12. FIG.

The conductive member of the electrode portion 13 is, for example, a paste containing a highly conductive metal. Good conductive metals include one or more selected from the group consisting of copper, silver, gold, nickel, tin, lead, zinc, bismuth, antimony, or alloys thereof. In particular, silver, silver chloride, and copper are suitable from the viewpoint of availability and conductivity.

When forming the electrode part 13 with a paste containing a highly conductive metal, the top of the protrusion 12 made of a rubber-like elastic body is dipped (immersion coating) in a paste-like conductive solution containing a highly conductive metal. do. As a result, the electrode portion 13 is formed on the surface of the tip portion of the projection portion 12 .

The electrode part 13 as a conductive resin layer may be formed by applying a conductive solution containing a conductive filler and a solvent to the tip portion of the protrusion 12 . At this time, by using the same type of material (silicone rubber) as the solvent for the protrusions 12, the adhesion of the electrode portions 13 (conductive resin layer) can be enhanced.

A conductive signal line 14 connected to the electrode portion 13 is provided inside the projection portion 12 . The material, thickness, and position of the signal line 14 are not particularly limited as long as the connected electroencephalogram display device 20 or the like can appropriately measure electroencephalograms. When the electrode portion 13 is provided on the surface of the tip portion of the projection portion 12, for example, as shown in FIG. Line 14 is connected.

A specific aspect of the signal line 14 suitable for the electroencephalogram measurement apparatus 10 of this embodiment will be described below.
The signal line 14 is electrically connected to the electrode portion 13 covering the tip of the protrusion 12 and is arranged inside the protrusion 12 from the tip toward the band member 11 .

The signal line 14 can use a known one, and can be made of conductive fiber, for example.
As the conductive fiber, one or more selected from the group consisting of metal fiber, metal-coated fiber, carbon fiber, conductive polymer fiber, conductive polymer-coated fiber, and conductive paste-coated fiber can be used. These may be used alone or in combination of two or more.

The metal material of the metal fibers and metal-coated fibers is not limited as long as it has conductivity, but copper, silver, gold, nickel, tin, lead, zinc, bismuth, antimony, stainless steel, aluminum, silver/silver chloride. and alloys thereof. These may be used alone or in combination of two or more. Among these, silver can be used from the viewpoint of conductivity. Moreover, it is preferable that the metal material does not contain a metal such as chromium that causes a load on the environment.

The fiber materials of the metal-coated fibers, conductive polymer-coated fibers, and conductive paste-coated fibers are not particularly limited, but may be synthetic fibers, semi-synthetic fibers, or natural fibers. Among these, it is preferable to use polyester, nylon, polyurethane, silk, cotton, and the like. These may be used alone or in combination of two or more.

Examples of the carbon fibers include PAN-based carbon fibers and pitch-based carbon fibers.

The conductive polymer material of the conductive polymer fiber and the conductive polymer-coated fiber is, for example, a mixture of a conductive polymer such as polythiophene, polypyrrole, polyaniline, polyacetylene, polyphenylene vinylene, polynaphthalene, and derivatives thereof and a binder resin, Alternatively, an aqueous solution of a conductive polymer such as PEDOT-PSS ((3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid)) is used.

The resin material contained in the conductive paste of the conductive paste-coated fiber is not particularly limited, but preferably has elasticity. It can contain one or more selected from the group consisting of propylene rubbers. These may be used alone or in combination of two or more.

The conductive filler contained in the conductive paste of the conductive paste-coated fiber is not particularly limited, and known conductive materials may be used, such as metal particles, metal fibers, metal-coated fibers, carbon black, acetylene black, graphite, carbon It may contain at least one selected from the group consisting of fibers, carbon nanotubes, conductive polymers, conductive polymer-coated fibers, and metal nanowires.

The metal constituting the conductive filler is not particularly limited, but for example, copper, silver, gold, nickel, tin, lead, zinc, bismuth, antimony, silver/silver chloride, or at least one of these alloys. or, alternatively, two or more of these. Among these, silver or copper is preferable because of its high conductivity and high availability.

The signal line 14 may be composed of twisted yarn obtained by twisting a plurality of linear conductive fibers. Thereby, disconnection of the signal line 14 at the time of deformation can be suppressed.

In the present specification, the coating of the conductive fiber means not only covering the outer surface of the fiber material, but also, in the case of a twisted yarn obtained by twisting single fibers, a metal or a conductive polymer is added between the fibers in the twisted yarn. , or impregnated with a conductive paste to cover each single fiber constituting the twisted yarn.

The tensile elongation at break of the signal line 14 is, for example, 1% to 50%, preferably 1.5% to 45%. By setting the value within such a numerical range, it is possible to suppress excessive deformation of the protrusion 12 while suppressing breakage during deformation.
The signal line 14 can adopt various arrangement structures as long as it is a mode that conducts the inside of the protrusion 12 .
For example, the tip of the signal line 14 may be any of a protruding structure, a structure on substantially the same plane, and a buried structure with respect to the tip of the protrusion 12 or the inclined surface of the tip. From the viewpoint of connection stability with the electrode portion 13, a projecting structure may be used. A projecting portion at the tip of the signal line 14 is partially or entirely covered with the electrode portion 13 .

The protruding structure of the tip of the signal line 14 may be unfolded, folded, or wrapped around the surface of the tip of the projection 12 . Also, the signal line 14 may not coincide with the vertical line extending from the tip (apex) of the protrusion 12 and may be inclined with respect to the vertical line.

7 shows another example of a cross-sectional view along the line X2-X2 in FIG. As shown in the cross-sectional view of FIG. 7, the signal line 14 is connected to the lower end of the electrode portion 13 (on the side of the band member 11), extends along the slope (surface) of the protrusion 12, and extends from a predetermined position. It may be in the form of being drawn into the protrusion 12 .
In addition, in the signal line 14 , the end on the side connected to the electrode portion 13 and the end on the opposite side may be individually pulled out of the band member 11 . Further, the plurality of signal lines 14 may be connected to a connector or the like provided on the band outer surface 11b of the band member 11 from inside the band member 11 and organized.

<Material of band member 11 and projection 12>
The band member 11 and the protrusion 12 are rubber-like elastic bodies, more specifically, rubber or thermoplastic elastomer (also simply referred to as "elastomer (TPE)"). Examples of rubber include silicone rubber. Examples of thermoplastic elastomers include styrene-based TPE (TPS), olefin-based TPE (TPO), vinyl chloride-based TPE (TPVC), urethane-based TPE (TPU), ester-based TPE (TPEE), and amide-based TPE (TPAE). There is

When the band member 11 and projections 12 of the electroencephalogram measurement device 10 are made of silicone rubber, the surface of the band member 11 (band inner surface 11a and band outer surface 11b) measured at 37°C in accordance with JIS K 6253 (1997). Rubber hardness A is, for example, 15 or more and 55 or less.

Here, the silicone rubber-based curable composition will be described.
The silicone rubber can be composed of a cured product of a silicone rubber-based curable composition. The curing step of the silicone rubber-based curable resin composition is, for example, heating at 100 to 250° C. for 1 to 30 minutes (primary curing), followed by post-baking (secondary curing) at 100 to 200° C. for 1 to 4 hours. It is done by

An insulating silicone rubber is a silicone rubber that does not contain a conductive filler, and a conductive silicone rubber is a silicone rubber that contains a conductive filler.

The silicone rubber-based curable composition according to this embodiment can contain a vinyl group-containing organopolysiloxane (A). The vinyl group-containing organopolysiloxane (A) is a polymer that is the main component of the silicone rubber-based curable composition of the present embodiment.

The insulating silicone rubber-based curable composition and the conductive silicone rubber-based curable composition may contain the same type of vinyl group-containing linear organopolysiloxane. The vinyl group-containing linear organopolysiloxane of the same kind includes at least the same vinyl group with the same functional group and has a linear shape. can be different.
The insulating silicone rubber-based curable composition and the conductive silicone rubber-based curable composition may further contain different vinyl group-containing organopolysiloxanes.

The vinyl group-containing organopolysiloxane (A) can contain a vinyl group-containing linear organopolysiloxane (A1) having a linear structure.

The vinyl group-containing linear organopolysiloxane (A1) has a linear structure and contains vinyl groups, and the vinyl groups serve as cross-linking points during curing.

The vinyl group content of the vinyl group-containing linear organopolysiloxane (A1) is not particularly limited, but for example, it preferably has two or more vinyl groups in the molecule and is 15 mol % or less. , 0.01 to 12 mol %. As a result, the amount of vinyl groups in the vinyl group-containing linear organopolysiloxane (A1) is optimized, and a network can be reliably formed with each component described later. In the present embodiment, "~" means including both numerical values.

In the present specification, the vinyl group content is the mol % of the vinyl group-containing siloxane units when the total units constituting the vinyl group-containing linear organopolysiloxane (A1) are taken as 100 mol %. . However, one vinyl group is considered to be one vinyl group-containing siloxane unit.

Although the degree of polymerization of the vinyl group-containing linear organopolysiloxane (A1) is not particularly limited, it is, for example, preferably in the range of about 1,000 to 10,000, more preferably in the range of about 2,000 to 5,000. The degree of polymerization can be determined, for example, as a polystyrene-equivalent number-average polymerization degree (or number-average molecular weight) in GPC (gel permeation chromatography) using chloroform as a developing solvent.

Furthermore, the specific gravity of the vinyl group-containing linear organopolysiloxane (A1) is not particularly limited, but is preferably in the range of about 0.9 to 1.1.

As the vinyl group-containing linear organopolysiloxane (A1), the heat resistance, flame retardancy, chemical stability, etc. of the obtained silicone rubber are improved by using those having the degree of polymerization and specific gravity within the ranges described above. can be improved.

As the vinyl group-containing linear organopolysiloxane (A1), those having a structure represented by the following formula (1) are particularly preferable.

In formula (1), R ¹ is a substituted or unsubstituted alkyl group, alkenyl group, aryl group, or a hydrocarbon group of a combination thereof having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms includes, for example, methyl group, ethyl group, propyl group, etc. Among them, methyl group is preferred. The alkenyl group having 1 to 10 carbon atoms includes, for example, vinyl group, allyl group, butenyl group, etc. Among them, vinyl group is preferred. The aryl group having 1 to 10 carbon atoms includes, for example, a phenyl group.

R ² is a substituted or unsubstituted alkyl group, alkenyl group, aryl group having 1 to 10 carbon atoms, or a hydrocarbon group combining these. The alkyl group having 1 to 10 carbon atoms includes, for example, methyl group, ethyl group, propyl group, etc. Among them, methyl group is preferable. Examples of alkenyl groups having 1 to 10 carbon atoms include vinyl groups, allyl groups and butenyl groups. Examples of the aryl group having 1 to 10 carbon atoms include a phenyl group.

R ³ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an aryl group, or a hydrocarbon group combining these. The alkyl group having 1 to 8 carbon atoms includes, for example, methyl group, ethyl group, propyl group, etc. Among them, methyl group is preferable. Examples of the aryl group having 1 to 8 carbon atoms include a phenyl group.

Furthermore, examples of substituents for R ¹ and R ² in formula (1) include methyl group and vinyl group, and examples of substituents for R ³ include methyl group.

In formula (1), a plurality of R ¹ are independent of each other and may be different or the same. Furthermore, the same applies to R ² and R ³ .

Furthermore, m and n are the numbers of repeating units constituting the vinyl group-containing linear organopolysiloxane (A1) represented by formula (1), m is an integer of 0 to 2000, and n is 1000 to 10000. is an integer of m is preferably 0-1000 and n is preferably 2000-5000.

Further, specific structures of the vinyl group-containing linear organopolysiloxane (A1) represented by formula (1) include, for example, those represented by the following formula (1-1).

In formula (1-1), R ¹ and R ² are each independently a methyl group or a vinyl group, and at least one is a vinyl group.

Furthermore, as the vinyl group-containing linear organopolysiloxane (A1), a first vinyl group-containing vinyl group having a vinyl group content of 2 or more vinyl groups in the molecule and not more than 0.4 mol% It contains a linear organopolysiloxane (A1-1) and a second vinyl group-containing linear organopolysiloxane (A1-2) having a vinyl group content of 0.5 to 15 mol%. It is preferable to have As crude rubber, which is a raw material of silicone rubber, a first vinyl group-containing linear organopolysiloxane (A1-1) having a general vinyl group content and a second vinyl group-containing linear organopolysiloxane having a high vinyl group content were used. By combining with the chain organopolysiloxane (A1-2), the vinyl groups can be unevenly distributed, and the crosslink density can be more effectively formed in the crosslink network of the silicone rubber. As a result, the tear strength of silicone rubber can be increased more effectively.

Specifically, as the vinyl group-containing linear organopolysiloxane (A1), for example, a unit in which R ¹ is a vinyl group and/or a unit in which R ² is a vinyl group in the above formula (1-1) , a first vinyl group-containing linear organopolysiloxane (A1-1) having 2 or more in the molecule and containing 0.4 mol% or less, and a unit in which R ¹ is a vinyl group and / or R It is preferable to use a second vinyl group-containing linear organopolysiloxane (A1-2) containing 0.5 to 15 mol % of units in which ² is a vinyl group.

Also, the first vinyl group-containing linear organopolysiloxane (A1-1) preferably has a vinyl group content of 0.01 to 0.2 mol %. The second vinyl group-containing linear organopolysiloxane (A1-2) preferably has a vinyl group content of 0.8 to 12 mol %.

Furthermore, when combining the first vinyl group-containing linear organopolysiloxane (A1-1) and the second vinyl group-containing linear organopolysiloxane (A1-2), (A1-1) and (A1-2) is not particularly limited, but for example, the weight ratio of (A1-1):(A1-2) is preferably 50:50 to 95:5, and 80:20 to 90: 10 is more preferred.

The first and second vinyl group-containing linear organopolysiloxanes (A1-1) and (A1-2) may be used singly or in combination of two or more. good.

The vinyl group-containing organopolysiloxane (A) may also contain a vinyl group-containing branched organopolysiloxane (A2) having a branched structure.

<<Organohydrogenpolysiloxane (B)>>
The silicone rubber-based curable composition of the present embodiment may contain a cross-linking agent. Cross-linking agents can include organohydrogenpolysiloxanes (B).
Organohydrogenpolysiloxane (B) is classified into linear organohydrogenpolysiloxane (B1) having a linear structure and branched organohydrogenpolysiloxane (B2) having a branched structure. Either or both may be included.

The insulating silicone rubber-based curable composition and the conductive silicone rubber-based curable composition may contain the same type of cross-linking agent. The same type of cross-linking agent should have at least a common structure such as a linear structure or a branched structure, and may contain different molecular weight distributions and different functional groups in the molecule, and the amount added may be different. may
The insulating silicone rubber-based curable composition and the conductive silicone rubber-based curable composition may further contain different cross-linking agents.

The linear organohydrogenpolysiloxane (B1) has a linear structure and a structure (≡Si—H) in which hydrogen is directly bonded to Si, and is the vinyl group-containing organopolysiloxane (A). It is a polymer that undergoes a hydrosilylation reaction with other vinyl groups and other vinyl groups contained in other components of the silicone rubber-based curable composition to crosslink these components.

Although the molecular weight of the linear organohydrogenpolysiloxane (B1) is not particularly limited, for example, the weight average molecular weight is preferably 20,000 or less, more preferably 1,000 or more and 10,000 or less.

The weight average molecular weight of the linear organohydrogenpolysiloxane (B1) can be measured, for example, by polystyrene conversion in GPC (gel permeation chromatography) using chloroform as a developing solvent.

In addition, it is generally preferred that the linear organohydrogenpolysiloxane (B1) does not have a vinyl group. Thereby, it is possible to accurately prevent the progress of the cross-linking reaction in the molecule of the linear organohydrogenpolysiloxane (B1).

As the above linear organohydrogenpolysiloxane (B1), for example, one having a structure represented by the following formula (2) is preferably used.

In formula (2), R ⁴ is a substituted or unsubstituted alkyl group, alkenyl group, aryl group having 1 to 10 carbon atoms, a hydrocarbon group combining these groups, or a hydride group. The alkyl group having 1 to 10 carbon atoms includes, for example, methyl group, ethyl group, propyl group, etc. Among them, methyl group is preferred. Examples of alkenyl groups having 1 to 10 carbon atoms include vinyl groups, allyl groups and butenyl groups. Examples of the aryl group having 1 to 10 carbon atoms include a phenyl group.

R ⁵ is a substituted or unsubstituted alkyl group, alkenyl group, aryl group having 1 to 10 carbon atoms, a hydrocarbon group combining these, or a hydride group. Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group and propyl group, with methyl group being preferred. Examples of alkenyl groups having 1 to 10 carbon atoms include vinyl groups, allyl groups and butenyl groups. Examples of the aryl group having 1 to 10 carbon atoms include a phenyl group.

In formula (2), a plurality of R ⁴ are independent of each other and may be different from each other or may be the same. The same is true for ^R5 . However, at least two or more of the plurality of R ⁴ and R ⁵ are hydride groups.

R ⁶ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an aryl group, or a hydrocarbon group combining these. The alkyl group having 1 to 8 carbon atoms includes, for example, methyl group, ethyl group, propyl group, etc. Among them, methyl group is preferable. Examples of the aryl group having 1 to 8 carbon atoms include a phenyl group. A plurality of R ⁶ are independent from each other and may be different from each other or may be the same.

Examples of substituents for R ⁴ , R ⁵ and R ⁶ in formula (2) include methyl group and vinyl group, and methyl group is preferred from the viewpoint of preventing intramolecular cross-linking reaction.

Further, m and n are the numbers of repeating units constituting the linear organohydrogenpolysiloxane (B1) represented by formula (2), m is an integer of 2 to 150, and n is an integer of 2 to 150. is. Preferably, m is an integer from 2-100 and n is an integer from 2-100.

The straight-chain organohydrogenpolysiloxane (B1) may be used alone or in combination of two or more.

Because the branched organohydrogenpolysiloxane (B2) has a branched structure, it is a component that forms regions with a high crosslink density and greatly contributes to the formation of a loose and dense structure of crosslink density in the silicone rubber system. Further, like the linear organohydrogenpolysiloxane (B1), it has a structure (≡Si—H) in which hydrogen is directly bonded to Si, and in addition to the vinyl group of the vinyl group-containing organopolysiloxane (A), silicone It is a polymer that undergoes a hydrosilylation reaction with the vinyl groups of the components blended in the rubber-based curable composition to crosslink these components.

Also, the specific gravity of the branched organohydrogenpolysiloxane (B2) is in the range of 0.9 to 0.95.

Furthermore, it is generally preferred that the branched organohydrogenpolysiloxane (B2) does not have a vinyl group. Thereby, it is possible to accurately prevent the progress of the cross-linking reaction in the molecule of the branched organohydrogenpolysiloxane (B2).

Also, as the branched organohydrogenpolysiloxane (B2), one represented by the following average compositional formula (c) is preferable.

Average composition formula (c)
(H _a (R ⁷ ) _3-a SiO _1/2 ) _m (SiO _4/2 ) _n
(In formula (c), R ⁷ is a monovalent organic group, a is an integer ranging from 1 to 3, m is the number of H _a (R ⁷ ) _3-a SiO _1/2 units, n is SiO _4/ is a number of ₂ units)

In formula (c), R ⁷ is a monovalent organic group, preferably a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an aryl group, or a hydrocarbon group combining these. The alkyl group having 1 to 10 carbon atoms includes, for example, methyl group, ethyl group, propyl group, etc. Among them, methyl group is preferred. Examples of the aryl group having 1 to 10 carbon atoms include a phenyl group.

In formula (c), a is the number of hydride groups (hydrogen atoms directly bonded to Si) and is an integer in the range of 1 to 3, preferably 1.

In formula (c), m is the number of H _a (R ⁷ ) _3-a SiO _1/2 units, and n is the number of SiO _4/2 units.

The branched organohydrogenpolysiloxane (B2) has a branched structure. The linear organohydrogenpolysiloxane (B1) and the branched organohydrogenpolysiloxane (B2) differ in that their structures are linear or branched. The number of bound alkyl groups R (R/Si) is 1.8 to 2.1 for the linear organohydrogenpolysiloxane (B1) and 0.8 to 1 for the branched organohydrogenpolysiloxane (B2). .7 range.

Since the branched organohydrogenpolysiloxane (B2) has a branched structure, for example, when heated to 1000° C. at a heating rate of 10° C./min in a nitrogen atmosphere, the residual amount is 5% or more. becomes. On the other hand, since the straight-chain organohydrogenpolysiloxane (B1) is straight-chain, the amount of residue after heating under the above conditions is almost zero.

Specific examples of the branched organohydrogenpolysiloxane (B2) include those having a structure represented by the following formula (3).

In formula (3), R ⁷ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an aryl group, a hydrocarbon group combining these, or a hydrogen atom. The alkyl group having 1 to 8 carbon atoms includes, for example, methyl group, ethyl group, propyl group, etc. Among them, methyl group is preferred. Examples of the aryl group having 1 to 8 carbon atoms include a phenyl group. Examples of the substituent of ^R7 include a methyl group and the like.

In formula (3), a plurality of R ⁷ are independent of each other and may be different from each other or may be the same.

Also, in formula (3), "--O--Si.ident." represents that Si has a branched structure that spreads three-dimensionally.

The branched organohydrogenpolysiloxane (B2) may be used alone or in combination of two or more.

Also, in the linear organohydrogenpolysiloxane (B1) and the branched organohydrogenpolysiloxane (B2), the amount of hydrogen atoms (hydride groups) directly bonded to Si is not particularly limited. However, in the silicone rubber-based curable composition, linear organohydrogenpolysiloxane (B1) and branched organohydrogenpolysiloxane are The total amount of hydride groups in the siloxane (B2) is preferably from 0.5 to 5 mol, more preferably from 1 to 3.5 mol. As a result, a crosslinked network is reliably formed between the linear organohydrogenpolysiloxane (B1), the branched organohydrogenpolysiloxane (B2), and the vinyl group-containing linear organopolysiloxane (A1). can be made

<<Silica particles (C)>>
The silicone rubber-based curable composition according to this embodiment contains a non-conductive filler. The non-conductive filler may contain silica particles (C) as needed. Thereby, the hardness and mechanical strength of the elastomer can be improved.

The insulating silicone rubber-based curable composition and the conductive silicone rubber-based curable composition may contain the same type of non-conductive filler. Non-conductive fillers of the same type may have at least common constituent materials, and may differ in particle size, specific surface area, surface treatment agent, or addition amount thereof.
The insulating silicone rubber-based curable composition and the conductive silicone rubber-based curable composition may further contain different silane coupling agents.

The silica particles (C) are not particularly limited, but for example, fumed silica, calcined silica, precipitated silica, etc. are used. These may be used alone or in combination of two or more.

The silica particles (C) preferably have a BET specific surface area of, for example, 50 to 400 m ² /g, more preferably 100 to 400 m ² /g. Also, the average primary particle size of the silica particles (C) is, for example, preferably 1 to 100 nm, more preferably about 5 to 20 nm.

By using silica particles (C) having a specific surface area and an average particle size within the above ranges, the hardness and mechanical strength of the formed silicone rubber can be improved, especially the tensile strength can be improved.

<<Silane coupling agent (D)>>
The silicone rubber-based curable composition of the present embodiment can contain a silane coupling agent (D).
Silane coupling agent (D) can have a hydrolyzable group. The hydrolyzable group is hydrolyzed with water to form a hydroxyl group, and the hydroxyl group undergoes a dehydration condensation reaction with the hydroxyl group on the surface of the silica particle (C), thereby modifying the surface of the silica particle (C).

The insulating silicone rubber-based curable composition and the conductive silicone rubber-based curable composition may contain the same type of silane coupling agent. The silane coupling agents of the same kind should have at least a common functional group, and may differ in other functional groups in the molecule and in the amount added.
The insulating silicone rubber-based curable composition and the conductive silicone rubber-based curable composition may further contain different silane coupling agents.

In addition, this silane coupling agent (D) can contain a silane coupling agent having a hydrophobic group. As a result, the hydrophobic group is imparted to the surface of the silica particles (C), so that the cohesive force of the silica particles (C) in the silicone rubber-based curable composition and further in the silicone rubber is reduced (hydrogen aggregation due to bonding is reduced), and as a result, it is presumed that the dispersibility of the silica particles (C) in the silicone rubber-based curable composition is improved. This increases the interface between the silica particles (C) and the rubber matrix, increasing the reinforcing effect of the silica particles (C). Furthermore, it is presumed that the slipperiness of the silica particles (C) within the matrix is improved when the rubber matrix is deformed. The improved dispersibility and slipperiness of the silica particles (C) improve the mechanical strength (for example, tensile strength and tear strength) of the silicone rubber due to the silica particles (C).

Furthermore, the silane coupling agent (D) can contain a silane coupling agent having a vinyl group. As a result, vinyl groups are introduced onto the surfaces of the silica particles (C). Therefore, during curing of the silicone rubber-based curable composition, that is, a hydrosilylation reaction occurs between the vinyl group of the vinyl group-containing organopolysiloxane (A) and the hydride group of the organohydrogenpolysiloxane (B). , When a network (crosslinked structure) is formed by these, the vinyl groups possessed by the silica particles (C) also participate in the hydrosilylation reaction with the hydride groups possessed by the organohydrogenpolysiloxane (B). Silica particles (C) also come to be taken in. As a result, it is possible to reduce the hardness and increase the modulus of the formed silicone rubber.

As the silane coupling agent (D), a silane coupling agent having a hydrophobic group and a silane coupling agent having a vinyl group can be used together.

Examples of the silane coupling agent (D) include those represented by the following formula (4).

_Yn -Si-(X) _4-n (4)
In the above formula (4), n represents an integer of 1-3. Y represents a functional group having a hydrophobic group, a hydrophilic group or a vinyl group, and when n is 1 it is a hydrophobic group, and when n is 2 or 3 at least one of It is a hydrophobic group. X represents a hydrolyzable group.

The hydrophobic group is an alkyl group having 1 to 6 carbon atoms, an aryl group, or a hydrocarbon group having a combination thereof, and examples thereof include a methyl group, an ethyl group, a propyl group, a phenyl group, and the like. Methyl groups are preferred.

In addition, the hydrophilic group includes, for example, a hydroxyl group, a sulfonic acid group, a carboxyl group, a carbonyl group, etc. Among them, a hydroxyl group is particularly preferable. The hydrophilic group may be contained as a functional group, but is preferably not contained from the viewpoint of imparting hydrophobicity to the silane coupling agent (D).

Further, the hydrolyzable group includes an alkoxy group such as a methoxy group and an ethoxy group, a chloro group, a silazane group, and the like. Among them, a silazane group is preferable because of its high reactivity with the silica particles (C). A compound having a silazane group as a hydrolyzable group has two structures of (Y _n —Si—) in the above formula (4) due to its structural characteristics.

Specific examples of the silane coupling agent (D) represented by the above formula (4) are as follows.
Those having a hydrophobic group as the functional group include, for example, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, alkoxysilanes such as n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane; chlorosilanes such as methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane; hexamethyldisilazane. is mentioned. Among these, a silane coupling agent having a trimethylsilyl group containing one or more selected from the group consisting of hexamethyldisilazane, trimethylchlorosilane, trimethylmethoxysilane, and trimethylethoxysilane is preferred.

Examples of those having a vinyl group as the functional group include methacryloxypropyltriethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropylmethyldimethoxysilane, vinyltriethoxysilane, and vinyltrimethoxysilane. alkoxysilanes such as silane and vinylmethyldimethoxysilane; chlorosilanes such as vinyltrichlorosilane and vinylmethyldichlorosilane; and divinyltetramethyldisilazane. Among these, methacryloxypropyltriethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropylmethyldimethoxysilane, divinyltetramethyldisilazane, vinyltriethoxysilane, vinyltrimethoxysilane, and vinyl A silane coupling agent having a vinyl group-containing organosilyl group containing one or more selected from the group consisting of methyldimethoxysilane is preferred.

Further, when the silane coupling agent (D) contains two kinds of a silane coupling agent having a trimethylsilyl group and a silane coupling agent having a vinyl group-containing organosilyl group, those having a hydrophobic group include hexamethyldisilazane, Divinyltetramethyldisilazane is preferably included as one having a vinyl group.

When a silane coupling agent (D1) having a trimethylsilyl group and a silane coupling agent (D2) having a vinyl group-containing organosilyl group are used in combination, the ratio of (D1) and (D2) is not particularly limited, but for example, (D1):(D2) in a weight ratio of 1:0.001 to 1:0.35, preferably 1:0.01 to 1:0.20, more preferably 1:0.03 to 1:0 .15. Desired physical properties of the silicone rubber can be obtained by setting it to such a numerical range. Specifically, it is possible to balance the dispersibility of silica in the rubber and the crosslinkability of the rubber.

In the present embodiment, the lower limit of the content of the silane coupling agent (D) is preferably 1% by mass or more with respect to 100 parts by weight of the total amount of the vinyl group-containing organopolysiloxane (A). It is more preferably at least 5% by mass, even more preferably at least 5% by mass. In addition, the upper limit of the content of the silane coupling agent (D) is preferably 100% by mass or less, and 80% by mass or less, with respect to 100 parts by weight of the total amount of the vinyl group-containing organopolysiloxane (A). It is more preferable that the content is 40% by mass or less.
By setting the content of the silane coupling agent (D) to the above lower limit or more, the adhesion between the columnar portion containing the elastomer and the conductive resin layer can be enhanced. Moreover, it can contribute to the improvement of the mechanical strength of silicone rubber. Moreover, by setting the content of the silane coupling agent (D) to the above upper limit or less, the silicone rubber can have appropriate mechanical properties.

<<platinum or platinum compound (E)>>
The silicone rubber-based curable composition according to this embodiment may contain a catalyst. The catalyst may contain platinum or a platinum compound (E). Platinum or a platinum compound (E) is a catalytic component that acts as a catalyst during curing. The amount of platinum or platinum compound (E) added is a catalytic amount.

The insulating silicone rubber-based curable composition and the conductive silicone rubber-based curable composition may contain the same type of catalyst. Catalysts of the same kind may have at least common constituent materials, and the catalysts may contain different compositions and may differ in addition amount.
The insulating silicone rubber-based curable composition and the conductive silicone rubber-based curable composition may further contain different catalysts.

As the platinum or platinum compound (E), a known one can be used, for example, platinum black, platinum supported on silica or carbon black, chloroplatinic acid or an alcohol solution of chloroplatinic acid, A complex salt of platinic acid and olefin, a complex salt of chloroplatinic acid and vinyl siloxane, and the like are included.

The platinum or platinum compound (E) may be used alone or in combination of two or more.

In the present embodiment, the content of platinum or platinum compound (E) in the silicone rubber-based curable composition means the amount of catalyst, and can be set as appropriate. (A), silica particles (C), the total amount of 100 parts by weight of the silane coupling agent (D), platinum group metal is an amount of 0.01 to 1000 ppm by weight unit, preferably 0. The amount is 1 to 500 ppm.
By setting the content of platinum or platinum compound (E) to the above lower limit or more, the silicone rubber-based curable composition can be cured at an appropriate rate. Moreover, by making the content of platinum or platinum compound (E) equal to or less than the above upper limit, it is possible to contribute to the reduction of production costs.

<<Water (F)>>
Further, the silicone rubber-based curable composition according to the present embodiment may contain water (F) in addition to the above components (A) to (E).

Water (F) is a component that functions as a dispersion medium for dispersing each component contained in the silicone rubber-based curable composition and contributes to the reaction between the silica particles (C) and the silane coupling agent (D). . Therefore, the silica particles (C) and the silane coupling agent (D) can be linked to each other more reliably in the silicone rubber, and uniform properties can be exhibited as a whole.

(other ingredients)
Furthermore, the silicone rubber-based curable composition of the present embodiment may further contain other components in addition to the above components (A) to (F). Other components include silica particles (C) such as diatomaceous earth, iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide, cerium oxide, calcium carbonate, magnesium carbonate, zinc carbonate, glass wool, and mica. additives such as inorganic fillers, reaction inhibitors, dispersants, pigments, dyes, antistatic agents, antioxidants, flame retardants, and thermal conductivity improvers.

The conductive solution (conductive silicone rubber composition) according to the present embodiment contains the conductive filler and solvent in addition to the silicone rubber-based curable composition containing no conductive filler.

Various known solvents can be used as the solvent, and for example, a high boiling point solvent can be included. These may be used alone or in combination of two or more.

Examples of the above solvents include aliphatic hydrocarbons such as pentane, hexane, cyclohexane, heptane, methylcyclohexane, ethylcyclohexane, octane, decane, dodecane, and tetradecane; benzene, toluene, ethylbenzene, xylene, trifluoromethylbenzene; , aromatic hydrocarbons such as benzotrifluoride; diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, cyclopentyl ethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, 1,4-dioxane, 1,3 - ethers such as dioxane and tetrahydrofuran; haloalkanes such as dichloromethane, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane and 1,1,2-trichloroethane; N,N-dimethyl Carboxylic acid amides such as formamide and N,N-dimethylacetamide; sulfoxides such as dimethylsulfoxide and diethylsulfoxide; These may be used alone or in combination of two or more.

By adjusting the amount of solid content in the solution, the conductive solution can have a viscosity suitable for various coating methods such as spray coating and dip coating.

Further, when the conductive solution contains the conductive filler and the silica particles (C), the lower limit of the content of the silica particles (C) contained in the electrode portion 13 is the amount of the silica particles (C) and the conductive filler. For example, it is 1% by mass or more, preferably 3% by mass or more, and more preferably 5% by mass or more, relative to the total amount of 100% by mass. Thereby, the mechanical strength of the electrode portion 13 can be improved. On the other hand, the upper limit of the content of the silica particles (C) contained in the electrode portion 13 is, for example, 20% by mass or less with respect to 100% by mass of the total amount of the silica particles (C) and the conductive filler, It is preferably 15% by mass or less, more preferably 10% by mass or less. Thereby, it is possible to achieve a balance between conductivity, mechanical strength, and flexibility in the electrode portion 13 .

A conductive silicone rubber can be obtained by heating and drying the conductive solution as necessary.
The conductive silicone rubber may be configured without silicone oil. As a result, it is possible to suppress a decrease in conductivity due to bleeding out of the silicone oil onto the surface of the electrode portion 13 .

As a result, it is possible to achieve both good followability to the head 99 and desired strength. In addition, it is possible to avoid discomfort caused by the protrusions 12 when the electroencephalogram measuring device 10 is worn. As a result, stable electroencephalogram detection becomes possible. Depending on the characteristics of the subject wearing the electroencephalogram measurement device 10, for example, whether the subject is an “adult” or a “child”, whether the scalp is sensitive or not, whether the hair is hard or soft, etc. A hardness of A may be selected.

When molding the band member 11 with silicone rubber, the band member 11 and the plurality of protrusions 12 are seamlessly joined by molding a curable elastomer composition such as a silicone rubber-based curable composition. you get a body As a result, the electroencephalogram measurement device 10 that is excellent in flexibility (that is, flexibility that can follow the head 99 ) and strength and that can follow the head 99 well can be realized. The rubber hardness A, ie flexibility, can be controlled by appropriately selecting the type and amount of each component contained in the silicone rubber curable composition, the preparation method of the silicone rubber curable composition, and the like.

<Manufacturing Method of Band Member 11>
An example of the method for manufacturing the band member 11 can include the following steps.
First, using a mold, the silicone rubber-based curable composition is molded under heat and pressure to obtain a molded body comprising the band member 11 and the protrusions 12 . Subsequently, the signal wire 14 was passed through the interior of each columnar portion of the molded body obtained using a sewing needle. A pasty conductive solution is dip-coated on the surface (predetermined height h2) of the tip portion of the protruding portion 12 of the molded body obtained thereafter, and post-curing is performed after heating and drying. Thereby, the electrode portion 13 can be formed on the surface of the projection portion 12 .
As described above, the band member 11 can be manufactured.
During the molding process, insert molding may be used in which the silicone rubber-based curable composition is introduced into the molding space in which the signal line 14 is arranged, and pressurized and heat-molded.

<Mounting portion 50>
The attachment portions 50 are attached to both longitudinal ends of the band outer surface 11 b of the band member 11 . The attachment portion 50 functions as a fixing portion that attaches the reference electrode 40 to the band member 11 and also functions as an adjustment portion that adjusts the attachment state of the band member 11 to the head portion 99 .

Specifically, the mounting portion 50 has a plate member 52 and a locking portion 51 . The plate-like member 52 has a long strip shape with a plurality of rows of teeth. The locking portion 51 is provided with an opening having a claw formed therein, and the plate-like member 52 is inserted through the opening and locked at a desired position. Further, the lock portion 51 is provided with a releasing portion that releases the locked state in conjunction with the claw.

Various plastics can be used as the material of the mounting portion 50, although there is no particular limitation. From the viewpoint of physical properties, workability, cost, etc., 66 nylon can be preferably used.

As examples of the mounting portion 50, a hook-and-loop fastener mechanism, a cam buckle mechanism, a buckle mechanism, a button mechanism, or the like can be adopted.

<Reference electrode 40>
FIG. 8 is a perspective view showing the reference electrode 40 with the female snap button electrode 49 provided at the end of the cable portion 60 removed. FIG. 9 is an exploded perspective view of the reference electrode 40. FIG. 10A and 10B are five views of the reference electrode 40. FIG. 10A is a front view, FIG. 10B is a left side view, FIG. 10C is a right side view, and FIG. 10D is a plan view. FIG. 10(e) is a bottom view. FIG. 11 is a cross-sectional view of the reference electrode 40, showing the X3-X3 cross section of FIG. 10(d).

The reference electrode 40 functions as an electrode device that is attached to the outer ear 80 and acquires a biopotential. The reference electrode 40 includes a mounting portion 70 to be mounted in the concave shape of the outer ear 80, a male snap button electrode 48, and a portion provided on the mounting portion 70 that contacts the outer ear 80 and is a biopotential electrode made of a conductive material. and an acquisition unit 46 . The male snap button electrode 48 is detachably connected to a female snap button electrode 49 provided at the end of the cable portion 60 .
When the reference electrode 40 is attached to the outer ear 80, the turbinate attachment part 45 is fitted into the turbinate 81, and the lower surface 43 of the base 41 is arranged to face the anterior crus.
Although the reference electrodes 40 are attached to both ears in this embodiment, they may be attached to only one ear from the viewpoint of function as a reference electrode.

<Mounting part 70>
The mounting portion 70 has a base portion 41 , an extension portion 44 , a concha navicular mounting portion 45 , and a biopotential acquisition portion 46 . The base portion 41, the extending portion 44, and the concha-navus mounting portion 45 are integrally formed of a resin material as a mounting portion main body. As the resin material, for example, the elastic material exemplified as the material of the band member 11 can be used. A silicone resin can be preferably used as the elastic material. Also, the entire mounting portion body (the base portion 41, the extension portion 44, and the turbinate mounting portion 45) may be made of a conductive material such as silicone rubber containing a conductive filler.

<Base 41>
The base portion 41 has a predetermined thickness and a substantially disk shape. The thickness can be, for example, about 1 to 2 mm. The disc-shaped outer diameter can be, for example, about 10 to 15 mm in diameter.
A male snap button electrode 48 is attached to the upper surface 42 of the base 41 . The outer diameter of the male snap button electrode 48 can be approximately the same as the outer diameter of the disc-shaped base 41 .

<Extension 44>
The extending portion 44 integrally extends from the side portion of the base portion 41 by a predetermined length. Here, the upper surface 42 of the base portion 41 and the upper surface of the extension portion 44 are flush with each other.

<Auricle turbinate mounting part 45>
The turbinate attachment part 45 protrudes from the lower surface side of the extension part 44 by a predetermined length.
The turbinate attachment part 45 fits into the concave shape (hollow) of the turbinate 81 when the reference electrode 40 is attached to the outer ear 80 .

The size of the turbinate mounting part 45 is such that when the base part 41 is placed on the contralateral leg, it fits into the concave turbinate 81, and the biopotential acquisition part 46 at the tip is the size of the turbinate. It is sized to contact 81 . The protrusion length of the turbinate attachment part 45 can be, for example, 5 to 10 mm. In addition, the tip of the turbinate attachment part 45 has a curved surface so that pain does not occur when it comes into contact with the turbinate 81 .

<Biopotential acquisition unit 46>
The biopotential acquisition part 46 is provided by coating the tip surface of the conchal scapular attachment part 45 with a conductive material. As the conductive material, the materials exemplified as the conductive member of the electrode portion 13 of the band member 11 can be used, for example, silver paste can be used. That is, it is obtained by dipping (immersion coating) the tip surface of the turbinate attachment part 45 in a pasty conductive solution containing a highly conductive metal.

In addition, the method of providing the biopotential acquisition part 46 on the surface of the projecting tip of the concha sac mounting part 45 can be the same as the method of providing the electrode part 13 .

<Signal line 47>
A signal path from the biopotential acquisition unit 46 to the male snap button electrode 48 will be described with reference to the cross-sectional view of FIG. As a signal path, a signal line 47 passing through the interior of the mounting portion main body (the base portion 41, the extension portion 44, and the conchal scapula mounting portion 45) is provided. The signal line 47 may be made of the same material as the signal line 14 of the band member 11 and have the same configuration. It should be noted that the signal line 47 may be omitted when the mounting portion main body is made of a conductive material.
The signal line 47 is electrically connected to the biopotential acquisition part 46 covering the tip surface of the concha navicular mounting part 45 , passes through the extension part 44 from the tip and the interior of the base 41 , and extends to the upper surface 42 of the base 41 . Protruding. A male snap button electrode 48 is attached so as to press the projecting portion of the upper surface 42 .

As described above, according to the present embodiment, when attaching the electrode device (here, the reference electrode 40) that acquires the biopotential to the outer ear 80, it is easy to attach and discomfort such as pain is less likely to occur. Since the reference electrode 40 is accommodated in the concave shape of the area surrounded by the auricle, it is possible to suppress the influence on the appearance. Since there is no part protruding from the edge of the ear (that is, the outer ear 80), it is possible to prevent it from coming off due to catching. In addition, when the reference electrode 40 is attached to the outer ear 80 , it is easy to attach the reference electrode 40 because only the turbinate attachment part 45 is engaged with the turbinate sac 81 . Further, by adjusting the length of the cable portion 60 between the reference electrode 40 and the band member 11, the band member 11 can appropriately follow the head portion 99. FIG.

<<Second Embodiment>>
The reference electrode 140 of this embodiment will be described with reference to FIGS. 12 to 14. FIG. The reference electrode 140 of this embodiment is a modified example of the first embodiment, and mainly different parts will be explained, and explanations of the same parts will be omitted as appropriate.

FIG. 12 is a diagram showing a state in which the reference electrode 140 is attached to the outer ear 80. FIG. FIG. 13 is a perspective view of the reference electrode 140. FIG. 14A and 14B are five views of the reference electrode 140. FIG. 14A is a front view, FIG. 14B is a left side view, FIG. 14C is a right side view, and FIG. 14D is a plan view. FIG. 14(e) is a bottom view.

The reference electrode 140 of this embodiment includes a mounting portion 170 that is mounted in the concave shape of the outer ear 80, a male snap button electrode 48, and a portion that is provided in the mounting portion 170 and contacts the outer ear 80, and is made of a conductive material.

biopotential acquisition units

146a and 146b.

The mounting portion 170 is made of a resin material as in the first embodiment, and includes a substantially disc-shaped base portion 141, an extension portion 144a extending from the base portion 141, and an extension portion 144a extending downward from the extension portion 144a. and a turbinate attachment part 145a. A biopotential acquisition section 146a made of the same conductive material as in the first embodiment is provided on the tip surface of the concha sac mounting section 145a.

Further, the mounting portion 170 has an extension portion 144b and a scaphoid mounting portion 145b.
The extending portion 144b extends integrally from the base portion 141 from a position facing the extending portion 144a with the base portion 141 interposed therebetween. The scaphoid mounting portion 145b integrally extends downward from the extension portion 144b. The scaphoid mounting part 145b is fitted into the concave shape (hollow) of the scaphoid 83. As shown in FIG. The size of the scaphoid mounting part 145 b is such that the biopotential acquisition part 146 b at the tip thereof contacts the scaphoid 83 . The shape and size of the scaphoid mounting part 145b may be the same as or different from the turbinate scapula mounting part 145a. Here, the scaphoid mounting portion 145b is provided shorter than the concha navicular mounting portion 145a. A biopotential acquiring section 146b is provided on the distal surface of the scaphoid mounting section 145b.

According to this embodiment, when the reference electrode 140 is attached to the outer ear 80, the turbinate attachment part 145a fits into the turbinate scapula 81, and the scaphoid attachment part 145b fits into the scaphoid fossa 83. , the reference electrode 140 is locked to the outer ear 80 at two points. As a result, the same effect as in the first embodiment can be obtained, and the attached state of the reference electrode 140 can be stabilized. In addition, since the reference potential can be obtained at two points, the scapula 81 and the scaphoid fossa 83, a stable reference potential can be obtained.
Since the functions of the turbinate scapula attachment part 145a and the scaphoid attachment part 145b are substantially the same, when the reference electrode 140 is used, the turbinate scapula attachment part 145a is fitted into the scaphoid fossa 83. In other words, the scaphoid mounting part 145b may be used to fit the turbinate navicular 81 .

<<Third Embodiment>>
The reference electrode 240 of this embodiment will be described with reference to FIGS. 15 to 18. FIG. Below, portions different from those of the first and second embodiments will be described, and descriptions of the same portions will be omitted as appropriate.

FIG. 15 is a diagram showing a state in which the reference electrode 240 is attached to the outer ear 80. FIG. FIG. 16 is a top perspective view of the reference electrode 240. FIG. FIG. 17 is a bottom perspective view of the reference electrode 240. FIG. 18 are five views of the reference electrode 240, FIG. 18(a) is a front view, FIG. 18(b) is a left side view, FIG. 18(c) is a right side view, and FIG. 18(d) is a plan view. FIG. 18(e) is a bottom view.

The reference electrode 240 includes a mounting portion 270 and a male snap button electrode 48 , is mounted in the auricle hole 84 of the outer ear 80 and is locked to the turbinate 81 . The mounting portion 270 is made of the same resin material as in the first and second embodiments, and includes an auricle hole mounting portion 271 that is mounted in the auricle hole 84 , an extension portion 244 , and a turbinate 81 . and a turbinate attachment 245 to be locked.

The auricle hole mounting part 271 has a cylindrical base part 241 and a curved surface part 242 provided on the lower side of the base part 241 , and a part of the curved surface part 242 is fitted into the auricle hole 84 . In other words, the sizes of the base portion 241 and the curved surface portion 242 are such that they can be fitted into the auricle hole 84 .

A male snap button electrode 48 is attached to the upper surface 243 of the base 241 . A biopotential acquiring portion 246b made of the same conductive material as in the first embodiment is provided in the lower surface region of the curved surface portion 242. It contacts the via hole 84 .

The extending portion 244 extends like a plate from the upper side surface of the base portion 241 . The upper surface 243 of the base portion 241 and the upper surface of the extending portion 244 are flush with each other.

A convexly extending turbinate attachment part 245 is provided on the lower surface of the extending tip of the extending part 244 . As shown in FIGS. 17 and 18(e), the turbinate attachment part 245 has a shape that draws an arc when viewed from below, and is related to the concave shape of the crustacean 81. It is easier to stop.

A biopotential acquisition section 246a made of the same conductive material as in the first embodiment is provided at the tip of the turbinate attachment section 245 . The turbinate attachment part 245 fits into the concave shape (hollow) of the turbinate 81 when the reference electrode 240 is attached to the outer ear 80 , and the biopotential acquisition part 246 a contacts the turbinate 81 . . Note that the concha navicular mounting portion 245 may be configured as a scaphoid mounting portion that fits into the scaphoid fossa 83 . That is, by extending the extension part 244 longer, it is possible to realize a configuration in which the extension part 244 is fitted into the scaphoid fossa 83 that is longer than the distance from the auricle hole 84 to the turbinate scapula 81 .

According to this embodiment, when the reference electrode 240 is attached to the outer ear 80, the auricle hole attachment part 271 fits into the auricle hole 84, and the concha navula attachment part 245 fits into the concha navula 81. , the reference electrode 240 is locked to the outer ear 80 at two points. This provides the same effects as those of the first and second embodiments.

<<Fourth Embodiment>>
The reference electrode 340 of this embodiment will be described with reference to FIGS. 19 to 21. FIG. In the following, portions different from those of the first to third embodiments will be described, and descriptions of the same portions will be omitted as appropriate.

FIG. 19 is a diagram showing a state in which the reference electrode 340 is attached to the outer ear 80. FIG. FIG. 20 is a perspective view of the reference electrode 340. FIG. 21A and 21B are five views of the reference electrode 340, in which FIG. 21(a) is a front view, FIG. 21(b) is a left side view, FIG. 21(c) is a right side view, and FIG. FIG. 21(e) is a bottom view.

The reference electrode 340 of this embodiment has a helix mounting part 370 and a male snap button electrode 48 and is mounted on the helix 82 of the outer ear 80 .

The ear ring mounting portion 370 is made of the same resin material as the mounting portions of the first to third embodiments, and includes an ear ring mounting portion 341, a first extension portion 342, and a second extension portion. 343 integrally.

The helix fitting part 341 is a plate-shaped member that is curved to have a C-shaped cross section.

The first extending portion 342 is a plate-like body integrally extending a predetermined length from one end (here, the upper end) of the C-shaped portion of the helix fitting portion 341 . A male snap button electrode 48 is provided on an upper surface 342 a of the first extension 342 .
The second extending portion 343 is a plate-like body integrally extending a predetermined length from the other end (here, the lower end) of the C-shaped portion of the helix fitting portion 341 .
The first extending portion 342 and the second extending portion 343 are spaced apart by a predetermined distance and extend substantially in parallel with approximately the same length.

The first extending portion 342 has a projecting portion 344 projecting in the direction of the second extending portion 343 from the lower surface 342b at a position extended by a predetermined length. A biopotential acquisition section 346 made of a conductive material is provided at the tip of the projecting section 344 . The tip of the projecting portion 344 and the second extending portion 343 are separated by a predetermined distance. When the reference electrode 340 is attached to the helix 82, the tip of the protrusion 344 and the second extension 343 sandwich the outer ear 80 (region near the fossa scaphoid 83), so that the tip of the protrusion 344 of the biopotential acquisition unit 346 contacts the outer ear 80 .

According to this embodiment, in the reference electrode 340, the helix fitting portion 341 fits the helix 82, and the outer ear 80 is sandwiched between the first extension portion 342 and the second extension portion 343. can be stabilized and can be prevented from coming off due to catching or the like. Furthermore, since the biopotential acquisition part 346 of the protruding part 344 can be reliably brought into contact with the outer ear 80 and the contact state can be appropriately maintained, stable biopotential measurement (here, electroencephalogram measurement) can be realized.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than those described above can also be adopted.

This application claims priority based on Japanese Patent Application No. 2021-127438 filed on August 3, 2021, and the entire disclosure thereof is incorporated herein.

1 electroencephalogram detection system 10 electroencephalogram detection electrode 11 band member 11a band inner surface 11b band outer surface 12 protrusion 13

electrodes

14, 47 signal line 20

electroencephalogram display device

40, 140, 240, 340

reference electrode

41, 141, 241

base

44, 144a , 144b extending

portions

45, 145a, 245 concha

navicular mounting portions

46, 146a, 146b, 246a, 246b, 346 biopotential acquisition portion 48 male snap button electrode 49 female snap button electrode 50 attaching portion 51 locking portion 52 Plate-like member 60

Cable portions

70, 170, 270 Mounting portion 81 Conch navula 82 Helix 83 Scaphoid fossa 84 Auricle hole 145b Scaphoid mounting portion 242 Curved surface portion 271 Auricle hole mounting portion 341 Helix fitting portion 342 1 extension part 343 second extension part 344 projection part 370 ear ring mounting part

Claims

An electrode device that is attached to the outer ear and acquires a biopotential,
a mounting portion to be mounted in the concave shape of the outer ear;
The electrode device, comprising: a biopotential acquisition section that is provided in the attachment section and that is a portion that contacts the outer ear and is made of a conductive material.
The electrode device according to claim 1, wherein the attachment part has a conchal sac attachment part that is fitted into the conchal sac of the outer ear.
The electrode device according to claim 2, wherein the turbinate attachment part has the biopotential acquisition part.
The electrode device according to claim 1 or 2, wherein the mounting part has a scaphoid mounting part that is fitted into the scaphoid fossa of the external ear.
The electrode device according to claim 4, wherein the scaphoid attachment part has the biopotential acquisition part.
The electrode device according to claim 1 or 2, wherein the mounting part has an auricle hole mounting part that is fitted into the auricle hole of the outer ear.
The electrode device according to claim 6, wherein the auricular hole attachment part has the biopotential acquisition part.
The wearing part has a helix-wearing part to be worn on the helix of the outer ear,
The ear ring mounting part
a helix fitting portion having a C-shaped opening at the tip and into which the helix is fitted;
a first extending portion extending from one end of the helix fitting portion;
a second extending portion extending from the other tip of the helix fitting portion;
has
The first extending portion has a protrusion projecting in the direction of the second extending portion at a position extended by a predetermined length,
2. The electrode device according to claim 1, wherein said biopotential acquisition section is provided on said projecting section.
The mounting part is
a mounting portion main body made of a resin material;
3. The electrode device according to claim 1, further comprising the biopotential acquisition section provided in the attachment section main body.
The electrode device according to claim 9, wherein the biopotential acquisition section is provided by coating the surface of the mounting section body with silver paste as the conductive material.
The electrode device according to claim 9, wherein the entire mounting portion main body is made of a conductive material.
The electrode device according to claim 9, wherein the mounting portion main body is made of an elastic material.
The electrode device according to claim 12, wherein the elastic material comprises silicone resin.
The electrode device according to claim 9, further comprising a signal extraction section provided in the attachment section body for extracting the acquired biopotential to the outside.
15. The electrode device according to claim 14, further comprising a conducting member that conducts the biopotential acquisition section and the signal extraction section through the attachment section main body.
An electroencephalogram measurement device having the electrode device according to claim 1 or 2 as a reference electrode for electroencephalogram measurement.