WO2018101438A1

WO2018101438A1 - Electrode structure, biosignal measurement device, and composition for adhesive agent formation use

Info

Publication number: WO2018101438A1
Application number: PCT/JP2017/043172
Authority: WO
Inventors: 田中　秀典; 徹平荒木; 毅関谷
Original assignee: 株式会社カネカ; 国立大学法人大阪大学
Priority date: 2016-11-30
Filing date: 2017-11-30
Publication date: 2018-06-07
Also published as: JPWO2018101438A1

Abstract

The purpose of the present invention is to provide: an electrode structure which is free of the problem of dryness caused by the volatilization of water or an organic solvent and is provided with an adhesive agent layer having sufficient electrical conductivity and excellent adhesiveness; a biosignal measurement device equipped with the electrode structure; and a composition for adhesive layer formation use, which can be used suitably as an adhesive agent layer in the electrode structure. An electrode structure provided with: an electrically conductive adhesive agent layer; a support for supporting the adhesive agent layer; and a wiring line or a terminal which is connected to the adhesive agent layer. In the electrode structure, the content of water and an organic solvent in the adhesive agent layer is 10% by mass or less and the volume resistivity of the adhesive agent layer is 1500 Ωcm or less.

Description

Electrode structure, biological signal measuring device, and adhesive forming composition

The present invention relates to an electrode structure, a biological signal measuring device, and a composition for forming an adhesive.

Conventionally, in order to acquire a biological signal, a skin surface electrode using a paste or a dry electrode for closely attaching a metal needle to the skin is used.

The paste used for the skin surface electrode is often prepared using a polymer and an organic solvent or using a water-soluble polymer and water. For example, Patent Document 1 discloses a biosignal measurement electrode paste prepared using a water-soluble polymer and water.

Further, as a dry electrode including a metal needle, Patent Document 2 discloses a sword-mount type electrode for bioelectric signal measurement including a plurality of needle-like electrode portions. The dry electrode described in Patent Document 2 is used by being fixed with a hair band, a headband, a velcro tape, a stocking band, or the like while being pressed against the scalp, for example.
However, the skin surface electrode using the paste may have a problem of irritation or discomfort depending on the type of polymer contained in the paste, or may have a problem of drying of the paste due to volatilization of water or an organic solvent during long-time measurement. .
Further, the dry electrode has problems such as discomfort caused by contact of the metal needle with the skin and generation of noise due to low adhesion to the skin.

JP 2013-034699 A JP 2012-019962 A

The present invention has been made in view of the above-described problems, and there is no problem of drying due to volatilization of water or an organic solvent, and an electrode structure including an adhesive layer exhibiting sufficient conductivity and excellent adhesiveness. Another object of the present invention is to provide a biological signal measuring device including the electrode structure, and a composition for forming an adhesive that is suitably used as an adhesive layer in the electrode structure.

As a result of intensive studies to solve the above problems, the present inventors have found the following and completed the present invention.
That is, the present invention
(I) An electrode structure comprising a conductive pressure-sensitive adhesive layer, a support that supports the pressure-sensitive adhesive layer, and a wiring or a terminal connected to the pressure-sensitive adhesive layer,
The content of water and organic solvent in the pressure-sensitive adhesive layer is 10% by mass or less,
The volume resistivity of the pressure-sensitive adhesive layer is 1500 Ωcm or less,
The pressure-sensitive adhesive layer consists of a cured product of a composition containing a polyoxyalkylene polymer (A) and a conductive filler (B),
An electrode structure, wherein the conductive filler (B) comprises a conductive polymer and / or a conductive carbon material;
(II) The polyoxyalkylene polymer (A) has the formula (1):
—CH ₂ —C (R ¹ ) ═CH ₂ (1)
(In Formula (1), R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)
The electrode structure according to (I), having one or more groups represented by:
(III) The pressure-sensitive adhesive layer comprises a cured product of a composition containing a polyoxyalkylene polymer (A), a conductive filler (B), a silicone compound (C), and a hydrosilylation catalyst (D). ,
The polyoxyalkylene polymer (A) has the formula (1):
—CH ₂ —C (R ¹ ) ═CH ₂ (1)
(In Formula (1), R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)
Having one or more groups represented by
The electrode structure according to (I) or (II), wherein the silicone compound (C) has 1 to 10 hydrosilyl groups in the molecule.
(IV) The electrode structure according to any one of (I) to (III), wherein the polyoxyalkylene polymer (A) is a polyoxypropylene polymer (A1),
(V) The electrode structure according to any one of (I) to (IV), wherein the conductive filler (B) includes a conductive polymer;
(VI) the conductive polymer is composed of poly (3,4-ethylenedioxythiophene), polyacetylene, polythiophene, poly (p-phenylene), polyfluorene, poly (p-phenylenevinylene), polyethylene vinylene, polypyrrole, and polyaniline The electrode structure according to (V), comprising one or more selected from the group consisting of:
(VII) The electrode structure according to (V) or (VI), wherein the conductive filler (B) contains a dopant,
(VIII) The electrode structure according to (VII), wherein the conductive filler (B) contains poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid as a dopant,
(IX) The content of the conductive filler (B) in the composition 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). Electrode structure,
(X) The electrode structure according to any one of (I) to (IX), wherein the composition contains a metal salt (E),
(XI) Metal salt (E) is silver chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, iron (III) chloride, iron (II) chloride, copper (II) chloride, copper (I) chloride, and chloride The electrode structure according to (X), which is at least one selected from the group consisting of zinc;
(XII) The content of the metal salt (E) in the composition is 0.01 to 10 parts by mass with respect to 100 parts by mass of the polyoxyalkylene polymer (A). XI),
(XIII) The electrode structure according to any one of claims (I) to (XII), wherein the polyoxyalkylene polymer (A) has a number average molecular weight of 3,000 or more,
(XIV) The total amount of hydrosilyl groups of the silicone compound (C) per mol of the total amount of alkenyl groups derived from the polyoxyalkylene polymer (A) is 0.1 to 2.0 mol, (III) to (III) XIII), the electrode structure according to any one of
(XV) The electrode structure according to any one of (I) to (XIV), wherein the conductive adhesive layer has a thickness of 1 to 500 μm,
(XVI) a biological signal measuring device comprising the electrode structure according to any one of (I) to (XV),
(XVII) A pressure-sensitive adhesive-forming composition comprising a polyoxyalkylene polymer (A) and a conductive filler (B),
The conductive filler (B) includes a conductive polymer and / or a conductive carbon material,
A composition that gives a pressure-sensitive adhesive whose volume resistivity is 1500 Ωcm or less by being cured,
I will provide a.

According to the present invention, there is no problem of drying due to volatilization of water or an organic solvent, and an electrode structure including an adhesive layer exhibiting sufficient conductivity and excellent adhesiveness, and a biological signal including the electrode structure A measuring apparatus and the composition for adhesive formation used suitably as an adhesive layer in the said electrode structure can be provided.

≪Electrode structure≫
The electrode structure includes a conductive pressure-sensitive adhesive layer, a support that supports the pressure-sensitive adhesive layer, and a wiring or a terminal connected to the pressure-sensitive adhesive layer.
By providing the conductive adhesive layer, the electrode structure can be used by being attached to the skin of humans and other various animals, for example. The application target of the electrode structure is not limited to a living body, and may be various structures made of an organic material or an inorganic material.

The purpose of use of the electrode structure is not particularly limited.
The electrode structure is typically
1) The purpose of giving an electric signal such as a current sent to the adhesive layer through the wiring or terminal to the application target of the electrode structure, or
2) The purpose of collecting electrical signals such as currents generated by the application target of the electrode structure and sending the collected electrical signals to various devices that process the electrical signals through wires or terminals,
Used in.

The volume resistivity of the pressure-sensitive adhesive layer is 1500 Ωcm or less. For this reason, in an electrode structure provided with such an adhesive layer, an electric signal is satisfactorily transmitted or received through the adhesive layer.
The volume resistivity of the pressure-sensitive adhesive layer is preferably 1000 Ωcm or less, and more preferably 500 Ω or less.

Moreover, content of the water and organic solvent in an adhesive layer is 10 mass% or less. For this reason, even when the electrode structure is used for a long period of time, problems such as peeling from the application target of the electrode structure and fluctuation of the volume resistivity of the pressure-sensitive adhesive layer due to volatilization of water and the organic solvent hardly occur. .
However, the organic solvent does not include polyethylene glycol described later.

<Adhesive layer>
The material of the pressure-sensitive adhesive layer has desired adhesiveness, exhibits a volume resistivity within the above predetermined range, and the contents of water and organic solvent are within the above predetermined range.
By changing the type and amount of the main material and conductive material as appropriate, it is easy to adjust various properties such as adhesiveness, mechanical properties, and conductivity. A material in which a conductive substance is dispersed in the main material is used.

Specifically, an adhesive layer consists of hardened | cured material of the composition containing a polyoxyalkylene type polymer (A) and an electroconductive filler (B).
Hereinafter, the components contained in the composition used for forming the pressure-sensitive adhesive layer 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 alkylene group as R ² has 1 to 14 carbon atoms, preferably 2 to 4 carbon atoms.

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, JP-B-46-27250, JP-B-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, The polymerization method using a double metal cyanide complex catalyst shown in each publication of 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, and more preferably 3,000 to 50,000 as the molecular weight in terms of polystyrene measured by GPC. 000 is particularly preferred, and 3,000 to 30,000 is most preferred.

If the number average molecular weight is too small, it may be difficult to form a pressure-sensitive adhesive layer having excellent stretchability using a composition containing the polyoxyalkylene polymer (A).
If the number average molecular weight is excessive, the pressure-sensitive adhesive layer formation method may be required due to the high viscosity of the polyoxyalkylene polymer (A).

The molecular weight distribution of the polyoxyalkylene polymer (A) is not particularly limited, but is preferably narrow, preferably less than 2.00, more preferably 1.60 or less, and particularly preferably 1.40 or less.
If the molecular weight distribution is too wide, the pressure-sensitive adhesive layer formation method may be required due to the high viscosity of the polyoxyalkylene polymer (A).

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). ˜5 are more preferred, 1 to 3 are more preferred, and 1 to 2 are particularly preferred.

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 filler (B))
The composition used for forming the pressure-sensitive adhesive layer preferably contains a conductive filler (B) together with the polyoxyalkylene polymer (A).
The conductive filler (B) contains a conductive polymer and / or a conductive carbon material. The conductive filler (B) may contain other conductive materials other than the conductive polymer and / or the conductive carbon material as long as the object of the present invention is not impaired. The other conductive material is not particularly limited as long as it is made of a material generally recognized as having conductivity. The other conductive material may be an organic material or an inorganic material.
The content of the conductive polymer and / or other conductive material other than the conductive carbon material in the conductive filler (B) is typically preferably 20% by mass or less, more preferably 10% by mass or less, 5 mass% or less is still more preferable, and 0 mass% is the most preferable.

Examples of the conductive carbon material include carbon black, carbon fiber, graphite, and carbon nanomaterial.
The conductive carbon material may contain a small amount of organic groups as long as the main skeleton does not contain organic groups.

Among conductive carbon materials, nanocarbon materials are preferred because they can easily reduce the volume resistivity of the pressure-sensitive adhesive layer to a desired level 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 an adhesive layer having a low volume resistivity.

The conductive polymer is not particularly limited as long as it is a polymer material having conductivity. Specific examples of the conductive polymer include polyacetylene, polythiophene, poly (3,4-ethylenedioxythiophene) (hereinafter also referred to as PEDOT), poly (p-phenylene), polyfluorene, and 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 forming the pressure-sensitive adhesive layer may contain two or more types of polymers as the conductive polymer.

When the conductive filler (B) is a conductive polymer, it is preferable that the conductive filler (B) contains a tomato together with the conductive polymer because an adhesive layer having a desired volume resistivity is easily formed. . The dopant is a component that enhances the conductivity of the conductive polymer.

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 can easily form a pressure-sensitive adhesive layer having a desired volume resistance value.
Hereinafter, the combination of PEDOT and PSS as the conductive filler is also referred to as PEDOT / PSS.

The production method of PEDOT / PSS is not particularly limited, and examples thereof include a chemical polymerization method, an electrolytic polymerization method, and a gas phase polymerization method.

In the conductive filler (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 the conductive polymer: dopant. .

The method of mixing the conductive filler (B) described above with the polyoxyalkylene polymer (A) is not particularly limited as long as a pressure-sensitive adhesive layer exhibiting a desired volume resistivity can be formed using a composition containing them. .

For example, after mixing the dispersion liquid of an electroconductive filler (B) with a polyoxyalkylene 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 an alcohol, more preferably 2-propanol or ethanol, and further preferably a mixed solvent of 2-propanol and ethanol.
The above alcohol is particularly preferable as a dispersion medium when PEDOT is used as a conductive filler.

In addition, 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 By mixing the coalesced (A) and the solid conductive filler (B) or the dispersion of the conductive filler (B) by a kneader such as a Hoover type Mahler, two rolls, three rolls, etc. The conductive filler (B) can also be dispersed in the polyoxyalkylene polymer (A).
It is preferable that water and an organic solvent are distilled off from the composition after the dispersion treatment of the conductive filler (B).

The content of the conductive filler (B) in the composition used for forming the pressure-sensitive adhesive layer is particularly as long as the pressure-sensitive adhesive layer having a desired value of volume resistivity and a desired pressure-sensitive adhesive layer can be formed. It is not limited.
The usage-amount of an electroconductive filler (B) is suitably set considering the volume resistivity of the adhesive layer formed.
The content of the conductive filler (B) in the composition is based on 100 parts by mass of the polyoxyalkylene polymer (A) from the viewpoint of the balance of the adhesiveness, conductivity, and mechanical properties of the adhesive layer. 3 parts by mass or more and 200 parts by mass or less is preferable.
The content of the conductive filler (B) in the composition may be 5 parts by mass or more, 8 parts or more, or 10 parts by mass with respect to 100 parts by mass of the polyoxyalkylene polymer (A). Or more.
The content of the conductive filler (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 with respect to 100 parts by mass of the polyoxyalkylene polymer (A). The following is more preferable, 50 parts by mass or less is even more preferable, and 20 parts by mass or less is particularly preferable.

When the conductive filler (B) is a conductive polymer or a combination of a conductive polymer and a dopant, the content of the conductive filler (B) is 100 parts by mass of the polyoxyalkylene polymer (A). It is preferably 3 to 100 parts by mass, more preferably 3 to 50 parts by mass, and particularly preferably 3 to 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 volume resistivity of the pressure-sensitive adhesive layer with the desired tackiness.

(Silicone compound (C))
The composition used for forming the pressure-sensitive adhesive layer preferably contains the silicone compound (C) together with the polyoxyalkylene polymer (A) and the conductive filler (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 properties suitable as an adhesive layer 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 2-8.
By using the silicone compound (C) having a number of hydrosilyl groups within such a range, a pressure-sensitive adhesive layer having both good strength and good stretchability can be easily formed.

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 value obtained by titration is preferably 400 to 3,000, more preferably 500 to 2,000.
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 an adhesive in a short time while suppressing volatilization of the silicone compound (C) during curing.

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 to 50. 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 methyl hydrogen silicone corresponds to a compound in which R ³ is all H, and is also described in “Silicon Market Outlook-Maker Strategy and Application Development” published 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) and the silicone compound (C) in the composition used for forming the pressure-sensitive adhesive layer 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 a pressure-sensitive adhesive layer 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 to 2.0 mol, more preferably 0.4 to 1.5 mol.

(Hydrosilylation catalyst (D))
The composition used for forming the pressure-sensitive adhesive layer contains the hydrosilylation catalyst (D) together with the polyoxyalkylene polymer (A), the conductive filler (B), and the silicone compound (C). preferable.

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 (eg, Pt ₁ (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 conjugated base of a strong acid as a ligand is preferable, a platinum-vinylsiloxane complex is more preferable, and platinum-1,3-divinyl-1,1 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 to 10 ⁻¹ mol, more preferably with respect to ¹ mol of the total amount of alkenyl groups of the polyoxyalkylene polymer (A). Is 10 ⁻⁶ to 10 ⁻² mol.
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 pressure-sensitive adhesive layer, 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.

The storage stabilizer suppresses the conversion of hydrosilyl groups (Si-H groups) to Si-OH groups in the silicone compound (C) (due to standing for a long time or mixing of moisture), and the pot life of the 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)
The composition used for forming the pressure-sensitive adhesive layer preferably 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 filler 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, it is easy to form an adhesive layer having a low volume resistivity by blending polyethylene glycol (PEG) having a high boiling point into the composition used for forming the adhesive layer.

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 addition amount of PEG is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the polyoxyalkylene polymer (A).
By using the amount of PEG in such a range, the PEG is compatible with the polyoxyalkylene polymer (A), thereby obtaining a desired effect relating to a decrease in volume resistivity and having a desired adhesiveness. Easy to form a layer.

(Other materials)
The composition used for forming the pressure-sensitive adhesive layer 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 pressure-sensitive adhesive layer may be formed by photocuring by reacting the alkenyl groups represented by (1).

Moreover, the composition used for forming the pressure-sensitive adhesive layer may contain a metal salt (E). When a biological signal is acquired using an electrode structure including an adhesive layer containing a metal salt (E) formed using such a composition, the biological signal is stably and satisfactorily reduced while reducing noise in the biological signal. Easy to get.

The metal salt (E) 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 (E) 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 (E) include chloride ions, bromide ions, iodide ions, fluoride ions, sulfate ions, sulfite ions, hydrogen sulfate ions, phosphate ions, nitrate ions, carbonate ions. And inorganic anions such as bicarbonate ion, acetate ion, formate ion, propionate ion, butyrate ion, valerate ion, isovalerate ion, lactate ion, oxalate ion, trichloroacetate ion, dichloroacetate ion, monochloroacetate Ion, trifluoroacetate ion, difluoroacetate ion, monofluoroacetate ion, benzoate ion, salicylate ion, methanesulfonate ion, ethanesulfonate ion, trifluoromethanesulfonate ion, benzenesulfonate ion, toluenesulfonate ion, etc. Organic anio And the like.

Since it is easy to obtain a biological signal stably and satisfactorily using an electrode structure having an adhesive layer, the metal salt (E) is a metal such as a metal chloride, metal bromide, metal iodide, or metal fluoride. Halogen compounds 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.

The usage-amount of the metal salt (E) in the composition used for formation of an adhesive layer is not specifically limited in the range which does not inhibit the objective of this invention. The amount of the metal salt (E) used is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 8 parts by mass with respect to 100 parts by mass of the polyoxyalkylene polymer (A). Part is particularly preferred.
When the amount of the metal salt (E) used 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 an adhesive layer that is not brittle is easily formed.

Furthermore, in addition to the components described above, the composition used for forming the pressure-sensitive adhesive layer 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.

(Method for forming pressure-sensitive adhesive layer)
The formation method of an adhesive layer is not specifically limited. Typically, the pressure-sensitive adhesive layer 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 filler (B), a silicone compound (C) having a hydrosilyl group, a hydrosilylation catalyst ( D), the curing conditions include heating at 40 to 180 ° C. for 1 to 180 minutes.
If it is desired to complete the curing, it may be left at 40 to 80 ° C. for several days.

The pressure-sensitive adhesive layer is preferably formed by applying a composition for forming a pressure-sensitive adhesive layer on a support described later, and then curing the resulting coating film.
The pressure-sensitive adhesive layer is preferably formed by, for example, applying a composition for forming a pressure-sensitive adhesive layer on a substrate such as a glass plate or a metal plate, and then curing the obtained coating film.
After the pressure-sensitive adhesive layer is formed on the substrate different from the support by such a method, the pressure-sensitive adhesive layer is peeled off from the substrate, and the obtained pressure-sensitive adhesive layer is laminated on the support described later.
The method for applying the composition for forming the pressure-sensitive adhesive layer is not particularly limited, and various coating methods and printing methods can be applied.
When applying the composition for forming the pressure-sensitive adhesive layer, it is also preferable to form a coating film while applying a shearing force in a certain direction to the composition, for example, by rubbing a blade against the composition. In this case, the conductive filler (B) is easily oriented in the coating film, and the volume resistivity of the formed pressure-sensitive adhesive layer is easily lowered by forming a conductive path in a good state.

The thickness of the adhesive layer is not particularly limited. The thickness of the pressure-sensitive adhesive layer is typically preferably 1 to 500 μm, and more preferably 10 to 100 μm.

<Support>
The support is provided in contact with the pressure-sensitive adhesive layer and supports the pressure-sensitive adhesive layer. Usually, an adhesive layer is supported on a support body by the adhesive force of an adhesive layer.
When the adhesive strength of the pressure-sensitive adhesive layer to the support is insufficient, the pressure-sensitive adhesive layer may be fixed on the support using an adhesive. A locking portion for locking the pressure-sensitive adhesive layer is provided on the support. The adhesive layer may be fixed on the support. Alternatively, for example, a locking tool such as a clip may be prepared separately from the support, and the adhesive layer may be fixed on the support with the locking tool. .

The support is typically a film and is preferably a resin film. Examples of the resin film material include polyester resins (for example, polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate), polyolefins (polyethylene, polypropylene), polystyrene, cyclic olefin resins, polyamide resins (nylon resins), and polycarbonate resins. , Acrylic resin, polyacetal resin, and fluororesin.

The shape and size of the support and the pressure-sensitive adhesive layer are appropriately selected according to the use of the electrode structure. The size of the support is not particularly limited as long as it can support the pressure-sensitive adhesive layer. The support preferably supports the pressure-sensitive adhesive layer in close contact with the entire surface of one main surface of the pressure-sensitive adhesive layer.
The area of the main surface of the support is preferably not less than the area of the main surface of the pressure-sensitive adhesive layer. The area of the main surface of the support and the area of the main surface of the pressure-sensitive adhesive layer are preferably the same or substantially the same.

The thickness of the support is not particularly limited. The thickness of the support is typically preferably 1 to 1000 μm and more preferably 5 to 500 μm from the viewpoint of the balance between mechanical strength and flexibility.

<Wiring or terminal>
In the electrode structure, the wiring or terminal is connected to the adhesive layer. The material of the wiring or terminal is not particularly limited, and is appropriately selected from materials generally used for forming electrical wiring, such as copper and aluminum.
Since it is easy to attach the electrode structure to the application target of the electrode structure, the wiring or the terminal is in contact with the side surface (the surface that is not the main surface) of the adhesive layer or the support of the adhesive layer. It is preferably connected to the main surface on the side.
The formation method of wiring or a terminal is not specifically limited. For example, when a wiring is formed using a metal wire or a terminal is formed using a needle-like metal member, a metal wire or a needle-like metal member may be inserted into the adhesive layer.
Alternatively, a wiring or a terminal may be formed by drawing a pattern of a conductive material on a surface of the support in contact with the pressure-sensitive adhesive layer by a method such as a printing method.
In such a case, the pattern of the conductive material protrudes from a blank portion generated when the adhesive layer and the support layer are laminated using a support having a major surface area larger than the area of the main surface of the adhesive layer. By forming the pattern in this way, the pattern of the conductive material on the margin can be used as a wiring or a terminal.

<Application of electrode structure>
Since the electrode structure described above includes a pressure-sensitive adhesive layer having a low volume resistivity and good adhesiveness, the electrode structure is attached to various application objects to give an electric signal to the application object, or from the application object. It is suitably used as an electrode for acquiring an electrical signal.
In particular, since the pressure-sensitive adhesive layer adheres well to living skin such as human skin, for example, the electrode structure described above serves as an electrode for giving an electrical signal to the living body or acquiring an electrical signal from the living body. Preferably used.
For this reason, for example, the above electrode structure is suitably used as an electrode for a biological signal measuring device.
Examples of the biological signal measuring device include a stationary electrocardiograph, an electroencephalograph, and an electromyograph that have been conventionally used.
The electrode structure can also be used as a biological electrode of a wearable biological signal measuring apparatus that has been actively developed in recent years.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.

[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 weight of n-hexane and 300 parts by weight of water with respect to 100 parts by weight 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.
Thus, 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 an allyl group at one end 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 2 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 (I) chloride (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) 500 parts by weight of the dispersed solution (containing 5 parts by weight of PEDOT / PSS (B-1)) was added and stirred.
Note that PEDT / PSS (B-1) and PEDOT: PSS (mass ratio) were 1: 2.5.
After stirring, 2-propanol and ethanol were removed by an evaporator at 80 ° C. to obtain a mixture of a polyoxypropylene polymer and PEDOT / PSS (B-1).

To the obtained mixture, platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (3 mass% platinum isopropanol solution) (D-1) as a platinum catalyst (D) was polyoxypropylene. 1000 μL of the polymer (A1-1 and A1-2) was added with respect to 100 parts by mass.
After adding a mixture of polyoxypropylene polymer (A1-1 and A1-2), PEDOT / PSS (B-1) and platinum catalyst (D-1) to the disposable cup, polyoxypropylene After adding 3.2 parts by mass of silicone compound (C-1) and 1.0 part by mass of dimethyl maleate to 100 parts by mass of polymer (A1-1 and A1-2), cup The mixture inside was stirred with a spatula for 5 minutes to obtain a composition for forming an adhesive layer.

Using the obtained composition, volume resistivity and peelability (skin residue) were evaluated according to the methods described below. These evaluation results are shown in Table 1.

[Example 2]
When a solution in which PEDOT / PSS (B-1) is dispersed is added to the polyoxypropylene polymer (A1-1 and A1-2), polyethylene glycol (G-1) (PEG200, manufactured by Wako Pure Chemical Industries, Ltd.) ) A composition for forming a pressure-sensitive adhesive layer was obtained in the same manner as in Example 1 except that 30 parts by mass and the amount of dimethyl maleate used were changed to 0.02 parts by mass.

Example 3
Formation of an adhesive layer in the same manner as in Example 2 except that polyethylene glycol (G-1) (PEG 200, manufactured by Wako Pure Chemical Industries) was changed to polyethylene glycol (G-2) (PEG 400, manufactured by Wako Pure Chemical Industries). A composition for use was obtained.

Example 4
Formation of an adhesive layer in the same manner as in Example 2 except that polyethylene glycol (G-1) (PEG200, manufactured by Wako Pure Chemical Industries) was changed to polyethylene glycol (G-3) (PEG 600, manufactured by Wako Pure Chemical Industries). A composition for use was obtained.

Example 5
The concentration of PEDOT / PSS (B-1) in the dispersion in 2-propanol and ethanol was changed from 1 wt% to 1.6 wt%, and the amount of the silicone compound (C-1) used was 3.2 masses. A composition for forming an adhesive layer was obtained in the same manner as in Example 1 except that the amount was changed from 2.5 parts to 2.5 parts by mass.

Example 6
The concentration of PEDOT / PSS (B-1) in the dispersion in 2-propanol and ethanol was changed from 1 wt% to 2 wt%, and the amount of silicone compound (C-1) used was changed from 3.2 parts by mass. A composition for forming an adhesive layer was obtained in the same manner as in Example 1 except that the content was changed to 2.5 parts by mass.

Example 7
Carbon black (B-2) with respect to a total of 100 parts by mass of 91.3 parts by mass of the polyoxypropylene polymer (A1-1) and 8.7 parts by mass of the polyoxypropylene polymer (A1-2) 3 parts by mass (Ketjen Black EC600JD, manufactured by Lion Specialty Chemicals) was added and mixed with stirring.
As a platinum catalyst (D), a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (3 mass% platinum isopropanol solution) (D-1) was used as a polyoxypropylene polymer (A1- 1) 500 μL was added to 100 parts by mass.
After adding 1.92 parts by mass of the silicone compound (C-1) and 0.02 parts by mass of dimethyl maleate to the polyoxypropylene polymer (A1-1), the mixture is stirred with a spatula for 5 minutes. A composition for forming an adhesive layer was obtained.

Example 8
The concentration of PEDOT / PSS (B-1) in the dispersion in 2-propanol and ethanol was changed from 1 wt% to 1.1 wt%, and the amount of silicone compound (C-1) used was 3.2 masses. Part to 2.46 parts by mass, and in addition to adding 6.9 parts by mass of silver chloride (I) (E-1) obtained in Synthesis Example 5, the same procedure as in Example 1 was performed. Thus, a composition for forming an adhesive layer was obtained.

[Comparative Example 1]
The concentration of PEDOT / PSS (B-1) in the dispersion in 2-propanol and ethanol was changed from 1 wt% to 0.2 wt%, and the amount of silicone compound (C-1) used was changed to polyoxy Changing from 3.2 parts by weight to 2.5 parts by weight with respect to 100 parts by weight of the propylene-based polymers (A1-1 and A1-2), and platinum-1,3-divinyl-1,1,3 , 3-tetramethyldisiloxane complex (3 mass% platinum isopropanol solution) (D-1) is used in an amount of 1000 μL to 100 parts by mass of the polyoxypropylene polymer (A1-1 and A1-2). A composition for forming an adhesive layer was obtained in the same manner as in Example 1 except that the amount was changed to 100 μL.

Using the obtained composition, volume resistivity and peelability (skin residue) were evaluated according to the methods described below. These evaluation results are shown in Table 2.

[Comparative Example 2]
Adhesive as in Comparative Example 1, except that the concentration of PEDOT / PSS (B-1) in the dispersion in 2-propanol and ethanol was changed from 0.2% by mass to 0.56% by mass. A layer forming composition was obtained.

[Comparative Example 3]
To 100 parts by mass of the polyoxypropylene polymer (A1-1), 3 parts by mass of silver powder (Silcoat AgC-G) manufactured by Fukuda Metal Foil Industry Co., Ltd. was added and mixed with stirring.
As a platinum catalyst (D), a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (3 mass% platinum isopropanol solution) (D-1) was used as a polyoxypropylene polymer (A1- 1) 500 μL was added to 100 parts by mass.
Silicone compound (C-1) 1 with respect to polyoxypropylene polymer (A1-1)
. After adding 76 mass parts and 0.1 mass part of dimethyl maleate, it stirred for 5 minutes with the spatula, and obtained the composition for adhesive layer formation.

[Comparative Example 4]
A composition for forming a pressure-sensitive adhesive layer was obtained in the same manner as in Comparative Example 3 except that the amount of sill coat AgC-G was changed to 5 parts by mass.
Using the obtained composition, volume resistivity and peelability (remaining skin) were evaluated according to the method described later. These evaluation results are shown in Table 2.

[Comparative Example 5]
A composition for forming a pressure-sensitive adhesive layer was obtained in the same manner as in Comparative Example 3 except that the amount of sill coat AgC-G was changed to 10 parts by mass.
Using the obtained composition, volume resistivity and peelability (remaining skin) were evaluated according to the method described later. These evaluation results are shown in Table 2.

(Volume resistivity)
The composition is coated on a glass substrate with a major axis direction of 25 mm, a minor axis direction of 5 mm, and a thickness of 50 μm, heated at 120 ° C. for 5 minutes, and then cured by heating at 40 ° C. for 24 hours to form an adhesive layer Formed.

The pressure-sensitive adhesive layer was formed according to the following method.
First, along the long axis direction of the pressure-sensitive adhesive layer to be formed, two tapes having a length of 25 mm and a thickness of 50 μm are arranged so that the distance between the two tapes is 5 mm and the two tapes are parallel to each other. Pasted on a glass substrate.
Next, the composition was deposited at a position corresponding to one end of the pressure-sensitive adhesive layer to be formed.
By rubbing the deposited composition from one end to the other end on the glass substrate with a spatula, the conductive filler (B) in the composition is oriented on the glass substrate. The composition was applied.
The formed coating film was cured under the above conditions to obtain an adhesive layer.

A silver paste was applied to the end of the pressure-sensitive adhesive layer in the major axis direction, and a tester probe was brought into contact with the room temperature dry silver paste to measure the electric resistance value of the cured product.
The volume resistivity (Ωcm) was calculated from the obtained electric resistance value and the size of the cured product.

(Peelability (remaining skin))
The composition was coated on paper with an applicator having a coating thickness of 25 μm, heated at 120 ° C. for 5 minutes, and then cured by heating at 40 ° C. for 24 hours to obtain an adhesive layer.
After sticking the release film on the pressure-sensitive adhesive layer, the film was peeled off to determine whether the pressure-sensitive adhesive layer was transferred to the release film.
The case where the pressure-sensitive adhesive layer was not transferred to the release film was evaluated as ◎, and the case where the pressure-sensitive adhesive layer was slightly transferred to the release film was evaluated as ◯.

As shown in Table 1, by using the compositions of Examples 1 to 8, the volume resistivity is low enough to be used for, for example, obtaining a biological signal. A pressure-sensitive adhesive layer that is not transferred and is suitably used in a bioelectrode was obtained.

As Comparative Examples 1 and 2, an example of forming a pressure-sensitive adhesive layer having a volume resistivity exceeding 1500 Ωcm while containing a conductive polymer was shown. However, the type of the conductive filler (B) was changed, Even when the amount of the conductive filler (B) used is less than 3 parts by mass relative to 100 parts by mass of the polyoxyalkylene polymer (A), the volume resistivity is 1500 Ωcm or less. An adhesive layer can be formed.

Claims

An electrode structure comprising a conductive pressure-sensitive adhesive layer, a support that supports the pressure-sensitive adhesive layer, and a wiring or a terminal connected to the pressure-sensitive adhesive layer,
The water and organic solvent content in the pressure-sensitive adhesive layer is 10% by mass or less,
The volume resistivity of the pressure-sensitive adhesive layer is 1500 Ωcm or less,
The pressure-sensitive adhesive layer comprises a cured product of a composition containing a polyoxyalkylene polymer (A) and a conductive filler (B),
The electrode structure in which the conductive filler (B) contains a conductive polymer and / or a conductive carbon material.
The polyoxyalkylene polymer (A) is represented by the formula (1):
—CH 2 —C (R 1 ) ═CH 2 (1)
(In Formula (1), R 1 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)
The electrode structure according to claim 1, comprising at least one group represented by the formula:
The pressure-sensitive adhesive layer comprises a cured product of a composition comprising a polyoxyalkylene polymer (A), a conductive filler (B), a silicone compound (C), and a hydrosilylation catalyst (D),
The polyoxyalkylene polymer (A) is represented by the formula (1):
—CH 2 —C (R 1 ) ═CH 2 (1)
(In Formula (1), R 1 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)
Having one or more groups represented by
The electrode structure according to claim 1 or 2, wherein the silicone compound (C) has 1 to 10 hydrosilyl groups in a molecule.
The electrode structure according to any one of claims 1 to 3, wherein the polyoxyalkylene polymer (A) is a polyoxypropylene polymer (A1).
The electrode structure according to any one of claims 1 to 4, wherein the conductive filler (B) contains a conductive polymer.
The conductive polymer is a group consisting of poly (3,4-ethylenedioxythiophene), polyacetylene, polythiophene, poly (p-phenylene), polyfluorene, poly (p-phenylene vinylene), polyethylene vinylene, polypyrrole, and polyaniline. The electrode structure according to claim 5, comprising one or more selected from the above.
The electrode structure according to claim 5 or 6, wherein the conductive filler (B) contains a dopant.
The electrode structure according to claim 7, wherein the conductive filler (B) contains poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid as the dopant.
The content of the conductive filler (B) in the composition 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). Electrode structure.
10. The electrode structure according to claim 1, wherein the composition contains a metal salt (E).
The metal salt (E) is silver chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, iron (III) chloride, iron (II) chloride, copper (II) chloride, copper (I) chloride, and zinc chloride. The electrode structure according to claim 10, wherein the electrode structure is at least one selected from the group consisting of:
The content of the metal salt (E) in the composition is 0.01 to 10 parts by mass with respect to 100 parts by mass of the polyoxyalkylene polymer (A). Electrode structure.
The electrode structure according to any one of claims 1 to 12, wherein the polyoxyalkylene polymer (A) has a number average molecular weight of 3,000 or more.
The total amount of hydrosilyl groups of the silicone compound (C) per 0.1 mol of the total amount of alkenyl groups derived from the polyoxyalkylene polymer (A) is 0.1 to 2.0 mol. The electrode structure according to any one of the above.
The electrode structure according to any one of claims 1 to 14, wherein a thickness of the conductive pressure-sensitive adhesive layer is 1 to 500 µm.
A biological signal measuring device comprising the electrode structure according to any one of claims 1 to 15.
A pressure-sensitive adhesive forming composition comprising a polyoxyalkylene polymer (A) and a conductive filler (B),
The conductive filler (B) includes a conductive polymer and / or a conductive carbon material,
The composition which gives the adhesive whose volume resistivity is 1500 ohm-cm or less by being hardened | cured.