CN118146606A

CN118146606A - Bioelectrode composition, bioelectrode, and bioelectrode manufacturing method

Info

Publication number: CN118146606A
Application number: CN202311647024.1A
Authority: CN
Inventors: 畠山润; 长泽贤幸; 池田让
Original assignee: Shin Etsu Chemical Co Ltd
Current assignee: Shin Etsu Chemical Co Ltd
Priority date: 2022-12-05
Filing date: 2023-12-04
Publication date: 2024-06-07

Abstract

The present invention relates to a biological composition, a biological electrode, and a method for producing a biological electrode. The present invention provides a bioelectrode composition, a bioelectrode, and a bioelectrode manufacturing method, which are thin films, high in transparency, high in sensitivity of a bioelectric signal, excellent in biocompatibility, light in weight, and capable of being manufactured at low cost, and even if the bioelectrode composition is wetted with water for a long period of time and is attached to skin for a long period of time, the sensitivity of the bioelectric signal is not greatly reduced, and skin itching, erythema and eruption are avoided, and the bioelectrode is comfortable. A bioelectrode composition comprising (A) a pi-conjugated polymer; (B) A conductive polymer composite containing a dope polymer which contains a repeating unit a1 having a hydroxyl group and/or a carboxyl group, and a repeating unit a2 having a sulfonic acid, a fluorosulfonyl imide, and an N-carbonyl fluorosulfonamide, and has a weight average molecular weight in the range of 1,000 ～ 500,000; and (C) a crosslinking agent.

Description

Bioelectrode composition, bioelectrode, and bioelectrode manufacturing method

Technical Field

The present invention relates to a bioelectrode composition, a bioelectrode, and a bioelectrode manufacturing method.

Background

In recent years, along with the popularization of IoT (Internet of Things), development of wearable devices has been actively performed. In the medical field and the sports field, there is also a need for a wearable device capable of monitoring the physical state at any time, which is a growing field in the future. In particular, the worldwide spread of new coronaruses (COVID-19) causes severe medical loads, and there is a call for the necessity of home medical treatment of people not infected with viruses and acceleration thereof.

In the medical field, for example, as electrocardiographic measurement for sensing heart beats by using electric signals, there are commercially available wearable devices for monitoring the state of a body organ by sensing weak current. Electrocardiogram is measured by attaching electrodes coated with hydrated gel to the body, which is a short measurement of only 1 time. In contrast, the development of wearable devices for medical use as described above has been aimed at developing devices for monitoring health status at any time for several consecutive weeks. Therefore, a bioelectrode used in a wearable medical device is required to be able to collect a bioelectric signal, free from itching, free from skin allergy, and comfortable even when used for a long period of time in daily life such as shower, bath, perspiration, and the like. In addition, the disposable diaper is required to be light and thin to such an extent that it is free from wearing feeling, and to be manufactured at low cost and with high productivity.

APPLE WATCH a clock-type device, and a noncontact type sensing using a radar, have been used to measure an electrocardiogram. However, in measurement of a high-precision electrocardiogram for medical use, a type of electrocardiograph in which bioelectrodes are attached to a plurality of positions of the body is required.

The medical wearable device is of a type to be attached to the body or of a type to be fitted into clothing, and the hydrated gel material is widely used as a bioelectrode using a hydrophilic gel containing water and an electrolyte, for example, as described in patent document 1. The hydrophilic gel contains sodium, potassium, and calcium as electrolytes in a hydrophilic polymer for retaining water, and changes in ion concentration from the skin are converted into electrical signals by a reduction reaction of silver chloride in contact with the hydrophilic gel. If the gel dries, the conductivity is lost, and the gel loses the function as a bioelectrode, swells in a bath or shower, and peels off.

On the other hand, as a type of the embedded clothes, there is proposed a method of using a conductive polymer such as PEDOT-PSS (Poly (3, 4-ethylenedioxythiophene) -Poly (styrene sulfonate, poly-3, 4-ethylenedioxythiophene-Polystyrenesulfonate) and a cloth of silver paste embedded fiber for an electrode (patent document 2).

Stretchable and highly conductive bioelectrode sheets have been developed (non-patent document 1). Here, silver nanowires are coated on a polyurethane film, flash annealing is applied, and the surfaces of the silver nanowires are instantaneously heated to 500 ℃ or higher and melted, thereby fusing the silver nanowires to each other.

Metallic bioelectrodes such as gold thin films and silver nanowires are metallic and are not transparent. If a transparent bioelectrode capable of viewing the skin can be developed, there is an advantage in that there is no visual discomfort when the bioelectrode is applied to the skin.

Here, PEDOT-PSS has been studied as a transparent conductive film for organic EL applications instead of ITO. Combinations of silver nanowires and PEDOT-PSS have also been carried out (non-patent document 2). But PEDOT-PSS is blue and not transparent. In order to improve transparency, polythiophenes, which are formed by combining a fluorine-doped dopant, have been disclosed as being used in transparent conductive films (patent documents 3 to 10).

Prior art literature

Patent literature

[ Patent document 1] International publication No. 2013/039151

Patent document 2 Japanese patent application laid-open No. 2015-100673

[ Patent document 3] Japanese patent publication No. 6661212

[ Patent document 4] Japanese patent publication No. 6450661

[ Patent document 5] Japanese patent publication No. 6335138

[ Patent document 6] Japanese patent No. 6271378

[ Patent document 7] Japanese patent publication No. 6407107

[ Patent document 8] Japanese patent No. 6496258

[ Patent document 9] Japanese patent publication No. 6483518

[ Patent document 10] Japanese patent No. 6438348

[ Patent document 11] Japanese patent application laid-open No. 2020-023668

[ Patent document 12] Japanese patent application laid-open No. 2018-044147

[ Patent document 13] Japanese patent application laid-open No. 2018-059050

[ Patent document 14] Japanese patent application laid-open No. 2018-059052

[ Patent document 15] Japanese patent application laid-open No. 2018-130534

Non-patent literature

[ Non-patent document 1] Nano Res.9,401 (2016)

[ Non-patent document 2]J.Photopolymer Sci.an Tech.Vol32 No.3p429 (2019)

[ Non-patent literature ] 3]Trulove C,Mantz R.2003.Ionic Liquids in Synthesis,Chapter3.6：Electrochemical Properties of Ionic Liquids.

Disclosure of Invention

[ Problem to be solved by the invention ]

The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a bioelectrode composition, a bioelectrode, and a bioelectrode manufacturing method, which are excellent in sensitivity of a bioelectrode, high in transparency, high in biocompatibility, lightweight, and capable of being manufactured at low cost, and which are free from significant deterioration in sensitivity of a bioelectric signal, and free from itching, erythema, and eruption of the skin even if the bioelectrode is wetted with water for a long period of time and applied to the skin for a long period of time.

[ Means for solving the problems ]

The present invention has been made in order to achieve the above object, and provides a bioelectrode composition comprising (A) a pi-conjugated polymer; (B) A conductive polymer composite containing a dope polymer which contains a repeating unit a1 having a hydroxyl group and/or a carboxyl group, and a repeating unit a2 having a sulfonic acid, a fluorosulfonyl imide, and an N-carbonyl fluorosulfonamide, and has a weight average molecular weight in the range of 1,000 ～ 500,000; and (C) a crosslinking agent.

The bioelectrode composition can provide a pi-conjugated polymer compounded with a dopant polymer having a crosslinkable group and a repeating unit of a sulfonic acid residue introduced therein, a composition of a crosslinking agent, a bioelectrode formed by curing the composition, and a bioelectrode comprising a conductive substrate, wherein the bioelectrode is usable without significantly decreasing sensitivity of a bioelectric signal even if the bioelectrode is wetted with water for a long period of time.

In this case, the crosslinking agent may have a reactive group selected from an isocyanate group, a blocked isocyanate group, a carbodiimide group, and an aziridine (aziridine) group.

Thereby, the conductive polymer composite can be prevented from peeling or swelling in water.

In this case, the pi-conjugated polymer (a) may be obtained by polymerizing 1 or more precursor monomers selected from the group consisting of monocyclic aromatic compounds, polycyclic aromatic compounds, acetylenes, and derivatives thereof.

Thereby, the ease of polymerization and the stability in air can be improved.

In this case, the monocyclic aromatic group may be any of pyrrole, thiophene vinylidene, selenophene, tellurophenone, phenylene vinylene, and aniline, and the polycyclic aromatic group may be acene.

This can more reliably improve the ease of polymerization and the stability in air.

In this case, the repeating unit A1 having a hydroxyl group and/or a carboxyl group of the dope polymer of (B) may have A1-1 and/or A1-2 represented by the following general formula (1).

[ Chemical 1]

Wherein R ¹、R³ is each independently a hydrogen atom or a methyl group. X ₁、X₂ is any one of a single bond, phenylene, naphthylene, ether, ester and amide groups, and R ²、R⁴ is a single bond, a straight-chain, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms, or an ether or ester group. m and n are integers of 1 to 5. a1-1 and a1-2 are 0 to or less than (a 1-1) <1.0,0 to or less than (a 1-2) <1.0,0 to or less than (a 1-1) + (a 1-2) <1.0.

This can surely react with the crosslinking agent, and peeling or swelling of the conductive polymer composite in water can be eliminated.

The dope polymer of the aforementioned (B) may have, as the repeating unit a2, a partial structure represented by the following general formulae (2) -1 to (2) -4.

[ Chemical 2]

Wherein Rf ₁～Rf₄ is a hydrogen atom, a fluorine atom or a trifluoromethyl group. Further, rf ₁、Rf₂ may be combined to form a carbonyl group. Rf ₅ is a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a fluorine atom. Rf ₆、Rf₇ is a fluorine atom or a linear or branched alkyl group having 1 to 4 carbon atoms and has at least 1 fluorine atom. m is an integer of 0 to 4. M ⁺ is an ion selected from the group consisting of hydrogen ion, ammonium ion, sodium ion, potassium ion.

This makes it possible to obtain a light-weight, high-conductivity, biocompatible material, and free from significant decrease in conductivity even if the material is wetted with water or dried.

In this case, the dope polymer (B) may have 1 or more kinds of repeating units A2-1 to A2-7 selected from the group consisting of the repeating units A2 represented by the following general formula (2).

[ Chemical 3]

In the general formula (2), R ⁵、R⁷、R⁹、R¹²、R¹⁴、R¹⁵ and R ¹⁷ are each independently a hydrogen atom or a methyl group, and R ⁶、R⁸、R¹⁰、R¹³、R¹⁶、R¹⁹ and R ²⁰ are each independently a single bond or a linear, branched or cyclic hydrocarbon group having 1 to 13 carbon atoms. The hydrocarbon group may have 1 or more kinds selected from an ester group, an ether group, an amide group, a urethane group, a thiocarbamate group, and a urea group. R ¹¹ is a linear or branched alkylene group having 1 to 4 carbon atoms, and 1 or 2 of the hydrogen atoms in R ¹¹ may be substituted with a fluorine atom. Y ₁、Y₂、Y₃、Y₄、Y₆ and Y ₇ are each independently any one of a single bond, a phenylene group, a naphthylene group, an ether group, an ester group, and an amide group, and Y ₅ is any one of a single bond, an ether group, and an ester group. Z is any one of an oxygen atom and a-NR ¹⁸ -group. R ¹⁸ is any one of a hydrogen atom, a linear, branched or cyclic alkyl group having 2 to 12 carbon atoms, and a phenyl group, and may have 1 or more kinds selected from an ether group, a carbonyl group, an ester group, and an amide group. Z may also form a ring together with R ⁸. Rf _1' and Rf _5' are each a fluorine atom, a trifluoromethyl group, or a linear or branched alkyl group having 1 to 4 carbon atoms, and have at least 1 fluorine atom. m is an integer of 0 to 4. a2-1, a2-2, a2-3, a2-4, a2-5, a2-6, and a2-7 are 0≤(a2-1)<1.0、0≤(a2-2)<1.0、0≤(a2-3)<1.0、0≤(a2-4)<1.0、0≤(a2-5)<1.0、0≤(a2-6)<1.0、0≤(a2-7)<1.0,0<(a2-1)+(a2-2)+(a2-3)+(a2-4)+(a2-5)+(a2-6)+(a2-7)<1.0.M⁺ which are ions selected from hydrogen ion, ammonium ion, sodium ion, and potassium ion.

Therefore, the effect of the invention can be improved.

In this case, in the general formula (2), rf _1' has at least 1 fluorine atom, and Rf _5' is a fluorine atom or a trifluoromethyl group.

This makes it possible to achieve a light weight, excellent electrical conductivity and biocompatibility, and even if the material is wet with water and dried, the electrical conductivity is not greatly reduced.

In this case, the dope polymer of the above (B) may contain an ammonium ion represented by the following general formula (3) as the above ammonium ion.

[ Chemical 4]

In the general formula (3), R ^101d、R^101e、R^101f and R ^101g are each a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 15 carbon atoms, a linear, branched, or cyclic alkenyl or alkynyl group having 2 to 12 carbon atoms, or an aromatic group having 4 to 20 carbon atoms, and may have 1 or more kinds selected from an ether group, a carbonyl group, an ester group, a hydroxyl group, a carboxyl group, an amino group, a nitro group, a sulfonyl group, a sulfinyl group, a halogen atom, and a sulfur atom. R ^101d and R ^101e, or R ^101d、R^101e and R ^101f may form a ring together with the nitrogen atom to which they are bonded, and R ^101d and R ^101e, or R ^101d、R^101e and R ^101f are an alkylene group having 3 to 10 carbon atoms or a heteroaromatic ring having the nitrogen atom in the general formula (3) in the ring.

This makes it possible to more reliably produce a biological signal with high sensitivity, light weight, and low cost, and even if the biological signal is wet with water and even if the biological signal is dried, the biological signal is not greatly reduced in sensitivity, and the biological signal is not itchy, erythema, eruption, and the like even if the biological signal is applied to the skin for a long period of time, and the biological signal can be used comfortably.

In this case, the component (D) may be composed of at least one resin selected from the group consisting of (meth) acrylate resins, (meth) acrylamide resins, urethane resins, polyvinyl alcohols, polyvinylpyrrolidone, polyoxazolines, polyglycerols, polyglycerol-modified polysiloxanes, celluloses, polyethylene glycols, and polypropylene glycols, in addition to the components (A), (B), and (C).

This makes it possible to prevent the complex from eluting by compatible with the salt, and to hold the conductivity improver such as the metal powder, carbon powder, silicon powder, lithium titanate powder, and the like.

In this case, the component (E) may further contain 1 or more kinds selected from carbon powder, metal powder, silicon powder, and lithium titanate powder.

Thus, the carbon powder and the metal powder can improve the electronic conductivity, and the silicon powder and the lithium titanate powder can improve the sensitivity of receiving ions.

In this case, the carbon powder may be either or both of carbon black and carbon nanotubes.

This can more reliably improve the electron conductivity.

The metal powder may be any one of gold nanoparticles, silver nanoparticles, copper nanoparticles, gold nanowires, silver nanowires, and copper nanowires.

This can more reliably improve the electron conductivity.

In order to achieve the above object, the present invention provides a bioelectrode comprising a conductive substrate and a bioelectrode contact layer formed on the conductive substrate, wherein the bioelectrode contact layer contains a conductive polymer composite contained in the bioelectrode composition described above.

The bioelectrode has high sensitivity of a biosignal, excellent biocompatibility, thin film, light weight, high transparency, and can be manufactured at low cost, and even if the bioelectrode is wetted with water for a long period of time and is stuck to the skin for a long period of time, the sensitivity of the biosignal is not greatly reduced, and the bioelectrode can be used comfortably without itching, erythema and eruption of the skin.

In this case, the conductive base material may contain 1 or more selected from gold, silver chloride, platinum, aluminum, magnesium, tin, tungsten, iron, copper, nickel, stainless steel, chromium, titanium, and carbon.

This can more reliably improve the electron conductivity.

The present invention has been made in order to achieve the above object, and provides a method for producing a bioelectrode having a conductive substrate and a bioelectrode contact layer formed on the conductive substrate, wherein the bioelectrode contact layer is formed by applying the bioelectrode composition described above to the conductive substrate and curing the composition.

The bioelectrode production method has high sensitivity of the bioelectrode, excellent biocompatibility, thin film, light weight, high transparency, and low cost production, and even if the bioelectrode is wetted with water for a long time and stuck to the skin for a long time, the bioelectrode has no significant decrease in sensitivity of the bioelectrode, and can be produced without itching, erythema or eruption of the skin, and is comfortable.

[ Effect of the invention ]

As described above, the bioelectrode composition and bioelectrode of the present invention have high sensitivity of a bioelectric signal, are excellent in biocompatibility, are thin films, are lightweight, are highly transparent, can be manufactured at low cost, and can be used comfortably without itching, erythema or eruption of the skin without greatly decreasing the sensitivity of the bioelectric signal even if the bioelectrode composition and bioelectrode are wetted with water for a long period of time and attached to the skin for a long period of time.

The bioelectrode production method of the present invention has high sensitivity of a bioelectric signal, excellent biocompatibility, thin film, light weight, high transparency, and low cost, and can produce a bioelectrode which is free from itching, erythema, eruption and comfort even if it is wetted with water for a long period of time and stuck to the skin for a long period of time.

Drawings

Fig. 1 is a cross-sectional view showing an example of a bioelectrode according to the present invention, and is a view when the bioelectrode is in contact with skin.

Fig. 2 is a cross-sectional view showing another example of the bioelectrode of the present invention, and is a view when the bioelectrode is in contact with skin.

Fig. 3 is a photograph of a conductive polymer composite solution used for the bioelectrode of the present invention coated on a quartz wafer covered with a TPU film screen-printed with silver paste in the shape of a padlock key.

Fig. 4 is a photograph of a bioelectrode obtained by cutting a TPU film, which is a conductive polymer composite film used for the bioelectrode of the present invention, in a padlock key shape by screen printing, and attaching a transparent adhesive tape to the back surface.

Fig. 5 is a photograph showing the biological signal measured by attaching the bioelectrode shown in fig. 4 to the wrist.

Fig. 6 is an ECG signal when the bioelectrode shown in fig. 5 is attached to the wrist.

Detailed Description

The present invention will be described in detail below, but the present invention is not limited thereto.

As described above, a bioelectrode composition, a bioelectrode, and a bioelectrode manufacturing method are required that are capable of measuring a bioelectric signal even when wetted with water and even when dried, and that are not rough and itchy, and that are light and capable of forming a thin film even when applied to the skin for a long period of time, in order to exhibit high conductivity of a bioelectric signal having high sensitivity and low noise, and that are excellent in biocompatibility, high transparency, light, and thin, and that can be manufactured at low cost.

Sodium, potassium and calcium ions are released from the skin surface in conjunction with the heart's movement. The bioelectrode is required to convert an increase or decrease in ions emitted from the skin into an electrical signal. Therefore, a material excellent in ion conductivity for transmitting an increase or decrease in ions is required. The potential at the skin surface also fluctuates in conjunction with the heart's agitation. This potential variation is small, and electron conductivity is also required to transfer a weak current to the device.

Hydrophilic gels containing sodium chloride and potassium chloride have high ionic conductivity and electronic conductivity, but lose conductivity if water is left alone. In addition, sodium chloride and potassium chloride are eluted out of the bioelectrode by bath and shower, which also causes a decrease in conductivity.

Since a bioelectrode using a metal such as gold or silver only detects a weak current and has low ion conductivity, the bioelectrode has low sensitivity. Carbon and metal also have electron conductivity, but electron conductivity is lower than that of metal, and sensitivity is lower than that of metal in the case of bioelectrodes.

The conductive polymer represented by PEDOT-PSS has both electron conductivity and ion conductivity, but has low ion conductivity due to low polarization. In addition, the PEDOT-PSS coated film has a problem of peeling from the substrate when immersed in water for a long period of time.

The acid and salt of fluorosulfonic acid, fluorosulfonimide and N-carbonyl fluorosulfonamide have high polarizability and high ionic conductivity. By compounding the dopant polymer with pi-conjugated polymer such as polythiophene, both high ion conductivity and electron conductivity can be exhibited.

Further, by adding a crosslinking agent having a reactive hydroxyl group and a reactive carboxyl group to the dope polymer, the film of the conductive polymer composite can be prevented from dissolving in water and peeling, and a biological signal can be obtained even when the film is applied to the skin, such as a bath or shower, and a movement accompanied by sweating is performed.

The present inventors have studied in view of the above-described problems and have found a bioelectrode composition, a bioelectrode, and a bioelectrode manufacturing method, which are described below, and completed the present invention.

That is, the present invention is a bioelectrode composition comprising:

(A) Pi conjugated polymers;

(B) A conductive polymer composite containing a dope polymer which contains a repeating unit a1 having a hydroxyl group and/or a carboxyl group, and a repeating unit a2 having a sulfonic acid, a fluorosulfonyl imide, and an N-carbonyl fluorosulfonamide, and has a weight average molecular weight in the range of 1,000 ～ 500,000; and (C) a crosslinking agent,

A bioelectrode comprising a conductive substrate and a bioelectrode contact layer formed on the conductive substrate, wherein the bioelectrode contact layer contains a conductive polymer composite contained in the bioelectrode composition. ", of (a)

The bioelectrode composition is applied to the conductive substrate and cured to form the bioelectrode contact layer. ".

The biological contact layer containing the conductive polymer composite is in contact with a conductive substrate, and the conductive substrate transmits a biological signal to the device. The conductive base material contains at least 1 selected from gold, silver chloride, platinum, aluminum, magnesium, tin, tungsten, iron, copper, nickel, stainless steel, chromium, titanium, and carbon.

The biological contact layer may be formed on the film surface of the conductive substrate or on the fiber surface of the conductive substrate.

Not only the electrocardiogram but also the electromyogram, brain waves and respiratory rate can be measured. In addition, not only the signal emitted from the skin but also the signal can be transmitted to the muscle by supplying an electric signal to the skin, thereby controlling brain waves. For example: it is considered that the use of the composition is useful for stimulating muscles during swimming to improve expression or reduce fatigue and for relaxing during bathing.

In order to construct a bioelectrode having high sensitivity, not only high ion conductivity but also high electron conductivity is required. The electron conductivity is ensured by pi-conjugated polymers, but it is effective to add metal powder or carbon powder in addition to the conductive polymer composite for further improvement.

The following description refers to the accompanying drawings.

(Embodiment 1)

< Bioelectrode >

First, an example of the bioelectrode of the present invention will be described.

Fig. 1 is a cross-sectional view showing an example of a bioelectrode according to the present invention, and is a view when the bioelectrode contacts the skin.

As shown in fig. 1, the bioelectrode 1 according to embodiment 1 of the present invention includes a conductive substrate 11 and a bioelectrode contact layer 12 formed on the conductive substrate 11.

In fig. 1, the conductive substrate 11 is provided with the substrate 10, but the substrate 10 is not necessarily configured.

Fig. 1 shows a state when the biological contact layer 12 contacts the skin.

One side of the biological contact layer 12 is in contact with the skin, and the other side is in contact with the conductive substrate 11.

The base material 10 is preferably a flexible and stretchable film. In the case of a foamed film or nonwoven fabric, it is desirable that the film is lightweight and has high stretchability, high sweat permeability, and respiratory properties.

(Biological contact layer)

The living body contact layer 12 is a portion that actually contacts a living body when a living body electrode is used.

The bioelectrode composition of the present invention contains the conductive polymer composite in the bioelectrode layer 12.

The biological contact layer 12 is a film containing a conductive polymer composite.

Since the film containing the conductive polymer composite has low tackiness, an adhesive layer may be provided around the film.

The adhesive force of the adhesive layer is preferably in the range of 0.5N/25mm to 20N/25 mm. The method for measuring the adhesion force is generally a method shown in JIS Z0237, and a metal substrate such as SUS (stainless steel) or PET (polyethylene terephthalate) substrate can be used as the base material, and the measurement can be performed using human skin. The surface energy of human skin is lower than that of metal and various plastics, and is low energy close to teflon (registered trademark), and is not easy to adhere.

The thickness of the biological contact layer 12 (film of the conductive polymer composite) is preferably 1nm to 1mm, more preferably 2nm to 0.5 mm.

The biological contact layer 12 (film of conductive polymer composite) is in contact with the conductive substrate 11, and the conductive substrate 11 transmits a biological signal to the device.

(Conductive substrate)

The conductive base material 11 preferably contains at least one selected from gold, silver chloride, platinum, aluminum, magnesium, tin, tungsten, iron, copper, nickel, stainless steel, chromium, titanium, and carbon.

(Embodiment 2)

Next, another example of the bioelectrode of the present invention will be described.

FIG. 2 is a cross-sectional view showing another example of the bioelectrode of the present invention, and is a view when the bioelectrode contacts the skin.

As shown in fig. 2, the bioelectrode 2 according to embodiment 2 of the present invention includes a conductive substrate 21 and a bioelectrode contact layer 22 formed on the conductive substrate 21.

In fig. 2, the substrate 10 is provided under the conductive substrate 21, but the substrate 10 is not necessarily configured. In fig. 2, the biological contact layer 22 is shown in contact with the skin.

In the bioelectrode 2 according to embodiment 2 of the present invention, the conductive base material 21 is a mesh body, and the living body contact layer 22 is formed so as to cover the mesh body and to enter into the mesh of the mesh body. Except for this, the bioelectrode 1 according to embodiment 1 of the present invention has the same structure as that of the bioelectrode.

When the conductive base material 21 is fibrous or linear, the conductive polymer composite is buried in the gaps between the fibers and the wires. When the conductive base material 21 is a fibrous self-standing film, the base material 10 is not necessarily required.

The bioelectrode composition contains (A) a pi-conjugated polymer and (B) a conductive polymer complex, contains a dopant polymer which contains a repeating unit a1 having a hydroxyl group and/or a carboxyl group, and a repeating unit a2 having a sulfonic acid, a fluorosulfonyl imide, and an N-carbonyl fluorosulfonamide, and has a weight average molecular weight in the range of 1,000 ～ 500,000, and (C) a crosslinking agent.

< Bioelectrode composition >

The components of the bioelectrode composition of the present invention will be described in more detail below.

[ (A) pi-conjugated polymer ]

The component (a) of the conductive polymer composite contained in the bioelectrode composition, which is the material for forming the bioelectrode contact layer of the present invention, may be polymerized from precursor monomers (organic monomer molecules) forming pi conjugated tethers (a structure in which single bonds and double bonds alternate and continue).

Such precursor monomers, for example: single ring aromatic compounds of pyrrole, thiophene vinylidene, selenophene, tellurophenone, phenylene vinylidene and aniline; polycyclic aromatic compounds of acenes; acetylene, a homopolymer or copolymer of the monomer may be used as the component (A).

Among the above monomers, pyrrole, thiophene, selenophene, telluro-thiophene, aniline, polycyclic aromatic compounds and their derivatives are preferable in view of ease of polymerization and stability in air, and pyrrole, thiophene, aniline and their derivatives are particularly preferable, but the present invention is not limited thereto.

The monomer constituting the pi-conjugated polymer can obtain sufficient conductivity even if it is not substituted, but a monomer substituted with an alkyl group, a carboxyl group, a sulfonic acid group, an alkoxy group, a hydroxyl group, a cyano group, a halogen atom or the like may be used to further improve conductivity.

Specific examples of the pyrrole, thiophene, aniline monomers include pyrrole, N-methylpyrrole, 3-ethylpyrrole, 3-N-propylpyrrole, 3-butylpyrrole, 3-octylpyrrole, 3-decylpyrrole, 3-dodecylpyrrole, 3, 4-dimethylpyrrole, 3, 4-dibutylpyrrole, 3-carboxypyrrole, 3-methyl-4-carboxyethylpyrrole, 3-methyl-4-carboxybutylpyrrole, 3-hydroxypyrrole, 3-methoxypyrrole, 3-ethoxypyrrole, 3-butoxypyrrole, 3-hexyloxypyrrole, 3-methyl-4-hexyloxypyrrole; thiophene, 3-methylthiophene, 3-ethylthiophene, 3-propylthiophene, 3-butylthiophene, 3-hexylthiophene, 3-heptylthiophene, 3-octylthiophene, 3-decylthiophene, 3-dodecylthiophene, 3-octadecylthiophene, 3-bromothiophene, 3-chlorothiophene, 3-iodothiophene, 3-cyanothiophene, 3-phenylthiophene, 3, 4-dimethylthiophene, 3, 4-dibutylthiophene, 3-hydroxythiophene, 3-methoxythiophene, 3-ethoxythiophene, 3-butoxythiophene, 3-hexyloxythiophene, 3-heptyloxy-thiophene, 3-octyloxy-thiophene, 3-decyloxy-thiophene, 3-dodecyloxy-thiophene, 3-octadecyloxy-thiophene 3, 4-dihydroxythiophene, 3, 4-dimethoxythiophene, 3, 4-diethoxythiophene, 3, 4-dipropoxythiophene, 3, 4-dibutoxythiophene, 3, 4-dihexyloxythiophene, 3, 4-bis (heptyloxy) thiophene, 3, 4-bis (octyloxy) thiophene, 3, 4-bis (decyloxy) thiophene, 3, 4-didodecyloxy) thiophene, 3, 4-ethylenedioxythiophene, 3, 4-propylenedioxythiophene, 3, 4-butylenedioxythiophene, 3-methyl-4-methoxythiophene, 3-methyl-4-ethoxythiophene, 3-carboxythiophene, 3-methyl-4-carboxyethylthiophene, 3-methyl-4-carboxybutylthiophene; aniline, 2-methylaniline, 3-isobutylaniline, 2-methoxyaniline, 2-ethoxyaniline, 2-aniline sulfonic acid, 3-aniline sulfonic acid and the like.

Among them, a (co) polymer composed of 1 or 2 selected from pyrrole, thiophene, N-methylpyrrole, 3-methylthiophene, 3-methoxythiophene, and 3, 4-ethylenedioxythiophene is preferable in view of resistance and reactivity. Further, the single polymer obtained from pyrrole or 3, 4-ethylenedioxythiophene has high conductivity, and is more preferable.

Further, for practical reasons, the number of repeating units (precursor monomers) in the component (A) is preferably in the range of 2 to 20, more preferably in the range of 6 to 15.

The molecular weight of the component (A) is preferably about 130 to 5,000.

(A) The amount of the component (A) to be added is preferably 5 to 150 parts by mass based on 100 parts by mass of the dope polymer of the component (B).

[ (B) dope Polymer (salt) ]

The (B) dopant polymer of the conductive polymer composite contained in the bioelectrode composition, which is a material for forming the bioelectrode contact layer of the present invention, contains a repeating unit a1 having a hydroxyl group and/or a carboxyl group, and a repeating unit a2 having a sulfonic acid, a fluorosulfonyl imide, and an N-carbonyl fluorosulfonamide, and has a weight average molecular weight in the range of 1,000 ～ 500,000. The dope polymer (B) may contain, as the ionic material, an ionic repeating unit a2 having any one of fluorosulfonic acid, fluorosulfonyl imide, and N-carbonyl fluorosulfonamide, for example, selected from the group consisting of a hydrogen ion, an ammonium salt, a sodium salt, and a potassium salt.

The repeating unit A1 having a hydroxyl group and/or a carboxyl group of the dope polymer of the above (B) preferably has A1-1 and/or A1-2 represented by the following general formula (1).

[ Chemical 5]

The monomer used to obtain the repeating unit a1 having a hydroxyl group and/or a carboxyl group is specifically exemplified as follows.

[ Chemical 6]

[ Chemical 7]

Wherein R ¹ and R ³ are as described above.

The ionic material of any one of sulfonic acid, fluorosulfonimide, and N-carbonyl fluorosulfonamide, for example, selected from the group consisting of hydrogen ions, ammonium salts, sodium salts, and potassium salts, may have a partial structure represented by the following general formulae (2) -1 to (2) -4.

[ Chemical 8]

Among the dope polymers of the above (B), 1 or more kinds selected from the repeating units A2-1 to A2-7 represented by the following general formula (2) are preferable as the repeating unit A2. The ionic polymer is preferably one having 1 or more repeating units selected from the group consisting of hydrogen ions, ammonium salts, sodium salts, and potassium salts of sulfonic acid represented by the general formula (2) -1, (2) -2, (2) -3, and N-carbonyl fluorosulfonamide represented by the general formula (2) -4, and having 1 or more repeating units A2-1 to A2-7 selected from the group consisting of the following general formula (2).

[ Chemical 9]

In the general formula (2), rf _1' has at least 1 fluorine atom, and Rf _5' is preferably a fluorine atom or a trifluoromethyl group.

(Repeating units A2-1 to A2-7)

The fluorosulfonic acid monomer and the fluorosulfonic acid salt monomer for obtaining the repeating units A2-1 to A2-5 represented by the above general formula (2) are specifically listed below.

[ Chemical 10]

[ Chemical 11]

[ Chemical 12]

[ Chemical 13]

[ Chemical 14]

[ 15]

[ 16]

[ Chemical 17]

[ Chemical 18]

[ Chemical 19]

[ Chemical 20]

[ Chemical 21]

[ Chemical 22]

[ Chemical 23]

[ Chemical 24]

[ Chemical 25]

[ Chemical 26]

[ Chemical 27]

[ Chemical 28]

[ Chemical 29]

[ Chemical 30]

[ 31]

[ Chemical 32]

[ 33]

[ Chemical 34]

[ 35]

[ 36]

[ 37]

[ 38]

[ 39]

[ 40]

[ Chemical 41]

[ Chemical 42]

[ Chemical 43]

[ 44]

[ 45]

[ Chemical 46]

[ 47]

[ 48]

The fluorosulfonyl imide monomer and the fluorosulfonyl imide salt monomer for obtaining the repeating units A2 to 6 are specifically exemplified as follows.

[ 49]

[ 50]

[ 51]

[ 52]

[ 53]

[ 54]

The N-carbonyl fluorosulfonamide monomer and N-carbonyl fluorosulfonamide salt monomer used to obtain the repeating units A2 to 7 are specifically exemplified as follows.

[ 55]

[ 56]

[ 57]

[ 58]

[ 59]

Wherein R ⁵、R⁷、R⁹、R¹²、R¹⁴、R¹⁵ and R ¹⁷ are as defined above.

(Repeating unit b)

In addition to the repeating units A1-1, A1-2, and A2-1 to A2-7, the polymer (B) component of the bioelectrode composition of the present invention may further copolymerize a repeating unit B having an ethylene glycol dimethyl ether chain in order to improve ion conductivity. In order to obtain a monomer having a repeating unit b of an ethylene glycol dimethyl ether chain, the following is specifically mentioned. By copolymerizing the repeating units having ethylene glycol dimethyl ether chains, the movement of ions emitted from the skin in the dry electrode film is promoted, and the sensitivity of the dry electrode can be improved.

[ Chemical 60]

[ Chemical 61]

[ 62]

[ 63]

R is a hydrogen atom or a methyl group.

(Repeating unit c)

In addition to the repeating units A1-1, A1-2, A2-1 to A2-7, and B, the component (B) of the bioelectrode composition of the present invention may have a hydrophilic repeating unit c having an ammonium salt, betaine, amide group, pyrrolidone, lactone ring, lactam ring, sultone ring, sulfonic acid, sodium salt of sulfonic acid, and potassium salt of sulfonic acid copolymerized for improving conductivity. The monomer used to obtain the hydrophilic repeating unit c is specifically exemplified as follows. By copolymerizing the repeating units containing the hydrophilic group, the sensitivity of ions emitted from the skin can be improved, and the sensitivity of the dry electrode can be improved.

[ 64]

[ 65]

[ Chemical 66]

(Repeating unit d)

The component (B) of the bioelectrode composition of the present invention may further have a fluorine-containing repeating unit d in addition to the repeating unit selected from the above-mentioned A1-1, A1-2, A2-1 to A2-7, B and c.

The monomer used to obtain the fluorine-containing repeating unit d is specifically exemplified as follows.

[ 67]

[ Chemical 68]

[ 69]

[ 70]

[ Chemical 71]

[ Chemical 72]

(Repeating unit e)

It may also have a repeating unit e having a nitro group.

The monomer used to obtain the nitro group-containing repeating unit e is specifically exemplified as follows.

[ 73]

[ Chemical 74]

[ 75]

[ Chemical 76]

[ Chemical 77]

[ 78]

(Repeating unit f)

It may also have a cyano-containing repeating unit f.

The monomer used to obtain the cyano group-containing repeating unit f is specifically exemplified as follows.

[ Chemical 79]

[ 80]

[ 81]

Here, R is a hydrogen atom or a methyl group.

The dope polymer (B) preferably contains an ammonium ion (ammonium cation) represented by the following general formula (3) as an ammonium ion constituting the ammonium salt.

[ Chemical 82]

The ammonium ion represented by the above general formula (3) is specifically exemplified as follows.

[ 83]

[ Chemical 84]

[ Chemical 85]

[ 86]

[ 87]

[ 88]

[ Chemical 89]

[ Chemical 90]

[ 91]

[ Chemical 92]

[ 93]

[ 94]

[ 95]

[ Chemical 96]

[ 97]

[ 98]

[ Chemical 99]

[ 100]

[ 101]

In the method for synthesizing the dope polymer of the component (B), for example, a desired monomer among the monomers providing the repeating units A1-1, A1-2, A2-1 to A2-7, B, c, d, e, f is added to an organic solvent, and a radical polymerization initiator is added thereto and heated and polymerized to obtain the dope polymer of the (co) polymer.

Organic solvents used in the polymerization, for example, toluene, benzene, tetrahydrofuran, diethyl ether, dioxane, cyclohexane, cyclopentane, methyl ethyl ketone, gamma-butyrolactone and the like.

Free radical polymerization initiators such as 2,2' -Azobisisobutyronitrile (AIBN), 2' -azobis (2, 4-dimethylvaleronitrile), dimethyl 2,2' -azobis (2-methylpropionate), benzoyl peroxide, lauroyl peroxide and the like.

The reaction temperature is preferably 50 to 80 ℃, the reaction time is preferably 2 to 100 hours, more preferably 5 to 20 hours.

(B) The monomer providing the repeating units A1-1, A1-2, A2-1 to A2-7 may be 1 or 2 or more in the dope polymer of the component (A).

The monomers having repeating units A1-1, A1-2, A2-1 to A2-7, b, c, d, e, f may be copolymerized randomly or separately in block mode.

In the random copolymerization by radical polymerization, a method of mixing a monomer to be copolymerized and a radical polymerization initiator and heating the mixture to polymerize is generally employed. When the polymerization is started in the presence of the 1 st monomer and the free radical polymerization initiator, and then the 2 nd monomer is added, one side of the polymer molecule has a structure in which the 1 st monomer is polymerized, and the other side has a structure in which the 2 nd monomer is polymerized. However, in this case, the repeating units of the 1 st monomer and the 2 nd monomer are mixed in the intermediate portion, and the morphology is different from that of the block copolymer. In order to form a block copolymer by radical polymerization, living radical polymerization is preferably employed.

The living radical polymerization method called RAFT polymerization (Reversible Addition Fragmentation CHAIN TRANSFER polymerization) always generates radicals at the ends of the polymer, so that a diblock copolymer can be formed from a block of repeating units of monomer 1 and a block of repeating units of monomer 2 by starting the polymerization with monomer 1 and adding monomer 2 at the stage it has consumed. In addition, when the polymerization is started with the 1 st monomer, the 2 nd monomer is added at the stage where the polymerization has been consumed, and then the 3 rd monomer is added, a triblock polymer can be formed.

When RAFT polymerization is performed, a narrow dispersion polymer having a narrow molecular weight distribution (dispersity) is formed, and particularly when RAFT polymerization is performed by adding a monomer at one time, a polymer having a narrower molecular weight distribution is formed.

In addition, the molecular weight distribution (Mw/Mn) of the dope polymer of the component (B) is preferably from 1.0 to 2.0, particularly from 1.0 to 1.5. The narrow dispersion prevents the transmittance of the conductive film formed of the conductive polymer composite using the same from decreasing.

The RAFT polymerization requires a chain transfer agent, specifically, for example, 2-cyano-2-propylthiobenzoate, 4-cyano-4-phenylthiocarbothiolane acid, 2-cyano-2-propyldodecyl trithiocarbonate, 4-cyano-4- [ (dodecylmercaptothiocarbonyl) hydrosulfide ] pentanoic acid, 2- (dodecylthiocarbonylthio) -2-methylpropanoic acid, cyanomethyldodecylthiocarbonate, cyanomethylmethyl (phenyl) thiocarbamate, bis (thiobenzoyl) disulfide, bis (dodecylmercaptothiocarbonyl) disulfide. Among them, 2-cyano-2-propylthiobenzoate is particularly preferred.

(B) The dope polymer of the component (A) has a weight average molecular weight of 1,000 ～ 500,000, preferably 2,000 ～ 200,000. If the weight average molecular weight is less than 1,000, the heat resistance is poor, and the uniformity of the composite solution of component (A) is deteriorated. On the other hand, if the weight average molecular weight exceeds 500,000, the conductivity is deteriorated, the viscosity is increased, the workability is deteriorated, and the dispersibility in water and organic solvents is lowered.

The weight average molecular weight (Mw) is a measured value in terms of polyethylene oxide, polyethylene glycol, or polystyrene obtained by Gel Permeation Chromatography (GPC) using water, dimethylformamide (DMF), or Tetrahydrofuran (THF) as a solvent.

The monomer constituting the dope polymer of the component (B) may be a monomer having a sulfonic acid group, or may be a monomer obtained by polymerization using a lithium salt, sodium salt, potassium salt, ammonium salt or sulfonium salt of a sulfonic acid group, and then converted into a sulfonic acid group using an ion exchange resin.

Here, the ratio of the repeating units A1-1, A1-2, A2-1 to A2-7, B, c, d, e, f in the dope polymer is 0≤(a1-1)<1.0、0≤(a1-2)<1.0、0<(a1-1)+(a1-2)<1.0、0≤(a2-1)<1.0、0≤(a2-2)<1.0、0≤(a2-3)<1.0、0≤(a2-4)<1.0、0≤(a2-5)<1.0、0≤(a2-6)<1.0、0≤(a2-7)<1.0、0<(a2-1)+(a2-2)+(a2-3)+(a2-4)+(a2-5)+(a2-6)+(a2-7)<1.0、0≤b<1.0、0≤c<1.0、0≤d<1.0、0≤e<1.0、0≤f<1.0,, preferably 0≤(a1-1)≤0.9、0≤(a1-2)≤0.9、0.01≤(a1-1)+(a1-2)≤0.9、0≤(a2-1)≤0.99、0≤(a2-2)≤0.99、0≤(a2-3)≤0.99、0≤(a2-4)≤0.99、0≤(a2-5)≤0.99、0≤(a2-6)≤0.99、0≤(a2-7)≤0.99、0.1≤(a2-1)+(a2-2)+(a2-3)+(a2-4)+(a2-5)+(a2-6)+(a2-7)≤0.99、0≤b≤0.9、0≤c≤0.9、0≤d≤0.9、0≤e≤0.9、0≤f≤0.9,, more preferably 0≤(a1-1)≤0.8、0≤(a1-2)≤0.8、0.01≤(a1-1)+(a1-2)≤0.8、0≤(a2-1)≤0.98、0≤(a2-2)≤0.98、0≤(a2-3)≤0.98、0≤(a2-4)≤0.98、0≤(a2-5)≤0.98、0≤(a2-6)≤0.98、0≤(a2-7)≤0.98、0.1≤(a2-1)+(a2-2)+(a2-3)+(a2-4)+(a2-5)+(a2-6)+(a2-7)≤0.98、0≤b≤0.7、0≤c≤0.7、0≤d≤0.7、0≤e≤0.7、0≤f≤0.7.b、c、d、e、f,, and the ratio of the repeating units B to f is each.

[ Conductive Polymer Complex ]

A conductive polymer composite comprising a pi-conjugated polymer as the component (A) and a dopant polymer as the component (B), wherein the dopant polymer as the component (B) is coordinated to the pi-conjugated polymer as the component (A) to form a composite.

The conductive polymer composite preferably has good dispersibility in water or an organic solvent, and can be formed into a film having good spin-coating film properties and film flatness on an inorganic or organic substrate (a substrate having an inorganic film or an organic film formed on the surface of the substrate).

(Method for producing conductive Polymer composite)

(A) The composite of the component (A) and the component (B) can be obtained, for example, by adding a monomer (preferably, pyrrole, thiophene, aniline, or derivative monomers thereof) as a raw material of the component (A) to an aqueous solution of the component (B) or a mixed solution of the component (B) and an aqueous/organic solvent, adding an oxidizing agent and optionally an oxidizing catalyst, and performing oxidative polymerization.

As the oxidizing agent and the oxidation catalyst, persulfate such as ammonium persulfate (Ammonium Peroxodisulfate), sodium persulfate (Sodium Peroxodisulfate), potassium persulfate (potassium Peroxodisulfate), transition metal compounds such as iron (III) chloride, iron (III) sulfate, copper (II) chloride, metal oxides such as silver oxide and cesium oxide, peroxides such as hydrogen peroxide and ozone, organic peroxides such as benzoyl peroxide, oxygen, and the like can be used.

The reaction solvent used in the oxidation polymerization may be water or a mixed solvent of water and a solvent. The solvent used herein is preferably a solvent which can be mixed with water and can dissolve or disperse the component (A) and the component (B). For example: polar solvents such as N-methyl-2-pyrrolidone, N' -dimethylacetamide, dimethyl sulfoxide, and hexamethylenephosphoric triamide, alcohols such as methanol, ethanol, propanol, and butanol, heterocyclic compounds such as ethylene glycol, propylene glycol, dipropylene glycol, 1, 3-butanediol, 1, 4-butanediol, D-glucose, D-glucitol, isopentane diol, butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 9-nonanediol, and neopentyl glycol, carbonate compounds such as ethylene carbonate and propylene carbonate, cyclic ether compounds such as dioxane and tetrahydrofuran, dialkyl ethers, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, polyethylene glycol dialkyl ethers, polypropylene glycol dialkyl ethers, heterocyclic compounds such as 3-methyl-2-oxazolidinone (oxazodone), nitrile compounds such as acetonitrile, methoxyacetonitrile, propionitrile, and benzonitrile, and the like. The solvent may be used alone or in a mixture of 2 or more. The amount of the solvent to be mixed with water is preferably 50% by mass or less based on the whole reaction solvent.

After the synthesis of the conductive polymer complex, neutralization reaction of M ⁺ of the general formulae (2), (2) -1 to (2) -4 into sodium ion, potassium ion, ammonium ion, sulfonium ion can be performed.

The composite of the component (A) and the component (B) thus obtained may be optionally granulated by a homogenizer, a ball mill or the like and used.

The fine particles are preferably formed by using a mixer-disperser capable of imparting high shear force. Mixing and dispersing machines, for example: homogenizers, high pressure homogenizers, bead mills, and the like, with high pressure homogenizers being preferred.

Specific examples of the high-pressure homogenizer include Microfluidizer manufactured by Nanoveita, powrex of Jitian mechanical, and Ultimizer manufactured by Sugino Machine.

Examples of the dispersion treatment using a high-pressure homogenizer include a treatment of causing the complex solution before the dispersion treatment to collide against each other under high pressure, a treatment of causing the complex solution to pass through an orifice or slit under high pressure, and the like.

Before or after the granulation, impurities can be removed by filtration, ultrafiltration, dialysis, etc., and refined with cation exchange resin, anion exchange resin, chelate resin, etc.

The total content of the component (a) and the component (B) in the conductive polymer composite solution is preferably 0.05 to 5.0 mass%. (A) When the total content of the component (a) and the component (B) is 0.05 mass% or more, sufficient conductivity can be obtained, and when it is 5.0 mass% or less, a uniform conductive coating film can be easily obtained.

The amount of the sulfonic acid group, the sulfonamide group and the sulfonimide group in the component (B) is preferably in the range of 0.1 to 10 mol, more preferably in the range of 1 to 7 mol, based on 1 mol of the component (A). (B) If the sulfonic acid group in the component (a) is 0.1 mol or more, the doping effect on the component (a) is high, and sufficient conductivity can be ensured. If the sulfonic acid group in the component (B) is 10 mol or less, the content of the component (a) is appropriate, and sufficient conductivity can be obtained.

An organic solvent which can be added to the aqueous polymerization reaction solution or which can dilute the monomer, such as methanol, ethyl acetate, cyclohexanone, methylpentanone, butanediol monomethyl ether, propanediol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propanediol monoethyl ether, ethylene glycol monoethyl ether, propanediol dimethyl ether, diethylene glycol dimethyl ether, propanediol monomethyl ether acetate, propanediol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, propylene glycol mono-t-butyl ether acetate, gamma-butyrolactone, a mixture thereof, and the like.

The amount of the organic solvent to be used is preferably 0 to 1,000mL, particularly preferably 0 to 500mL, based on 1 mol of the monomer. If the concentration is 1,000mL or less of the organic solvent, the reaction vessel will not become excessively large, and therefore it is economical.

The component (A) may be polymerized and compounded in the presence of a dope polymer of the component (B), and then a neutralizing agent may be added. By adding the neutralizing agent, M ⁺ of the general formulae (2), (2) -1 to (2) -4 becomes other than hydrogen ions. When M ⁺ in the general formulae (2), (2) -1 to (2) -4 is a hydrogen ion, if the proportion of the hydrogen ion is large, the bioelectrode solution of the present invention has a high acidity, and the skin side of the bioelectrode may be acidic due to perspiration when the bioelectrode solution is applied to the skin, which may cause skin allergy. In order to prevent this, it is preferable to perform the neutralization treatment. But M ⁺ can tolerate a small residual hydrogen ion.

(C) Crosslinking agent

In the present invention, a crosslinking agent is added to eliminate peeling or swelling of the conductive polymer composite in water. The crosslinking agent is selected, for example, from isocyanate groups, blocked isocyanate groups, carbodiimide groups, aziridine groups.

Crosslinking agents containing isocyanate groups, for example compounds having a plurality of isocyanate groups. Compounds having a plurality of isocyanate groups are described in paragraphs [0082], [0083] of patent document 11.

Specific examples of the blocked isocyanate group-containing crosslinking agent include MEIKANATE series in the chemical industry (strand), blonate series in the great-Rong industry (strand), and Elastron series in the first industry (strand). After coating, the protecting groups are removed by heating and isocyanate groups are generated, which react with the hydroxyl and carboxyl groups of the dopant polymer.

Crosslinking agents having carbodiimide groups, such as V-02, V-02-L2 of Nisshink chemistry (Strand).

Crosslinking agents having an aziridine group, such as CHEMITITE DZ-22E, DZ-33 of Japanese catalyst (Strand).

Among these, the crosslinking agent which is stable in the aqueous solution of the bioelectrode is preferably a crosslinking agent containing a blocked isocyanate group.

The amount is preferably 1 to 50 parts by mass based on 100 parts by mass of the total of the component A and the component B.

[ Other Components ]

(Surfactant)

In the present invention, a surfactant may be added to improve the moisture permeability of a workpiece such as a substrate of the complex solution. Such surfactants include nonionic surfactants, cationic surfactants, and anionic surfactants. Specifically, for example: nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene carboxylic acid ester, sorbitan ester, and polyoxyethylene sorbitan ester, cationic surfactants such as alkyl trimethylammonium chloride and alkyl benzyl ammonium chloride, anionic surfactants such as alkyl or alkyl allyl sulfate, alkyl or alkyl allyl sulfonate, and dialkyl sulfosuccinate, and amphoteric surfactants such as amino acid type and betaine type surfactants.

The amount is preferably 0.001 to 50 parts by mass based on 100 parts by mass of the total of the component A and the component B.

(Highly conductive agent)

In the present invention, a high-conductivity agent may be added separately from the main agent in order to improve the conductivity of the conductive polymer composite. Such highly conductive agents, for example, polar solvents, specifically, for example, ethylene glycol, diethylene glycol, polyethylene glycol, glycerol, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), N-methyl-2 pyrrolidone (NMP), sulfolane, and mixtures thereof. The amount to be added is preferably 1.0 to 40.0 mass%, particularly 3.0 to 30.0 mass%, based on 100 parts by mass of the conductive polymer composite dispersion.

In the case of the conductive polymer composite described above, the filterability and spin-coating film forming property are good, and a conductive film having high transparency and low surface roughness can be formed.

[ Biological contact layer ]

The bioelectrode can be formed by coating the conductive polymer composite (solution) obtained as described above on a conductive substrate of 1 or more selected from gold, silver chloride, platinum, aluminum, magnesium, tin, tungsten, iron, copper, nickel, stainless steel, chromium, titanium, and carbon. A method for coating a conductive polymer composite (solution), for example: coating using a spin coater or the like, coating a rod, dipping, unfilled corner coating, spraying, roll coating, screen printing, flexography, gravure, inkjet printing, and the like. After the application, the bioelectrodes may be formed by heat treatment using a hot air circulating furnace, a hot plate, or the like.

[ (D) resin ]

The resin (D) blended in the bioelectrode composition of the present invention is a component compatible with the dopant polymer (salt) of the above (B) to prevent elution of the conductive polymer composite, and is a conductive promoter component for holding metal powder, carbon powder, silicon powder, lithium titanate powder, and the like. Preferably, the resin is at least 1 resin selected from the group consisting of (meth) acrylate resins, (meth) acrylamide resins, urethane resins, polyvinyl alcohols, polyvinyl pyrrolidones, polyoxazolines, polyglycerols, polyglycerol-modified polysiloxanes, celluloses, polyethylene glycols, and polypropylene glycols.

The amount of the component (A) is preferably 0 to 200 parts by mass based on 100 parts by mass of the total of the component (A) and the component (B).

[ (E) component ]

The bioelectrode composition of the present invention may further contain 1 or more kinds selected from carbon powder, metal powder, silicon powder, and lithium titanate powder as the component (E). (E) Among the components, carbon powder and metal powder are added to improve electron conductivity, and silicon powder and lithium titanate powder are added to improve ion acceptance sensitivity.

[ Metal powder ]

In the bioelectrode composition of the present invention, a metal powder selected from the group consisting of gold, silver, platinum, copper, tin, titanium, nickel, aluminum, tungsten, molybdenum, ruthenium, chromium, and indium may be added to improve electron conductivity. The amount of the metal powder to be added is preferably in the range of 1 to 50 parts by mass based on 100 parts by mass of the resin.

Gold, silver, and platinum are preferable from the viewpoint of conductivity and the viewpoint of price, and silver, copper, tin, titanium, nickel, aluminum, tungsten, molybdenum, ruthenium, and chromium are preferable from the viewpoint of metal powder type. Noble metals are desirable from the standpoint of biocompatibility, which is comprehensively considered, and silver is most desirable.

The shape of the metal powder is preferably spherical, disk-shaped, chip-shaped, or needle-shaped, and the conductivity is the highest when the chip-shaped or needle-shaped powder is added. In the case of the chip-like shape, the metal powder preferably has a size of 100 μm or less, a tap density of 5g/cm ³ or less, and a specific surface area of 0.5m ²/g or more, and is preferably a chip having a relatively low density and a large specific surface area. The needle-like shape is preferably 1 to 200nm in diameter and 1 to 500 μm in length.

The metal powder is preferably any one of gold nanoparticles, silver nanoparticles, copper nanoparticles, gold nanowires, silver nanowires, and copper nanowires.

[ Carbon powder ]

Carbon powder may be added as a conductivity enhancer. Carbon powder such as carbon black, graphite, carbon nanotubes, carbon fibers, and the like. The carbon nanotubes may be single-layered or multi-layered, and the surface may be modified with an organic group. In particular, either or both of carbon black and carbon nanotubes are preferred. The amount of carbon powder to be added is preferably in the range of 1 to 50 parts by mass based on 100 parts by mass of the conductive polymer composite.

[ Silica powder ]

In the bioelectrode composition of the present invention, silicon powder may be added to improve the sensitivity to ion acceptance. Silicon powder is, for example, powder composed of silicon, silicon monoxide, and silicon carbide. The particle diameter of the powder is preferably smaller than 100. Mu.m, more preferably 1. Mu.m or less. The finer particles have a larger surface area, and therefore can receive many ions, and become a bioelectrode with high sensitivity. The amount of the silicon powder to be added is preferably in the range of 1 to 50 parts by mass relative to 100 parts by mass of the resin.

[ Lithium titanate powder ]

In the bioelectrode composition of the present invention, lithium titanate powder may be added to improve the sensitivity to ion acceptance. Lithium titanate powder such as Li ₂TiO₃、LiTiO₂, molecular formula of Li ₄Ti₅O₁₂ of spinel structure, spinel structure is preferable. Lithium titanate particles obtained by compounding with carbon may also be used. The particle diameter of the powder is preferably smaller than 100. Mu.m, more preferably 1. Mu.m or smaller. The finer particles have a larger surface area, so that many ions can be accepted, and the electrode becomes a bioelectrode with high sensitivity. They may also be composite powders with carbon. The amount of the lithium titanate powder to be added is preferably in the range of 1 to 50 parts by mass based on 100 parts by mass of the resin.

When silver nanowires or carbon nanotubes are added with needle-shaped or fibrous conductive additives to the conductive polymer composite solution, sufficient conductivity as a bioelectrode can be ensured even if the substrate is not provided with a conductive layer.

[ Optional ingredients ]

The bioelectrode composition of the present invention may contain any component such as an ionic additive and a solvent.

[ Ionic additives ]

The bioelectrode composition of the present invention may be added with an ionic additive for improving ion conductivity. In consideration of biocompatibility, examples thereof include sodium chloride, potassium chloride, calcium chloride, saccharin, acesulfame potassium, and salts described in patent documents 12 to 15.

Ammonium salts of fluorosulfonic acid, fluoroimide acid, fluoromethylated acid are known to be ionic liquids. Specifically, non-patent document 3 describes the present invention. The ionic liquid may also be added.

[ Silicone Compound having polyglycerin Structure ]

In the bioelectrode composition of the present invention, a silicone compound having a polyglycerin structure may be added to improve the sensitivity and ion conductivity of ions emitted from the skin in order to improve the moisture retention of the film. The amount of the silicone compound having a polyglycerin structure to be blended is preferably 0.01 to 100 parts by mass, more preferably 0.5 to 60 parts by mass, based on 100 parts by mass of the total of the component (A) and the component (B). The silicone compound having a polyglycerin structure may be used alone in an amount of 1 kind or in an amount of 2 or more kinds.

The silicone compound having a polyglycerin structure is preferably represented by the following general formulae (4) 'and (5)' below.

[ Chemical 102]

In the formulae (4) ' and (5) ', R ^1' are each independently the same or different and each independently a hydrogen atom, a linear or branched alkyl group having 1 to 50 carbon atoms, or a phenyl group, or may contain an ether group, or a silicone chain represented by the general formula (6) ' R ^2' is a group having a polyglyceryl structure represented by the formula (4) ' -1 or the formula (4) ' -2, R ^3' are each independently the same or different and each independently the R ^1' group or the R ^2' group, and R ^4' is each independently the same or different and is the R ^1' group, the R ^2' group or an oxygen atom. When R ^4' is an oxygen atom, the R ^4' group may be bonded to form 1 ether group, and form a ring together with the silicon atom. a 'may be the same or different and is 0 to 100, b' is 0 to 100, and a '+b' is 0 to 200. However, when b' is 0, at least one of R ^3' is the aforementioned R ^2' group. In the formulae (4) '-1 and (4)' -2, R ^5' is an alkylene group having 2 to 10 carbon atoms or an aralkylene group having 7 to 10 carbon atoms, R ^5'、R^6'、R^7' in the formula (5) is an alkylene group having 2 to 6 carbon atoms, R ^7' may be an ether bond, c 'is 0 to 20, and d' is 1 to 20.

Examples of such a silicone compound having a polyglycerin structure include the following.

[ 103]

[ Chemical 104]

[ 105]

[ 106]

[ Chemical 107]

[ Chemical 108]

[ 109]

[ 110]

[ Chemical 111]

/>

[ Chemical 112]

Wherein a ', b', c 'and d' are as described above.

If such a silicone compound having a polyglycerin structure is contained, it is possible to exhibit more excellent moisture retention, and as a result, a bioelectrode composition capable of forming a bioelectrode contact layer which exhibits more excellent sensitivity to ions emitted from the skin can be obtained.

[ Solvent ]

The bioelectrode composition of the present invention may be added with a solvent. The solvent is used, in particular, for example, water, heavy water, alcohols such as methanol, ethanol, propanol and butanol, polyvalent aliphatic alcohols such as ethylene glycol, propylene glycol, 1, 3-propanediol, dipropylene glycol, 1, 3-butanediol, 1, 4-butanediol, D-glucose, D-glucitol, isopentane diol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 2, 3-butanediol, 1, 2-pentanediol, 1, 5-pentanediol, 1, 2-hexanediol, 1, 6-hexanediol, 1, 9-nonanediol and neopentyl glycol, chain ethers such as dialkyl ethers, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, polyethylene glycol dialkyl ethers and polypropylene glycol dialkyl ethers cyclic ether compounds such as dioxane and tetrahydrofuran, cyclohexanone, methylpentanone, ethyl acetate, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, propylene glycol monobutyl ether acetate, gamma-butyrolactone, N-methyl-2-pyrrolidone, N, polar solvents such as N '-dimethylformamide, N' -dimethylacetamide, dimethylsulfoxide, hexamethylenephosphoric triamide, carbonate compounds such as ethylene carbonate and propylene carbonate, heterocyclic compounds such as 3-methyl-2-oxazolidinone, acetonitrile, and the like, and nitrile compounds such as glutaronitrile, methoxyacetonitrile, propionitrile and benzonitrile, and mixtures thereof.

The amount of the solvent to be added is preferably in the range of 10 to 50,000 parts by mass per 100 parts by mass of the resin.

< Method for producing bioelectrodes >

The method for producing a bioelectrode according to the present invention will be described below.

The bioelectrode manufacturing method of the present invention is a bioelectrode manufacturing method comprising a conductive substrate and a bioelectrode formed on the conductive substrate, wherein the bioelectrode composition is applied and cured on the conductive substrate to form the bioelectrode.

The invention provides a method for manufacturing a bioelectrode, which comprises the steps of manufacturing a conductive base material and forming a bioelectric contact layer containing a conductive polymer complex on the skin side adhered to the conductive base material.

The method of applying the biological contact layer containing the conductive polymer composite to the conductive substrate is not particularly limited, and there are a direct application method and a transfer method after application to another substrate. Among the methods, dip coating, spray coating, spin coating, roll coating, flow coating, doctor blade coating, screen printing, flexography, gravure printing, inkjet printing, and the like are preferable.

The method for forming the conductive substrate may be the same as the method for coating the biological contact layer containing the conductive polymer composite.

After the application of the conductive substrate and the application of the biological contact layer containing the conductive polymer composite, the film is cured to evaporate the solvent and heated.

The temperature at which the bioelectrode composition containing the conductive polymer composite is applied and heated is not particularly limited, and may be appropriately selected depending on the types of the components (a) and (B) used in the bioelectrode composition, and is preferably, for example, about 50 to 250 ℃.

When silver nanowires or the like are used as the conductive substrate, the heating temperature after the conductive substrate is applied is set to a temperature of 200 to 600 ℃ in order to weld silver to each other. In this case, in order to prevent thermal decomposition of the substrate, a flash annealing method of irradiating high-intensity ultraviolet rays for a short period of time may be used.

In the case of combining heating and irradiation, heating and irradiation may be performed simultaneously, or heating may be performed after irradiation, or irradiation may be performed after heating. The film may be air-dried before heating after coating to evaporate the solvent.

If water drops are dropped or water vapor or mist is blown onto the surface of the hardened living body contact layer containing the conductive polymer composite, affinity with the skin is improved, and a living body signal can be obtained quickly. In order to make the water vapor and mist have a small droplet size, water mixed with alcohol may be used. The surface of the film may also be wetted by contacting the surface with a water-containing absorbent cotton or cloth.

The water that wets the surface of the biological contact layer containing the conductive polymer composite after hardening may contain a salt. Water-soluble salts, preferably selected from sodium, potassium, calcium, magnesium, betaine, mixed with water.

The water-soluble salt may be, specifically, a salt selected from sodium chloride, potassium chloride, calcium chloride, magnesium chloride, saccharin sodium salt, acesulfame potassium, sodium carboxylate, potassium carboxylate, calcium carboxylate, sodium sulfonate, potassium sulfonate, calcium sulfonate, sodium phosphate, potassium phosphate, calcium phosphate, magnesium phosphate, and betaine. The dope polymer (B) is not contained in the water-soluble salt.

More specifically, examples of the sodium salts include sodium acetate, sodium propionate, sodium trimethylacetate, sodium glycolate, sodium butyrate, sodium valerate, sodium caproate, sodium heptanoate, sodium caprylate, sodium pelargonate (pelargonic acid), sodium caprate, sodium undecanoate, sodium laurate, sodium tridecanoate, sodium meat bean, sodium caprate, sodium pentadecanoate, sodium palmitate, sodium heptadecanoate, sodium stearate, sodium benzoate, disodium adipate, disodium maleate, disodium phthalate, sodium 2-hydroxybutyrate, sodium 3-hydroxybutyrate, sodium 2-oxobutyrate, sodium gluconate, sodium methanesulfonate, sodium 1-nonanesulfonate, sodium 1-decanesulfonate, sodium 1-dodecanesulfonate, sodium 1-undecanesulfonate, sodium cocoyl isethionate, sodium lauroyl methylalaninate, sodium cocoyl methyltaurine, sodium cocoyl glutamate, sodium cocoyl methyltaurine, sodium lauroyl propylbetaine, potassium isobutyrate, potassium propionate, potassium trimethylacetate, potassium gluconate, potassium methanesulfonate, calcium methyl sulfonate, calcium methyl 2-glycolate, calcium methyl sulfonate, calcium methyl-2-oxobutyrate, and calcium methyl-2-oxobutyrate. Betaine is a generic term for intramolecular salts, specifically, for example, compounds in which an amino group of an amino acid is added with 3 methyl groups, and more specifically, trimethylglycine, carnitine (carnitine) and proline betaine are exemplified.

The water-soluble salt may further contain a 1-or polyhydric alcohol having 1 to 4 carbon atoms, and the alcohol is preferably selected from ethanol, isopropanol, ethylene glycol, diethylene glycol, triethylene glycol, glycerin, polyethylene glycol, polypropylene glycol, polyglycerol, diglycerol, and a silicone compound having a polyglycerol structure, and the silicone compound having a polyglycerol structure is more preferably represented by the general formula (4)'.

The bioelectrode membrane may be wetted with the bioelectrode composition (bioelectrode contact layer) after curing by a pretreatment method using an aqueous solution containing an aqueous salt, by spraying, water droplet dispensing, or the like. It can also be moistened in a high temperature and high humidity state such as sauna. After wetting, the sheet may also be covered to prevent drying. The sheet needs to be peeled off immediately before being applied to the skin, and thus a release agent is applied or a teflon (registered trademark) film having peelability is used. The dry electrode covered with the release sheet is sealed with a bag covered with aluminum or the like for long-term storage. In order to prevent drying in the aluminum-coated bag, it is preferable to enclose moisture therein in advance.

When the skin on the side to which the bioelectrodes are applied is rubbed with a cloth containing water, ethanol containing water, glycerin, or the like or sprayed immediately before application, the surface of the skin can be wetted, and a high-sensitivity and high-precision bioelectric signal can be obtained in a shorter time. The wiping with the aqueous cloth has not only the effect of wetting the skin but also the effect of removing the grease on the skin surface, thereby improving the sensitivity of the biological signal.

As described above, according to the method for producing a bioelectrode of the present invention, the bioelectrode of the present invention which is excellent in conductivity and biocompatibility, light in weight, and not greatly reduced in conductivity even if it is wet with water and even if it is dried can be produced easily at low cost.

Examples (example)

The present invention will be specifically described below using examples and comparative examples, but the present invention is not limited thereto.

[ 113]

Monomer 1

Under nitrogen, a solution of 49.1g of monomer 1 and 1.0g of hydroxyethyl acrylate, 4.19g of dimethyl 2,2' -azobis (isobutyrate) dissolved in 112.5g of methanol was added dropwise over 4 hours to 37.5g of methanol stirred at 64 ℃. Stirred at 64℃for 4 hours. After cooling to room temperature, 1,000g of ethyl acetate were added dropwise with vigorous stirring. The resulting solid was collected by filtration and dried at 50℃for 15 hours under vacuum to obtain 45.3g of a white polymer.

The white polymer obtained was dissolved in 396g of methanol, and the ammonium salt was converted into a sulfonic acid group using an ion exchange resin. The polymer thus obtained was subjected to ¹⁹F、¹ H-NMR and GPC measurement to obtain the following analysis results.

Weight average molecular weight (Mw) =10,500

Molecular weight distribution (Mw/Mn) =1.59

This high molecular compound was designated as dope polymer 1.

Dope polymer 1

[ 114]

In the same manner, the following dope polymers 2 to 32 were polymerized.

Dope Polymer 2

Mw＝12,000

Mw/Mn＝1.79

[ 115]

/>

Dope Polymer 3

Mw＝9,700

Mw/Mn＝1.66

[ 116]

Dope polymer 4mw=12,500 Mw/mn=1.53

[ Chemical 117]

Dope polymer 5 mw=8, 900 Mw/mn=1.69

[ Chemical 118]

Dope polymer 6mw=10, 800 Mw/mn=1.92

[ 119]

Dope polymer 7

Mw＝14,500

Mw/Mn＝1.71

[ 120]

Dope polymer 8

Mw＝14,500

Mw/Mn＝1.77

[ Chemical 121]

Dope polymer 9

Mw＝10,300

Mw/Mn＝1.61

[ Chemical 122]

Dope polymer 10

Mw＝9,200

Mw/Mn＝1.57

[ 123]

Dope polymer 11

Mw＝11,100

Mw/Mn＝1.74

[ Chemical 124]

Dope polymer 12

Mw＝16,100

Mw/Mn＝1.73

[ 125]

Dope polymer 13

Mw＝14,200

Mw/Mn＝1.71

[ 126]

Dope polymer 14

Mw＝14,500

Mw/Mn＝1.69

[ 127]

/>

Dope polymer 15

Mw＝11,400

Mw/Mn＝1.76

[ 128]

Dope polymer 16

Mw＝13,500

Mw/Mn＝1.73

[ 129]

Dope polymer 17

Mw＝12,600

Mw/Mn＝1.62

[ 130]

Dope polymer 18

Mw＝10,600

Mw/Mn＝1.61

[ 131]

Dope polymer 19

Mw＝12,600

Mw/Mn＝1.83

[ Chemical 132]

Dope polymer 20

Mw＝12,600

Mw/Mn＝1.89

[ Chemical 133]

Dope polymer 21

Mw＝11,900

Mw/Mn＝1.88

[ 134]

Dope polymer 22

Mw＝12,800

Mw/Mn＝1.59

[ Chemical 135]

Dope polymer 23

Mw＝12,800

Mw/Mn＝1.79

[ Chemical 136]

Dope polymer 24

Mw＝14,500

Mw/Mn＝1.95

[ 137]

Dope polymer 25

Mw＝14,100

Mw/Mn＝1.69

[ 138]

Dope polymer 26

Mw＝12,100

Mw/Mn＝1.51

[ Chemical 139]

Dope polymer 27

Mw＝14,100

Mw/Mn＝1.71

[ 140]

Dope polymer 28

Mw＝13,800

Mw/Mn＝1.63

[ 141]

Dope polymer 29

Mw＝13,800

Mw/Mn＝1.89

[ 142]

Dope polymer 30

Mw＝13,900

Mw/Mn＝1.81

[ 143]

Dope polymer 31

Mw＝20,600

Mw/Mn＝1.91

[ 144]

/>

Dope polymer 32

Mw＝14,200

Mw/Mn＝1.70

[ Chemical 145]

[ Preparation of conductive Polymer Complex solution containing Polythiophene as pi-conjugated Polymer ]

Preparation example 1

A solution of 3.82g of 3, 4-ethylenedioxythiophene and 1,000mL of ultrapure water in which 15.0g of dope polymer 1 was dissolved was mixed at 30 ℃.

The thus-obtained mixed solution was kept at 30℃and an oxidation catalyst solution of 8.40g of sodium persulfate and 2.3g of iron (III) sulfate dissolved in 100mL of ultrapure water was slowly added thereto with stirring, and the mixture was stirred for 4 hours to react.

To the obtained reaction solution, 1,000mL of ultrapure water was added, and about 1,000mL of the solution was removed by ultrafiltration. This operation was repeated 3 times.

200ML of 10 mass% sulfuric acid and 2,000mL of ion-exchanged water were added to the treated liquid subjected to the filtration treatment, about 2,000mL of the treated liquid was removed by ultrafiltration, 2,000mL of ion-exchanged water was added thereto, and about 2,000mL of the liquid was removed by ultrafiltration. This operation was repeated 3 times.

The obtained treatment solution was purified with a cation exchange resin and an anion exchange resin, and then 2,000mL of ion exchange water was added thereto, and about 2,000mL of the treatment solution was removed by ultrafiltration. This operation was repeated 5 times to obtain a conductive polymer composite solution 1 of 1.0 mass%.

The ultrafiltration conditions were as follows.

Fractional molecular weight of ultrafiltration membrane: 30K

Cross-flow type

Flow rate of feed liquid: 3,000 mL/min

Film partial pressure: 0.12Pa

In other preparation examples, ultrafiltration was performed under the same conditions.

Preparation example 2

A solution of 3.02g of 3-hydroxythiophene and 15.0g of dope polymer 1 in 1,000mL of pure water was mixed at 30 ℃.

200ML of 10 mass% diluted sulfuric acid and 2,000mL of ion-exchanged water were added to the treated liquid after the filtration treatment, about 2,000mL of the treated liquid was removed by ultrafiltration, 2,000mL of ion-exchanged water was added thereto, and about 2,000mL of the liquid was removed by ultrafiltration. This operation was repeated 3 times.

The obtained treatment solution was purified with a cation exchange resin and an anion exchange resin, and then 2,000mL of ion exchange water was added thereto, and about 2,000mL of the treatment solution was removed by ultrafiltration. This operation was repeated 5 times to obtain 1.0 mass% of the electroconductive polymer composite solution 2.

The dope polymer 1 of the above preparation example 1 was changed to the dope polymer 2, and a conductive polymer composite solution 3 was obtained.

The dope polymer 1 of the above preparation example 1 was changed to the dope polymer 3, and a conductive polymer composite solution 4 was obtained.

The dope polymer 1 of the above preparation example 1 was changed to the dope polymer 4, and a conductive polymer composite solution 5 was obtained.

The dope polymer 1 of the above preparation example 1 was changed to the dope polymer 5, and a conductive polymer composite solution 6 was obtained.

The dope polymer 1 of the above preparation example 1 was changed to the dope polymer 6, and a conductive polymer composite solution 7 was obtained.

The dope polymer 1 of the above preparation example 1 was changed to the dope polymer 7, and a conductive polymer composite solution 8 was obtained.

The dope polymer 1 of the above preparation example 1 was changed to the dope polymer 8, and a conductive polymer composite solution 9 was obtained.

The dope polymer 1 of the above preparation example 1 was changed to the dope polymer 9, and a conductive polymer composite solution 10 was obtained.

The dope polymer 1 of the above preparation example 1 was changed to the dope polymer 10, and a conductive polymer composite solution 11 was obtained.

The dope polymer 1 of the above preparation example 1 was changed to the dope polymer 11, and a conductive polymer composite solution 12 was obtained.

The dope polymer 1 of the above preparation example 1 was changed to the dope polymer 12, and a conductive polymer composite solution 13 was obtained.

The dope polymer 1 of the above preparation example 1 was changed to the dope polymer 13, and a conductive polymer composite solution 14 was obtained.

The dope polymer 1 of the above preparation example 1 was changed to the dope polymer 14, and a conductive polymer composite solution 15 was obtained.

The dope polymer 1 of the above preparation example 1 was changed to the dope polymer 15, and a conductive polymer composite solution 16 was obtained.

The dope polymer 1 of the above preparation example 1 was changed to the dope polymer 16, and a conductive polymer composite solution 17 was obtained.

The dope polymer 1 of the above preparation example 1 was changed to the dope polymer 17, and a conductive polymer composite solution 18 was obtained.

The dope polymer 1 of the above preparation example 1 was changed to the dope polymer 18, and a conductive polymer composite solution 19 was obtained.

The dope polymer 1 of the above preparation example 1 was changed to the dope polymer 19, and a conductive polymer composite solution 20 was obtained.

The dope polymer 1 of the above preparation example 1 was changed to the dope polymer 20, and a conductive polymer composite solution 21 was obtained.

The dope polymer 1 of the above preparation example 1 was changed to the dope polymer 21, and a conductive polymer composite solution 22 was obtained.

The dope polymer 1 of the above preparation example 1 was changed to the dope polymer 22, and a conductive polymer composite solution 23 was obtained.

The dope polymer 1 of the above preparation example 1 was changed to the dope polymer 23, and a conductive polymer composite solution 24 was obtained.

The dope polymer 1 of the above preparation example 1 was changed to the dope polymer 24, and a conductive polymer composite solution 25 was obtained.

The dope polymer 1 of the above preparation example 1 was changed to the dope polymer 25, and a conductive polymer composite solution 26 was obtained.

The dope polymer 1 of the above preparation example 1 was changed to the dope polymer 26, and a conductive polymer composite solution 27 was obtained.

The dope polymer 1 of the above preparation example 1 was changed to the dope polymer 27, and a conductive polymer composite solution 28 was obtained.

The dope polymer 1 of the above preparation example 1 was changed to the dope polymer 28, and a conductive polymer composite solution 29 was obtained.

The dope polymer 1 of the above preparation example 1 was changed to the dope polymer 29, and a conductive polymer composite solution 30 was obtained.

The dope polymer 1 of the above preparation example 1 was changed to the dope polymer 30, and a conductive polymer composite solution 31 was obtained.

The dope polymer 1 of the above preparation example 1 was changed to the dope polymer 31, and a conductive polymer composite solution 32 was obtained.

The dope polymer 1 of the above preparation example 1 was changed to the dope polymer 32, and a conductive polymer composite solution 33 was obtained.

As shown in tables 1 to 3, a crosslinking agent, a solvent and an additive were added to the conductive polymer composite solution, and the solution was filtered and prepared using regenerated cellulose having a pore size of 1.0 μm except for examples 23 and 24.

(Measurement of thickness of biological contact layer)

The conductive polymer composite solution was spin-coated on a Si substrate, baked at 125 ℃ for 30 minutes on a hot plate, and the film thickness was measured by an optical film thickness meter. The results are shown in tables 1 to 3.

(Preparation of conductive substrate)

Conductive paste, DOTITE FA-333, prepared by rattan cell formation was applied by screen printing on ST-604 of thermoplastic urethane (TPU) film of Bemis company, baked in an oven at 120 ℃ for 10 minutes, and a round padlock-shaped conductive pattern of 18mm diameter was printed to prepare a conductive base material. Teflon (registered trademark) adhesive masking tapes are attached to four corners of a key hole of a padlock, a ST-604 film is attached to a quartz wafer, a conductive polymer composite solution is spin-coated thereon, and the key hole is baked at 120 ℃ for 10 minutes on a hot plate, and the Teflon (registered trademark) adhesive tapes are peeled off (FIG. 3).

The bioelectrode was immersed in pure water at 40℃for 1 hour while applying ultrasonic vibration, and then taken out of the water to visually observe whether or not the bioelectrode was peeled off.

(Measurement of biological Signal)

The bioelectrodes (circular shape with a diameter of 1.8cm at the contact with the skin) were cut as shown in FIG. 4, and a transparent adhesive tape was attached to the back, and the resultant was attached to the wrist as shown in FIG. 5, and ECG was measured. In fig. 5, 31 is a positive electrode, 32 is a negative electrode, and 33 is a ground.

Cross-linking agent 1MEIKANATE CX SU-268A (manufactured by Ming Chemie Co., ltd.)

Additive agent

[ 146]

Fluoroalkyl nonionic surfactant FS-31 (DuPont Co.)

Amine Compound 1

[ Chemical 147]

Amine Compound 2

[ 148]

The silver nanowire solution 1 added to the conductive polymer complex solution was a product having a diameter of 20nm, a length of 12 μm, and a concentration of 5mg/mL, which was obtained from Sigma-Aldrich.

As silver nanoparticle solution 1 added to the conductive polymer complex solution, a product of Sigma-Aldrich having a diameter of 20nm and a concentration of 0.02mg/mL was used.

The TPU substrate used was ST-604 of a thermoplastic urethane (TPU) film from Bemis company.

PEDOT-PSS of the comparative example, a high conductivity grade of Sigma-Aldrich was used.

TABLE 1

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TABLE 2

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TABLE 3

Examples 1 to 39 using the bioelectrode composition of the present invention showed no peeling in the impregnated water, and also showed good ECG signal. The ECG signal of example 1 is shown in FIG. 6.

As in the case of the waveform signal of fig. 6, it was evaluated as good.

On the other hand, in comparative examples 1 and 3, in which the dope polymer does not contain hydroxyl groups or carboxyl groups, and in comparative example 2, in which the crosslinking agent is not added, the biological contact layer is peeled off due to the immersion water, and the ECG signal cannot be measured.

The present specification includes the following aspects.

[1]: A bioelectrode composition comprising:

(A) Pi conjugated polymers;

(B) A conductive polymer composite containing a dope polymer which contains a repeating unit a1 having a hydroxyl group and/or a carboxyl group, and a repeating unit a2 having a sulfonic acid, a fluorosulfonyl imide, and an N-carbonyl fluorosulfonamide, and has a weight average molecular weight in the range of 1,000 ～ 500,000; and

(C) A cross-linking agent.

[2]: The bioelectrode composition according to item [1], wherein the crosslinking agent has a reactive group selected from the group consisting of an isocyanate group, a blocked isocyanate group, a carbodiimide group and an aziridine group.

[3]: The bioelectrode composition according to the above [1] or the above [2], wherein the (A) pi-conjugated polymer is obtained by polymerizing 1 or more precursor monomers selected from the group consisting of monocyclic aromatics, polycyclic aromatics, acetylenes, and derivatives thereof.

[4]: The bioelectrode composition according to item [3], wherein the monocyclic aromatic compound is any one of pyrrole, thiophene vinylidene, selenophene, tellurophenone, phenylene vinylidene, and aniline, and the polycyclic aromatic compound is acene.

[5]: The bioelectrode material composition as claimed in any one of the above [1] to [4], wherein the repeating unit A1 having a hydroxyl group and/or a carboxyl group of the dope polymer (B) has A1-1 and/or A1-2 represented by the following general formula (1),

[ 149]

[6]: The bioelectrode composition as described in any one of [1] to [5] above, wherein the dope polymer (B) has a partial structure represented by the following general formulae (2) -1 to (2) -4 as the repeating unit a2,

[ 150]

[7]: The bioelectrode composition according to [6], wherein the dope polymer of (B) has 1 or more kinds of repeating units selected from the repeating units A2-1 to A2-7 represented by the following general formula (2) as the repeating unit A2,

[ 151]

[8]: The bioelectrode composition according to the above item [7], wherein in the general formula (2), rf _1' has at least 1 fluorine atom and Rf _5' is a fluorine atom or a trifluoromethyl group.

[9]: The bioelectrode composition according to the above [7] or the above [8], wherein the dope polymer (B) contains an ammonium ion represented by the following general formula (3) as the ammonium ion,

[ 152]

[10]: The bioelectrode composition according to any of the above [1] to [9], wherein the bioelectrode composition further comprises a component (D) in addition to the components (A), (B) and (C), and the component (D) is composed of at least one resin selected from the group consisting of (meth) acrylate resins, (meth) acrylamide resins, urethane resins, polyvinyl alcohols, polyvinylpyrrolidone, polyoxazolines, polyglycerols, polyglycerol-modified polysilicones, celluloses, polyethylene glycols and polypropylene glycols.

[11]: The bioelectrode composition according to any of the above [1] to [10], further comprising 1 or more kinds selected from the group consisting of carbon powder, metal powder, silicon powder, and lithium titanate powder as the component (E).

[12]: The bioelectrode composition according to item [11], wherein the carbon powder is either one or both of carbon black and carbon nanotubes.

[13]: The bioelectrode composition according to the item [11] or the item [12], wherein the metal powder is any one of gold nanoparticles, silver nanoparticles, copper nanoparticles, gold nanowires, silver nanowires, and copper nanowires.

[14]: A bioelectrode comprising a conductive substrate and a bioelectrode contact layer formed on the conductive substrate, characterized in that:

the bioelectrode composition according to any one of the above [1] to [13], wherein the bioelectrode composition comprises a conductive polymer composite.

[15]: The bioelectrode according to item [14], wherein the conductive base material contains 1 or more selected from gold, silver chloride, platinum, aluminum, magnesium, tin, tungsten, iron, copper, nickel, stainless steel, chromium, titanium, and carbon.

[16]: A method for producing a bioelectrode comprising a conductive substrate and a bioelectrode contact layer formed on the conductive substrate, characterized by comprising: the bioelectrode composition according to any one of the above [1] to [13] is applied to the conductive substrate and cured, thereby forming the bioelectrode contact layer.

The present invention is not limited to the above embodiments. The above embodiments are exemplified, and the technical scope of the present invention is intended to include the embodiments having substantially the same constitution as the technical idea described in the claims of the present invention and exerting the same effects.

Description of the reference numerals

1,2 Biological electrode

10 Substrate material

11,21 Conductive substrate

12,22 Biological contact layer

31 Positive electrode

32 Negative electrode

33, Ground connection

Claims

1. A bioelectrode composition comprising:

(A) Pi conjugated polymers;

(C) A cross-linking agent.

2. The bioelectrode composition according to claim 1, wherein the crosslinking agent has a reactive group selected from the group consisting of an isocyanate group, a blocked isocyanate group, a carbodiimide group and an aziridine group.

3. The bioelectrode composition according to claim 1, wherein the (a) pi-conjugated polymer is obtained by polymerizing 1 or more precursor monomers selected from the group consisting of monocyclic aromatics, polycyclic aromatics, acetylenes, and derivatives thereof.

4. The bioelectrode composition according to claim 3, wherein the monocyclic aromatic compound is any one of pyrrole, thiophene vinylidene, selenophene, tellurophenone, phenylene vinylidene, and aniline, and the polycyclic aromatic compound is acene.

5. The bioelectrode material composition according to claim 1, wherein the repeating unit A1 having a hydroxyl group and/or a carboxyl group of the (B) dope polymer has A1-1 and/or A1-2 represented by the following general formula (1),

Wherein R ¹、R³ is a hydrogen atom or a methyl group, X ₁、X₂ is any one of a single bond, a phenylene group, a naphthylene group, an ether group, an ester group, and an amide group, R ²、R⁴ is any one of a single bond, a straight-chain, branched, or cyclic hydrocarbon group having 1 to 20 carbon atoms, an ether group, an ester group, m, and n are each an integer of 1 to 5, a1-1, and a1-2 are 0.ltoreq.a 1-1) <1.0, 0.ltoreq.a 1-2 <1.0, and 0< (a 1-1) + (a 1-2) <1.0.

6. The bioelectrode composition according to claim 1, wherein the (B) dope polymer has a partial structure represented by the following general formulae (2) -1 to (2) -4 as the repeating unit a2,

Wherein Rf ₁～Rf₄ is a hydrogen atom, a fluorine atom or a trifluoromethyl group, rf ₁、Rf₂ may be combined to form a carbonyl group, rf ₅ is a hydrogen atom, a fluorine atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and may be substituted with a fluorine atom, rf ₆、Rf₇ is a fluorine atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and has at least 1 fluorine atom, M is an integer of 0 to 4, and M ⁺ is an ion selected from the group consisting of a hydrogen ion, an ammonium ion, a sodium ion and a potassium ion.

7. The bioelectrode composition according to claim 6, wherein the (B) dopant polymer has 1 or more kinds of repeating units selected from the group consisting of repeating units A2-1 to A2-7 represented by the following general formula (2) as a repeating unit A2,

In the general formula (2), R ⁵、R⁷、R⁹、R¹²、R¹⁴、R¹⁵ and R ¹⁷ are each independently a hydrogen atom or a methyl group, R ⁶、R⁸、R¹⁰、R¹³、R¹⁶、R¹⁹ and R ²⁰ are each independently a single bond, or a linear, branched or cyclic hydrocarbon group having 1 to 13 carbon atoms, which may have 1 or more selected from an ester group, an ether group, an amide group, a urethane group, a thiocarbamate group and a urea group, R ¹¹ is a linear or branched alkylene group having 1 to 4 carbon atoms, 1 or 2 of hydrogen atoms in R ¹¹ may be substituted with a fluorine atom, Y ₁、Y₂、Y₃、Y₄、Y₆, And Y ₇ is each independently any one of a single bond, a phenylene group, a naphthylene group, an ether group, an ester group, and an amide group, Y ₅ is any one of a single bond, an ether group, and an ester group, Z is any one of an oxygen atom, and a-NR ¹⁸ -group, R ¹⁸ is any one of a hydrogen atom, a linear, branched, or cyclic alkyl group having 2 to 12 carbon atoms, and a phenyl group, and may have 1 or more selected from an ether group, a carbonyl group, an ester group, and an amide group, Z may form a ring together with R ⁸, and Rf _1' and Rf _5' are each a fluorine atom, Trifluoromethyl, or straight-chain or branched alkyl having 1 to 4 carbon atoms, and having at least 1 fluorine atom, m is an integer of 0 to 4, and a2-1, a2-2, a2-3, a2-4, a2-5, a2-6, and a2-7 are 0≤(a2-1)<1.0、0≤(a2-2)<1.0、0≤(a2-3)<1.0、0≤(a2-4)<1.0、0≤(a2-5)<1.0、0≤(a2-6)<1.0、0≤(a2-7)<1.0,0<(a2-1)+(a2-2)+(a2-3)+(a2-4)+(a2-5)+(a2-6)+(a2-7)<1.0,M⁺ ions selected from hydrogen ions, ammonium ions, sodium ions, and potassium ions.

8. The bioelectrode composition as claimed in claim 7, wherein in the general formula (2), rf _1' has at least 1 or more fluorine atoms, and Rf _5' is a fluorine atom or a trifluoromethyl group.

9. The bioelectrode composition as claimed in claim 7, wherein the (B) dope polymer contains an ammonium ion represented by the following general formula (3) as the ammonium ion,

In the general formula (3), R ^101d、R^101e、R^101f and R ^101g are each a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, a linear, branched or cyclic alkenyl or alkynyl group having 2 to 12 carbon atoms, or an aromatic group having 4 to 20 carbon atoms, and may have 1 or more kinds selected from an ether group, a carbonyl group, an ester group, a hydroxyl group, a carboxyl group, an amino group, a nitro group, a sulfonyl group, a sulfinyl group, a halogen atom, and a sulfur atom, and R ^101d and R ^101e, or R ^101d、R^101e and R ^101f may form a ring together with the nitrogen atom to which they are bonded, and when forming a ring, R ^101d and R ^101e, or R ^101d、R^101e and R ^101f are alkylene groups having 3 to 10 carbon atoms, or form a heteroaromatic ring having the nitrogen atom in the general formula (3) in the ring.

10. The bioelectrode composition according to claim 1, wherein the bioelectrode composition further comprises a component (D) in addition to the components (A), (B) and (C), and the component (D) is composed of at least 1 resin selected from the group consisting of (meth) acrylate resins, (meth) acrylamide resins, urethane resins, polyvinyl alcohols, polyvinylpyrrolidone, polyoxazolines, polyglycerols, polyglycerol-modified polysiloxanes, celluloses, polyethylene glycols and polypropylene glycols.

11. The bioelectrode composition as claimed in claim 1, further comprising 1 or more kinds selected from the group consisting of carbon powder, metal powder, silicon powder, and lithium titanate powder as component (E).

12. The bioelectrode composition as claimed in claim 11, wherein the carbon powder is either one or both of carbon black and carbon nanotubes.

13. The bioelectrode composition according to claim 11, wherein the metal powder is any one of gold nanoparticles, silver nanoparticles, copper nanoparticles, gold nanowires, silver nanowires, copper nanowires.

14. A bioelectrode comprising a conductive substrate and a bioelectrode contact layer formed on the conductive substrate, characterized in that:

the bioelectrode composition according to any one of claims 1 to 13, wherein the bioelectrode composition comprises a conductive polymer composite.

15. The bioelectrode according to claim 14, wherein the conductive base material contains 1 or more selected from gold, silver chloride, platinum, aluminum, magnesium, tin, tungsten, iron, copper, nickel, stainless steel, chromium, titanium, and carbon.

16. A method for producing a bioelectrode comprising a conductive substrate and a bioelectrode contact layer formed on the conductive substrate, characterized by comprising: the bioelectrode composition according to any one of claims 1 to 13 is applied on the conductive substrate and hardened to form the bioelectrode contact layer.