Biological electrode composition, biological electrode, and method for manufacturing biological electrode

Abstract

The present invention relates to a living body electrode composition, a living body electrode, and a manufacturing method of a living body electrode. The present invention provides a living body electrode composition capable of forming a living body contact layer for a living body electrode that is excellent in conductivity and biocompatibility, lightweight, and capable of being manufactured at low cost, whose conductivity does not greatly decrease regardless of being wetted with water or dried, and that is soft and excellent in stretchability and adhesiveness. The present invention provides a living body electrode composition containing (A) a polysiloxane; the (A) polysiloxane is bonded to an ionic polymer and has a structure (except for a cage structure) containing a T unit represented by the following general formula (T1); (R 0 SiO 3 / 2 )(T1) In the formula, R 0 is a linking group to the aforementioned ionic polymer; and the aforementioned ionic polymer is a polymer containing a repeating unit having a structure selected from any one of an ammonium salt, a lithium salt, a sodium salt, a potassium salt, a silver salt of a fluorosulfonic acid, a fluorosulfonimide, and an N-carbonylfluorosulfonamide.

Description

Technical Field

[0001] This invention relates to a bioelectrode that comes into contact with the skin of a living organism and can detect bodily states such as heart rate by utilizing electrical signals from the skin, a method for manufacturing the same, and a bioelectrode composition that can be ideally used as a bioelectrode. Existing technology

[0002] In recent years, with the popularization of the Internet of Things (IoT), the development of wearable devices has also progressed. Clocks and glasses that can connect to the Internet are representative examples. Furthermore, the medical and sports fields also require wearable devices that can monitor physical condition at any time, representing promising areas for future growth.

[0003] In the medical field, for example, some researchers are exploring wearable devices that monitor the state of bodily organs by sensing weak electrical currents, similar to electrocardiograms (ECG) which use electrical signals to sense the heartbeat. ECG measurements are performed by attaching electrodes coated with a conductive paste to the body, but this is a short, one-time measurement. In contrast, the development of wearable medical devices aims to provide continuous, weekly monitoring of health. Therefore, the bioelectrodes used in medical wearable devices must not exhibit changes in conductivity or cause skin allergies during prolonged use. Furthermore, they must be lightweight and manufactured at low cost.

[0004] Wearable medical devices include those that are attached to the body and those that are incorporated into clothing. For the body-attached type, a bioelectrode using a material containing a conductive paste, namely a water-soluble gel containing water and electrolytes, has been proposed (Patent Document 1). The water-soluble gel contains sodium, potassium, and calcium as electrolytes in a water-soluble polymer used to retain water, converting changes in ion concentration from the skin into electricity. On the other hand, for the clothing-incorporated type, a method has been proposed using a fabric containing conductive polymers such as poly-3,4-ethylenedioxythiophene-polystyrenesulfonate (PEDOT-PSS) and a silver paste as electrodes (Patent Document 2).

[0005] However, when using the aforementioned water-soluble gels containing water and electrolytes, there is a problem that the conductivity will also disappear if the water is lost due to drying. On the other hand, when using metals with high ionization tendency, such as copper, there is a risk of skin allergies for some people. When using conductive polymers such as PEDOT-PSS, there is also a risk of skin allergies due to the strong acidity of the conductive polymer, and there is also a problem of the conductive polymer peeling off from the fibers during washing.

[0006] Furthermore, metal nanowires, carbon black, and carbon nanotubes possess excellent electrical conductivity, leading to discussions about their use as electrode materials (Patent Documents 3, 4, 5). Metal nanowires, due to their increased contact probability with each other, can conduct electricity with even small amounts. However, metal nanowires are thin, pointed materials, which can cause skin allergies. As mentioned above, even if the material itself does not cause allergic reactions, its shape and irritant properties can sometimes lead to deterioration in biocompatibility, making it difficult to balance conductivity and biocompatibility.

[0007] It is believed that metal films have very high conductivity, thus making them excellent bioelectrodes. However, this is not necessarily the case. The heartbeat releases not only a weak current from the skin, but also sodium, potassium, and calcium ions. Therefore, it is necessary to convert the change in ion concentration into an electric current. However, precious metals, which are not easily ionized, are not very efficient at converting ions from the skin into an electric current. Therefore, bioelectrodes using precious metals have high impedance, resulting in high resistance during electrical conduction with the skin.

[0008] On the other hand, some researchers have studied batteries containing ionic liquids (Patent Document 6). Ionic liquids are characterized by high thermal and chemical stability and excellent conductivity, and their applications in batteries are expanding. However, as shown in Patent Document 6, ionic liquids with small molecular weights are soluble in water. Therefore, if bioelectrodes containing them are used, the ionic liquids can be extracted from sweat on the skin. This not only reduces conductivity but also causes the liquids to penetrate the skin and contribute to roughness.

[0009] Furthermore, some researchers have studied batteries using lithium salts of polymeric sulfonylimide (Non-Patent Literature 1). However, although lithium ions are highly mobile and used in batteries, they are not biocompatible materials. Additionally, some researchers have studied lithium salts suspended in polysiloxane-fluorosulfonic acid (Non-Patent Literature 2).

[0010] If bioelectrodes are removed from the skin, they cannot obtain information from the body. Furthermore, even a change in the contact area will alter the electrical charge, affecting the baseline of the electrocardiogram (electrocardiogram) signal. Therefore, to obtain a stable electrical signal from the body, bioelectrodes must maintain constant contact with the skin and their contact area must remain unchanged. Consequently, bioelectrodes should ideally be adhesive. Moreover, they need to be elastic and flexible, adapting to the stretching and bending of the skin.

[0011] Some researchers have studied bioelectrodes consisting of silver chloride layered with silver in contact with the skin, forming the conductive portion for communication with a device. Solid silver chloride has no adhesion or elasticity to the skin, so its ability to collect biological signals decreases, especially during bodily movement. Therefore, the silver chloride-silver composite film is used as a bioelectrode formed by layering a water-soluble gel between the silver chloride and the skin. In this case, degradation can occur due to the drying of the aforementioned gel.

[0012] In recent years, there have been proposals for bioelectrode compositions containing suspended silsesquioxanes with salts. For example: bioelectrode compositions containing suspended fluorosulfonate silsesquioxanes (Patent Document 7), bioelectrode compositions containing suspended fluorosulfonamide silsesquioxanes (Patent Document 8), and bioelectrode compositions containing suspended fluorosulfonamide silsesquioxanes (Patent Document 9).

[0013] Salts with highly polarizable silsesquioxane suspensions exhibit high ionic conductivity, resulting in high sensitivity as bioelectrodes. However, silsesquioxanes are rigid and lack elasticity. For wearable devices that adhere to elastic skin, they must possess not only high sensitivity as bioelectrodes but also flexibility and elasticity.

[0014] The examples describe the co-aggregation containing POSS R Ionic polymers (Patent Documents 10, 11, 12). POSS is a type of silsesquioxane, but it has a rigid cage-like structure, in which case the adhesion is not improved.

[0015] One proposal describes a bioelectrode material obtained by mixing an ionic polymer with a soft polyurethane containing silsesquioxanes (Patent Document 13). In this case, the silsesquioxanes, formed after polymer polymerization, have a stepped or random structure rather than a cage-like structure. The soft polyurethane containing stepped or random silsesquioxanes exhibits adhesiveness, offering the advantage of improved skin adhesion.

[0016] Existing technical documents

[0017] Patent documents

[0018] [Patent Document 1] International Publication No. WO2013-039151 (Supplementary Booklet)

[0019] [Patent Document 2] Japanese Patent Application Publication No. 2015-100673

[0020] [Patent Document 3] Japanese Patent Application Publication No. 5-095924

[0021] [Patent Document 4] Japanese Patent Application Publication No. 2003-225217

[0022] [Patent Document 5] Japanese Patent Application Publication No. 2015-019806

[0023] [Patent Document 6] Japanese Patent Publication No. 2004-527902

[0024] [Patent Document 7] Japanese Patent Application Publication No. 2020-31722

[0025] [Patent Document 8] Japanese Patent Application Publication No. 2020-28515

[0026] [Patent Document 9] Japanese Patent Application Publication No. 2020-006069

[0027] [Patent Document 10] Japanese Patent Application Publication No. 2018-99504

[0028] [Patent Document 11] Japanese Patent Application Publication No. 2018-126496

[0029] [Patent Document 12] Japanese Patent Application Publication No. 2018-130533

[0030] [Patent Document 13] Japanese Patent Application Publication No. 2019-93118

[0031] Non-patent literature

[0032] [Non-patent literature 1] J. Mater. Chem. A, 2016, 4, pp. 10038-10069

[0033] [Non-Patent Literature 2] J. of the Electrochemical Society, 150(8)A1090-A1094(2003) Summary of the Invention

[0034] [The problem that the invention aims to solve]

[0035] The present invention is made to solve the above-mentioned problems, and aims to provide a bioelectric electrode composition for forming a bioelectric contact layer for a bioelectric electrode that is lightweight, can be manufactured at low cost, does not significantly reduce conductivity when wetted or dried, and is soft, flexible and adhesive; a bioelectric electrode having a bioelectric contact layer formed on the bioelectric electrode composition; and a method thereof for manufacturing the same.

[0036] [Methods for solving the problem]

[0037] To address the aforementioned issues, the present invention provides...

[0038] A bioelectrode component,

[0039] Contains (A) polysiloxane; the (A) polysiloxane is bonded to an ionic polymer and has a structure containing T units represented by the following general formula (T1) (except for cage structures);

[0040] (R 0 SiO 3 / 2 (T1)

[0041] In the formula, R 0 For the linking group of the aforementioned ionic polymer; and

[0042] The aforementioned ionic polymer is a polymer containing repeating units having a structure of an ammonium salt, lithium salt, sodium salt, potassium salt, or silver salt selected from any of fluorosulfonic acid, fluorosulfonamide, and N-carbonyl fluorosulfonamide.

[0043] If so, it is a bioelectric electrode composition that can form a bioelectric contact layer for bioelectric electrodes with excellent conductivity and biocompatibility, is lightweight, can be manufactured at low cost, has conductivity that does not decrease significantly when wetted or dried, and is soft, flexible and adhesive.

[0044] Furthermore, the repeating unit having a structure of an ammonium salt, lithium salt, sodium salt, potassium salt, or silver salt selected from any of fluorosulfonic acid, fluorosulfonamide, and N-carbonyl fluorosulfonamide should preferably have a structure represented by any of the following general formulas (1)-1 to (1)-4.

[0045] [Chemistry 1]

[0046]

[0047] In the formula, Rf1 and Rf2 are hydrogen atoms, fluorine atoms, oxygen atoms, methyl groups, or trifluoromethyl groups. When Rf1 and Rf2 are oxygen atoms, Rf1 and Rf2 are one oxygen atom bonded to one carbon atom to form a carbonyl group. Rf3 and Rf4 are hydrogen atoms, fluorine atoms, or trifluoromethyl groups. One or more of Rf1 to Rf4 are fluorine atoms or trifluoromethyl groups. Rf5, Rf6, and Rf7 are fluorine atoms, straight-chain or branched alkyl groups having 1 to 4 carbon atoms, and having at least one fluorine atom. m is an integer from 1 to 4. M + The ions are selected from ammonium ions, lithium ions, sodium ions, potassium ions, and silver ions.

[0048] Furthermore, the repeating unit having a structure of an ammonium salt, lithium salt, sodium salt, potassium salt, or silver salt selected from any of fluorosulfonic acid, fluorosulfonamide, and N-carbonyl fluorosulfonamide should preferably be one or more repeating units (2-1) to (2-7) of the following general formula (2).

[0049] [Chemistry 2]

[0050]

[0051] In the formula, R 1 R 3 R 5 R 8 R 10 R 11 and R 13 Each is independently a hydrogen atom or a methyl group, R 2 R 4 R 6 R 9 R 12 and R 14 Each is independently a single bond, or may also have an ester group or an ether group or both, and is a straight-chain, branched, or cyclic hydrocarbon group with 1 to 13 carbon atoms. R 7 R is a straight-chain or branched alkylene group having 1 to 4 carbon atoms. 7 One or two hydrogen atoms in the group may be replaced by fluorine atoms. X1, X2, X3, X4, X6, and X7 are each independently a single bond, phenylene, naphthylene, ether, ester, or amide group; X5 is a single bond, ether, or ester group. Y is an oxygen atom, -NR 19 -base, R 19 It is a straight-chain or branched alkyl group with hydrogen atoms and 1 to 4 carbon atoms, and can also react with R. 4 Bonding and forming a ring. m is an integer from 1 to 4. a1, a2, a3, a4, a5, a6, and a7 are 0≤a1≤1.0, 0≤a2≤1.0, 0≤a3≤1.0, 0≤a4≤1.0, 0≤a5≤1.0, 0≤a6≤1.0, and 0≤a7≤1.0, and 0 <a1+a2+a3+a4+a5+a6+a7≤1.0。M + The ions are selected from ammonium ions, lithium ions, sodium ions, potassium ions, and silver ions. Rf5, Rf6, and Rf7 are fluorine atoms, straight-chain or branched alkyl groups having 1 to 4 carbon atoms, and having at least one fluorine atom.

[0052] If an ionic polymer has such repeating units, it can form a bioelectrode composition that can form a bio-contact layer that can obtain biological signals in a short time after being attached to the body.

[0053] Furthermore, the aforementioned component (A) should preferably be a condensation reaction product of an ionic intermediate polymer having an alkoxysilyl repeating unit, in addition to containing the repeating unit of the aforementioned general formula (2), also copolymerizing the repeating unit of the following general formula (3).

[0054] [Chemistry 3]

[0055]

[0056] In the formula, R20 X is a hydrogen atom or a methyl group, X8 is any one of a single bond, phenylene, naphthylene, ether, ester, or amide group, and R 21 It consists of single bonds, and is a straight-chain, branched, or cyclic alkylene or phenylene chain with 1 to 10 carbon atoms, and may also contain oxygen or nitrogen atoms. R 22 These are alkyl groups with 1 to 4 carbon atoms, which may be the same or different. b1 is 0. <b1<1.0。

[0057] At this point, the aforementioned condensation reaction product should preferably have repeating units of the following general formula (4).

[0058] [Chemistry 4]

[0059]

[0060] In the formula, R 20 X8, R 21 b1 is the same as mentioned above.

[0061] If it is such a component (A), it can be easily synthesized.

[0062] Furthermore, the aforementioned component (A) should preferably contain ammonium ions represented by the following general formula (5) as ammonium ions constituting the aforementioned ammonium salt.

[0063] [Chemistry 5]

[0064]

[0065] In the formula, R 101d R 101e R 101f R 101g Each group comprises a hydrogen atom, a straight-chain, branched, or cyclic alkyl group having 1 to 13 carbon atoms, a straight-chain, 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 also have one or more of the following groups: ether, carbonyl, ester, hydroxyl, amino, nitro, sulfonyl, sulfinyl, halogen atom, and sulfur atom. 101d With R 101e R 101d With R 101e With R 101f They can also form rings together with the nitrogen atoms they are bonded to. When a ring is formed, R 101d With R 101e and R 101d With R 101e With R 101f It is an alkylene group having 3 to 10 carbon atoms, or an aromatic heterocycle containing a nitrogen atom in the formula in the ring.

[0066] When the ionic polymer in component (A) has an ammonium salt structure, such ammonium ions can be used.

[0067] It should contain more adhesive resin as component (B).

[0068] At this time, the aforementioned component (B) should preferably be selected from one or more of polysiloxane resin, (meth)acrylate resin, and urethane resin.

[0069] If this is the case, it can remain in close contact with the skin and receive a stable electrical signal for an extended period of time.

[0070] Furthermore, the aforementioned component (B) should preferably contain an alkenyl diorganosiloxane and an organohydrogen polysiloxane with a SiH group.

[0071] At this point, the aforementioned component (B) should preferably contain more of R. x SiO (4-x) / 2 Polysiloxane resins with unit and SiO2 unit; R is a substituted or unsubstituted monovalent hydrocarbon group with 1 to 10 carbon atoms, and x is in the range of 2.5 to 3.5.

[0072] If so, it can be ideally used as a component of bioelectrodes.

[0073] It is advisable to include a high molecular weight compound with ionic repeating units as component (C).

[0074] At this time, the aforementioned ionic repeating unit of the aforementioned component (C) preferably contains repeating units of the following general formula (2) having a structure selected from the ammonium salt, lithium salt, sodium salt, potassium salt, and silver salt of any of fluorosulfonic acid, fluorosulfonamide, and N-carbonylfluorosulfonamide.

[0075] [Chemistry 6]

[0076]

[0077] In the formula, R 1 R 3 R 5 R 8 R 10 R 11 and R 13 Each is independently a hydrogen atom or a methyl group, R 2 R 4 R 6 R 9 R 12 and R 14 Each is independently a single bond, or may also have an ester group or an ether group or both, and is a straight-chain, branched, or cyclic hydrocarbon group with 1 to 13 carbon atoms. R 7 R is a straight-chain or branched alkylene group having 1 to 4 carbon atoms. 7One or two hydrogen atoms in the group may be replaced by fluorine atoms. X1, X2, X3, X4, X6, and X7 are each independently a single bond, phenylene, naphthylene, ether, ester, or amide group; X5 is a single bond, ether, or ester group. Y is an oxygen atom, -NR 19 -base, R 19 It is a straight-chain or branched alkyl group with hydrogen atoms and 1 to 4 carbon atoms, and can also react with R. 4 Bonding and forming a ring. m is an integer from 1 to 4. a1, a2, a3, a4, a5, a6, and a7 are 0≤a1≤1.0, 0≤a2≤1.0, 0≤a3≤1.0, 0≤a4≤1.0, 0≤a5≤1.0, 0≤a6≤1.0, and 0≤a7≤1.0, and 0 <a1+a2+a3+a4+a5+a6+a7≤1.0。M + The ions are selected from ammonium ions, lithium ions, sodium ions, potassium ions, and silver ions. Rf5, Rf6, and Rf7 are fluorine atoms, straight-chain or branched alkyl groups having 1 to 4 carbon atoms, and having at least one fluorine atom.

[0078] The effectiveness of the present invention can be further enhanced if the bioelectrode composition contains a polymeric compound having such repeating units.

[0079] It is advisable to include carbon powder and / or metal powder as component (D).

[0080] At this point, the aforementioned toner should preferably be either carbon black or carbon nanotubes, or both.

[0081] Furthermore, the aforementioned metal powder should preferably be selected from gold, silver, platinum, copper, tin, titanium, nickel, aluminum, tungsten, molybdenum, ruthenium, chromium, and indium.

[0082] At this point, the aforementioned metal powder should preferably be silver powder.

[0083] If so, the conductivity will be better.

[0084] It is advisable to include organic solvents as component (E).

[0085] If so, the coating properties of bio-electrode components will be better.

[0086] Furthermore, the present invention provides a bioelectrode having a conductive substrate and a bio-contact layer formed on the conductive substrate, wherein the aforementioned bio-contact layer is a hardened form of the aforementioned bioelectrode composition.

[0087] If the bioelectrode of the present invention is used, it is a bioelectrode with excellent conductivity and biocompatibility, lightweight, and can be manufactured at low cost. Its conductivity does not decrease significantly whether it is wetted or dried. It is also a soft, flexible, and adhesive bioelectrode.

[0088] Furthermore, the aforementioned conductive substrate preferably contains one or more of the following: gold, silver, silver chloride, platinum, aluminum, magnesium, tin, tungsten, iron, copper, nickel, stainless steel, chromium, titanium, carbon, and conductive polymers.

[0089] The bioelectrode of the present invention is particularly suitable for use with such a conductive substrate.

[0090] Furthermore, the present invention provides a method for manufacturing a bioelectrode, which is a method for manufacturing a bioelectrode having a conductive substrate and a bioelectrode contact layer formed on the conductive substrate, characterized in that: the bioelectrode composition is coated on the aforementioned conductive substrate and hardened thereon to form the aforementioned bioelectrode contact layer.

[0091] The bioelectrode manufacturing method of the present invention can easily produce bioelectrodes with excellent conductivity and biocompatibility, lightweight, and low cost. The conductivity will not be significantly reduced whether the bioelectrode is wetted or dried. The bioelectrode is also soft, flexible, and has excellent adhesion.

[0092] Furthermore, regarding the aforementioned conductive substrate, it is preferable to use one or more materials selected from gold, silver, silver chloride, platinum, aluminum, magnesium, tin, tungsten, iron, copper, nickel, stainless steel, chromium, titanium, carbon, and conductive polymers.

[0093] Such a conductive substrate is particularly suitable for use in the method of manufacturing the bioelectrode of the present invention.

[0094] [The effects of the invention]

[0095] As described above, the present invention provides a bioelectric electrode composition for forming a bioelectric contact layer for a bioelectric electrode that is lightweight, can be manufactured at low cost, does not significantly reduce conductivity when wetted or dried, and is soft, flexible and adhesive; a bioelectric electrode having a bioelectric contact layer formed on the bioelectric electrode composition; and a method thereof for manufacturing the present invention. Attached Figure Description

[0096] [ Figure 1 [Illustration 1] is a schematic cross-sectional view showing an example of the bioelectrode of the present invention.

[0097] [ Figure 2 [ ] is a schematic cross-sectional view showing an example of the bioelectrode of the present invention being installed in a living organism.

[0098] [ Figure 3 [Image 1] is a schematic diagram of the printed bio-electrode obtained in an embodiment of the present invention.

[0099] [ Figure 4[Illustrated diagram of a bioelectrode prepared in an embodiment of the present invention, wherein an adhesive layer and wires are installed.]

[0100] [ Figure 5 [Illustration] is a diagram showing the attachment positions of the electrodes and grounding to the human body during biosignal measurement in an embodiment of the present invention.

[0101] [ Figure 6 [Illustration] is an electrocardiogram waveform obtained using the bioelectrode of an embodiment of the present invention. Detailed Implementation

[0102] As mentioned above, there is a need to develop a bioelectrode composition for a bioelectrode that can form a bioelectrode contact layer with excellent conductivity and biocompatibility, is lightweight, can be manufactured at low cost, is soft, elastic and adhesive, can stably collect biological signals when attached to the skin for a long time, whether wet or dry due to bathing, etc., and leaves no residue on the skin after being peeled off, a bioelectrode composition having a bioelectrode contact layer formed therefrom, and a method for manufacturing the same.

[0103] In conjunction with the heartbeat, sodium, potassium, and calcium ions are released from the skin's surface. Bioelectrodes must convert the increase or decrease in ion release from the skin into electrical signals. Therefore, materials with excellent ion conductivity are needed to transmit these ion changes.

[0104] To adhere to the skin and stably acquire biological signals, the bioelectrode membrane must possess softness, elasticity, and adhesion. The stratum corneum of the epidermis regenerates daily, accumulating dead skin cells (sludge) between the bioelectrode membrane and the skin. These dead skin cells easily peel off the epidermis, causing the bioelectrode to detach and preventing signal collection. Therefore, the bioelectrode must maintain its adhesion even after prolonged use. On the other hand, if residue remains on the skin after prolonged application and removal, it can potentially cause rashes and rough skin.

[0105] Regarding the composition of polysiloxane adhesives, some use a combination of cross-linked polysiloxane and MQ resin. Polysiloxane, which originally has excellent peel properties, exhibits adhesive properties when combined with MQ resin.

[0106] To improve the adhesion of bioelectrodes, the ionic polymer material itself must possess adhesive properties. Therefore, the inventors of this application propose designing stepped T-units (RSiO) bonded to the ionic polymer material... 3 / 2 The morphology of polysiloxane resin is effective, which led to the idea of ​​this invention.

[0107] The inventors of this application propose a bio-electrode composition containing a stepped T-unit (RSiO) bonded to an ionic polymer material. 3 / 2 The composition of the bioelectrode is a polysiloxane, and a bioelectrode obtained by curing it is proposed.

[0108] If the acid forming the neutral salt is highly acidic, the ions will be strongly polarized, increasing ionic conductivity. In lithium-ion batteries, lithium salts of bis(trifluoromethanesulfonyl)imide acid and tri(trifluoromethanesulfonyl)methyl acid exhibit high ionic conductivity for this reason. On the other hand, there is a problem that the higher the acid strength in the acidic state before neutralization, the stronger the biological irritation of the salt. In other words, there is a trade-off between ionic conductivity and biological irritation. However, salts used in biological electrodes must balance high ionic conductivity with low biological irritation.

[0109] Ionic compounds have the property that the larger the molecular weight, the lower the skin permeability and the lower the skin irritation. Considering this, ionic compounds are preferably high molecular weight polymers. Therefore, the inventors of this application conceived of designing this ionic compound to have polymerizable double bonds, polymerizing it into a polymer, copolymerizing it with a monomer having an alkoxysilyl group, and then using a condensation reaction to prepare a step-type T-unit (RSiO). 3 / 2 Polysiloxane is used to obtain a soft, stretchable, and adhesive biological contact layer with high sensitivity to biological signals.

[0110] Furthermore, the inventors of this application have discovered that by mixing this salt (polysiloxane) with adhesives (resins) such as polysiloxane, acrylic, or urethane, it is possible to maintain close contact with the skin and obtain a stable electrical signal for a longer period of time.

[0111] As mentioned above, ionomers themselves have adhesive properties, so they do not necessarily need to be mixed with the aforementioned adhesives.

[0112] When bioelectrodes are applied and removed intermittently, peelability is also necessary. In such cases, they are sometimes mixed with non-adhesive or slightly adhesive polysiloxane, acrylic, or urethane resins. While this improves peelability, it reduces adhesion to the skin, potentially leading to the inability to collect stable biosignals. Therefore, one objective of this invention is to achieve a stable biosignal even when mixed with non-adhesive or slightly adhesive polysiloxane, acrylic, or urethane resins, thus balancing peelability and biosignal stability through the use of adhesive ionomers.

[0113] That is, the present invention is

[0114] A bioelectrode component,

[0115] Contains (A) polysiloxane; the (A) polysiloxane is bonded to an ionic polymer and has a structure containing T units represented by the following general formula (T1) (except for cage structures);

[0116] (R 0 SiO 3 / 2 (T1)

[0117] In the formula, R 0 For the linking group of the aforementioned ionic polymer; and

[0118] The aforementioned ionic polymer is a polymer containing repeating units having a structure of an ammonium salt, lithium salt, sodium salt, potassium salt, or silver salt selected from any of fluorosulfonic acid, fluorosulfonamide, and N-carbonyl fluorosulfonamide.

[0119] The present invention will now be described in detail, but the invention is not limited thereto.

[0120] <Bioelectrode Components>

[0121] The bioelectrode composition of the present invention contains (A) a polysiloxane bonded to an ionic polymer and having a structure containing T units (except for a cage-like structure), and preferably further contains (B) an adhesive resin. The components are described in further detail below.

[0122] [(A) Polysiloxanes bonded to ionic polymers and having a structure containing T units (excluding cage structures)]

[0123] The component (A) in this invention is a polysiloxane that is bonded to an ionic polymer containing repeating units having a structure of an ammonium salt, lithium salt, sodium salt, potassium salt, or silver salt selected from fluorosulfonic acid, fluorosulfonamide, and N-carbonyl fluorosulfonamide, and has a structure (excluding cage structures) containing T units represented by the following general formula (T1).

[0124] (R 0 SiO 3 / 2 (T1)

[0125] In the formula, R 0 This refers to the linking group with the aforementioned ionic polymer.

[0126] (A) Components, such as ionic polymers and step-type or random T-units (RSiO). 3 / 2(A) is a polysiloxane complex (bound salt). Such a component (A) can be obtained, for example, by condensation reaction of a polymeric compound (ionic intermediate polymer) copolymerized with repeating units having the structure of an ammonium salt, lithium salt, sodium salt, potassium salt, or silver salt selected from fluorosulfonic acid, fluorosulfonamide, and N-carbonyl fluorosulfonamide.

[0127] The following section describes the structures (repeating units) contained in ionic polymers and ionic intermediate polymers.

[0128] The repeating unit having a structure of an ammonium salt, lithium salt, sodium salt, potassium salt, or silver salt selected from any of fluorosulfonic acid, fluorosulfonamide, or N-carbonylfluorosulfonamide, preferably has a structure represented by any of the following general formulas (1)-1 to (1)-4.

[0129] [Chemistry 7]

[0130]

[0131] In the formula, Rf1 and Rf2 are hydrogen atoms, fluorine atoms, oxygen atoms, methyl groups, or trifluoromethyl groups. When Rf1 and Rf2 are oxygen atoms, Rf1 and Rf2 are one oxygen atom bonded to one carbon atom to form a carbonyl group. Rf3 and Rf4 are hydrogen atoms, fluorine atoms, or trifluoromethyl groups. One or more of Rf1 to Rf4 are fluorine atoms or trifluoromethyl groups. Rf5, Rf6, and Rf7 are fluorine atoms, straight-chain or branched alkyl groups having 1 to 4 carbon atoms, and having at least one fluorine atom. m is an integer from 1 to 4. M + The ions are selected from ammonium ions, lithium ions, sodium ions, potassium ions, and silver ions.

[0132] (Repeating units a1~a7)

[0133] The repeating unit having a structure selected from the ammonium salt, lithium salt, sodium salt, potassium salt, and silver salt of fluorosulfonic acid represented by the above general formulas (1)-1 and (1)-2, the ammonium salt, lithium salt, sodium salt, potassium salt, and silver salt of sulfonamide represented by (1)-3, and the ammonium salt, lithium salt, sodium salt, potassium salt, and silver salt of N-carbonylsulfonamide represented by (1)-4, is preferably one or more of the repeating units (2-1) to (2-7) (repeating units a1 to a7) of the following general formula (2).

[0134] [Chemistry 8]

[0135]

[0136] In the formula, R 1 R 3 R 5 R 8 R 10 R11 and R 13 Each is independently a hydrogen atom or a methyl group, R 2 R 4 R 6 R 9 R 12 and R 14 Each is independently a single bond, or may also have an ester group or an ether group or both, and is a straight-chain, branched, or cyclic hydrocarbon group with 1 to 13 carbon atoms. R 7 R is a straight-chain or branched alkylene group having 1 to 4 carbon atoms. 7 One or two hydrogen atoms in the group may be replaced by fluorine atoms. X1, X2, X3, X4, X6, and X7 are each independently a single bond, phenylene, naphthylene, ether, ester, or amide group; X5 is a single bond, ether, or ester group. Y is an oxygen atom, -NR 19 -base, R 19 It is a straight-chain or branched alkyl group with hydrogen atoms and 1 to 4 carbon atoms, and can also react with R. 4 Bonding and forming a ring. m is an integer from 1 to 4. a1, a2, a3, a4, a5, a6, and a7 are 0≤a1≤1.0, 0≤a2≤1.0, 0≤a3≤1.0, 0≤a4≤1.0, 0≤a5≤1.0, 0≤a6≤1.0, and 0≤a7≤1.0, and 0 <a1+a2+a3+a4+a5+a6+a7≤1.0。M + The ions are selected from ammonium ions, lithium ions, sodium ions, potassium ions, and silver ions. Rf5, Rf6, and Rf7 are fluorine atoms, straight-chain or branched alkyl groups having 1 to 4 carbon atoms, and having at least one fluorine atom.

[0137] Specifically, the following can be cited as examples of fluorosulfonate monomers used to obtain repeating units a1 to a5 in repeating units a1 to a7 represented by the above general formula (2).

[0138] [Chemistry 9]

[0139]

[0140] [Chemistry 10]

[0141]

[0142] [Chemistry 11]

[0143]

[0144] [Chemistry 12]

[0145]

[0146] [Chemistry 13]

[0147]

[0148] [Chemistry 14]

[0149]

[0150] [Chemistry 15]

[0151]

[0152] [Chemistry 16]

[0153]

[0154] [Chemistry 17]

[0155]

[0156] [Chemistry 18]

[0157]

[0158] [Chemistry 19]

[0159]

[0160] [Chemistry 20]

[0161]

[0162] [Chemistry 21]

[0163]

[0164] [Chemistry 22]

[0165]

[0166] [Chemistry 23]

[0167]

[0168] [Chemistry 24]

[0169]

[0170] [Chemistry 25]

[0171]

[0172] [Chemistry 26]

[0173]

[0174] [Chemistry 27]

[0175]

[0176] [Chemistry 28]

[0177]

[0178] [Chemistry 29]

[0179]

[0180] The sulfonyl imide salt monomer used to obtain the repeating unit a6 in the above general formula (2) can be specifically exemplified as follows.

[0181] [Chemistry 30]

[0182]

[0183] [Chemistry 31]

[0184]

[0185] [Chemistry 32]

[0186]

[0187] [Chemistry 33]

[0188]

[0189] [Chemistry 34]

[0190]

[0191] The N-carbonylsulfonamide salt monomer used to obtain the repeating unit a7 in the above general formula (2) can be specifically exemplified as follows.

[0192] [Chemistry 35]

[0193]

[0194] [Chemistry 36]

[0195]

[0196] In the formula, R 1 R 3 R 5 R 8 R 10 R 11 and R 13 Same as above.

[0197] Furthermore, component (A) should preferably contain ammonium ions (ammonium cations) represented by the following general formula (5) as ammonium ions constituting ammonium salts, especially as M in repeating unit a (repeating units a1 to a7). + .

[0198] [Chemistry 37]

[0199]

[0200] In the formula, R 101d R 101e R 101f R 101g Each group comprises a hydrogen atom, a straight-chain, branched, or cyclic alkyl group having 1 to 13 carbon atoms, a straight-chain, 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 also have one or more of the following groups: ether, carbonyl, ester, hydroxyl, amino, nitro, sulfonyl, sulfinyl, halogen atom, and sulfur atom. 101d With R 101e R 101d With R 101e With R 101f They can also form rings together with the nitrogen atoms they are bonded to. When a ring is formed, R 101d With R 101e and R 101d With R 101e With R 101f It is an alkylene group having 3 to 10 carbon atoms, or an aromatic heterocycle containing a nitrogen atom in the formula in the ring.

[0201] Specifically, the following can be exemplified as the ammonium ion represented by the above general formula (5).

[0202] [Chemistry 38]

[0203]

[0204] [Chemistry 39]

[0205]

[0206] [Chemistry 40]

[0207]

[0208] [Chemistry 41]

[0209]

[0210] [Chemistry 42]

[0211]

[0212] [Chemistry 43]

[0213]

[0214] [Chemistry 44]

[0215]

[0216] [Chemistry 45]

[0217]

[0218] [Chemistry 46]

[0219]

[0220] [Chemistry 47]

[0221]

[0222] [Chemistry 48]

[0223]

[0224] [Chemistry 49]

[0225]

[0226] [Transformation 50]

[0227]

[0228] [Chemistry 51]

[0229]

[0230] [Chemistry 52]

[0231]

[0232] [Chemistry 53]

[0233]

[0234] It is preferable that the ammonium ion represented by the above general formula (5) is a tertiary or quaternary ammonium ion.

[0235] (Repeating unit b1)

[0236] In addition to the aforementioned repeating units a1 to a7, the ionic intermediate polymer of the present invention preferably contains repeating units b1 of the following general formula (3) having a trialkoxysilyl group.

[0237] [Chemistry 54]

[0238]

[0239] In the formula, R 20 X is a hydrogen atom or a methyl group, X8 is any one of a single bond, phenylene, naphthylene, ether, ester, or amide group, and R 21 It consists of single bonds, and is a straight-chain, branched, or cyclic alkylene or phenylene chain with 1 to 10 carbon atoms, and may also contain oxygen or nitrogen atoms. R 22 These are alkyl groups with 1 to 4 carbon atoms, which may be the same or different. b1 is 0. <b1<1.0。

[0240] The monomer used to obtain the repeating unit b1 of general formula (3) can be specifically exemplified as follows.

[0241] [Chemistry 55]

[0242]

[0243] In the formula, R 20 Same as above.

[0244] (Repeating unit c)

[0245] In addition to the repeating units a1 to a7 and b1 described above, the ionic polymer and ionic intermediate polymer in component (A) of the bio-electrode composition of the present invention may also copolymerize repeating unit c having a ethylene glycol dimethyl ether chain to improve conductivity. Specifically, examples of monomers having repeating unit c with a ethylene glycol dimethyl ether chain can be shown below. Copolymerization of the repeating unit having a ethylene glycol dimethyl ether chain promotes the movement of ions released from the skin within the dry electrode membrane, thereby improving the sensitivity of the dry electrode.

[0246] [Chemistry 56]

[0247]

[0248] [Chemistry 57]

[0249]

[0250] [Chem.58]

[0251]

[0252] [Chemistry 59]

[0253]

[0254] R is a hydrogen atom or a methyl group.

[0255] (Repeating unit d)

[0256] In the ionic polymer and ionic intermediate polymer of component (A) of the bio-electrode composition of the present invention, in addition to the repeating units a1-a7, b1, and c described above, hydrophilic repeating units d having hydroxyl, carboxyl, ammonium salt, betaine, amide, pyrrolidone, lactone ring, lactam ring, sulopentalide ring, sodium salt of sulfonic acid, or potassium salt of sulfonic acid can be copolymerized to improve conductivity. Monomers used to obtain hydrophilic repeating units d are specifically exemplified below. By copolymerizing these repeating units containing hydrophilic groups, the sensitivity to ions released from the skin can be improved, and the sensitivity of the dry electrode can be enhanced.

[0257] [Transformation 60]

[0258]

[0259] [Chemistry 61]

[0260]

[0261] R is a hydrogen atom or a methyl group.

[0262] (Repeating unit e)

[0263] The ionic polymer and ionic intermediate polymer in component (A) of the bioelectrode composition of the present invention may contain repeating units e that impart adhesive ability. Specifically, the following may be examples of monomers used to obtain repeating units e.

[0264] [Chemistry 62]

[0265]

[0266] [Chemistry 63]

[0267]

[0268] [Chemistry 64]

[0269]

[0270] [Chemistry 65]

[0271]

[0272] [Chemistry 66]

[0273]

[0274] (Repeating unit f)

[0275] The crosslinking repeating unit f can also be further copolymerized. Examples of crosslinking repeating units include repeating units having an oxerocyclopropane ring or an oxerocyclobutane ring.

[0276] Monomers used to obtain repeating units f having oxetine or butane rings can be specifically listed below.

[0277] [Chemistry 67]

[0278]

[0279] [Chemistry 68]

[0280]

[0281] Here, R represents a methyl group or a hydrogen atom.

[0282] (Repeating unit g)

[0283] The ionic polymer and ionic intermediate polymer in component (A) of the bioelectrode composition of the present invention, in addition to the repeating units selected from a1 to a7, b1, c to f above, may also contain repeating units g having silicon. Specifically, the following examples can be cited.

[0284] [Chemistry 69]

[0285]

[0286] n is a number between 0 and 100.

[0287] [Chemistry 70]

[0288]

[0289] (Repeating unit h)

[0290] The ionic polymer and ionic intermediate polymer in component (A) of the bioelectrode composition of the present invention may contain a repeating unit h containing fluorine, in addition to the repeating units selected from a1 to a7 and b1 to g mentioned above.

[0291] Monomers used to obtain repeating units h having fluorine can be specifically exemplified as follows.

[0292] [Chemistry 71]

[0293]

[0294] [Chemistry 72]

[0295]

[0296] [Chemistry 73]

[0297]

[0298] [Chemistry 74]

[0299]

[0300] [Chemistry 75]

[0301]

[0302] [Chemistry 76]

[0303]

[0304] [Chemistry 77]

[0305]

[0306] Here, R represents a hydrogen atom or a methyl group.

[0307] [Ionic intermediate polymers]

[0308] One method for synthesizing an ionic intermediate polymer for obtaining component (A) is as follows: a desired monomer provided with repeating units a1 to a7, b1, c, d, e, f, g, h is added to an organic solvent with a free radical polymerization initiator and heated to polymerize, thereby obtaining a copolymer polymer compound.

[0309] Examples of organic solvents used in polymerization include toluene, benzene, tetrahydrofuran, diethyl ether, and dioxane. Examples of polymerization initiators include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylpentanonitrile), dimethyl 2,2-azobis(2-methylpropionic acid), benzoyl peroxide, and lauroyl peroxide. The heating temperature is preferably 50–80°C, and the reaction time is preferably 2–100 hours, more preferably 5–20 hours.

[0310] Here, the proportions of the repeating units a1 to a7, b1, c, d, e, f, g, h in the ionic intermediate polymer are 0 ≤ a1 < 1.0, 0 ≤ a2 < 1.0, 0 ≤ a3 < 1.0, 0 ≤ a4 < 1.0, 0 ≤ a5 < 1.0, 0 ≤ a6 < 1.0, 0 ≤ a7 < 1.0, 0 < a1 + a2 + a3 + a4 + a5 + a6 + a7 < 1.0, 0 < b1 < 1.0, 0 ≤ c < 1.0, 0 ≤ d < 1.0, 0 ≤ e < 0.9, 0 ≤ f < 0.9, 0 ≤ g < 0.9, 0 ≤ h < 0.9. Preferably, 0 ≤ a1 ≤ 0.9, 0 ≤ a2 ≤ 0.9, 0 ≤ a3 ≤ 0.9, 0 ≤ a4 ≤ 0.9, 0 ≤ a5 ≤ 0.9, 0 ≤ a6 ≤ 0.9, 0 ≤ a7 ≤ 0.9, 0.01 ≤ a1 + a2 + a3 + a4 + a5 + a6 + a7 ≤ 0.99, 0.001 ≤ b1 ≤ 0.8, 0 ≤ c ≤ 0.8, 0 ≤ d ≤ 0.8, 0 ≤ e < 0.8, 0 ≤ f < 0.8, 0 ≤ g < 0.8, 0 ≤ h < 0.8. More preferably, 0 ≤ a1 ≤ 0.8, 0 ≤ a2 ≤ 0.8, 0 ≤ a3 ≤ 0.8, 0 ≤ a4 ≤ 0.8, 0 ≤ a5 ≤ 0.8, 0 ≤ a6 ≤ 0.8, 0 ≤ a7 ≤ 0.8, 0.02 ≤ a1 + a2 + a3 + a4 + a5 + a6 + a7 ≤ 0.95, 0.01 ≤ b1 ≤ 0.7, 0 ≤ c ≤ 0.7, 0 ≤ d ≤ 0.5, 0 ≤ e < 0.3, 0 ≤ f < 0.7, 0 ≤ g < 0.7, 0 ≤ h < 0.7.

[0311] In addition, for example, a1 + a2 + a3 + a4 + a5 + a6 + a7 + b1 + c + d + e + f + g + h = 1 means that in the polymer compound containing the repeating units a1, a2, a3, a4, a5, a6, a7, b1, c, d, e, f, g, h, the total amount of the repeating units a1, a2, a3, a4, a5, a6, a7, b1, c, d, e, f, g, h is 100 moles relative to the total amount of all repeating units; a1 + a2 + a3 + a4 + a5 + a6 + a7 + b1 + c + d + e + f + g + h < 1 means that the total amount of the repeating units a1, a2, a3, a4, a5, a6, a7, b1, c, d, e, f, g, h is less than 100 mol% relative to the total amount of all repeating units, that is, in addition to a1, a2, a3, a4, a5, a6, a7, b1, c, d, e, f, g, h, other repeating units are also contained.

[0312] The molecular weight of the ionic intermediate polymer, based on weight average molecular weight, should preferably be 500 or more, more preferably 1,000 or more and 1,000,000 or less, and even more preferably 2,000 or more and 500,000 or less. Furthermore, if the amount of ionic monomers not incorporated into the ionic intermediate polymer after polymerization (residual monomers) is small, there is no risk of skin penetration and allergic reactions during biocompatibility testing; therefore, the amount of residual monomers should be minimized. The amount of residual monomers should preferably be 10 parts by mass or less per 100 parts by mass of the total ionic intermediate polymer. Also, a single ionic intermediate polymer can be used, or two or more polymers with different molecular weights, dispersities, and monomers can be mixed and used.

[0313] [(A) Polysiloxanes bonded to ionic polymers and having a structure containing T units (excluding cage structures)]

[0314] Component (A) in this invention can be obtained in the form of the condensation reaction product of the above-mentioned ionic intermediate polymer. If, in addition to the repeating unit of the above-mentioned general formula (2), the repeating unit of the following general formula (3) is copolymerized, the condensation reaction product will be a polysiloxane with a stepped or random T-unit structure bonded to the ionic polymer and having the repeating unit of the following general formula (4).

[0315] [Chemistry 78]

[0316]

[0317] In the formula, R 20 X is a hydrogen atom or a methyl group, X8 is any one of a single bond, phenylene, naphthylene, ether, ester, or amide group, and R 21 It consists of single bonds, and is a straight-chain, branched, or cyclic alkylene or phenylene chain with 1 to 10 carbon atoms, and may also contain oxygen or nitrogen atoms. R 22 These are alkyl groups with 1 to 4 carbon atoms, which may be the same or different. b1 is 0. <b1<1.0。

[0318] [Chemistry 79]

[0319]

[0320] In the formula, R 20 X8, R 21 b1 is the same as mentioned above.

[0321] The molecular weight increases by hydrolyzing the alkoxysilyl group of an ionic intermediate polymer copolymerized with repeating units of general formula (3) to form a step-type or random polysiloxane.

[0322] Regarding T-unit polysiloxanes, stepped, random, and cage-like structures can be listed. Cage-like polysiloxane copolymers have been illustrated in Japanese Patent Application Publication Nos. 2018-110845, 2018-99504, and 2019-011454, but no improvement in adhesion was observed. However, adhesion is improved by copolymerizing stepped and random polysiloxanes. This is believed to be due to the structure of the stepped and random polysiloxanes.

[0323] Cage-shaped monomers containing T units have been described in the specific examples of repeating unit g above. Cage-shaped T-unit polysiloxanes are formed during the monomer synthesis stage. On the other hand, T-unit polysiloxanes formed by condensation reaction of monomers containing trialkoxysilanes after polymerization are not cage-shaped but step-shaped or random-shaped.

[0324] In addition, the polysiloxane in component (A) is not particularly limited as long as it has a structure containing T units other than a cage structure, such as a stepped or random structure. In addition to these structures, it may also have a cage structure.

[0325] The polymer (component A) after condensation reaction can be represented by the following general formula (2)'.

[0326] [Chemistry 80]

[0327]

[0328] In the formula, R 1 ~R 14 R 20 R 21 X1~X8, Y, m, M + Rf5~Rf7, a1~a7, and b1 are the same as described above.

[0329] During the condensation reaction in the synthesis of component (A), co-condensation with other alkoxysilanes is also possible. Examples of repeating units b2 obtained from other alkoxysilanes are shown below.

[0330] [Chemistry 81]

[0331]

[0332] [Chemistry 82]

[0333]

[0334] [Chemistry 83]

[0335]

[0336] [Chemistry 84]

[0337]

[0338] Sulfonate silsesquioxanes can also be copolymerized as repeating unit b2 obtained from other alkoxysilanes. Sulfonate silsesquioxanes preferably have repeating units represented by the following general formula.

[0339] [Chemistry 85]

[0340]

[0341] In the formula, R 30 It is a straight-chain, branched, or cyclic alkylene group with 1 to 20 carbon atoms, and may also contain aromatic, ether, ester, or fluorine atoms, or be an aryl group with 6 to 10 carbon atoms. Rf1' to Rf4' are hydrogen atoms, fluorine atoms, or trifluoromethyl groups, and Rf1' to Rf4' have more than one fluorine atom. Rf3' and Rf4' may also merge with each other to form an oxygen atom and form a double bond. M + It can be lithium ions, sodium ions, potassium ions, or silver ions.

[0342] Specifically, the following can be exemplified as repeating units of sulfonate silsesquioxanes represented by the above general formula.

[0343] [Chemistry 86]

[0344]

[0345] [Chemistry 87]

[0346]

[0347] [Chemistry 88]

[0348]

[0349] [Chemistry 89]

[0350]

[0351] [Chemistry 90]

[0352]

[0353] [Chemistry 91]

[0354]

[0355] [Chemistry 92]

[0356]

[0357] [Chemistry 93]

[0358]

[0359] [Chemistry 94]

[0360]

[0361] [Chemistry 95]

[0362]

[0363] [Chemistry 96]

[0364]

[0365] Sulfonyl imide salt silsesquioxanes can also be copolymerized as repeating unit b2 obtained from other alkoxysilanes. Sulfonyl imide salt silsesquioxanes preferably have repeating units represented by the following general formula.

[0366] [Chemistry 97]

[0367]

[0368] In the formula, R 31 It is a straight-chain, branched, or cyclic alkylene group having 2 to 20 carbon atoms, and may also have an aromatic group, ether group, ester group, or an aryl group having 6 to 10 carbon atoms. Rf' is a straight-chain, branched, or cyclic alkyl group having 1 to 4 carbon atoms, and has at least one fluorine atom. M + It can be lithium ions, sodium ions, potassium ions, or silver ions.

[0369] Specifically, the following can be exemplified as repeating units of sulfonylimide salt silsesquioxanes represented by the above general formula.

[0370] [Chem. 98]

[0371]

[0372] [Chemistry 99]

[0373]

[0374] [Chemistry 100]

[0375]

[0376] Silsesquioxanes bonded to N-carbonylsulfonamide salts can also be copolymerized as repeating units b2 obtained from other alkoxysilanes. Silsesquioxanes bonded to N-carbonylsulfonamide salts preferably have repeating units represented by the following general formula.

[0377] [Chemistry 101]

[0378]

[0379] In the formula, R32 It is a straight-chain, branched, or cyclic alkylene group having 2 to 20 carbon atoms, and may also have an aromatic group, ether group, ester group, or an aryl group having 6 to 10 carbon atoms. Rf' is a straight-chain, branched, or cyclic alkyl group having 1 to 4 carbon atoms, and has at least one fluorine atom. M + It can be lithium ions, sodium ions, potassium ions, or silver ions.

[0380] Specifically, the repeating units of sesquioxanes bonded to N-carbonylsulfonamide salts as represented by the above general formula can be exemplified by the following.

[0381] [Chemistry 102]

[0382]

[0383] [Chemistry 103]

[0384]

[0385] [Chemistry 104]

[0386]

[0387] M here + Same as above.

[0388] In the bioelectrode composition (A) of the present invention, regarding the repeating unit b2 obtained from other alkoxysilanes, in addition to the repeating units described above, repeating units composed of silsesquioxanes having ethylene glycol dimethyl ether chains may also be copolymerized to improve conductivity. Specifically, the following examples can be cited.

[0389] [Chemistry 105]

[0390]

[0391] [Chemistry 106]

[0392]

[0393] In the formula, 0≤m≤20, 0≤n≤20, and 1≤m+n≤20.

[0394] By incorporating polysiloxane with both T-units and Q-units in component (A), adhesion is improved, resulting in a stable biological signal with reduced baseline drift and less noise. Furthermore, by incorporating highly polarizable T-units such as cyano or nitro groups, ionic T-units, or T-units with ethylene glycol dimethyl ether chains in component (A), ionic conductivity can be enhanced.

[0395] Here, the ratio of b1 to b2 is 0 < b1 / (b1 + b2) ≤ 1.0 and 0 ≤ b2 / (b1 + b2) < 1.0. It is preferably 0.1 ≤ b1 / (b1 + b2) ≤ 1.0 and 0 ≤ b2 / (b1 + b2) ≤ 0.8, and more preferably 0.3 ≤ b1 / (b1 + b2) ≤ 1.0 and 0 ≤ b2 / (b1 + b2) ≤ 0.7.

[0396] In the biological electrode composition of the present invention, the blending amount of component (A) is preferably 0.1 to 300 parts by mass with respect to 100 parts by mass of component (B) described below, and more preferably 1 to 200 parts by mass. Component (A) can be used alone or in combination of two or more.

[0397] [(B) Adhesive resin]

[0398] The (B) adhesive resin blended in the biological electrode composition of the present invention is a component that is compatible with the complex (salt) of the above-mentioned component (A) to prevent salt dissolution, holds conductive improvers such as metal powder, carbon powder, silicon powder, and lithium titanate powder, and improves adhesiveness. When component (A) has sufficient adhesiveness, component (B) adhesive resin is not necessarily required. In addition, the resin of component (B) may be any resin other than the above-mentioned component (A), preferably any one of thermosetting resins and photocurable resins, or both of them, and particularly preferably one or more selected from polysiloxane-based, acrylic-based, and urethane-based resins.

[0399] Regarding the adhesive polysiloxane-based resin, addition reaction-curable or free radical crosslinking reaction-curable types can be mentioned. As the addition reaction-curable type, for example, those described in Japanese Patent Application Laid-Open No. 2015-193803 containing an alkenyl-containing diorganosiloxane, an MQ resin having R3SiO 0.5 and SiO2 units, an organohydrogenpolysiloxane having a plurality of SiH groups, a platinum catalyst, an addition reaction control agent, and an organic solvent can be used. Also, as the free radical crosslinking reaction-curable type, for example, those described in Japanese Patent Application Laid-Open No. 2015-193803 containing a diorganopolysiloxane that may or may not have an alkenyl group, an MQ resin having R3SiO 0.5 and SiO2 units, an organic peroxide, and an organic solvent can be used. Here, R is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms.

[0400] Also, a polysiloxane-resin integrated compound formed by a condensation reaction of a polysiloxane having silanol at the polymer terminal and side chain with an MQ resin can be used. Since the MQ resin contains a lot of silanol, the adhesive force is increased by adding this resin, but it has no crosslinkability, so it does not form a molecular bond with the polysiloxane. If the polysiloxane and the resin are made into an integrated type as described above, the adhesive force can be increased.

[0401] Furthermore, modified siloxanes having groups selected from amino, oxetyl, oxetyl, polyether, hydroxyl, carboxyl, mercapto, methacrylate, acrylate, phenol, silanol, carboxylic anhydride, aryl, aralkyl, amide, ester, and lactone rings can also be added to polysiloxanes. Adding modified siloxanes improves the dispersibility of component (A) in the polysiloxane. It is acceptable for the modified siloxane to be obtained by modifying any one end, two ends, or side chain of the siloxane.

[0402] As an adhesive acrylic resin, for example, hydrophilic (meth)acrylates and long-chain hydrophobic (meth)acrylates as repeating units can be used as disclosed in Japanese Patent Application Publication No. 2016-011338. Depending on the situation, (meth)acrylates with functional groups or (meth)acrylates with siloxane bonds can also be copolymerized.

[0403] As an adhesive urethane resin, for example, those having urethane bonds and polyether bonds, polyester bonds, polycarbonate bonds, and siloxane bonds as described in Japanese Patent Application Publication No. 2016-065238 can be used.

[0404] Furthermore, to prevent a decrease in conductivity due to the detachment of component (A) from the bio-contact layer, the resin of component (B) in the bio-electrode composition of the present invention should preferably have high compatibility with component (A). Also, to prevent the bio-contact layer from peeling off from the conductive substrate, the resin of component (B) in the bio-electrode composition of the present invention should preferably have high adhesion to the conductive substrate. Using a highly polar resin is effective in making the resin of component (B) highly compatible with the conductive substrate and salt. Examples of such resins include resins having one or more groups selected from ether bonds, ester bonds, amide bonds, imide bonds, urethane bonds, thiourethane bonds, and thiol groups, or polyacrylic acid resins, polyamide resins, polyimide resins, polyurethane resins, and polythiourethane resins. On the other hand, since the bio-contact layer comes into contact with the organism, it is easily affected by the organism's sweat. Therefore, in the bioelectrode composition of the present invention, resin (B) is preferably highly hydrophobic and not easily hydrolyzed. Using a silicon-containing resin is effective in making the resin of component (B) highly hydrophobic and not easily hydrolyzed.

[0405] Regarding polyacrylic resins containing silicon atoms, polymers with polysiloxane in the main chain and polymers with silicon atoms in the side chains are both applicable. As a polymer with polysiloxane in the main chain, siloxanes or silsesquioxanes containing (meth)acrylate propyl groups can be used. In this case, curing can be achieved by adding a photoradical generator to partially polymerize the (meth)acrylate groups.

[0406] As a polyamide resin containing silicon atoms, the polyamide polysiloxane resin disclosed in Japanese Patent Application Publication No. 2011-079946 and US Patent No. 5981680 can be ideally used. Such a polyamide polysiloxane resin can be synthesized by combining, for example, a polysiloxane compound with amino groups at both ends or a non-polysiloxane compound with amino groups at both ends, and a non-polysiloxane compound with carboxyl groups at both ends or a polysiloxane compound with carboxyl groups at both ends.

[0407] Alternatively, un-cyclized polyamic acid obtained by reacting carboxylic anhydride with an amine can be used. The carboxyl groups of the polyamic acid can be crosslinked using epoxy or oxetane crosslinking agents, or by esterification of the carboxyl groups with hydroxyethyl (meth)acrylate, followed by photoradical crosslinking of the (meth)acrylate portion.

[0408] As a polyimide resin containing silicon atoms, the polyimide polysiloxane resin disclosed in Japanese Patent Application Publication No. 2002-332305 is an ideal example. Polyimide resins have very high viscosity, but by incorporating (meth)acrylic acid monomers as solvents and crosslinking agents, they can be made to have low viscosity.

[0409] As a polyurethane resin containing silicon atoms, polyurethane polysiloxane resin can be cited as an example. Such a polyurethane polysiloxane resin can be cross-linked using urethane bonds by blending a compound with isocyanate groups at both ends and a compound with hydroxyl groups at both ends and heating. Furthermore, in this case, either or both of the compound with isocyanate groups at both ends or the compound with hydroxyl groups at both ends must contain silicon atoms (siloxane bonds). Alternatively, as described in Japanese Patent Application Publication No. 2005-320418, a polysiloxane can be blended with a urethane (meth)acrylate monomer and photocrosslinked. Furthermore, a polymer that simultaneously possesses both siloxane bonds and urethane bonds and has (meth)acrylate groups at the ends can also be photocrosslinked. In particular, materials with polysiloxane side chains and polyurethane main chains as described in Japanese Patent Application Publication No. 2018-123304 and Japanese Patent Application Publication No. 2019-70109 have high strength and high elasticity, and are therefore more ideal.

[0410] Polysulfide urethane resins containing silicon atoms can be obtained by reacting a compound with a thiol group with a compound with an isocyanate group, either of which must contain silicon atoms. Furthermore, if the resin has (meth)acrylate groups at the end, it can also be photocured.

[0411] In polysiloxane resins, besides the aforementioned diorganosiloxanes with alkenyl groups and those with R3SiO 0.5In addition to MQ resins with SiO2 units and organohydrogen polysiloxanes with multiple SiH groups, if modified siloxanes with groups selected from amino, oxetyl propane, oxetyl butane, polyether, hydroxyl, carboxyl, mercapto, methacrylic acid, acrylic acid, phenolic, silanol, carboxylic anhydride, aryl, aralkyl, amide, ester, and lactone rings are added, the compatibility with the above salts will be improved.

[0412] Alkenyl diorganosiloxanes and organohydrogen polysiloxanes with multiple SiH groups can be crosslinked via an addition reaction using a platinum catalyst.

[0413] Platinum catalysts include: platinum chloride, alcoholic solutions of platinum chloride, reaction products of platinum chloride and alcohols, reaction products of platinum chloride and olefin compounds, reaction products of platinum chloride and vinyl-containing siloxanes, platinum-olefin complexes, platinum-vinyl-containing siloxane complexes, and other platinum-based catalysts; as well as platinum group metal catalysts such as rhodium complexes and ruthenium complexes. Alternatively, catalysts can be obtained by dissolving and dispersing these catalysts in alcohol-based, hydrocarbon-based, or siloxane-based solvents.

[0414] In addition, the amount of platinum catalyst added should preferably be 5 to 2,000 ppm relative to 100 parts by weight of resin of component (B), especially in the range of 10 to 500 ppm.

[0415] In the bioelectrode composition of the present invention, the amount of component (B) is preferably 0 to 2000 parts by mass, and more preferably 10 to 1000 parts by mass, relative to 100 parts by mass of the composite of ionomer and T-unit polysiloxane (component (A)). Furthermore, component (B) can be used alone or in combination with two or more other components.

[0416] Furthermore, when using addition-curing polysiloxane resins, addition reaction control agents may also be added. These addition reaction control agents are added as quenchers to prevent the platinum catalyst from reacting in solution and at low temperatures before heat curing after coating formation. Specifically, examples include 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-ethynylcyclohexanol, 3-methyl-3-trimethylsiloxy-1-butyn, 3-methyl-3-trimethylsiloxy-1-pentyn, 3,5-dimethyl-3-trimethylsiloxy-1-hexyn, 1-ethynyl-1-trimethylsiloxycyclohexane, bis(2,2-dimethyl-3-butynoxy)dimethylsilane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, and 1,1,3,3-tetramethyl-1,3-divinyldisiloxane.

[0417] The amount of addition reaction control agent added should preferably be 0 to 10 parts by weight relative to 100 parts by weight of resin of component (B), especially 0.05 to 3 parts by weight.

[0418] When component (B) contains double bonds that can be cross-linked by free radicals, adding a free radical generator is effective. Free radical generators include photoradiative free radical generators and thermal free radical generators.

[0419] Photoradical generators include: acetophenone, 4,4'-dimethoxydiphenylethylenedione, phenylethylenedione, benzoin, diphenyl ketone, 2-benzoylbenzoic acid, 4,4'-bis(dimethylamino)diphenyl ketone, 4,4'-bis(diethylamino)diphenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, benzoin isobutyl ether, 4-benzoylbenzoic acid, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, methyl 2-benzoylbenzoate, 2-(1,3-benzodioxane-5-yl)-4,6-bis(trichloromethyl)- 1,3,5-Triazine, 2-Benzyl-2-(dimethylamino)-4'-morpholinophenylbutanone, 4,4'-dichlorodiphenyl ketone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,4-diethylthioxanthone-9-one, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO), 1,4-dibenzoylbenzene, 2-ethylanthraquinone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methylphenylacetone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone, 2-isonitrosophenylacetone, 2-phenyl-2-(p-toluenesulfonyloxy)acetophenone.

[0420] Thermally decomposable free radical generators can also be added to harden it. Examples of thermal free radical generators include: 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylpentanitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(methylpropanediidine) hydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] hydrochloride, 2,2'-azobis(4-methoxy-2,4-dimethylpentanitrile), 2,2'-azobis(cyclohexane-1-formonitrile), 1[(1-cyano-1-methylethyl)azo]formamide, 2,2'-azobis[ [2-Methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2'-azobis(isobutyric acid) dimethyl ester, 4,4'-azobis(4-cyanopentanoic acid), 2,2'-azobis(2-methylpropionate) dimethyl ester, benzoyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide, di-tert-pentyl peroxide, di-n-butyl peroxide, dicumene peroxide, etc.

[0421] In addition, the amount of free radical generator added should preferably be in the range of 0.1 to 50 parts by weight relative to 100 parts by weight of resin of component (B).

[0422] Among them, the resin of component (B) is preferably one containing an organosiloxane with an alkenyl group and an organohydrogen polysiloxane with a SiH group, and preferably one containing more R x SiO (4-x) / 2 Polysiloxane resins with units (R being a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and x being in the range of 2.5 to 3.5) and SiO2 units are particularly preferred.

[0423] Furthermore, as described later, the bio-contact layer is a hardened form of the bio-electrode composition. By hardening it, the bio-contact layer achieves good adhesion to both the skin and the conductive substrate. Furthermore, the hardening method is not particularly limited; general methods can be used, such as cross-linking reactions utilizing either or both of heat and light, or acid or base catalysts. Regarding the cross-linking reaction, for example, the methods described in Chapter 2, pp. 51–371 of the cross-linking reaction manual published by Yasuharu Maruzen (2013) can be appropriately selected.

[0424] [(C) Blended with ionic polymers]

[0425] In addition to component (A), the bioelectrode composition of the present invention may also contain an ionic polymer (a blended ionic polymer). The repeating units of the blended ionic polymer may be used in the form described in component (A) above, particularly those represented by the general formula (2) above. The amount of the blended ionic polymer added is preferably in the range of 0.1 to 100 parts by weight relative to 100 parts by weight of the resin in component (B).

[0426] [(D) Conductive powder]

[0427] [Metallic powder]

[0428] In order to improve electronic conductivity, metal powder selected from gold, silver, platinum, copper, tin, titanium, nickel, aluminum, tungsten, molybdenum, ruthenium, chromium, and indium may be added as component (D) in the bioelectrode composition of the present invention. The amount of metal powder added is preferably in the range of 1 to 50 parts by weight relative to 100 parts by weight of resin in component (B).

[0429] In terms of the types of metal powders, gold, silver, and platinum are preferable considering conductivity; silver, copper, tin, titanium, nickel, aluminum, tungsten, molybdenum, ruthenium, and chromium are preferable considering price; and precious metals are preferable considering biocompatibility. Taking all these factors into account, silver is the best choice.

[0430] Regarding the shape of metal powder, spherical, disc-shaped, flake-shaped, and needle-shaped forms can be listed. Adding flake-shaped powder results in the highest and most ideal conductivity. The metal powder should have a size of less than 100 μm and a tap density of 5 g / cm³. 3 The following has a specific surface area of ​​0.5m². 2 Thin flakes with lower density and larger specific surface area (g / g or higher) are preferred.

[0431] [Toner]

[0432] Carbon materials (carbon powder) can be added as conductivity improvers. Examples of carbon materials include carbon black, graphite, carbon nanotubes, carbon fibers, and graphene. Carbon nanotubes can be single-layered or multi-layered, and surface modification with organic groups is also acceptable. The amount of carbon material added should preferably be in the range of 1 to 50 parts by weight relative to 100 parts by weight of resin component (B).

[0433] Silicon powder

[0434] In the bioelectrode composition of the present invention, silicon powder may be added to improve the sensitivity of ion acceptance. Examples of silicon powder include powders composed of silicon, silicon monoxide, and silicon carbide. The particle size of the powder is preferably less than 100 μm, more preferably less than 1 μm. Smaller particles have a larger surface area, thus accepting more ions, resulting in a highly sensitive bioelectrode. The amount of silicon powder added is preferably in the range of 1 to 50 parts by weight relative to 100 parts by weight of the resin in component (B).

[0435] [Lithium titanate powder]

[0436] In the bioelectrode composition of the present invention, lithium titanate powder may be added to improve the sensitivity of ion acceptance. Examples of lithium titanate powder include Li₂TiO₃, LiTiO₂, and spinel-structured Li₄Ti₅O₃. 12 The molecular formula should preferably be spinel-structured lithium titanate powder. Alternatively, lithium titanate particles that have been composited with carbon can also be used. The particle size of the powder should preferably be less than 100 μm, more preferably less than 1 μm. Smaller particles have a larger surface area, so they can accept many ions, making them highly sensitive bioelectrodes. These can also be composite powders with carbon. The amount of lithium titanate powder added should preferably be in the range of 1 to 50 parts by weight relative to 100 parts by weight of resin component (B).

[0437] [(E) Organic solvents]

[0438] Furthermore, organic solvents can be added as component (E) to the bioelectrode composition of the present invention. Specific examples of organic solvents include: toluene, xylene, cumene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, styrene, α-methylstyrene, butylbenzene, sec-butylbenzene, isobutylbenzene, isopropyltoluene, diethylbenzene, 2-ethyl-p-xylene, 2-propyltoluene, 3-propyltoluene, 4-propyltoluene, 1,2,3,5-tetramethyltoluene, 1,2,4,5-tetramethyltoluene, tetrahydronaphthalene, 4-phenyl-1-butene, tert-pentylbenzene, pentylbenzene, 2-tert-butyltoluene, 3-tert-butyltoluene, 4-tert-butyltoluene, 5-isopropyl-m-xylene, 3-methylethylbenzene, tert-butyl-3-ethylbenzene, 4-tert-butyl-o-xylene, 5-tert-butyl-m-xylene. Aromatic hydrocarbon solvents such as xylene, tert-butyl-p-xylene, 1,2-diisopropylbenzene, 1,3-diisopropylbenzene, 1,4-diisopropylbenzene, dipropylbenzene, pentamethylbenzene, hexamethylbenzene, hexylbenzene, and 1,3,5-triethylbenzene; n-heptane, isoheptane, 3-methylhexane, 2,3-dimethylpentane, 3-ethylpentane, 1,6-heptadiene, 5-methyl-1-hexyne, norbornene, norbornene, dicyclopentadiene, 1-methyl-1,4-cyclohexadiene, 1-heptyne, 2-heptyne, cycloheptane, cycloheptene, 1,3-dimethylcyclopentane, ethylcyclopentane, methylcyclohexane, 1-methyl-1-cyclohexene, 3-methyl-1-cyclohexene, methylenecyclohexane, 4-methyl-1-cyclohexene, 2- Methyl-1-hexene, 2-methyl-2-hexene, 1-heptene, 2-heptene, 3-heptene, n-octane, 2,2-dimethylhexane, 2,3-dimethylhexane, 2,4-dimethylhexane, 2,5-dimethylhexane, 3,3-dimethylhexane, 3,4-dimethylhexane, 3-ethyl-2-methylpentane, 3-ethyl-3-methylpentane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 2,2,3-trimethylpentane, 2,2,4-trimethylpentane, cyclooctane, cyclooctene, 1,2-dimethylcyclohexane, 1,3-dimethylcyclohexane, 1,4-dimethylcyclohexane, ethylcyclohexane, vinylcyclohexane, isopropylcyclopentane, 2,2-dimethyl-3-hexene, 2, 4-Dimethyl-1-hexene, 2,5-Dimethyl-1-hexene, 2,5-Dimethyl-2-hexene, 3,3-Dimethyl-1-hexene, 3,4-Dimethyl-1-hexene, 4,4-Dimethyl-1-hexene, 2-Ethyl-1-hexene, 2-Methyl-1-heptene, 1-Octenene, 2-Octenene, 3-Octenene, 4-Octenene, 1,7-Ocadiene, 1-Octyne, 2-Octyne, 3-Octyne, 4-Octyne, n-Nonane, 2,3-Dimethylheptane, 2,4-Dimethylheptane, 2,5-Dimethylheptane, 3,3-Dimethylheptane, 3,4-Dimethylheptane, 3,5-Dimethylheptane, 4-Ethylheptane, 2-Methyloctane, 3-Methyloctane, 4-Methyloctane, 2,2,4,4-Tetramethylpentane, 2,2,4-trimethylhexane, 2,2,5-trimethylhexane, 2,2-dimethyl-3-heptene, 2,3-dimethyl-3-heptene, 2,4-dimethyl-1-heptene, 2,6-dimethyl-1-heptene, 2,6-dimethyl-3-heptene, 3,5-dimethyl-3-heptene, 2,4,4-trimethyl-1-hexene, 3,5,5-trimethyl-1-hexene, 1-ethyl-2-methylcyclohexane, 1-ethyl-3-methylcyclohexane, 1-ethyl-4 -Methylcyclohexane, propylcyclohexane, isopropylcyclohexane, 1,1,3-trimethylcyclohexane, 1,1,4-trimethylcyclohexane, 1,2,3-trimethylcyclohexane, 1,2,4-trimethylcyclohexane, 1,3,5-trimethylcyclohexane, allylcyclohexane, octahydroindene, 1,8-nonadiene, 1-nonyne, 2-nonyne, 3-nonyne, 4-nonyne, 1-nonene, 2-nonene, 3-nonene, 4-nonene, n-decane, 3,3-dimethyloctane, 3,5-dimethyloctane, 4,4- Dimethyl octane, 3-ethyl-3-methylheptane, 2-methylnonane, 3-methylnonane, 4-methylnonane, tert-butylcyclohexane, butylcyclohexane, isobutylcyclohexane, 4-isopropyl-1-methylcyclohexane, pentylcyclopentane, 1,1,3,5-tetramethylcyclohexane, cyclododecane, 1-decene, 2-decene, 3-decene, 4-decene, 5-decene, 1,9-decadiene, decahydronaphthalene, 1-decyne, 2-decyne, 3-decyne, 4-decyne, 5-decyne, 1,5,9-decadiene, 2 ,6-Dimethyl-2,4,6-octtriene, limonene, geraniol, 1,2,3,4,5-pentamethylcyclopentadiene, α-phellandrene, pinene, terpinene, tetrahydrodicyclopentadiene, 5,6-dihydrodicyclopentadiene, 1,4-decadiyne, 1,5-decadiyne, 1,9-decadiyne, 2,8-decadiyne, 4,6-decadiyne, n-undecane, pentylcyclohexane, 1-undecane, 1,10-undecadiene, 1-undecaneyne, 3-undecaneyne, 5-undecaneyne, tricyclic [6.2.1.0, 2,7Aliphatic hydrocarbon solvents such as undecane-4-ene, n-dodecane, n-tridecane, n-pentadecane, n-hexadecane, 2-methylundecane, 3-methylundecane, 4-methylundecane, 5-methylundecane, 2,2,4,6,6-pentamethylheptane, 1,3-dimethyladamantane, 1-ethyladamantane, 1,5,9-cyclododecanetriene, 1,2,4-trivinylcyclohexane, and isoparaffin; ketone solvents such as cyclohexanone, cyclopentanone, 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclohexanone, and methyl n-pentanone; alcohol solvents such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; propylene glycol monomethyl ether, Ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monopentyl ether, diethylene glycol monoheptyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, diisopropyl ether, diisobutyl ether, diisopentyl ether, di-n-pentyl ether, methylcyclopentyl ether, methylcyclohexyl ether, di-n-butyl ether Ether solvents such as ether, di-sec-butyl ether, diisopentyl ether, di-sec-pentyl ether, di-tert-pentyl ether, di-n-hexyl ether, and anisole; ester solvents such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol monotert-butyl ether acetate; lactone solvents such as γ-butyrolactone; and water.

[0439] In addition, the amount of organic solvent added should preferably be in the range of 10 to 50,000 parts by weight relative to 100 parts by weight of resin of component (B).

[0440] [(F) Other additives]

[0441] In the bioelectrode composition of this invention, in addition to the platinum catalyst, addition reaction controller, and free radical generator described in component (B), a crosslinking agent, a crosslinking catalyst, and ionic additives may also be mixed. Furthermore, silica particles, polyether polysiloxane, and polyglycerol polysiloxane may also be mixed. The surface of the silica particles is hydrophilic, exhibiting good affinity with hydrophilic ionic polymers, polyether polysiloxane, and polyglycerol polysiloxane, thus improving the dispersion of these polymers in the hydrophobic polysiloxane adhesive. Silica particles are ideally suited for both dry and wet applications.

[0442] [Cross-linking agent]

[0443] An epoxy-based crosslinking agent may also be added to the bioelectrode composition of the present invention. In this case, the crosslinking agent is a compound containing multiple epoxy groups and oxocyclic butyl groups within one molecule. The amount added is 1 to 30 parts by weight relative to 100 parts by weight of the resin in component (B).

[0444] [Cross-linking catalyst]

[0445] A catalyst for crosslinking epoxy groups and oxetyl groups may also be added to the bioelectrode composition of the present invention. The catalyst used in this case may be the one described in paragraphs 0027 to 0029 of Japanese Patent Application Publication No. 2019-503406. The amount added is 0.01 to 10 parts by weight relative to 100 parts by weight of resin (B).

[0446] [Ionic additives]

[0447] In the bioelectrode composition of the present invention, ionic additives for improving ionic conductivity can be added. Considering biocompatibility, examples include sodium chloride, potassium chloride, calcium chloride, magnesium chloride, sodium saccharin, acesulfame potassium, sodium carboxylate, potassium carboxylate, calcium carboxylate, sodium sulfonate, potassium sulfonate, calcium sulfonate, sodium phosphate, potassium phosphate, calcium phosphate, magnesium phosphate, betaine, and salts disclosed in Japanese Patent Application Publication Nos. 2018-44147, 2018-59050, 2018-59052, and 2018-130534.

[0448] [Polysiloxane compounds with a polyglycerol structure]

[0449] In the bioelectrode composition of the present invention, to improve the membrane's moisturizing properties and thus enhance the sensitivity and conductivity of ions released from the skin, a polyglycerol-based polysiloxane compound may be added. The amount of the polyglycerol-based polysiloxane compound incorporated is preferably 0.01 to 100 parts by weight, and more preferably 0.5 to 60 parts by weight, relative to the total of 100 parts by weight of components (A) and (B). Furthermore, a single polyglycerol-based polysiloxane compound may be used, or two or more may be used in combination.

[0450] Polysiloxane compounds having a polyglycerol structure are preferably represented by the following general formulas (4)' and (5)'.

[0451] [Chemistry 107]

[0452]

[0453] In equations (4)' and (5)', R 1Each is independent and may be the same as or different from the others. It is a straight-chain or branched alkyl or phenyl group with hydrogen atoms or 1 to 50 carbon atoms. It may also contain ether groups and may be a polysiloxane chain represented by general formula (6). 2 ' is a group with a polyglycerol structure represented by formula (4)'-1 or formula (4)'-2, R 3 Each is independent, and they may be the same as or different from each other, as mentioned above in R. 1 'Group or the aforementioned R 2 'Group, R 4 Each is independent, and they may be the same as or different from each other, as mentioned above in R. 1 'Group, the aforementioned R 2 'Group or oxygen atom. When R 4 When R is an oxygen atom 4 The groups can also merge into a single ether group and form a ring with the silicon atom. a' can be the same or different, ranging from 0 to 100, b' from 0 to 100, and a'+b' from 0 to 200. However, when b' is 0, R... 3 At least one of ' is the aforementioned R 2 'Group. In formulas (4)'-1 and (4)'-2, (5)', R 5 ' is an alkylene group having 2 to 10 carbon atoms or an arylene group having 7 to 10 carbon atoms, R 6 '、R 7 ' is an alkylene group having 2 to 6 carbon atoms, R 7 It can also be an ether bond, with c' ranging from 0 to 20 and d' ranging from 1 to 20.

[0454] Such polysiloxane compounds having a polyglycerol structure can be exemplified as follows.

[0455] [Chemistry 108]

[0456]

[0457] [Chemistry 109]

[0458]

[0459] [Chemical 110]

[0460]

[0461] [Chemistry 111]

[0462]

[0463] [Chemistry 112]

[0464]

[0465] [Chemistry 113]

[0466]

[0467] [Chemistry 114]

[0468]

[0469] [Chemistry 115]

[0470]

[0471] [Chemistry 116]

[0472]

[0473] [Chemistry 117]

[0474]

[0475] In the formula, a', b', c' and d' are the same as above.

[0476] If a polysiloxane compound with such a polyglycerol structure is contained, it can exhibit superior moisturizing properties. As a result, it can be made into a bioelectrode composition that can form a biocontact layer that exhibits superior sensitivity to ions released from the skin.

[0477] As described above, the bio-electrode composition of the present invention is capable of forming a bio-electrode composition with high adhesion, maintaining sufficient adhesion even after being peeled off and reattached to the skin, efficiently transmitting electrical signals from the skin to the device (i.e., excellent conductivity), and without causing allergies even after prolonged skin contact (i.e., excellent biocompatibility). It is lightweight, can be manufactured at low cost, and its conductivity does not significantly decrease regardless of whether it is wetted or dried. Furthermore, by adding conductive powders (carbon powder, metal powder), conductivity can be improved. By combining it with a resin possessing adhesiveness and elasticity, a bio-electrode with particularly high adhesion and elasticity can be manufactured. In addition, elasticity and adhesion to the skin can be improved by additives, and elasticity and adhesion can be adjusted by appropriately regulating the resin composition and the thickness of the bio-electrode contact layer.

[0478] <Bioelectrodes>

[0479] Furthermore, the present invention provides a bioelectrode having a conductive substrate and a bio-contact layer formed on the conductive substrate, wherein the aforementioned bio-contact layer is a hardened form of the bioelectrode composition of the present invention.

[0480] The following describes the bioelectrode of the present invention in detail with reference to the drawings, but the present invention is not limited thereto.

[0481] Figure 1 This is a schematic cross-sectional view showing an example of the bioelectrode of the present invention. Figure 1 The bio-electrode 1 has a conductive substrate 2 and a bio-contact layer 3 formed on the conductive substrate 2. The bio-contact layer 3 is composed of a hardened form of the bio-electrode composition of the present invention. The composite 5 constituting the bio-contact layer 3 is a composite of an ionic polymer and polysiloxane having T units and Q units. The bio-contact layer 3 may further contain an adhesive resin 6 and a conductive powder 4, in addition to the aforementioned composite 5 of an ionic polymer and polysiloxane having T units and Q units. (Refer to the following...) Figure 1 , 2 The present invention describes a case in which an ionic polymer, a polysiloxane composite 5 having T units and Q units, and a conductive powder 4 are dispersed in an adhesive resin 6 to form a biocontact layer 3. However, the bioelectrode of the present invention is not limited to this form.

[0482] Using such Figure 1 When using bioelectrode 1, such as Figure 2 As shown, the bio-contact layer 3 (i.e., a layer formed by dispersing an ionic polymer, a polysiloxane composite 5 having T-units and Q-units, and conductive powder 4 in an adhesive resin 6) is brought into contact with the bio-body 7. The ionic polymer, the polysiloxane composite 5 having T-units, and the conductive powder 4 are used to extract electrical signals from the bio-body 7, and these signals are conducted to a sensing device (not shown) via a conductive substrate 2. Thus, for the bio-electrode of the present invention, the aforementioned ionic polymer and polysiloxane composite with T-units and Q-units achieve both conductivity and biocompatibility. Furthermore, due to its adhesive properties, the contact area with the skin is constant, allowing for stable and highly sensitive acquisition of electrical signals from the skin.

[0483] The following is a detailed description of the constituent materials of the bioelectrode of the present invention.

[0484] [Conductive substrate]

[0485] The bioelectrode of the present invention has a conductive substrate. This conductive substrate is typically electrically connected to a sensing device and conducts electrical signals taken from the organism via the bioelectrode contact layer to the sensing device, etc.

[0486] The conductive substrate is only required to be conductive and is not particularly limited. For example, it is preferable to contain one or more of the following: gold, silver, silver chloride, platinum, aluminum, magnesium, tin, tungsten, iron, copper, nickel, stainless steel, chromium, titanium, carbon, and conductive polymers.

[0487] Furthermore, the conductive substrate is not particularly limited and can be a rigid conductive substrate, a flexible conductive film, a fabric coated with a conductive paste, or a fabric mixed with a conductive polymer. The conductive substrate can be flat or uneven, or it can be a mesh made of woven metal wires, and can be appropriately selected according to the application of the bioelectrode.

[0488] [Biological Contact Layer]

[0489] The bioelectrode of the present invention has a bio-contact layer formed on a conductive substrate. This bio-contact layer is the portion that actually contacts the bioelectrode when it is used, and it has conductivity and adhesion. The bio-contact layer is a hardened form of the bioelectrode composition of the present invention, that is, it is an adhesive resin layer composed of a hardened form containing the above-described component (A) and, if desired, components (B), (C), (D), (E), and other components (F).

[0490] Furthermore, the adhesion of the biological contact layer should ideally be in the range of 0.01 N / 25 mm to 20 N / 25 mm. The method for measuring adhesion is generally as shown in JIS Z 0237. For the substrate, metal substrates such as SUS (stainless steel) and PET (polyethylene terephthalate) substrates can be used, but human skin can also be used for measurement. Human skin has a surface energy lower than that of metals and various plastics, approaching the low energy of Teflon (registered trademark), making it less prone to adhesion.

[0491] The thickness of the bio-contact layer of a bioelectrode should ideally be between 1 μm and 5 mm, with 2 μm to 3 mm being even better. A thinner bio-contact layer results in lower adhesion but increased flexibility, lighter weight, and better skin affinity. The thickness of the bio-contact layer should be selected by comprehensively considering adhesion and the texture it provides to the skin.

[0492] Furthermore, the bioelectrode of the present invention can also, like conventional bioelectrodes (e.g., the bioelectrode disclosed in Japanese Patent Application Publication No. 2004-033468), have an additional adhesive film provided on the bio-contact layer to prevent the bioelectrode from peeling off during use. When an additional adhesive film is provided, an adhesive film material such as acrylic, urethane, or polysiloxane can be used to form the adhesive film. Polysiloxane is particularly desirable because its high oxygen permeability allows the skin to breathe even when it is attached, and its high water repellency minimizes the reduction in adhesion due to sweat. Moreover, it has low skin irritation. In addition, the bioelectrode of the present invention can prevent peeling off from the bioelectrode by adding an adhesive agent to the bioelectrode composition or by using a resin with good adhesion to the bioelectrode, as described above. Therefore, the additional adhesive film is not necessarily required.

[0493] The wiring and other components between the bioelectrode and the sensing device when the bioelectrode of the present invention is used in a wearable device are not particularly limited, and for example, those described in Japanese Patent Application Publication No. 2004-033468 may be used.

[0494] As described above, the bioelectrode of the present invention, having a biocontact layer formed from a hardened composition of the bioelectrode of the present invention, can efficiently transmit electrical signals from the skin to the device (i.e., excellent conductivity), and even with prolonged skin contact, does not cause allergies (i.e., excellent biocompatibility). It is lightweight, can be manufactured at low cost, and its conductivity does not significantly decrease whether wetted or dry. Furthermore, by adding conductive powder, conductivity can be further improved; by combining it with a resin possessing adhesiveness and elasticity, a bioelectrode with exceptionally high adhesion and elasticity can be manufactured. Moreover, elasticity and adhesion to the skin can be improved by additives, and elasticity and adhesion can be adjusted by appropriately regulating the resin composition and the thickness of the biocontact layer. Therefore, the bioelectrode of the present invention, in this way, is particularly ideal as a bioelectrode for use in medical wearable devices.

[0495] <Manufacturing Methods of Bioelectrodes>

[0496] Furthermore, the present invention provides a method for manufacturing a bioelectrode, which is a method for manufacturing a bioelectrode having a conductive substrate and a bioelectrode contact layer formed on the conductive substrate, characterized in that: the bioelectrode composition of the present invention is coated on the aforementioned conductive substrate and hardened thereon to form the aforementioned bioelectrode contact layer.

[0497] Furthermore, the conductive substrate and the like used in the manufacturing method of the bioelectrode of the present invention can be the same as those described above.

[0498] The method for coating bio-electrode components onto a conductive substrate is not particularly limited. For example, dip coating, spray coating, spin coating, roll coating, flow coating, doctor blade coating, screen printing, flexographic printing, gravure printing, inkjet printing, etc. are all suitable methods.

[0499] The method of curing the resin is not particularly limited; it can be appropriately selected based on components (A) and (B) used in the bioelectrode composition. For example, it is advisable to use either heat or light, or both, to cure it. Furthermore, adding a catalyst that generates acids or bases to the above-mentioned bioelectrode composition can also induce a cross-linking reaction and cure the resin.

[0500] In addition, the heating temperature is not particularly limited, and can be appropriately selected according to the (A) and (B) components used in the bio-electrode composition, for example, about 50 to 250°C.

[0501] Furthermore, when combining heating and light exposure, heating and light exposure can be performed simultaneously, or heating can be performed after light exposure, or light exposure can be performed after heating. Alternatively, air drying can be performed after coating and before heating to allow the solvent to evaporate.

[0502] Applying water droplets, water vapor, or mist to the hardened membrane surface enhances its affinity with the skin and allows for rapid reception of biological signals. To reduce the size of the water droplets, water mixed with alcohol can be used. Alternatively, the membrane surface can be moistened by contact with water-containing absorbent cotton or cloth.

[0503] The water that wets the hardened membrane surface may also contain salt. Water-soluble salts that mix with water are selected from sodium salts, potassium salts, calcium salts, magnesium salts, and betaine.

[0504] Specifically, the aforementioned water-soluble salt may be a salt selected from sodium chloride, potassium chloride, calcium chloride, magnesium chloride, sodium saccharin, acesulfame potassium, sodium carboxylate, potassium carboxylate, calcium carboxylate, sodium sulfonate, potassium sulfonate, calcium sulfonate, sodium phosphate, potassium phosphate, calcium phosphate, magnesium phosphate, and betaine. Furthermore, the aforementioned water-soluble salt does not include components (A) and (C) above.

[0505] More specifically, in addition to the above, the following can also be listed: sodium acetate, sodium propionate, sodium trimethylacetate, sodium glycolate, sodium butyrate, sodium valerate, sodium hexanoate, sodium heptanoate, sodium octanoate, sodium nonanoate, sodium decanoate, sodium undecanoate, sodium laurate, sodium tridecanoate, sodium myristate, sodium pentadecanoate, sodium palmitate, sodium heptadecanate, sodium stearate, sodium benzoate, disodium adipic acid, 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 ethyl sulfonate. Betaine, sodium lauroyl methyl alanine, sodium cocoyl methyl taurate, sodium cocoyl glutamate, sodium cocoyl sarcosinate, sodium lauroyl methyl taurate, lauramidopropyl betaine, potassium isobutyrate, potassium propionate, potassium trimethylacetate, potassium glycolate, potassium gluconate, potassium methanesulfonate, calcium stearate, calcium glycolate, calcium gluconate, calcium 3-methyl-2-oxobutyrate, and calcium methanesulfonate. Betaine is a general term for intramolecular salts, specifically compounds formed by the addition of three methyl groups to the amino group of amino acids. More specifically, examples include trimethylglycine, carnitine, and proline betaine.

[0506] The water that wets the hardened membrane surface may contain monohydric or polyhydric alcohols with 1 to 4 carbon atoms. The alcohols mentioned above are preferably selected from ethanol, isopropanol, ethylene glycol, diethylene glycol, triethylene glycol, glycerol, polyethylene glycol, polypropylene glycol, polyglycerol, diglycerol, or polysiloxane compounds with a polyglycerol structure. It is more preferable that the polysiloxane compounds with a polyglycerol structure are represented by the above general formulas (4)' and (5)'.

[0507] Pretreatment methods using aqueous solutions containing water-soluble salts can be employed to wet the hardened bioelectrode membrane via spraying or droplet application. Wetting can also be performed under high temperature and humidity conditions, similar to a sauna. To prevent drying after wetting, a protective film can be layered on top of the permeable layer. This protective film must be peeled off just before application to the skin; therefore, a release agent or a release-resistant Teflon film can be used. For long-term storage, the dry electrode covered with the release film should be sealed in a bag coated with aluminum or similar material. To prevent drying in the aluminum-coated bag, moisture should be pre-sealed within it.

[0508] When attaching the bioelectrode of the present invention to the skin, the skin side may first be moistened with water, alcohol, or the skin may be wiped with a cloth or absorbent cotton containing water or alcohol. The water or alcohol may also contain the aforementioned salts.

[0509] As described above, the bioelectrode manufacturing method of the present invention can easily manufacture bioelectrodes with excellent conductivity and biocompatibility, lightweight, and whose conductivity will not be significantly reduced whether wetted or dried, at low cost.

[0510] Example

[0511] The present invention will now be specifically described using examples and comparative examples, but the invention is not limited thereto. Furthermore, "Me" represents methyl and "Vi" represents vinyl.

[0512] (Ionic intermediate polymer)

[0513] The ionic intermediate polymers 1-15 of the present invention (A), used to obtain ionic materials (conductive materials) incorporated into bio-electrode composition solutions, namely ionic polymer composite polysiloxane, are synthesized as follows: A 30% by mass solution of each monomer cyclopentanone is added to a reaction vessel and mixed. The reaction vessel is cooled to -70°C under nitrogen atmosphere, and the degassing and nitrogen blowing are repeated three times under reduced pressure. After heating to room temperature, 0.02 mol of azobisisobutyronitrile (AIBN) relative to 1 mol of the total monomers is added as a polymerization initiator. The temperature is raised to 60°C, and the reaction is allowed to proceed for 15 hours. The composition of the obtained polymer is obtained by drying the solvent and then... 1The results were confirmed by ¹H-NMR. Furthermore, the molecular weight (Mw) and dispersion (Mw / Mn) of the obtained polymers were confirmed by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent. The ionic intermediate polymers 1–15 with alkoxysilane groups synthesized in this manner are shown below.

[0514] Ionic intermediate polymer 1

[0515] Mw = 14,600

[0516] Mw / Mn = 1.81

[0517] [Chemistry 118]

[0518]

[0519] Ionic intermediate polymer 2

[0520] Mw = 16,600

[0521] Mw / Mn = 1.65

[0522] [Chemistry 119]

[0523]

[0524] Ionic intermediate polymer 3

[0525] Mw = 15,400

[0526] Mw / Mn = 1.81

[0527] [Chemistry 120]

[0528]

[0529] Ionic intermediate polymer 4

[0530] Mw = 16,500

[0531] Mw / Mn = 1.79

[0532] [Chemistry 121]

[0533]

[0534] The number of repetitions in the formula represents the average value.

[0535] Ionic intermediate polymer 5

[0536] Mw = 20,100

[0537] Mw / Mn = 1.78

[0538] [Chemistry 122]

[0539]

[0540] Ionic intermediate polymer 6

[0541] Mw = 27,400

[0542] Mw / Mn = 1.91

[0543] [Chemistry 123]

[0544]

[0545] Ionic intermediate polymer 7

[0546] Mw = 42,100

[0547] Mw / Mn = 2.11

[0548] [Chemistry 124]

[0549]

[0550] The number of repetitions in the formula represents the average value.

[0551] Ionic intermediate polymer 8

[0552] Mw = 17,100

[0553] Mw / Mn = 1.88

[0554] [Chemistry 125]

[0555]

[0556] The number of repetitions in the formula represents the average value.

[0557] Ionic intermediate polymer 9

[0558] Mw = 15,500

[0559] Mw / Mn = 1.87

[0560] [Chemistry 126]

[0561]

[0562] The number of repetitions in the formula represents the average value.

[0563] Ionic intermediate polymer 10

[0564] Mw = 21,500

[0565] Mw / Mn = 1.70

[0566] [Chemistry 127]

[0567]

[0568] Ionic intermediate polymer 11

[0569] Mw = 16,500

[0570] Mw / Mn = 1.96

[0571] [Chemistry 128]

[0572]

[0573] Ionic intermediate polymer 12

[0574] Mw = 21,500

[0575] Mw / Mn = 1.75

[0576] [Chemistry 129]

[0577]

[0578] Ionic intermediate polymer 13

[0579] Mw = 13,100

[0580] Mw / Mn = 1.55

[0581] [Chemistry 130]

[0582]

[0583] The number of repetitions in the formula represents the average value.

[0584] Ionic intermediate polymer 14

[0585] Mw = 17,500

[0586] Mw / Mn = 1.83

[0587] [Chemistry 131]

[0588]

[0589] The number of repetitions in the formula represents the average value.

[0590] Ionic intermediate polymer 15

[0591] Mw = 19,600

[0592] Mw / Mn = 1.87

[0593] [Chemistry 132]

[0594]

[0595] The number of repetitions in the formula represents the average value.

[0596] The following are examples of the ionic polymer 1, the comparative ionic intermediate polymer 1 used in the comparative example, and the comparative ionic polymer composite polysiloxane 2-1:

[0597] 1. Doping with ionic polymers

[0598] Mw = 39,100

[0599] Mw / Mn = 1.91

[0600] [Chemistry 133]

[0601]

[0602] The number of repetitions in the formula represents the average value.

[0603] Comparison of ionic intermediate polymers 1

[0604] Mw = 26,900

[0605] Mw / Mn = 1.99

[0606] [Chemistry 134]

[0607]

[0608] Comparison of ionic polymer composites of polysiloxane 2-1

[0609] Mw = 22,300

[0610] Mw / Mn = 1.98

[0611] [Chemistry 135]

[0612]

[0613] (Ionic polymer composite polysiloxane)

[0614] In a 0.5L glass flask, 10g of pure water and 0.1g of nitric acid were added to 100g of the cyclopentanone solution of the aforementioned ionic intermediate polymer 1 obtained by polymerization. After stirring at 40°C for 8 hours, 30g of cyclopentanone was added. The mixture was then concentrated, dehydrated, and simultaneously denitric acid was removed under reduced pressure to obtain a cyclopentanone solution containing 30% by mass of the ionic polymer composite polysiloxane 1-1.

[0615] Ionic polymer composite polysiloxane 1-1

[0616] Mw = 23,600

[0617] Mw / Mn = 2.35

[0618] [Chemistry 136]

[0619]

[0620] Ionic polymer composite polysiloxane 2-1 to ionic polymer composite polysiloxane 15-1 were synthesized using the same method, and compared with ionic polymer composite polysiloxane 1-1. Ionic polymer composite polysiloxane 8-2 was obtained by co-condensation with vinyltrimethoxysilane, ionic polymer composite polysiloxane 8-3 was obtained by co-condensation with allyltrimethoxysilane, ionic polymer composite polysiloxane 13-1 was obtained by co-condensation with tetramethoxysilane, and ionic polymer composite polysiloxane 13-2 to 15-1 were obtained by co-condensation with trimethoxysilanes containing cyano, nitro, fluorosulfonic acid potassium salt, fluorosulfonamide sodium salt, and N-carbonylfluorosulfonamide potassium salt, respectively.

[0621] Ionic polymer composite polysiloxane 2-1

[0622] Mw = 39,100

[0623] Mw / Mn = 3.12

[0624] [Chemistry 137]

[0625]

[0626] Ionic polymer composite polysiloxane 3-1

[0627] Mw = 23,400

[0628] Mw / Mn = 2.61

[0629] [Chemistry 138]

[0630]

[0631] Ionic polymer composite polysiloxane 4-1

[0632] Mw = 21,500

[0633] Mw / Mn = 2.23

[0634] [Chemistry 139]

[0635]

[0636] The number of repetitions in the formula represents the average value.

[0637] Ionic polymer composite polysiloxane 5-1

[0638] Mw = 33,100

[0639] Mw / Mn = 2.68

[0640] [Chemistry 140]

[0641]

[0642] Ionic polymer composite polysiloxane 6-1

[0643] Mw = 35,100

[0644] Mw / Mn = 2.88

[0645] [Chemistry 141]

[0646]

[0647] Ionic polymer composite polysiloxane 7-1

[0648] Mw = 57,900

[0649] Mw / Mn = 3.93

[0650] [Chemistry 142]

[0651]

[0652] The number of repetitions in the formula represents the average value.

[0653] Ionic polymer composite polysiloxane 8-1

[0654] Mw = 32,100

[0655] Mw / Mn = 3.11

[0656] [Chemistry 143]

[0657]

[0658] The number of repetitions in the formula represents the average value.

[0659] Ionic polymer composite polysiloxane 8-2

[0660] Mw = 35,100

[0661] Mw / Mn = 3.31

[0662] [Chemistry 144]

[0663]

[0664] The number of repetitions in the formula represents the average value.

[0665] Ionic polymer composite polysiloxane 8-3

[0666] Mw = 35,800

[0667] Mw / Mn = 3.38

[0668] [Chemistry 145]

[0669]

[0670] The number of repetitions in the formula represents the average value.

[0671] Ionic polymer composite polysiloxane 9-1

[0672] Mw = 37,500

[0673] Mw / Mn = 3.13

[0674] [Chemistry 146]

[0675]

[0676] Ionic polymer composite polysiloxane 10-1

[0677] Mw = 25,600

[0678] Mw / Mn = 2.88

[0679] [Chemistry 147]

[0680]

[0681] Ionic polymer composite polysiloxane 11-1

[0682] Mw = 23,500

[0683] Mw / Mn = 2.46

[0684] [Chemistry 148]

[0685]

[0686] Ionic polymer composite polysiloxane 12-1

[0687] Mw = 32,500

[0688] Mw / Mn = 2.75

[0689] [Chemistry 149]

[0690]

[0691] Ionic polymer composite polysiloxane 13-1

[0692] Mw = 35,100

[0693] Mw / Mn = 3.35

[0694] [Chemistry 150]

[0695]

[0696] Ionic polymer composite polysiloxane 13-2

[0697] Mw = 38,100

[0698] Mw / Mn = 3.77

[0699] [Chemistry 151]

[0700]

[0701] The number of repetitions in the formula represents the average value.

[0702] Ionic polymer composite polysiloxane 13-3

[0703] Mw = 35,700

[0704] Mw / Mn = 3.66

[0705] [Chemistry 152]

[0706]

[0707] The number of repetitions in the formula represents the average value.

[0708] Ionic polymer composite polysiloxane 13-4

[0709] Mw = 36,100

[0710] Mw / Mn = 3.95

[0711] [Chemistry 153]

[0712]

[0713] The number of repetitions in the formula represents the average value.

[0714] Ionic polymer composite polysiloxane 13-5

[0715] Mw = 38,400

[0716] Mw / Mn = 3.69

[0717] [Chemistry 154]

[0718]

[0719] The number of repetitions in the formula represents the average value.

[0720] Ionic polymer composite polysiloxane 13-6

[0721] Mw = 38,800

[0722] Mw / Mn = 3.94

[0723] [Chemistry 155]

[0724]

[0725] The number of repetitions in the formula represents the average value.

[0726] Ionic polymer composite polysiloxane 13-7

[0727] Mw = 36,300

[0728] Mw / Mn = 3.96

[0729] [Chemistry 156]

[0730]

[0731] The number of repetitions in the formula represents the average value.

[0732] Ionic polymer composite polysiloxane 13-8

[0733] Mw = 33,600

[0734] Mw / Mn = 4.22

[0735] [Chemistry 157]

[0736]

[0737] The number of repetitions in the formula represents the average value.

[0738] Ionic polymer composite polysiloxane 14-1

[0739] Mw = 31,700

[0740] Mw / Mn = 3.64

[0741] [Chemistry 158]

[0742]

[0743] The number of repetitions in the formula represents the average value.

[0744] Ionic polymer composite polysiloxane 15-1

[0745] Mw = 36,800

[0746] Mw / Mn = 4.13

[0747] [Chemistry 159]

[0748]

[0749] The number of repetitions in the formula represents the average value.

[0750] Comparison of ionic polymer composites of polysiloxane 1-1

[0751] Mw = 46,000

[0752] Mw / Mn = 3.02

[0753] [Chemistry 160]

[0754]

[0755] The siloxane compounds 1 to 4, which are incorporated into the bio-electrode composition solution as polysiloxane resins, are shown below.

[0756] (Siloxane compound 1)

[0757] The vinyl-containing polydimethylsiloxane with a viscosity of 27,000 mPa·s when prepared as a 30% toluene solution, an alkenyl content of 0.007 mol / 100g, and a molecular chain end capped with SiMe2Vi groups is siloxane compound 1.

[0758] (Siloxane compound 2)

[0759] Let Me3SiO 0.5 The polysiloxane (Me3SiO) of MQ resin composed of unit and SiO2 unit 0.5 A 60% toluene solution of unit / SiO2 unit = 0.8 is a siloxane compound 2.

[0760] (Siloxane compound 3)

[0761] Let 40 parts by mass of a vinyl-containing polydimethylsiloxane, with a viscosity of 42,000 mPa·s when prepared as a 30% toluene solution, an alkenyl content of 0.007 mol / 100g, and OH-terminated molecular chains, be prepared from Me3SiO4. 0.5 The polysiloxane (Me3SiO) of MQ resin composed of unit and SiO2 unit 0.5 A solution consisting of 100 parts by mass of a 60% toluene solution (unit / SiO2 unit = 0.8) and 26.7 parts by mass of toluene was heated for 4 hours by dry distillation and then cooled to bond polydimethylsiloxane to MQ resin, thus obtaining siloxane compound 3.

[0762] (Siloxane compound 4)

[0763] Shin-Etsu Chemical Industry Co., Ltd.'s KF-99 was used as the methylhydrosilicone oil.

[0764] The polysiloxane suspended urethane (meth) acrylate 1 incorporated into the bio-electrode composition solution is shown below.

[0765] [Chemistry 161]

[0766]

[0767] The number of repetitions in the formula represents the average value.

[0768] The acrylic polymer 1, which is incorporated into the bioelectrode composition solution as an acrylic resin, is shown below.

[0769] Acrylic polymer 1

[0770] Mw = 127,000

[0771] Mw / Mn = 2.28

[0772] [Chemistry 162]

[0773]

[0774] The number of repetitions in the formula represents the average value.

[0775] Polyglycerol polysiloxane 1 is shown below.

[0776] [Chemistry 163]

[0777]

[0778] The organic solvents incorporated into the bio-electrode composition solution are shown below.

[0779] EDE: Diethylene glycol diethyl ether

[0780] ISOPAR G: Standard petroleum-based solvent for isoalkane systems.

[0781] ISOPAR M: Standard petroleum-based solvent for isoalkane systems

[0782] The lithium titanate powder, free radical generator, platinum catalyst, and conductivity improver (carbon black, carbon nanotubes, graphite, metal powder) incorporated into the bio-electrode composition solution as additives are shown below.

[0783] Lithium titanate powder and spinel: manufactured by Sigma-Aldrich, with a particle size below 200nm.

[0784] Free radical generator: Irgacure TPO manufactured by BASF

[0785] Platinum catalyst: Shin-Etsu Chemical Industry Co., Ltd. CAT-PL-50T

[0786] Carbon black: Denka Black Li-400 manufactured by Denka Corporation

[0787] Multilayer carbon nanotubes: manufactured by Sigma-Aldrich, with diameters of 110–170 nm and lengths of 5–9 μm.

[0788] Graphite: manufactured by Sigma-Aldrich, diameter less than 20μm

[0789] Silver powder: Silver flakes manufactured by Sigma-Aldrich, 10μm in diameter.

[0790] [Examples 1-26, Comparative Examples 1-3]

[0791] Ionic polymer composite polysiloxane, resin, ionic polymer, organic solvent, and additives (free radical generator, platinum catalyst, conductivity improver, etc.) are blended according to the compositions recorded in Tables 1 to 3 to prepare bio-electrode composition solutions (bio-electrode composition solutions 1 to 26, comparative bio-electrode composition solutions 1 to 3).

[0792] [Table 1]

[0793]

[0794] [Table 2]

[0795]

[0796] [Table 3]

[0797]

[0798] (Adhesion evaluation)

[0799] Bioelectrode composition solutions 1-15, 17-26, and comparative bioelectrode composition solutions 1-3 were applied to a 100 μm thick PEN (polyethylene naphthalate) substrate using a spreader. After air drying at room temperature for 30 minutes, they were cured by baking in an oven at 120°C under nitrogen for 10 minutes to form an adhesive film. For bioelectrode composition solution 16, after coating, air drying, and baking, it was irradiated with a 1000W xenon lamp at 500 mJ / cm² under nitrogen. 2 The light causes the components to harden into a coating film, which is then used to create an adhesive film.

[0800] A 25mm wide tape was cut from the adhesive film and pressed onto a stainless steel plate (SUS304). After being left at room temperature for 20 hours, a tensile testing machine was used to measure the force (N / 25mm) required to peel the tape from the stainless steel plate at an angle of 180 degrees and a speed of 300mm / min. The results are shown in Table 4.

[0801] (Fabrication of bioelectrodes)

[0802] like Figure 3 As shown, on the ST-604 thermoplastic urethane (TPU) film 20 of Bemis Corporation, a conductive paste DOTITE FA-333 manufactured by Fujikura Chemicals was screen-printed onto the film. The film was then baked in an oven at 120°C for 10 minutes to print a circular keyhole-shaped conductive pattern 2 with a diameter of 2 cm. The circular portion superimposed on this pattern was then screen-printed with the bio-electrode composition solution described in Tables 1-3. After air drying at room temperature for 10 minutes, the solution was baked in an oven at 125°C for 10 minutes to evaporate the solvent and harden the material, forming a bio-contact layer 3, thus fabricating the bio-electrode 1. Additionally, for Example 16, a conductive paste was applied under a nitrogen atmosphere at 200 mJ / cm². 2 It is hardened by being exposed to a xenon lamp. Then, as... Figure 4 As shown, a thermoplastic urethane film 20 printed with bioelectrode 1 was cut out and double-sided tape 21 was attached. Three bioelectrode samples 10 were made from each composition solution.

[0803] (Measuring the thickness of the contact layer in organisms)

[0804] The thickness of the biological contact layer of the bioelectrodes prepared above was measured using a micrometer. The results are shown in Table 4.

[0805] (Measurement of biological signals)

[0806] The conductive wiring pattern formed by the bio-electrode using conductive paste is connected to the OMRON HEALTHCARE portable electrocardiogram (ECG-901) using conductive wires. The positive electrode of the ECG is then attached to... Figure 5 The negative electrode is attached to the LA position of the human body, and the grounding electrode is attached to the LL position. Electrocardiogram (ECG) measurement begins immediately after attachment and continues until... Figure 6 The time elapsed until the appearance of the electrocardiogram waveform (ECG signal) consisting of P, Q, R, S, and T waves is shown in Table 4. The results are shown in Table 4.

[0807] [Table 4]

[0808]

[0809] As shown in Table 4, Examples 1 to 26, which use bio-electrode compositions of the present invention incorporating a composite of an ionic polymer and T-unit polysiloxane to form a bio-contact layer, exhibit excellent adhesion and can obtain bio-signals in a short time after being applied to the body. On the other hand, in Comparative Example 2, which does not contain an ionic component with a specific structure, bio-signals cannot be obtained. Furthermore, in Comparative Example 1, which only added an ionic polymer, and in Comparative Example 3, which added an ionic polymer that is a composite of cage-like T-unit polysiloxane, adhesion is low and the time from application to bio-signal appearance is long.

[0810] Furthermore, the present invention is not limited to the embodiments described above. The embodiments described above are illustrative, and those that have substantially the same structure and perform the same effect as the technical concept described in the claims of the present invention are all included within the technical scope of the present invention.

[0811] Explanation of reference numerals in the attached figures

[0812] 1: Bioelectrodes

[0813] 2: Conductive substrate (conductive pattern)

[0814] 3: Contact layer of organism

[0815] 4: Conductive powder

[0816] 5: Composites of ionic polymers with polysiloxanes containing T and Q units

[0817] 6: Adhesive resin

[0818] 7: Organisms

[0819] 10: Bioelectrode Samples

[0820] 20: Thermoplastic urethane film

[0821] 21: Double-sided tape

[0822] LA: Positive electrode attachment location

[0823] LL: Attachment position of the negative electrode

[0824] RA: Grounding attachment position

Claims

1. A bio-electrode composition, characterized by: Contains (A) polysiloxane, which is bonded to an ionic polymer and has a structure containing T units represented by the following general formula (T1), but the structure does not include a cage structure; (R 0 SiO 3 / 2 )(T1) In the formula, R 0 For the linking group of the ionic polymer; and The ionic polymer is a polymer containing repeating units having a structure of an ammonium salt, lithium salt, sodium salt, potassium salt, or silver salt selected from fluorosulfonic acid, fluorosulfonamide, and N-carbonyl fluorosulfonamide. The repeating unit having a structure of an ammonium salt, lithium salt, sodium salt, potassium salt, or silver salt selected from any of fluorosulfonic acid, fluorosulfonamide, and N-carbonyl fluorosulfonamide is selected from one or more repeating units (2-1) to (2-7) of the following general formula (2); In the formula, R 1 R 3 R 5 R 8 R 10 R 11 and R 13 Each is independently a hydrogen atom or a methyl group, R 2 R 4 R 6 R 9 R 12 and R 14 Each is independently a single bond, or may also have any of the following: an ester group or an ether group, or both of these, and is a straight-chain, branched, or cyclic hydrocarbon group having 1 to 13 carbon atoms; R 7 R is a straight-chain or branched alkylene group having 1 to 4 carbon atoms. 7 One or two hydrogen atoms in the group may be replaced by fluorine atoms; X1, X2, X3, X4, X6, and X7 are each independently a single bond, phenylene, naphthylene, ether, ester, or amide group; X5 is a single bond, ether, or ester group; Y is an oxygen atom, -NR 19 -base, R 19 It is a straight-chain or branched alkyl group with hydrogen atoms and 1 to 4 carbon atoms, and can also react with R. 4 Bonding and forming a ring; m is an integer from 1 to 4; a1, a2, a3, a4, a5, a6, and a7 are 0≤a1≤1.0, 0≤a2≤1.0, 0≤a3≤1.0, 0≤a4≤1.0, 0≤a5≤1.0, 0≤a6≤1.0, 0≤a7≤1.0, and 0 <a1+a2+a3+a4+a5+a6+a7≤1.0;M + The ions are selected from ammonium ions, lithium ions, sodium ions, potassium ions, and silver ions; Rf5, Rf6, and Rf7 are fluorine atoms, straight-chain or branched alkyl groups having 1 to 4 carbon atoms, and having at least one fluorine atom. (A) is a condensation reaction product of an ionic intermediate polymer, which, in addition to containing the repeating unit of the general formula (2), also copolymerizes the repeating unit of the following general formula (3) having an alkoxysilyl group. In the formula, R 20 X is a hydrogen atom or a methyl group, X8 is any one of a single bond, phenylene, naphthylene, ether, ester, or amide group, and R 21 It consists of single bonds, and is a straight-chain, branched, or cyclic alkylene or phenylene chain with 1 to 10 carbon atoms; it may also contain oxygen and nitrogen atoms; R 22 b1 is an alkyl group with the same or different carbon numbers of 1 to 4; b1 is 0. <b1<1.0。 2. The bioelectrode composition according to claim 1, wherein, The condensation reaction product has repeating units of the following general formula (4); In the formula, R 20 X8, R 21 b1 is the same as mentioned above.

3. The bioelectrode composition according to claim 1 or 2, wherein, The component (A) contains ammonium ions represented by the following general formula (5) as ammonium ions constituting the ammonium salt; In the formula, R 101d R 101e R 101f R 101g Each of the following groups comprises a hydrogen atom, a straight-chain, branched, or cyclic alkyl group having 1 to 13 carbon atoms, a straight-chain, 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 also have one or more of the following groups: ether, carbonyl, ester, hydroxyl, amino, nitro, sulfonyl, sulfinyl, halogen atom, and sulfur atom; R 101d With R 101e R 101d With R 101e With R 101f They can also form rings together with the nitrogen atoms they are bonded to. When a ring is formed, R 101d With R 101e and R 101d With R 101e With R 101f It is an alkylene group having 3 to 10 carbon atoms, or an aromatic heterocycle containing a nitrogen atom in the formula in the ring.

4. The bioelectrode composition according to claim 1 or 2, further comprising an adhesive resin as component (B).

5. The bioelectrode composition according to claim 4, wherein, The component (B) is selected from one or more of polysiloxane resin, (meth)acrylate resin, and urethane resin.

6. The bioelectrode composition according to claim 4, wherein, Component (B) contains an alkenyl diorganosiloxane and an organohydrogen polysiloxane with a SiH group.

7. The bioelectrode composition according to claim 6, wherein, Component (B) further contains R x SiO (4-x) / 2 Polysiloxane resins with unit and SiO2 unit; R is a substituted or unsubstituted monovalent hydrocarbon group with 1 to 10 carbon atoms, and x is in the range of 2.5 to 3.

5.

8. The bio-electrode composition according to claim 1 or 2, further comprising a polymeric compound having ionic repeating units as component (C).

9. The bioelectrode composition according to claim 8, wherein, The ionic repeating unit of component (C) contains repeating units of the following general formula (2) having a structure selected from the ammonium salt, lithium salt, sodium salt, potassium salt, and silver salt of any of fluorosulfonic acid, fluorosulfonamide, and N-carbonyl fluorosulfonamide. In the formula, R 1 R 3 R 5 R 8 R 10 R 11 and R 13 Each is independently a hydrogen atom or a methyl group, R 2 R 4 R 6 R 9 R 12 and R 14 Each is independently a single bond, or may also have any of the following: an ester group or an ether group, or both of these, and is a straight-chain, branched, or cyclic hydrocarbon group having 1 to 13 carbon atoms; R 7 R is a straight-chain or branched alkylene group having 1 to 4 carbon atoms. 7 One or two hydrogen atoms in the group may be replaced by fluorine atoms; X1, X2, X3, X4, X6, and X7 are each independently a single bond, phenylene, naphthylene, ether, ester, or amide group; X5 is a single bond, ether, or ester group; Y is an oxygen atom, -NR 19 -base, R 19 It is a straight-chain or branched alkyl group with hydrogen atoms and 1 to 4 carbon atoms, and can also react with R. 4 Bonding and forming a ring; m is an integer from 1 to 4; a1, a2, a3, a4, a5, a6, and a7 are 0≤a1≤1.0, 0≤a2≤1.0, 0≤a3≤1.0, 0≤a4≤1.0, 0≤a5≤1.0, 0≤a6≤1.0, 0≤a7≤1.0, and 0 <a1+a2+a3+a4+a5+a6+a7≤1.0;M + The ions are selected from ammonium ions, lithium ions, sodium ions, potassium ions, and silver ions; Rf5, Rf6, and Rf7 are fluorine atoms, straight-chain or branched alkyl groups having 1 to 4 carbon atoms, and having at least one fluorine atom.

10. The bio-electrode composition according to claim 1 or 2, further comprising carbon powder and / or metal powder as component (D).

11. The bioelectrode composition according to claim 10, wherein, The toner is either carbon black or carbon nanotubes, or both.

12. The bioelectrode composition according to claim 10, wherein, The metal powder is selected from gold, silver, platinum, copper, tin, titanium, nickel, aluminum, tungsten, molybdenum, ruthenium, chromium, and indium.

13. The bioelectrode composition according to claim 12, wherein, The metal powder is silver powder.

14. The bioelectrode composition according to claim 1 or 2, further comprising an organic solvent as component (E).

15. A bioelectrode, comprising a conductive substrate and a bio-contact layer formed on the conductive substrate, characterized in that: The bio-contact layer is a hardened version of the bio-electrode composition according to any one of claims 1 to 14.

16. The bioelectrode according to claim 15, wherein, The conductive substrate contains one or more of the following: gold, silver, silver chloride, platinum, aluminum, magnesium, tin, tungsten, iron, copper, nickel, stainless steel, chromium, titanium, carbon, and conductive polymers.

17. A method for manufacturing a bioelectrode, comprising a conductive substrate and a bioelectrode contact layer formed on the conductive substrate, characterized in that: At The bio-electrode composition according to any one of claims 1 to 14 is coated onto the conductive substrate and then hardened to form the bio-contact layer.

18. The method for manufacturing a bioelectrode according to claim 17, wherein, The conductive substrate contains one or more of the following: gold, silver, silver chloride, platinum, aluminum, magnesium, tin, tungsten, iron, copper, nickel, stainless steel, chromium, titanium, carbon, and conductive polymer.

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