KR101947895B1 - Method for manufacturing dry electrode based on elastic nanofiber web - Google Patents

Abstract

The present invention discloses a method for manufacturing a dry electrode based on elastic nanofibrous webs. A method of manufacturing a dry electrode based on an elastic nanofiber web according to an embodiment of the present invention includes the steps of preparing an electrospinning liquid by dissolving an elastic polymer and a silver ion- ; Electrospinning the electrospinning liquid to produce an elastic nanofiber web comprising reduced silver nanoparticles; And immersing the nanofiber web in a silver plating solution to perform electroless silver plating.

Description

METHOD FOR MANUFACTURING DRY ELECTRODE BASED ON ELASTIC NANOFIBER WEB BACKGROUND OF THE INVENTION [0001]

The present invention relates to a method of manufacturing a dry electrode based on an elastic nanofiber web, and more particularly, to a method of manufacturing a dry electrode based on an elastic nanofiber web that prevents a decrease in electric conductivity caused by external force or folding.

Recently, interest in the research and development of smart apparel, which has the function of measuring the human bio-signal anytime and anywhere through the fusion of the textile industry and the IT industry, is increasing. Especially, clothes are suitable for measuring biological signals since they are in contact with human bodies anytime and anywhere. Therefore, studies and attempts have been made to easily mount various kinds of bio signal measurement sensors in such clothes.

Electrocardiogram (ECG), which is the most important bio-signal among various bio-signals measured and mounted on smart clothes, is a phenomenon in which a current generated by a minute action potential difference generated in the myocardium when the heart muscle contracts and relaxes (ECG), it is necessary to attach the conductive electrode to the skin at the corresponding position. In order to measure the electrocardiogram (ECG), it is necessary to attach the conductive electrode to the skin at the corresponding position.

In order to measure ECG, it is common to use a conductive Ag / AgCl gel electrode, which is a patch type electrode which is directly adhered to the skin in a hospital. However, when the conductive Ag / AgCl gel electrode is attached to the skin for a long period of time and the electrocardiogram is measured, if the wearer who measures the electrocardiogram is an irritable skin, it may cause erythema or severe inflammation There was a problem.

In addition, when such a conductive Ag / AgCl gel electrode is used for a long time, the gel electrode is dried and the electrical conductivity is reduced, thereby deteriorating the quality of the ECG signal. In addition, The Ag / AgCl gel electrode can not be used for disposable applications. Therefore, it is difficult to use the Ag / AgCl gel electrode as an electrode for smart clothing requiring repeated use.

Recently, a clamp-type stainless steel electrode or a silver-plated cloth electrode has been used as a dry-type electrode which can be repeatedly used while minimizing adhesion to the skin.

However, there is no compatibility with clothes for stainless steel electrodes and silver plating on thick fibers for silver-plated electrodes. Therefore, the difference in mechanical properties (strength and elongation) between the fibers and silver is large, There is a problem that the silver plated on the thick fiber is severely detached by the bending and the folding, the abrasion resistance is poor, and the silver or silver plated fiber is large, so that it is felt to be rough when the skin is attached.

Korean Patent Laid-Open Publication No. 10-2016-0113603, " Korean Patent Registration No. 10-1008879, "Electrocardiogram Electrode Having Electrode for Obtaining Motion Noise"

The present invention relates to a method for producing an elastic nanofiber web comprising silver nanoparticles reduced by electrospinning an electrospinning liquid containing an elastic polymer and a silver ion containing material, Based dry electrode is provided.

A method of manufacturing a dry electrode based on an elastic nanofiber web according to an embodiment of the present invention includes the steps of preparing an electrospinning liquid by dissolving an elastic polymer and a silver ion- ; Electrospinning the electrospinning liquid to produce an elastic nanofiber web comprising reduced silver nanoparticles; And immersing the elastic nanofiber web in a silver plating solution to perform electroless silver plating.

The elastic polymer may be at least one selected from the group consisting of poly (styrene-b-butadiene-b-styrene (SBS), nitrile-butadiene rubber, elastic polyurethane, At least one selected from the group consisting of polyester-polyurethane, polyether-polyurethane, latex, and silicone rubber.

The silver ion-containing material is silver chloride (AgCl), silver nitrate (AgNO _3), formic acid (HCOOAg), acetic acid (CH ₃ COOAg), trifluoride plants acid (CF ₃ COOAg)), carbonate (Ag ₂ CO _3), sulfuric acid Silver (Ag ₂ SO ₄ ), and silver phosphate (Ag ₃ PO ₄ ).

The electrospinning liquid may include 5 to 40 parts by weight of the elastic polymer and 0.01 to 1 part by weight of the silver ion-containing material with respect to 100 parts by weight of the organic solvent.

The elastic nanofiber web may be composed of elastic nanofibers, and the elastic nanofibers may have a diameter ranging from 10 nm to 10 μm.

The organic solvent may be selected according to the elastic polymer.

The organic solvent may be selected from the group consisting of tetrahydrofuran (THF), toluene, xylene, benzene, N, N-dimethylacetamide (DMAc) At least one selected from the group consisting of N, N-dimethylformamide (DMF), N-methylpyrrolidinone (NMP) and dimethyl sulfoxide (DMSO) .

The electrospinning liquid may further comprise a co-solvent having a polarity for promoting the electrospinning, and the co-solvent is selected from the group consisting of N, N-dimethylacetamide (DMAc), N, N-dimethylformamide (DMF), N-methylpyrrolidinone (NMP), dimethyl sulfoxide (DMSO), acetone, methyl ethyl ketone, methanol , Ethanol, propanol, butanol, t-butyl alcohol, isopropylalcohol (iPA, 2-propanol), benzyl alcohol, tetrahydrofuran (THF), ethyl acetate ethyl acetate), butyl acetate, propylene glycol diacetate, propylene glycol methyl ether acetate (PGMEA), acetonitrile, chloroform, dichloromethane dichloromethane), At least one selected from the group consisting of trifluoroacetonitrile, ethylene glycol, pyridine, and pyrrolidine may be included.

The electrospinning liquid may further include a reducing solvent that promotes reduction of silver ions contained in the silver ion-containing material, and the reducing solvent may include N, N-dimethylacetamide, DMAc, At least one selected from the group consisting of N, N-dimethylformamide (DMF), N-methylpyrrolidinone (NMP) and dimethyl sulfoxide (DMSO) .

In the step of preparing the elastic nanofiber web, a metal sheet, a paper sheet, a Teflon sheet, a fiber fabric, or a nonwoven fabric may be used as a support for the elastic nanofibers.

The method of claim 1, further comprising the step of treating the elastic nanofiber web with an alcohol, wherein the alcohol may include at least one selected from the group consisting of ethanol, methanol and isopropanol have.

The method may further include heating and pressing the electroless silver plated elastic nanofiber web after electroless silver plating the elastic nanofiber web.

The step of heating and pressing the electroless silver plated elastic nanofiber web may be performed by ultrasonic thermal welding or pressure thermal welding.

The elastic nanofibrous web-based dry electrode according to an embodiment of the present invention is manufactured by a method of manufacturing an elastic nanofiber web-based dry electrode according to an embodiment of the present invention.

The elastic nanofibrous web-based dry electrode can be used as an electrocardiogram (ECG), an electromyography (EMG), an electroencephalogram, an electroencephalogram, an electrooculogram (EOG) or an electric impedance tomography ). ≪ / RTI >

A method of manufacturing a dry electrode based on an elastic nanofiber web according to an embodiment of the present invention includes the steps of electrospinning an electrospinning liquid containing an elastic polymer and a silver ion containing material to form an elastic nanofiber By manufacturing the web, a separate process for forming silver nanoparticles can be omitted.

The method of manufacturing a dry electrode based on the elastic nanofibrous web according to an embodiment of the present invention can reduce the occurrence frequency of cracks caused by external force or folding by preparing an electrolessly silver plated elastic nanofiber web using an elastic polymer.

The method of manufacturing the dry electrode based on the elastic nanofibrous web according to the embodiment of the present invention can produce an electroconductive nanofiber web having a high metal surface density by conducting electroless silver plating on the elastic nanofiber having a large surface area.

The method of manufacturing a dry electrode based on elastic nanofibrous web according to an embodiment of the present invention is a method in which an electroless silver plating is performed on an elastic nanofiber web to be harmless to the human body and is a fibrous dry electrode, Can be improved.

The elastic nanofibrous web-based dry electrode according to the embodiment of the present invention can reduce the signal to noise ratio (SNR) as compared with the wet gel electrode.

FIG. 1 is a flowchart illustrating a method of manufacturing a dry electrode based on an elastic nanofiber web according to an embodiment of the present invention. FIG. 2 is a view illustrating a method of manufacturing a dry electrode based on an elastic nanofiber web according to an embodiment of the present invention. It is an image.
FIG. 3A illustrates an elastic nanofiber web-based dry electrode fabricated according to a method of manufacturing an elastic nanofiber web-based dry electrode according to an embodiment of the present invention. FIG. FIG. 1 illustrates an elastic nanofibrous web-based dry electrode fabricated according to a method of manufacturing an elastic nanofiber web-based dry electrode according to an embodiment of the present invention.
FIG. 4A is a scanning electron microscope (FE-SEM) photograph of the elastic nanofiber web prepared according to the method of manufacturing an elastic nanofiber web-based dry electrode according to Example 1 of the present invention, and FIG. 1 is a scanning electron micrograph of an electroless silver plated elastic nanofiber web prepared according to a method of manufacturing an elastic nanofiber web-based dry electrode according to Example 1 of the present invention.
FIG. 5A is a scanning electron micrograph of an elastic nanofiber web prepared according to the method of manufacturing an elastic nanofiber web-based dry electrode according to Example 2 of the present invention, and FIG. 5B is a scanning electron micrograph of an elastic nanofiber web prepared according to Example 2 FIG. 2 is a scanning electron microscope (SEM) image of an electrolessly silver plated elastic nanofiber web prepared according to a method of manufacturing a dry electrode based on an elastic nanofiber web.
5C is a transmission electron microscope (TEM) photograph showing a transverse section of an electroless silver plated elastic nanofiber web prepared according to the method of manufacturing an elastic nanofiber web-based dry electrode according to Example 2 of the present invention And FIG. 5D is a transmission electron micrograph showing two electroless silver plated elastic nanofiber webs prepared according to the method of manufacturing a dry electrode based on elastic nanofibrous web according to Example 2 of the present invention.
FIG. 6 is a graph showing the results of a comparison between a dry electrode based on an elastic nanofiber web prepared according to the method of manufacturing a dry electrode based on elastic nanofibers according to the first and second embodiments of the present invention and a comparative electrode using an Ag / AgCl gel electrode. (Contact capacitances) and contact resistances of the respective electrodes, which are calculated on the basis of the impedance measured by the three-electrode method and the four-electrode method, respectively, on the Agar Phantom.
FIG. 7 is a graph showing the results of simulation of a human body using an elastic nanofiber web-based dry electrode manufactured according to the method of manufacturing a dry electrode based on elastic nanofibers according to an embodiment of the present invention and a Ag / AgCl gel electrode as a comparative electrode (50% duty cycle square wave) current for 100 ms cycles after adhering to the agan phantom.
FIG. 8A is a graph showing the results of a comparison between a dry electrode based on an elastic nanofibrous web prepared according to the method of manufacturing a dry electrode based on the elastic nanofibrous web according to Example 1 of the present invention and an Ag / AgCl gel electrode Position and ECG (electrocardiography) signals of 7 cycles measured at the same time.
8B is a graph showing only one cycle (P, Q, R, S, T, and U) of the ECG signal shown in FIG. 8A in order to facilitate comparison of characteristics of the electrodes of Embodiment 1 and Comparative Example.
FIG. 9A is a graph showing the results of comparison between the elastic nanofibrous web-based dry electrode prepared according to the method of manufacturing the elastic nanofibrous web-based dry electrode according to the second embodiment of the present invention and the Ag / AgCl gel electrode as the comparative electrode, (ECG) signals measured at the same position and simultaneously measured.
9B is a graph showing only one cycle (P, Q, R, S, T, and U) of the ECG signal shown in FIG. 9A in order to facilitate comparison of the characteristics of the electrode of Example 2 and the electrode of Comparative Example.
FIGS. 10A and 10B are graphs showing the safety latitude of the dry electrode based on the elastic nanofibrous web prepared according to the method of manufacturing the dry electrode based on the elastic nanofibrous web according to the second embodiment of the present invention and the Ag / AgCl gel electrode according to the comparative example (EOG, electrooculogram) signal.
FIG. 10B is a graph showing the relationship between the dry nanofiber web-based dry electrode prepared according to the method of manufacturing the elastic nanofiber web-based dry electrode according to the second embodiment of the present invention and the Ag / AgCl gel electrode And the EOG signal measured when the eye is moved while the eye is closed.
FIG. 11A is a graph showing the results of a comparison between a dry electrode based on a resilient nanofibrous web prepared according to the method of manufacturing a dry electrode based on the elastic nanofibrous web according to the second embodiment of the present invention and an Ag / AgCl gel electrode (EEG, eletroencephalography) signal measured at the same position and simultaneously measured.
FIG. 11B is a graph showing the results of the comparison between the dry nanofibrous web-based dry electrode prepared according to the method of manufacturing the elastic nanofiber web-based dry electrode according to the second embodiment of the present invention and the Ag / AgCl gel electrode FIG. 3 is a graph showing power spectral densities of frequencies in an alpha wave range of an EEG (Electroencephalogram) signal measured at the same position. FIG.
FIG. 11C is a graph showing the results of a comparison between a dry electrode based on an elastic nanofiber web prepared according to the method of manufacturing an elastic nanofiber web-based dry electrode according to Example 2 of the present invention and an Ag / AgCl gel electrode as a comparative electrode And a multiscale entropy profile of an EEG (eletroencephalogram) signal simultaneously measured at the same position.
FIG. 12A is a graph showing the results of a comparison between an elastic nanofiber web-based dry electrode manufactured according to the method of manufacturing a dry electrode based on the elastic nanofibrous web according to Example 1 of the present invention and an Ag / AgCl gel electrode as a comparative electrode (EMG, electromyography) signal simultaneously measured while holding the fist and spreading at the same position.
FIG. 12B is a schematic view showing an elastic nanofiber web-based dry electrode manufactured according to the method of manufacturing a dry electrode based on the elastic nanofibrous web according to the first embodiment of the present invention. And a linear envelope obtained by averaging them.
FIG. 12C is a graph showing an averaged linear envelope of electromyogram signals of the forearm simultaneously measured with two electrodes in order to visually compare the EMG characteristics of the electrodes of the embodiment 1 and the comparative example.
FIG. 13A is a graph showing the results of comparison between the dry nanofibrous web-based dry electrode prepared according to the method of manufacturing the elastic nanofibrous web-based dry electrode according to Example 1 of the present invention and the Ag / AgCl gel electrode as the comparative electrode (EMG, electromyography) signals of the leg muscles measured at the same position while walking at different speeds.
FIG. 13B shows a rectified signal of the EMG signal measured by the elastic nanofibrous web-based dry electrode manufactured according to the method of manufacturing the dry electrode based on the elastic nanofibrous web according to the first embodiment of the present invention, A plot of the averaged linear envelope by walking speed is shown.
FIG. 13C is a graph showing only the linearized envelope of the EMG signals of the thigh measured by the two electrodes at the same time in order to visually compare the EMG characteristics of the electrode of Example 1 and Comparative Example.
FIG. 14A is a graph showing the results of comparison between the dry nanofibrous web-based dry electrode prepared according to the method of manufacturing the elastic nanofiber web-based dry electrode according to the second embodiment of the present invention and the Ag / AgCl gel electrode (EMG, electromyography) signal simultaneously measured while holding the fist and spreading at the same position.
FIG. 14B is a graph showing the relationship between the rectified signal (EMG) of electromyography signals of the forearm measured by the elastic nanofibrous web-based dry electrode manufactured according to the method of manufacturing the elastic nanofiber web-based dry electrode according to the second embodiment of the present invention Rectified signal) and a linear envelope obtained by averaging the signal.
FIG. 14C is a graph showing only the linearized envelope of the electromyogram signals of the forearm measured simultaneously with the two electrodes in order to visually compare the EMG characteristics of the electrode according to the embodiment 2 and the comparative electrode.
FIG. 15 is a graph showing the results of measurement of 16 dry type elastic nanofibrous web-based dry nanoparticle webs prepared according to the method of manufacturing elastic nanofibrous web-based electrodes according to Example 2 of the present invention, EIT (electric impedance tomography) image according to difference in electric conductivity obtained by measuring voltage after applying current of 1 mA at various frequencies after attaching at equal intervals around the electrode. EIT The image is shown by the frequency of the applied current.
FIG. 16 is a graph showing the results obtained by attaching 16 elastic electrodes based on the elastic nanofibrous web manufactured according to the method of manufacturing a dry electrode based on the elastic nanofibrous web according to Example 1 of the present invention at regular intervals around the chest of the subject, The EIT image according to the inspiration and expiration in the chest obtained from the measured voltage while applying the current of 50 kHz and 1 mA during the rest, and the EIT image measured using the Ag / AgCl gel electrode as the comparative electrode, respectively.
FIG. 17 is a graph showing the results obtained by attaching 16 elastic electrodes based on the elastic nanofibrous web manufactured according to the method of manufacturing a dry electrode based on the elastic nanofibrous web according to Example 2 of the present invention at regular intervals around the chest of the subject, The EIT image according to the inspiration and expiration in the chest obtained by measuring the voltage while applying the current of 100 kHz and 1 mA during the rest, and the EIT image measured using the Ag / AgCl gel electrode as the comparative electrode, respectively.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings and accompanying drawings, but the present invention is not limited to or limited by the embodiments.

The terminology used herein is for the purpose of illustrating embodiments and is not intended to be limiting of the present invention. In the present specification, the singular form includes plural forms unless otherwise specified in the specification. It is noted that the terms "comprises" and / or "comprising" used in the specification are intended to be inclusive in a manner similar to the components, steps, operations, and / Or additions.

As used herein, the terms "embodiment," "example," "side," "example," and the like should be construed as advantageous or advantageous over any other aspect or design It does not.

Also, the term 'or' implies an inclusive or 'inclusive' rather than an exclusive or 'exclusive'. That is, unless expressly stated otherwise or clear from the context, the expression 'x uses a or b' means any of the natural inclusive permutations.

Also, the phrase "a" or "an ", as used in the specification and claims, unless the context clearly dictates otherwise, or to the singular form, .

It will also be understood that when an element such as a film, layer, region, configuration request, etc. is referred to as being "on" or "on" another element, And the like are included.

Hereinafter, a method of manufacturing an elastic nanofiber web-based dry electrode according to an embodiment of the present invention will be described with reference to FIGS. 1 and 2. FIG.

FIG. 1 is a flowchart illustrating a method of manufacturing a dry electrode based on an elastic nanofiber web according to an embodiment of the present invention. FIG. 2 is a view illustrating a method of manufacturing a dry electrode based on an elastic nanofiber web according to an embodiment of the present invention. It is an image.

1 and 2, a method of manufacturing a dry electrode based on elastic nanofibrous web according to an embodiment of the present invention includes dissolving an elastic polymer and a silver (Ag) ion-containing material having an ability to form a fiber in an organic solvent, (S110) producing liquid 110, electro-spinning electrospinning liquid 110 to produce an elastic nanofiber web 122 comprising reduced silver nanoparticles S120) and electroless silver plating (S130) of immersing the elastic nanofiber web in a silver plating solution.

The step S110 of producing the electrospinning liquid 110 may be performed by dissolving an elastic polymer and a silver (Ag) ion-containing material capable of forming a fiber in an organic solvent.

The elastic polymer means a polymer having elasticity capable of being dissolved in an organic solvent, i.e., a rubber which is not crosslinked.

As the elastic polymer, poly (styrene-b-butadiene-b-styrene (SBS), nitrile-butadiene rubber, elastic polyurethane, polyester At least one selected from the group consisting of polyester-polyurethane, polyether-polyurethane, latex, and silicone rubber.

In addition, polyester-polyurethane may be a material capable of making elastic fibers, commonly referred to as spandex.

A method of manufacturing a dry electrode based on an elastic nanofiber web according to an embodiment of the present invention includes fabricating an electrolessly silver plated elastic nanofiber web 160 using an elastic polymer and measuring the frequency and the electrical conductivity Can be reduced.

When a polymer having no elasticity is used, the produced fiber is not easily broken or restored upon deformation. As a result, since the electrode is supported by the ductility of the silver plating layer itself formed by progressing the electroless silver plating, The layer is peeled or cracked and the electrical conductivity of the electrode is reduced.

However, since the method of manufacturing the dry electrode based on the elastic nanofibrous web according to the embodiment of the present invention uses the elastic polymer, even if external force or folding is applied to the elastic nanofibers 121, due to the elasticity of the elastic nanofibers 121 itself It can be restored to its original shape and thus the frequency of cracking of the dry electrode can be remarkably reduced.

Furthermore, since the dry electrode formed by electroless silver plating on the elastic nanofibers 121 is deformed according to the shape of the measurement medium, the contact surface is greatly increased and the characteristics of the conventional wet gel electrode can be perfectly reproduced, It is possible.

(AgCl), silver nitrate (AgNO ₃ ), formic acid silver (HCOOAg), silver nitrate (CH ₃ COOAg), triethyl ammonium chloride, and the like can be used as the silver ion- plants acid (CF ₃ COOAg)), carbonate (Ag ₂ CO _3), silver sulfate (available from Ag ₂ SO ₄₎ and phosphoric acid (include any one selected from the group consisting of Ag ₃ PO _4).

The electrospinning liquid 110 may include 5 to 40 parts by weight of the elastic polymer and 0.01 to 1 part by weight of the silver ion-containing material, based on 100 parts by weight of the organic solvent.

In the case of the elastic polymer contained in the electrospinning liquid 110, the range of electrospinning can be determined according to the molecular weight of the elastic polymer. For example, in the case of an elastic polymer having a relatively low molecular weight and a low viscosity, it may be up to about 40 parts by weight, but as the molecular weight increases, the weight of the elastic polymer may be set low.

In the case of the silver ion-containing material contained in the electrospinning liquid 110, the silver nanoparticles are reduced in the electrospinning process and the reduced silver nanoparticles do not need a large amount because they act as nucleating agents in the next step. Therefore, when a silver ion-containing material (silver ion concentration) is contained in an amount of 1 part by weight or more, a part of the silver ion-containing material is not made of silver nanoparticles and exists in a silver salt state. Can be inhibited.

The organic solvent used for the electrospinning liquid 110 can be used without limitation as long as it is a good solvent for the elastically-stretched polymer. The usual good solvent for the elastic polymer depends on the kind of the elastic polymer to be used, and it may vary depending on the intention of the producer or custom in the industry, and the definition should be based on the contents throughout the specification.

The organic solvent may be used to dissolve the elastic polymer and the organic solvent may include tetrahydrofuran (THF), toluene, xylene, benzene, N, N-dimethylacetamide N-dimethylacetamide (DMAc), N-dimethylformamide (DMF), N-methylpyrrolidinone (NMP) and dimethyl sulfoxide And the like.

In addition, the organic solvent may be selected according to the elastic polymer in the electrospinning liquid 110.

Preferably, when poly (styrene-b-butadiene-b-styrene) and nitrile-butadiene rubber, latex or silicone rubber are used as the elastic polymer, a hydrocarbon-based solvent can be generally used, and hydrocarbons hydrocarbon solvents such as tetrahydrofuran (THF), toluene, xylene, and benzene may be used.

On the other hand, when polyurethane, polyester-polyurethane, or polyether-polyurethane is used as the elastic polymer, N, N-dimethylacetamide ( N, N-dimethylacetamide, DMAc, N, N-dimethylformamide, N-methylpyrrolidinone or dimethylsulfoxide Can be used.

Further, the electrospinning liquid 110 may further include a co-solvent having a polarity for advancing electrospinning. The electrospinning liquid 110 is mainly required to have an organic solvent for dissolving the elastic polymer, and a polar solvent for electrospinning. Organic solvents having polarity for conducting electrospinning can be used as co-solvents for electrospinning and can be used alone or as a mixture.

The co-solvent may be selected from the group consisting of N, N-dimethylacetamide, DMAc, N, N-dimethylformamide, N-methylpyrrolidinone, Dimethyl sulfoxide (DMSO), acetone, methyl ethyl ketone, methanol, ethanol, propanol, butanol, t-butyl alcohol, isopropylalcohol, iPA 2-propanol, benzyl alcohol, tetrahydrofuran (THF), ethyl acetate, butyl acetate, propylene glycol diacetate, propylene glycol methyl ether But are not limited to, propylene glycol methyl ether acetate (PGMEA), acetonitrile, chloroform, dichloromethane, trifluoroacetonitrile, ethylene glycol, pyridine, Pyrrole At least it may include any one selected from the group consisting of a Dean (pyrrolidine).

The electrospinning liquid 110 may further include a reducing solvent that promotes reduction of silver ions contained in the ion-containing material, and the reducing solvent may include N, N-dimethylacetamide, DMAc, At least one selected from the group consisting of N, N-dimethylformamide (DMF), N-methylpyrrolidinone (NMP), and dimethyl sulfoxide .

In the step S120 of manufacturing the elastic nanofiber web, the elastic nanofiber web 122 including the reduced silver nanoparticles can be prepared by electrospinning the electrospun fluid 110. [

A conventional technique for manufacturing a dry electrode using a polymer material and a silver-plated catalyst comprises forming a solution for nanofiber preparation by electrospinning at a temperature of about 70 DEG C at a temperature of about 1 DEG C to form silver (Ag) nanoparticles to act as a nucleating agent in the nanofiber The silver nanoparticles are formed in situ and then electrospun. The silver nanoparticles formed in the electrospinning over a long period of time are agglomerated in a process step such as precipitation and agglomeration of silver nanoparticles Bad things can happen.

But. A method of manufacturing a dry electrode based on an elastic nanofiber web according to an embodiment of the present invention uses an electrospinning liquid 110 containing an elastic polymer and a silver ion containing material in an organic solvent, Containing material may be reduced and silver nanoparticles may be formed on the elastic nanofibers 121.

The step S120 of fabricating the elastic nanofiber web injects electrons into the solution or nanofibers discharged through the injection needle during the electrospinning by the flow of a weak current, that is, the flow of electrons formed under a high voltage, Silver (Ag) ions in the electrospinning liquid 110 or the elastic nanofibers 121 may be reduced to form silver nanoparticles.

Accordingly, in the method of manufacturing a dry electrode based on elastic nanofibers according to an embodiment of the present invention, a separate process for forming silver nanoparticles can be omitted.

In addition, since the method for manufacturing the dry electrode based on the elastic nanofibrous web according to the embodiment of the present invention is such that the silver (Ag) nanoparticles are formed on the surface as well as inside the elastic nanofibers 121, The silver (Ag) nanoparticles formed serve as a nucleating agent, and the electroplating is selectively performed on the elastic nanofibers 121, so that a dry electrode having excellent electrical characteristics can be produced.

Preferably, the step of fabricating the elastic nanofiber web 122 (S120) includes the steps of electrospinning the electrospun fluid 110 to the support 140 so that the elastic nanofiber web 122 is formed on the support 140 A metal sheet, a paper sheet, a Teflon sheet, a fiber fabric, or a nonwoven fabric may be used as the support 140 of the elastic nanofiber web 122.

Since the elastic nanofiber web 122 is very thin in character due to its nature, it is not easy to handle in the succeeding continuous process. Thus, it is generally desirable that subsequent steps be carried out in a state where the support 140 is placed or fixed.

Various materials may be used for the support 140, but a metal sheet such as an aluminum sheet, a conductive polymer film, a Teflon sheet, a paper, a textile fabric or a nonwoven fabric may be used.

In particular, when a synthetic fiber fabric or a synthetic fiber nonwoven fabric is used, there is no deformation in the process of wetting with ethanol or wetting with a silver plating solution, and after silver plating is completed, it becomes easy to release the silver- plated elastic nanofiber web from the support 140, It is possible to prevent silver ions from being unnecessarily consumed in the silver plating solution.

Since the components constituting the silver plating solution are generally expensive, it is very important to reduce unnecessary waste in mass production, etc., and the synthetic fiber support 140 can be very advantageous in continuously processing the silver plating after electrospinning.

In the continuous process, the support 140 is placed on a conveyor-type metal collector 130, and the elastic nanofibers generated by electrospinning through a multi-spinning nozzle arranged in a two-dimensional array 121 may be randomly stacked and fixed on the support 140 to form the elastic nanofiber web 122.

However, in the case of a small batch production, the supporter 140 is wound on the cylindrical collector 130 so that the elastic nanofibers 121 generated during electrospinning are fixed to the supporter 140, ) May be formed.

At this time, the collector 130 is preferably configured to be able to control the temperature. A method of manufacturing a dry electrode based on an elastic nanofiber web according to an embodiment of the present invention includes electrospinning an electrospinning solution 110 in which an elastic polymer having a fiber forming ability and a silver ion-containing material are dissolved in an organic solvent, When the elastic nanofibers 121 are manufactured through vaporization of the organic solvent, the elastic nanofibrous web 122 of good quality can be manufactured.

Therefore, it is preferable to adjust the collector 130 to an appropriate temperature according to the configuration of the electrospinning liquid 110 to induce the vaporization of the organic solvent.

The elastic nanofiber web 122 may be composed of elastic nanofibers 121. The elastic nanofibers 121 may have a diameter of 10 nm to 10 탆 and the elastic nanofibers 121 may have a diameter of 10 nm or less There is a problem that the nanofibers are difficult to be formed by the silver nanoparticles formed on the back surface of the elastic nanofibers 121 and the strength of the elastic nanofibers 121 is reduced. , Surface area, etc.) can not be used.

The elastic nanofibers 121 produced by electrospinning are known to have a large surface area compared to ordinary fabrics or fibers. In addition, since the elastic nanofibers 121 are very small in diameter, a two-dimensional product such as a web composed of the elastic nanofibers 121 has a considerably high tissue density.

Therefore, when silver is plated (coated) on the elastic nanofibers 121 through electroless plating, electroless silver plated nanofibers having a very high density and surface area can be obtained. Such a web made of electroless silver-plated elastic nanofibers can be manufactured in various thicknesses ranging from several micrometers to several millimeters in thickness, and the thickness of the plated metal can be from a few nanometers to a few micrometers.

4A to 5D, the dry electrode based on the elastic nanofibrous web according to the embodiment of the present invention uses a nanoscale elastic nanofiber to have a high surface area-to-volume ratio Therefore, it can be confirmed that the capacitive of the electroless silver plated elastic nanofiber web is reduced, and the signal distortion can be reduced.

Referring to FIG. 7, the dry electrode based on the elastic nanofibrous web according to the embodiment of the present invention is manufactured by manufacturing the dry electrode based on the elastic nanofibrous web having the compact structure using the elastic nanofibers, It can be seen that there is no signal distortion and it is the same as the result of the gel electrode.

Figs. 4A to 5D and Figs. 7 to 17 will be described in detail below with reference to production examples.

The electroless silver-plated elastic nanofiber web 160 manufactured according to the method of manufacturing a dry electrode based on the elastic nanofibrous web according to the embodiment of the present invention has a low level of metal thickness and a random shape of the elastic nanofibers 121 It can be easily used for a flexible display, a wearable computer, a hot wire for clothes, etc., because it has durability against external deformation such as bending.

In addition, since such electrolessly-resilient nano-fiber web 160 exhibits a net effect between the elastic nanofibers 121, even if the silver is detached, it can be caught in the fiber without being released to the outside. Therefore, The disease can be reduced.

Also, according to the embodiment, the step of manufacturing the elastic nanofiber web 122 (S120) may be followed by the step of treating the elastic nonwoven fiber web 122 with an alcohol.

The alcohol used for the alcohol treatment may include at least one selected from the group consisting of ethanol, methanol and isopropanol, and preferably ethanol may be used.

A method of manufacturing a dry electrode based on an elastic nanofiber web according to an embodiment of the present invention includes a step of applying an alcohol treatment to the elastic nanofibrous web 122 to form a silver plating solution 150 at a time of electroless silver plating, And the inside of the elastic nanofiber web 122 can be easily silvered.

In the case where the elastic nanofiber web 122 is not subjected to the alcohol treatment and the alcohol treatment is performed, the silver nanofibrous web 122 can be effectively silvered to the inside of the elastic nanofiber web, ) Can be improved.

In the electroless silver plating step S130, the elastic nanofiber web 122 may be immersed in the silver plating solution 150 to conduct silver plating to produce the electroless silver plated elastic nanofiber web 160. [

In the step of electroless silver plating (S130), the elastic nanofiber web 122 fixed to the support 130 is wetted with alcohol, soaked in an aqueous solution of the reducing agent, and then moistened with a silver plating solution 150 containing no reducing agent .

Electroless silver plating utilizes a substitution reaction. Substance to be silver plated is immersed in a solution containing a silver complex (Ag (NH ₃ ) ₂ OH) which is generally in a state capable of being reduced, and a reducing agent is added to the silver The surface of the material is silver plated.

In this case, when a reducing agent is added to the silver plating solution 150, a reducing reaction takes place not only on the surface of the silver plating material but also on the surface of the silver plating solution 150.

However, if the elastic nanofiber web 122 is immersed in the aqueous solution of the reducing agent before the silver plating solution 150 is soaked in the aqueous solution as described above, the reducing agent is present in a concentrated form on the surface of the elastic nanofibers 121, The reduction reaction occurs intensively on the surface of the elastic nanofibers 121, so that unnecessary reduction reaction in the silver plating solution 150 can be prevented, and silver plating can be effectively performed.

Examples of the inorganic reducing agent that can be used as a reducing agent include hydrazine (N ₂ H ₄ ), lithium borohydride (sodium borohydride) or aluminum borohydride, and sodium hypophosphite (NaH ₂ PO ₂ ) is formaldehyde (HCHO), acetaldehyde (CH ₃ CHO, benzaldehyde (C ₆ H ₅ CHO), the _{(CH 2 = CH-CHO)} , glucose (glucose) and the like. preferably, the glucose as a reducing agent in Acre (glucose) may be used, and as the reducing agent aqueous solution, an aqueous solution having a concentration of the reducing agent of 2 to 20% (w / v) may be used.

Since the electroless silver plated elastic nanofiber web 160 forms the electroless silver plating layer 161 on the surface of the strands of the elastic nanofibers 121 while maintaining the shape of the elastic nanofibers 121, ). ≪ / RTI > As a result, the surface area due to the silver nanoparticles is widened while retaining the inherent resistance of the metal, so that it can be used as an excellent dry electrode since it has a high surface area-to-volume ratio.

Conventionally, a method of forming a dry electrode by using a silver mesh already formed and impregnating silver mesh into a polymer solution has been used. However, in this method, the surface area of the silver mesh exposed to the surface area is extremely limited, So it is extremely limited in terms of efficiency. In addition, the silver mesh can not be used as a desirable dry electrode because the thickness of the manufacturing net has a relatively thick thickness of more than micrometers.

However, according to the method of manufacturing an elastic nanofiber web-based dry electrode according to the embodiment of the present invention, since the electrodes are formed in the elastic nanofibers 121 in the form of small silver nanoparticles, the surface area is absolutely large, Since the web 122 is formed, the feeling of contact with the skin can be improved.

In addition, according to the embodiment, after the step of electroless silver plating the elastic nanofiber web 122, the step of heating and pressing the electroless silver plated elastic nanofiber web 160 may be performed.

The step of heating and pressurizing the electrolessly silvered elastic nanofiber web 160 may be performed by melting the elastic polymer constituting the elastic nanofiber web 122 by heating and then removing the air layer that can be formed inside by pressing And then cooled to form a polymer again.

The electroless silver plated elastic nanofiber web 160 can be used as an electrode for transmitting an electrical signal of the human body. The electrode for this purpose is preferably excellent in sensitivity to an electrical signal.

In the method of manufacturing a dry electrode based on elastic nanofibrous web according to an embodiment of the present invention, the elastic nanofiber web 122 after the electroless silver plating step (S130) contains a large amount of air in the inner space. Noise may be included when an electric signal is transmitted.

However, if the step of heating and pressing the electroless silver plated elastic nanofiber web 160 is performed, the elastic nanofiber web 122 is formed more densely, so that the noise can be reduced and the durability can be improved.

The step of heating and pressing the electroless silver plated elastic nanofiber web 160 may be performed by ultrasonic thermal welding or pressure thermal welding.

For example, an electroless silver plated elastic nanofiber web 160 is sandwiched between two sheets of polyimide film, and a silver-plated elasticity (not shown) inserted between the polyimide films as an apparatus for generating high heat such as an ultrasonic generator or a heater A method of rubbing or pressing the nanofiber web can be used.

The elastic nanofibrous web-based dry electrode according to an embodiment of the present invention is manufactured by a method of manufacturing an elastic nanofiber web-based dry electrode according to an embodiment of the present invention.

The dry electrode based on the elastic nanofibrous web according to the embodiment of the present invention includes an electroless silver plated layer 161 coated (plated) on the surface of the elastic nanofibrous web 122 containing reduced silver nanoparticles.

The dry electrode based on the elastic nanofibrous web according to the embodiment of the present invention has a high metal density by forming the electroless silver plating layer 161 on the elastic nanofiber web 122 having a large surface area, The electrical conductivity of the electrode can be improved.

Referring to FIG. 6, the dry electrode based on the elastic nanofibrous web according to the embodiment of the present invention has a reduced contact resistance and a contact capacitance comparable to that of the Ag / AgCl gel electrode, which is a comparative electrode, It can be seen that the electrical conductivity of the elastic nanofiber web-based dry electrode is improved.

6 will be described in detail in the production example and the following.

The elastic nanofibrous web-based dry electrode according to the embodiment of the present invention can reduce the signal to noise ratio (SNR) as compared with the wet gel electrode. Since the gel electrode fundamentally utilizes ionic conductivity, the surface resistance is low, but the resistance of the electrode itself is large, so it is vulnerable to external noise.

On the other hand, the elastic nanofiber-based silver (Ag) dry electrode is fundamentally formed of a small nanoparticle-type electrode on the elastic nanofiber 121, so that the electrode resistance has almost the pure silver resistance value, The surface area is absolutely large, so that the signal-to-noise ratio is excellent.

It can be seen from the results shown in FIG. 6 that the resistance value is lower than that of the comparative example.

The dry electrode based on the elastic nanofibrous web according to the embodiment of the present invention is harmless to the human body and improves the feeling of contact with the skin by forming the electroless silver plating layer 161 on the elastic nanofiber web 122 .

The elastic nanofiber web-based dry electrode according to an embodiment of the present invention can be used for electrocardiogram (ECG), electromyography (EMG), electroencephalogram (EEG), electroencephalogram (EEG) and electric impedance tomography (EIT).

For example, an elastic nanofiber web-based dry electrode according to an embodiment of the present invention can be used in a sports bra for electrocardiogram measurement.

A sports bra for electrocardiogram measurement including an elastic electrode based on elastic nanofibrous web according to an embodiment of the present invention includes a sports bra having an elastic band for close contact with a body under the chest, A base, and a dry electrode having a coupling base that can be attached to and detached from the support base and made of a conductive material that senses an electrical signal generated in the body.

The controller may further include a control unit connected to the dry electrode for transmitting the sensed electric signal, a control unit for storing the electric signal received through the electric wire, or transmitting the sensed electric signal to the user and measuring the electrocardiogram of the wearer.

(+) Electrode, (-) electrode and ground electrode may be formed as a total of three dry electrodes so as to form a positive electrode, a negative electrode and a ground electrode, respectively. Three electrodes may be arranged in a triangular shape to form dry electrodes of each group capable of receiving electrical signals.

Since the dry electrode is formed of three dry electrodes, three of the arm islets constituting the support base can be provided at different positions so that the dry electrodes of the respective sets can be coupled.

In this case, among the dry electrodes, the support base to which the (+) electrode is coupled is installed near the heart, and the support base to which the (-) electrode of the dry electrode is coupled is installed at a part far from the heart, It is preferable that the support base to which it is coupled is configured to be installed at the furthest part from the heart.

Therefore, the support base to which the (+) electrode is attached is installed inside the elastic band below the left chest where the heart is located, and the support base to which the (-) electrode is attached is installed inside the elastic band below the left back, The support base to which the ground electrode is coupled is provided inside the elastic band on the lower right side of the right side so that the dry electrodes of each group can be adhered to the skin close to the heart and farther and farther from the heart.

Manufacturing example

Comparative Example

An Ag / AgCl gel electrode (3M Red Dot ^TM 50-2237) was used.

Example 1

(3/5) in N, N-dimethylformamide (DMF, Aldrich, USA) / 20 mL of tetrahydrofuran (THF, 15 g of SBS (LG Chem. Ltd., Korea) and 0.15 g of silver nitrate (AgNO ₃ , Dae Jung, Korea) were dissolved in a ternary-solvent system of 2 v / Respectively.

Then, an elastic nanofiber web was prepared by electrospinning an electrospinning liquid at an injection rate of 1.5 mL h ^-1 using a 27 gauge needle at an applied voltage of 24 kV.

When 100 mL of 0.1 M silver nitrate solution and 50 mL of 0.8 M sodium hydroxide solution (Sam Chun Chemical Co., Korea) were mixed, when a brown precipitate was formed, the soluble diamine was dissolved in a water-soluble diamine silver complex (Ag) complex solution was prepared by dropping the ammonia solution until the compound was formed.

The diamine silver (Ag) complex solution thus formed was filled in a silver plating solution container, and 0.25 M dextrose solution was added so that the final ratio of silver nitrate / sodium hydroxide / dextrose solution in the silver plating solution container was 10/5/1 v / v / (Duksan Co., Korea) was added to prepare a silver plating solution.

The plating apparatus was rotated at a speed of 10 rpm to form an electroless silver plated layer on the elastic nanofiber web to prepare SBS-AgNFw (SBS- is an elastic nanofiber web).

Example 2

A two-part solvent system of 40 mL tetrahydrofuran (THF, Aldrich, USA) / 60 mL N, N-dimethylformamide, DMF, Aldrich, 10 g of polyurethane (Estane R190A, Lubrizol, USA) and 0.15 g of silver nitrate (AgNO ₃ , Dae Jung, Korea) were dissolved in a binary solvent system to prepare an electrospinning solution.

Then, an elastic nanofiber web was prepared by electrospinning an electrospinning liquid at an injection rate of 1.5 mL h ^-1 using a 27 gauge needle at an applied voltage of 18 kV.

Silver plating method was the same as in Example 1, except that PU-AgNFw (PU- is an elastic nanofiber web) was prepared.

Hereinafter, characteristics of the elastic nanofibrous web-based dry electrode manufactured according to the method of manufacturing the dry electrode based on the elastic nanofibrous web according to the embodiment of the present invention will be described with reference to FIG. 3A to FIG.

FIG. 3A illustrates an elastic nanofiber web-based dry electrode fabricated according to a method of manufacturing an elastic nanofiber web-based dry electrode according to an embodiment of the present invention. FIG. FIG. 1 illustrates an elastic nanofibrous web-based dry electrode fabricated according to a method of manufacturing an elastic nanofiber web-based dry electrode according to an embodiment of the present invention.

FIG. 4A is a scanning electron microscope (FE-SEM) photograph of the elastic nanofiber web prepared according to the method of manufacturing an elastic nanofiber web-based dry electrode according to Example 1 of the present invention, and FIG. 1 is a scanning electron micrograph of an electroless silver plated elastic nanofiber web prepared according to a method of manufacturing an elastic nanofiber web-based dry electrode according to Example 1 of the present invention.

4A to 4B, it can be seen that the electroless silver plating is performed on the elastic nanofiber web to form an electroless silver plated layer on the surface of the elastic nanofiber web to increase the diameter of the electroless silver plated elastic nanofiber web .

FIG. 5A is a scanning electron micrograph of an elastic nanofiber web prepared according to the method of manufacturing an elastic nanofiber web-based dry electrode according to Example 2 of the present invention, and FIG. 5B is a scanning electron micrograph of an elastic nanofiber web prepared according to Example 2 FIG. 2 is a scanning electron microscope (SEM) image of an electrolessly silver plated elastic nanofiber web prepared according to a method of manufacturing a dry electrode based on an elastic nanofiber web.

5A and 5B, it can be seen that the electroless silver plating is performed on the elastic nanofiber web to form an electroless silver plating layer on the elastic nanofiber web, thereby increasing the diameter of the electroless silver plated elastic nanofiber web .

5C is a transmission electron microscope (TEM) photograph showing a transverse section of an electroless silver plated elastic nanofiber web prepared according to the method of manufacturing an elastic nanofiber web-based dry electrode according to Example 2 of the present invention And FIG. 5D is a transmission electron micrograph showing two electroless silver plated elastic nanofiber webs prepared according to the method of manufacturing a dry electrode based on elastic nanofibrous web according to Example 2 of the present invention.

Referring to FIGS. 5C and 5D, it can be seen that the electroless silver plated layer formed on the elastic nanofibrous web is formed thicker than the elastic nanofibers, and the thickness of the silver plated layer can be controlled by electroless plating time.

In addition, by using nanoscale elastic nanofibers, they have a high surface area-to-volume ratio, thereby reducing the capacitances of electroless silvered nanofiber webs and reducing signal distortion .

Also, the capacitance generated by the contact resistance caused by the contact between the electroless silver plated elastic nanofiber and the electroless silver plated elastic nanofiber is less than that of the elastic nanofibrous web-based dry electrode according to the first or second embodiment of the present invention It is possible to improve the impedance performance of the elastic nanofibrous web-based dry electrode manufactured according to the manufacturing method of the present invention.

FIG. 6 is a graph showing the results of a comparison between a dry electrode based on an elastic nanofiber web prepared according to the method of manufacturing a dry electrode based on elastic nanofibers according to the first and second embodiments of the present invention and a comparative electrode using an Ag / AgCl gel electrode. (Contact capacitances) and contact resistances of the respective electrodes, which are calculated on the basis of the impedance measured by the three-electrode method and the four-electrode method, respectively, on the Agar Phantom.

Figure 6 shows the average values measured at 10 BIS frequencies (BIS frequencies) ranging from 10 Hz to 500 kHz.

Referring to FIG. 6, the electrodes of Example 1 and Example 2 exhibited a contact resistance lower than that of the comparative electrode Ag / AgCl gel electrode and exhibited a contact capacitance similar to that of the comparative electrode Ag / AgCl gel electrode. 1 and the elastic nanofibrous web-based dry electrode according to Example 2 have a high contact surface area, and thus exhibit high electrical conductivity.

FIG. 7 is a graph showing the results of simulation of a human body using an elastic nanofiber web-based dry electrode manufactured according to the method of manufacturing a dry electrode based on elastic nanofibers according to an embodiment of the present invention and a Ag / AgCl gel electrode as a comparative electrode (50% duty cycle square wave) current for 100 ms cycles after adhering to the agan phantom.

Referring to FIG. 7, the Ag / AgCl gel electrode as the comparative electrode, and the dry electrode based on the elastic nanofibrous web according to Example 1 and Example 2 exhibited similar voltage waveforms without signal distortion.

In particular, the elastic nanofibrous web-based dry electrode according to Examples 1 and 2 can be regarded as having a reduced structure of the elastic nanofibrous web-based dry electrode due to a compact structure.

FIG. 8A is a graph showing the results of a comparison between a dry electrode based on an elastic nanofibrous web prepared according to the method of manufacturing a dry electrode based on the elastic nanofibrous web according to Example 1 of the present invention and an Ag / AgCl gel electrode Position and ECG (electrocardiography) signals of 7 cycles measured at the same time.

Referring to FIG. 8A, the elastic nanofibrous web-based dry electrode manufactured according to the method of manufacturing the elastic nanofibrous web-based dry electrode according to the first embodiment of the present invention and the ECG signal of the comparative electrode Ag / AgCl gel electrode The correlation is 1.00, which shows that the two signals are identical.

8B is a graph showing only one cycle (P, Q, R, S, T, and U) of the ECG signal shown in FIG. 8A in order to facilitate comparison of characteristics of the electrodes of Embodiment 1 and Comparative Example.

8B, P, Q, R, S, T and U peaks were clearly observed in both the dry electrode according to Example 1 and the comparative electrode Ag / AgCl gel electrode, The R peak electrocardiogram signal of the dry electrode based on the elastic nanofibrous web manufactured according to the method of manufacturing the nanofiber web-based dry electrode is in perfect agreement with the comparative electrode Ag / AgCl gel electrode.

FIG. 9A is a graph showing the results of comparison between the elastic nanofibrous web-based dry electrode prepared according to the method of manufacturing the elastic nanofibrous web-based dry electrode according to the second embodiment of the present invention and the Ag / AgCl gel electrode as the comparative electrode, (ECG) signals measured at the same position and simultaneously measured.

Referring to FIG. 9A, the elastic nanofibrous web-based dry electrode manufactured according to the method of manufacturing the elastic nanofiber web-based dry electrode according to the second embodiment of the present invention and the comparative electrode Ag / AgCl gel electrode The correlation is 0.99 and the two signals are almost identical.

9B is a graph showing only one cycle (P, Q, R, S, T, and U) of the ECG signal shown in FIG. 9A in order to facilitate comparison of the characteristics of the electrode of Example 2 and the electrode of Comparative Example.

Referring to FIG. 9B, P, Q, R, S, T and U peaks were clearly observed in both the dry electrode according to Example 2 and the comparative electrode Ag / AgCl gel electrode.

FIGS. 10A and 10B are graphs showing the relationship between the safety latitude of the elastic nanofibrous web-based dry electrode and the comparative electrode Ag / AgCl gel electrode fabricated according to the method of manufacturing the elastic nanofiber web-based dry electrode according to the second embodiment of the present invention EOG, electrooculogram) signal.

FIG. 10A is a graph showing the relationship between the dry nanofiber web-based dry electrode prepared according to the method of manufacturing the elastic nanofiber web-based dry electrode according to the second embodiment of the present invention and the Ag / AgCl gel electrode (EOG, electrooculography) signals measured when the eyes are flickered or the eyes are moved up and down.

Figure 10a shows that the EOG signal measurement was rolling three times, blinking the eyes, then rolling the eyes up and down twice immediately.

10A, the elastic nanofibrous web-based dry electrode manufactured according to the method of manufacturing the elastic nanofiber web-based dry electrode according to the second embodiment of the present invention and the Ag / AgCl gel electrode of the comparative electrode Is 0.99, indicating that the EOG signal from the two electrodes is almost the same.

Also, there was a clear signal difference in the blinking of the eyes and rolling of the eyeballs.

FIG. 10B is a graph showing the relationship between the dry nanofiber web-based dry electrode prepared according to the method of manufacturing the elastic nanofiber web-based dry electrode according to the second embodiment of the present invention and the Ag / AgCl gel electrode And the EOG signal measured when the eye is moved while the eye is closed.

Referring to FIG. 10B, the elastic nanofibrous web-based dry electrode fabricated according to the method of manufacturing the elastic nanofibrous web-based dry electrode according to the second embodiment of the present invention and the eye movement of the Ag / AgCl gel electrode The EOG signal of the two electrodes is almost the same.

In addition, it can be seen that the EOG signal is generated mainly by a change in the muscle system around the eye, but has a completely different pattern from the EMG (electromyography) signal.

FIG. 11A is a graph showing the results of a comparison between a dry electrode based on a resilient nanofibrous web prepared according to the method of manufacturing a dry electrode based on the elastic nanofibrous web according to the second embodiment of the present invention and an Ag / AgCl gel electrode (EEG, eletroencephalography) signal measured at the same position and simultaneously measured.

11A, the elastic nanofibrous web-based dry electrode prepared according to the method of manufacturing the dry electrode based on the elastic nanofibrous web according to the second embodiment of the present invention and the EEG signal of the Ag / AgCl gel electrode of the comparative electrode And the EEG signal by the two electrodes is almost the same.

FIG. 11B is a graph showing the results of the comparison between the dry nanofibrous web-based dry electrode prepared according to the method of manufacturing the elastic nanofiber web-based dry electrode according to the second embodiment of the present invention and the Ag / AgCl gel electrode FIG. 3 is a graph showing power spectral densities of frequencies in an alpha wave range of an EEG (Electroencephalogram) signal measured at the same position. FIG.

Referring to FIG. 11B, the output spectral densities of the elastic nanofibrous web-based dry electrode and the comparative electrode Ag / AgCl gel electrode fabricated according to the method of manufacturing the elastic nanofiber web-based dry electrode according to the second embodiment of the present invention (power spectral density) was 0.96 at 0.05 Hz - 35 Hz and 0.98 at 8 Hz - 13 Hz, and the EEG output spectral density of the two electrodes was almost the same.

FIG. 11C is a graph showing the results of a comparison between a dry electrode based on an elastic nanofiber web prepared according to the method of manufacturing a dry electrode based on the elastic nanofibrous web according to Example 2 of the present invention and an Ag / AgCl gel electrode And a multiscale entropy profile of an EEG (eletroencephalogram) signal simultaneously measured at the same position.

Referring to FIG. 11C, the elastic nanofibrous web-based dry electrode prepared according to the method of manufacturing the elastic nanofiber web-based dry electrode according to the second embodiment of the present invention and the multi-scale entropy of the comparative electrode Ag / AgCl gel electrode Is 0.99, indicating that the EEG characteristics of the two electrodes are almost the same.

FIG. 12A is a graph showing the results of a comparison between an elastic nanofiber web-based dry electrode manufactured according to the method of manufacturing a dry electrode based on the elastic nanofibrous web according to Example 1 of the present invention and an Ag / AgCl gel electrode as a comparative electrode (EMG, electromyography) signal simultaneously measured while holding the fist and spreading at the same position.

Referring to FIG. 12A, the elastic nanofibrous web-based dry electrodes and the comparative electrode Ag / AgCl gel electrode fabricated according to the method of manufacturing the elastic nanofibrous web-based dry electrode according to the first embodiment of the present invention and the EMG signal The correlation was 0.999, indicating that the EMG signals from the two electrodes are almost the same.

FIG. 12B is a schematic view showing an elastic nanofiber web-based dry electrode manufactured according to the method of manufacturing a dry electrode based on the elastic nanofibrous web according to the first embodiment of the present invention. And a linear envelope obtained by averaging them.

FIG. 12C is a graph showing an averaged linear envelope of electromyogram signals of the forearm simultaneously measured with two electrodes in order to visually compare the EMG characteristics of the electrodes of the embodiment 1 and the comparative example.

Referring to FIG. 12C, the elastic nanofibrous web-based dry electrodes and the comparative electrode Ag / AgCl gel electrodes fabricated according to the method of manufacturing the elastic nanofibrous web-based dry electrode according to the first embodiment of the present invention, The linear envelope correlation is 1.00 and the EMG signals from the two electrodes are the same.

FIG. 13A is a graph showing the results of comparison between the dry nanofibrous web-based dry electrode prepared according to the method of manufacturing the elastic nanofibrous web-based dry electrode according to Example 1 of the present invention and the Ag / AgCl gel electrode as the comparative electrode (EMG, electromyography) signals of the leg muscles measured at the same position while walking at different speeds.

Referring to FIG. 13A, the elastic nanofibrous web-based dry electrode and the comparative electrode Ag / AgCl gel electrode fabricated according to the method of manufacturing the elastic nanofibrous web-based dry electrode according to the first embodiment of the present invention, The correlation was 0.9997 for no walking, 0.9995 for walking at 3 km / h, 0.9997 for walking at 6 km / h, and 0.9997 for walking at 9 km / h. The accuracy of the EMG signal is almost the same.

FIG. 13B shows a rectified signal of the EMG signal measured by the elastic nanofibrous web-based dry electrode manufactured according to the method of manufacturing the dry electrode based on the elastic nanofibrous web according to the first embodiment of the present invention, A plot of the averaged linear envelope by walking speed is shown.

FIG. 13C is a graph showing only the linearized envelope of the EMG signals of the thigh measured by the two electrodes at the same time in order to visually compare the EMG characteristics of the electrode of Example 1 and Comparative Example.

13C, elastic nanofibrous web-based dry electrodes prepared according to the method of manufacturing elastic nanofibrous web-based dry electrodes according to Example 1 of the present invention according to movement of leg muscles and comparative electrodes Ag / AgCl The linear envelope correlation of the EMG signal of the gel electrode is 1.00, so that the EMG signals by the two electrodes are the same.

FIG. 14A is a graph showing the results of comparison between the dry nanofibrous web-based dry electrode prepared according to the method of manufacturing the elastic nanofiber web-based dry electrode according to the second embodiment of the present invention and the Ag / AgCl gel electrode (EMG, electromyography) signal simultaneously measured while holding the fist and spreading at the same position.

Referring to FIG. 14A, the elastic nanofibrous web-based dry electrode manufactured according to the method of manufacturing the dry electrode based on the elastic nanofibrous web according to the second embodiment of the present invention, and the comparative electrode Ag / AgCl gel electrode The correlation was 0.95, indicating that the accuracy was slightly lower than that of the elastic nanofiber web-based dry electrode manufactured according to the method of manufacturing the elastic nanofiber web-based dry electrode according to Example 1 of the present invention.

FIG. 14B is a graph showing the relationship between the rectified signal (EMG) of electromyography signals of the forearm measured by the elastic nanofibrous web-based dry electrode manufactured according to the method of manufacturing the elastic nanofiber web-based dry electrode according to the second embodiment of the present invention Rectified signal) and a linear envelope obtained by averaging the signal.

FIG. 14C is a graph showing only the linearized envelope of the electromyogram signals of the forearm measured simultaneously with the two electrodes in order to visually compare the EMG characteristics of the electrode according to the embodiment 2 and the comparative electrode.

Referring to FIG. 14C, the elastic nanofibrous web-based dry electrode and the comparative electrode Ag / AgCl gel electrode fabricated according to the method of manufacturing the elastic nanofiber web-based dry electrode according to the second embodiment of the present invention, The averaged linear envelope correlation is 0.99, so EMG signals from both electrodes are almost the same.

FIG. 15 is a graph showing the results of measurement of 16 dry type elastic nanofibrous web-based dry nanoparticle webs prepared according to the method of manufacturing elastic nanofibrous web-based electrodes according to Example 2 of the present invention, EIT (electric impedance tomography) image according to difference in electric conductivity obtained by measuring voltage after applying current of 1 mA at various frequencies after attaching at equal intervals around the electrode. EIT The image is shown by the frequency of the applied current.

15, the blue dot represents the lowest electrical conductivity (0.02 wt% NaCl), the yellow dot represents the intermediate electrical conductivity (0.1 wt%) and the red dot represents the highest electrical conductivity (0.5 wt% NaCl) .

15, the elastic nanofibrous web-based dry electrode manufactured according to the method of manufacturing the dry electrode based on the elastic nanofibrous web according to the second embodiment of the present invention is compared with the Ag / AgCl gel electrode It can be seen that the area of the red dot showing high electrical conductivity is wide and the area of the blue dot showing the lowest electric conductivity is narrow.

FIG. 16 is a graph showing the results obtained by attaching 16 elastic electrodes based on the elastic nanofibrous web manufactured according to the method of manufacturing a dry electrode based on the elastic nanofibrous web according to Example 1 of the present invention at regular intervals around the chest of the subject, The EIT image according to the inspiration and expiration in the chest obtained from the measured voltage while applying the current of 50 kHz and 1 mA during the rest, and the EIT image measured using the Ag / AgCl gel electrode as the comparative electrode, respectively.

16, the elastic nanofibrous web-based dry electrode manufactured according to the method of manufacturing the dry electrode based on the elastic nanofibrous web according to the first embodiment of the present invention is similar to the Ag / AgCl gel electrode of the comparative example, Lung images.

FIG. 17 is a graph showing the results obtained by attaching 16 elastic electrodes based on the elastic nanofibrous web manufactured according to the method of manufacturing a dry electrode based on the elastic nanofibrous web according to Example 2 of the present invention at regular intervals around the chest of the subject, The EIT image according to the inspiration and expiration in the chest obtained by measuring the voltage while applying the current of 100 kHz and 1 mA during the rest, and the EIT image measured using the Ag / AgCl gel electrode as the comparative electrode, respectively.

17, the elastic nanofibrous web-based dry electrode prepared according to the method of manufacturing the dry electrode based on the elastic nanofibrous web according to the second embodiment of the present invention is also similar to the dry electrode of the comparative example Ag / AgCl gel electrode. Image.

While the invention has been shown and described with reference to certain preferred embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. This is possible. Therefore, the scope of the present invention should not be limited to the described embodiments, but should be determined by the equivalents of the claims, as well as the claims.

110: electrospinning liquid 121: elastic nanofibers
122: elastic nanofiber web 130: collector
140: Support 150: silver plating solution
160: Electroless silver plated elastic nanofiber web 161: Electroless silver plated layer

Claims (15)

Preparing an electrospinning liquid by dissolving an elastic polymer and a silver (Ag) ion-containing material capable of forming a fiber in an organic solvent;
Preparing an elastic nanofiber web including silver nanoparticles reduced in the electron emission by electro spinning the electrospinning liquid;
Immersing the elastic nanofiber web in a silver plating solution and electroless silver plating
Lt; / RTI >
Wherein the silver ion-containing material contained in the electrospun solution is reduced by electrons injected during the electrospinning in the step of producing the elastic nanofiber web, and the reduced silver nanoparticles are formed in the step of producing the elastic nanofiber web As a nucleating agent,
Wherein the elastic polymer is a non-crosslinked rubber, and the elastic nanofibrous web-based dry electrode (hereinafter, referred to as " elastic nanofibrous web ") is used to reduce the frequency of occurrence of cracks caused by external force or folding, dry electrode.
The method according to claim 1,
The elastic polymer may be at least one selected from the group consisting of poly (styrene-b-butadiene-b-styrene (SBS), nitrile-butadiene rubber, elastic polyurethane, At least one selected from the group consisting of polyester-polyurethane, polyether-polyurethane, latex, and silicone rubber. A method of manufacturing a dry electrode based on a resilient nanofiber web.
The method according to claim 1,
The silver ion-containing material is silver chloride (AgCl), silver nitrate (AgNO _3), formic acid (HCOOAg), acetic acid (CH ₃ COOAg), trifluoride plants acid (CF ₃ COOAg)), carbonate (Ag ₂ CO _3), sulfuric acid (Ag ₂ SO ₄ ) and silver phosphate (Ag ₃ PO ₄ ). The method of claim 1,
The method according to claim 1,
Wherein the electrospun fluid comprises 5 to 40 parts by weight of the elastic polymer and 0.01 to 1 part by weight of the silver ion-containing material based on 100 parts by weight of the organic solvent. / RTI >
The method according to claim 1,
Wherein the elastic nanofiber web is made of elastic nanofibers, and the elastic nanofibers have a diameter ranging from 10 nm to 10 μm.
The method according to claim 1,
Wherein the organic solvent is selected in the electrospinning liquid according to the elastic polymer.
The method according to claim 1,
The organic solvent may be selected from the group consisting of tetrahydrofuran (THF), toluene, xylene, benzene, N, N-dimethylacetamide (DMAc) At least one selected from the group consisting of N, N-dimethylformamide (DMF), N-methylpyrrolidinone (NMP) and dimethyl sulfoxide (DMSO) Wherein the method comprises the steps of:
The method according to claim 1,
The electrospinning liquid may further comprise a co-solvent having a polarity for advancing the electrospinning,
The co-solvent may be selected from the group consisting of N, N-dimethylacetamide, DMAc, N, N-dimethylformamide, N-methylpyrrolidinone, , Dimethyl sulfoxide (DMSO), acetone, methyl ethyl ketone, methanol, ethanol, propanol, butanol, t-butyl alcohol, isopropylalcohol, propylene glycol diacetate, propyleneglycol methyl ether, propyleneglycol methyl ether, propyleneglycol diacetate, propyleneglycol diacetate, and the like. But are not limited to, propylene glycol methyl ether acetate (PGMEA), acetonitrile, chloroform, dichloromethane, trifluoroacetonitrile, ethylene glycol, pyridine, And Wherein the first electrode comprises at least one selected from the group consisting of pyrrolidine and pyrrolidine.
delete The method according to claim 1,
In the step of producing the elastic nanofiber web,
Characterized in that a metal sheet, paper, Teflon sheet, fiber fabric or nonwoven fabric is used as a support for the elastic nanofibers.
The method according to claim 1,
After the step of producing the elastic nanofiber web,
Further comprising the step of treating the elastic nanofiber web with an alcohol,
Wherein the alcohol comprises at least one selected from the group consisting of ethanol, methanol and isopropanol.
The method according to claim 1,
After the step of electroless silver plating the elastic nanofiber web,
Further comprising heating and pressurizing the electrolessly silvered elastomeric nanofiber web. ≪ RTI ID = 0.0 > 8. < / RTI >
13. The method of claim 12,
The step of heating and pressing the electroless silver plated elastic nanofiber web comprises:
Wherein the elastic nanofibers are formed by ultrasonic thermal welding or pressure thermal welding.
An elastic nanofiber web-based dry electrode fabricated by the method of any one of claims 1 to 8 and 10-13.
15. The method of claim 14,
The elastic nanofibrous web-based dry electrode can be used as an electrocardiogram (ECG), an electromyography (EMG), an electroencephalogram, an electroencephalogram, an electrooculogram (EOG) or an electric impedance tomography ). ≪ / RTI > The nanofiber web-based dry electrode of claim 1,

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