KR20160142192A - Organogel conductor and an electronic device comprising the same - Google Patents

Abstract

The present invention relates to an organic gel conducting material and an electronic device comprising the same. The organic gel conducting material comprises: a matrix polymer; conductive dopants dispersed in the matrix polymer; and an organic solvent impregnated in the matrix polymer. The organic gel conducting material can be used to obtain a conducting material having sufficient elasticity and dimensional stability while providing excellent electrical conductivity.

Description

Organic gel conductive agents and electronic devices comprising same

TECHNICAL FIELD The present invention relates to an organic gel conductive agent and an electronic device including the organic gel conductive agent, and more particularly, to an organic gel conductive material having excellent electrical conductivity with sufficient stretchability and dimensional stability and an electronic device including the same.

Recently, with the development of wearable electronic devices, there is a growing interest in electric conductors that can have elasticity.

Conductive hydrogel is a substance in which a conductive polymer material is dispersed in a matrix of hydrosilylated polymer capable of crosslinking. Since it has inherent elasticity and human suitability as well as electric conductivity, it is utilized as an electrode material of a stretchable flexible element that can be bonded to a body part It is possible. However, since water is used as a solvent, there arises a problem that when exposed to air for a long time, the gel is changed from a gel state to a rigid solid due to evaporation of water. Furthermore, ion conduction occurs in which electrons move according to the voltage due to voltage application, and electrolysis of water occurs at a voltage higher than a certain voltage, thereby generating an electrochemical current. As a result, uniform electrical transfer is difficult to achieve and part of the hydrogel may be damaged as a result of chemical reactions.

The first object of the present invention is to provide an organic gel conductor having sufficient elasticity and dimensional stability and having excellent electrical conductivity.

SUMMARY OF THE INVENTION The first object of the present invention is to provide an electronic device including an organic gel conductor having sufficient elasticity and dimensional stability and having excellent electrical conductivity.

A third object of the present invention is to provide a method for producing an organic gel conductor having sufficient elongation and dimensional stability and having excellent electrical conductivity.

In order to accomplish the first object of the present invention, Conductive dopants dispersed in the matrix polymer; And an organic solvent impregnated in the matrix polymer to maintain the gel state.

The organic solvent may be a liquid whose vapor pressure at 20 [deg.] C is from about 0.01% to about 5% of the vapor pressure of water. The organic solvent may have a boiling point of about 150 ° C to about 400 ° C. The solvent is, for example, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylenephosphoric triamide, 1, 3-butylene glycol, 1, 3-butylene glycol, 1, 3-butylene glycol, N-vinylpyrrolidone, N-vinylformamide, N-vinyl-acetamide, cresol, phenol, xylenol, ethylene glycol, diethylene glycol, triethylene glycol, Butylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, 1,4-butanediol, 1,4-butylene glycol, glycerin, diglycerin, D-glucose, D-glucitol, , Ethylene carbonate, propylene carbonate, dioxane, diethyl ether, dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether, 3-methyl-2-oxazolidinone, acetonitrile, Glutaronitrile, methoxy And at least one selected from the group consisting of cyanuric chloride, cyanuric chloride, cyanuric chloride, cyanuric chloride, cyanuric chloride, cyanuric chloride, cyanuric chloride, cyanuric chloride, cyanuric chloride,

The organic gel conductor may have an increase in current substantially linearly with an increase in the voltage applied across it. Also, the content of the organic solvent may be about 10 wt% to about 60 wt%. In addition, the organic gel conductor may be freestanding and may have stretchability.

Wherein the matrix polymer is selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, polypyrrole, polyvinyl chloride (PVC), poly (alkyl acrylate), poly (ethyl acrylate), poly (ethylene terephthalate), polymethyl methacrylate PMMA), polyaniline, polyvinyl acetate, poly (ethyl vinyl acetate), poly (ethyl-co-vinyl acetate), polyvinyl butyrate, polyacrylate, polyacrylate, polyacrylamide, polymethacrylate, But are not limited to, polyacrylonitrile, polyacrylonitrile (PAN), polycaprolactone (PCL), polyvinylidene fluoride (PVDF), poly (2-vinylpyridine), polyvinyl methyl ether, polyvinyl butyral, Polyether ether ketone, styrene / acrylate ester, vinyl acetate / acrylate ester, ethylene / vinyl acetate copolymer, polybutadiene, Polyimide, polythiophene, polyacetylene, polyetherimide, polysulfone, polyethersulfone, polyimide, polyimide, polyimide, polyimide, polyimide, polyimide, polyimide, polyimide, (PEO), polydimethylsiloxane, CYTOP ( ^TM) , poly (styrene), poly (styrene), poly (styrene), polystyrene sulfonate, polystyrene sulfonyl fluoride, melamine-formaldehyde resin, nylon, epoxy resin, polylactide, polyethylene oxide (styrene-co-butadiene), poly (styrene-co-divinylbenzene), poly (dimethylsiloxane-co-polyethylene oxide), poly A resin, and a cellulose.

In order to achieve the second object, the present invention provides an electronic device comprising: an electronic element having two electrodes; A power supply for supplying power to the electronic element; And a wiring portion connecting the electronic element and the power supply portion. At this time, the wiring portion may include the organic gel conductor described above.

According to a third aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: preparing a material mixture including a monomer of a conductive dopant, an organic solvent, and a matrix polymer; Polymerizing the monomer of the matrix polymer to obtain a matrix polymer; And performing dialysis against the resultant product of the polymerization.

The material mixture may further comprise water. In addition, the method of manufacturing the organic gel conductor may further include drying the water after performing the dialysis. The conductive dopant may be PEDOT: PSS, and the organic solvent may be ethylene glycol, dimethyl sulfoxide, or a mixture thereof.

The method of fabricating the organic gel conductor may further include drying the conductive dopant prior to preparing the mixture.

When the organic gel conductive agent of the present invention is used, a conductor having excellent electrical conductivity can be obtained while having sufficient stretchability and dimensional stability.

FIG. 1 is a schematic view conceptually showing a configuration of an organic gel conductor according to an embodiment of the present invention.
2 is a conceptual diagram showing an electronic device including an organic gel conductor according to an embodiment of the present invention.
3 is a flowchart illustrating a method of fabricating an organic gel conductor according to an embodiment of the present invention.
4 is a schematic view conceptually showing a state immediately after polymerization of a matrix polymer in the production of an organic gel conductor according to an embodiment of the present invention.
5 is a flowchart illustrating a method of fabricating an organic gel conductor according to another embodiment of the present invention.
6 is a circuit diagram showing a closed circuit using the organic gel conductor manufactured in Production Example 1. FIG.
FIGS. 7A and 7B are images showing a state in which a light emitting device emits light by applying power to a closed circuit formed using the organic gel conductor manufactured in Production Example 1. FIG.
FIGS. 8A and 8B are graphs showing IV sweep test results on the gel conductors manufactured in Production Examples 1 to 5 and Comparative Production Example 1. FIG.
FIG. 9 is a graph showing the results of measurement of resistance changes according to deformation of the organic gels prepared in Production Examples 1 to 5.
FIG. 10A is a graph showing a change in weight of a solvent according to elapsed time with respect to the organic gel prepared in Production Examples 1 to 4 and the hydrogel prepared in Comparative Production Example 1. FIG. 10B are images showing the shape changes of the organic gel of Production Example 1 and the hydrogel of Comparative Production Example 1 after 24 hours.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, embodiments of the inventive concept may be modified in various other forms, and the scope of the present invention should not be construed as being limited by the embodiments described below. Embodiments of the inventive concept are desirably construed as providing a more complete understanding of the inventive concept to those skilled in the art. The same reference numerals denote the same elements at all times. Further, various elements and regions in the drawings are schematically drawn. Accordingly, the inventive concept is not limited by the relative size or spacing depicted in the accompanying drawings.

The terms first, second, etc. may be used to describe various components, but the components are not limited by the terms. The terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the first component may be referred to as a second component, and conversely, the second component may be referred to as a first component.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the inventive concept. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this application, the expressions "comprising" or "having ", etc. are intended to specify the presence of stated features, integers, steps, operations, elements, parts, or combinations thereof, It is to be understood that the invention does not preclude the presence or addition of one or more other features, integers, operations, components, parts, or combinations thereof.

Unless otherwise defined, all terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the inventive concept belongs, including technical terms and scientific terms. In addition, commonly used, predefined terms are to be interpreted as having a meaning consistent with what they mean in the context of the relevant art, and unless otherwise expressly defined, have an overly formal meaning It will be understood that it will not be interpreted.

If certain embodiments are otherwise feasible, the particular process sequence may be performed differently from the sequence described. For example, two processes that are described in succession may be performed substantially concurrently, or may be performed in the reverse order to that described.

In the accompanying drawings, for example, variations in the shape shown may be expected, depending on manufacturing techniques and / or tolerances. Accordingly, embodiments of the present invention should not be construed as limited to any particular shape of the regions shown herein, but should include variations in shape resulting from, for example, manufacturing processes. All terms "and / or" as used herein encompass each and every one or more combinations of the recited elements. In addition, the term "substrate" as used herein can mean a substrate itself, or a laminated structure including a substrate and a predetermined layer or film formed on the surface thereof. Further, in the present specification, the term "surface of a substrate" may mean an exposed surface of the substrate itself, or an outer surface such as a predetermined layer or a film formed on the substrate.

<Organic gel conductor>

One embodiment of the present invention provides organogel conductors having stretchability and flexibility even at room temperature. The organic gel conductor may comprise a matrix polymer, conductive dopants impregnated in the matrix polymer, and an organic solvent.

FIG. 1 is a conceptual view showing a configuration of an organic gel conductor 100 according to an embodiment of the present invention.

Referring to FIG. 1, the matrix polymer 110 may be arranged randomly or with a certain regularity. In some embodiments, the matrix polymer 110 may be crosslinked. That is, two or more chains of the matrix polymer 110 may be crosslinked by having a covalent bond 112. In some embodiments, the covalent bond 112 may be one in which two or more chains are directly bonded, and a portion branched from one chain is bonded to another chain. In some embodiments, the covalent bond 112 may be a covalent bond connected by the addition of a separate cross-linking agent.

In FIG. 1, the matrix polymer 110 is shown as constituting a polygonal cell, but this is for convenience of understanding only, and the present invention is not limited thereto.

The matrix polymer 110 may be selected from the group consisting of polyvinyl alcohol, polyvinyl pyrrolidone, polypyrrole, polyvinyl chloride (PVC), poly (alkyl acrylate), poly (ethyl acrylate), poly (ethylene terephthalate ), Polymethyl methacrylate (PMMA), polyaniline, polyvinyl acetate, poly (ethyl vinyl acetate), polyvinyl butyrate, polyacrylate, polyacrylate, polyacrylamide, polymethacrylate, , Polyacrylonitrile (PAN), polycaprolactone (PCL), polyvinylidene fluoride (PVDF), poly (2-vinylpyridine), polyvinyl methyl ether, polyvinyl butyral, polybenzimidazole, polyether Styrene / acrylic acid esters, vinyl acetate / acrylic acid esters, ethylene / vinyl acetate copolymers, polybutadiene, polyisoprene, Polyimide, polythiophene, polyacetylene, polyetherimide, polysulfone, polyethersulfone, polyimide, polyimide, polyimide, polyimide, polyimide, (PEO), polydimethylsiloxane, CYTOP ( ^TM) , poly (styrene-co), poly (styrene-co-methylstyrene), polystyrene sulfonate, polystyrene sulfonyl fluoride, melamine-formaldehyde resin, nylon, epoxy resin, polylactide, polyethylene oxide Poly (ethylene-co-vinyl acetate), poly (styrene-co-butadiene) -co-glycolic acid), silicone resin, cellulose, and the like, but is not limited thereto.

The matrix polymer 110 may have a weight average molecular weight of about 10,000 to about 1,000,000. If the weight average molecular weight of the matrix polymer (110) is too small, the function as a matrix is lost and it is difficult to maintain the shape of the organic gel. On the contrary, if the weight average molecular weight of the matrix polymer 110 is too large, it may become insufficient in elasticity and / or flexibility. The weight average molecular weight may be, for example, a value measured by gel permeation chromatography (GPC) using a polystyrene standard.

The conductive dopants 130 may be dispersed between the matrix polymers 100. The conductive dopants may be, for example, metals such as Al, Si, Sc, Ti, V, Cr, Mn, Fe, Y, Zr, Nb, Mo, Ta, W, Ni, Cu, Ag, Such as indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), fluorine-doped tin oxide (FTO) conductor; Doped silicon, such as doped silicon, doped germanium; Or a conductive polymer such as polyaniline (PANI), polypyrrole (PPy), poly (3,4-ethylenedioxythiophene) (PEDOT), and PEDOT: polystyrene sulfonate (PSS). However, it is not limited thereto. In particular, PEDOT: PSS is preferred as the conductive dopant 130 and is commercially available, for example, from H. C. Starck, GmbH (Leverkusen, Germany) under the trade name Baytron ㄾ -P.

Although the conductive dopants 130 are shown in the form of particles in FIG. 1, they need not necessarily be in the form of particles. The conductive dopants 130 may also be distributed in the space formed between the molecules of the matrix polymer 100 and / or on the surface of the molecules of the matrix polymer 100.

The organic solvent 120 can be an organic solvent having a significantly lower vapor pressure than water (H ₂ O). For example, the vapor pressure of the organic solvent 120 may be from about 0.01% to about 5% of the vapor pressure of water at 20 占 폚. If the vapor pressure of the organic solvent 120 is too low, the elasticity and flexibility of the produced organic gel may be insufficient. If the vapor pressure of the solvent is too high, it is easily vaporized and the organic gel can be cured within a short time. In some embodiments, the organic solvent 120 can be polar organic daily.

In some embodiments, the organic solvent 120 may be a solvent with a boiling point of about 150 ° C to 400 ° C. In some embodiments, the organic solvent 120 is selected from the group consisting of, but not limited to, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, Polar solvents such as hexamethylenephosphoramide, N-vinylpyrrolidone, N-vinylformamide and N-vinyl-acetamide; Phenols such as cresol, phenol and xylenol; Diethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, glycerin, diglycerin, D-glucose, D- Polyhydric alcohols such as glycol, butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol and neopentyl glycol; Carbonate compounds such as ethylene carbonate, propylene carbonate and the like; Ether compounds such as dioxane and diethyl ether; Chain ethers such as dialkyl ethers, propylene glycol dialkyl ethers, polyethylene glycol dialkyl ethers, and polypropylene glycol dialkyl ethers; Heterocyclic compounds such as 3-methyl-2-oxazolidinone; And nitrile compounds such as acetonitrile, glutaronitrile, methoxyacetonitrile, propionitrile, benzonitrile and the like. These organic solvents 120 may be used alone or in combination of two or more.

Particularly, the organic solvent 120 is preferably ethylene glycol or dimethylsulfoxide.

The content of the organic solvent 120 may be about 10 wt% to about 60 wt% of the weight of the organic gel conductor 100.

If the content of the organic solvent 120 is too small, the elasticity of the organic gel conductor 100 may be insufficient. If the content of the organic solvent 120 is too high, the organic gel conductor 100 may not be freestanding. Here, 'self-standing' refers to a property that can maintain a constant shape and strength independently without depending on other substrates. In other words, the organic gel conductor according to the embodiments of the present invention can be used stand-alone because it has elasticity and flexibility and has a certain shape and strength by itself without having to depend on other substrates.

<Electronic device>

2 is a conceptual diagram showing an electronic device 200 including an organic gel conductor according to an embodiment of the present invention.

2, the electronic device 200 includes an electronic element 210 having two electrodes 210a and 210b, a power source 202 for supplying power to the electronic element 210, And a wiring part 220 connecting the electronic element 210 and the power supply part 202.

The electronic element 210 may be a light emitting device such as a light emitting diode, an active device such as a thin film transistor, a liquid crystal display, a solid state lighting device, an OLED display, a quantum dot display, a transistor, a semiconductor memory device, And is not particularly limited. Further, the electronic element 210 may be an electronic system having a controller, a display device, an input / output device, a memory device, and the like.

The power source unit 202 may be any power source capable of supplying power to the electronic element 210, such as a solar cell, a secondary battery, a dry battery, or the like.

The wiring part 220 is an arbitrary wiring that electrically connects the electronic element 210 and the power source part 202 and may include at least a part of the organic gel conductor 100 described above. Furthermore, the wiring part 220 may include a general wiring 105 other than the organic gel conductor 100. The general wiring 105 may be a metal wiring, a coated wire, or the like formed on the substrate. 2, the organic gel conductor 100 is electrically connected to the electrode 210a via the common wiring 105, but the organic gel conductor 100 may be electrically connected directly to the electrode 210a. The organic gel conductor 100 may not be formed on the substrate. In addition, the organic gel conductor 100 may be provided in a stand-alone manner.

&Lt; Method for producing organic gel conductor >

Hereinafter, a method for manufacturing the organic gel conductor 100 as described above will be described.

3 is a flowchart illustrating a method of fabricating an organic gel conductor according to an embodiment of the present invention.

Referring to FIG. 3, a mixture of an aqueous solution of a conductive dopant, an organic solvent, and a monomer of a matrix polymer is prepared (S110).

The conductive dopant solution may be prepared by mixing a conductive dopant with water, and mixing the conductive dopant and water at a weight ratio of about 1:30 to about 1: 200. When the conductive dopant is water-soluble, the conductive dopant may be stirred to dissolve well in water. When the conductive dopant is non-aqueous, the conductive dopant may be agitated so as to be well dispersed in water.

(Conductive dopant)

The conductive dopant may be, for example, a metal such as Al, Si, Sc, Ti, V, Cr, Mn, Fe, Y, Zr, Nb, Mo, Ta, W, Ni, Cu, Ag, Au or Cu; Inorganic electrical conductors such as indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), fluorine-doped tin oxide (FTO); Doped silicon, such as doped silicon, doped germanium; Or a conductive polymer such as polyaniline (PANI), polypyrrole (PPy), poly (3,4-ethylenedioxythiophene) (PEDOT), and PEDOT: polystyrene sulfonate (PSS). However, it is not limited thereto. Particularly, the conductive dopant is preferably PEDOT: PSS.

(Organic solvent)

The aqueous solution of the conductive dopant is mixed with an organic solvent. The organic solvent may be a solvent having a boiling point of about 150 ° C to 400 ° C, and may be, but is not limited to, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide , A polar solvent such as dimethylsulfoxide, hexamethylenephosphotriamide, N-vinylpyrrolidone, N-vinylformamide and N-vinyl-acetamide; Phenols such as cresol, phenol and xylenol; Diethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, glycerin, diglycerin, D-glucose, D- Polyhydric alcohols such as glycol, butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol and neopentyl glycol; Carbonate compounds such as ethylene carbonate, propylene carbonate and the like; Ether compounds such as dioxane and diethyl ether; Chain ethers such as dialkyl ethers, propylene glycol dialkyl ethers, polyethylene glycol dialkyl ethers, and polypropylene glycol dialkyl ethers; Heterocyclic compounds such as 3-methyl-2-oxazolidinone; And nitrile compounds such as acetonitrile, glutaronitrile, methoxyacetonitrile, propionitrile, benzonitrile and the like. These organic solvents may be used alone or in combination of two or more.

The volume ratio of the organic solvent and the aqueous solution of the conductive dopant may be about 1: 3 to about 1:20. If the amount of the organic solvent is too small, the elasticity and / or flexibility of the produced organic gel conductor may be insufficient. If the amount of the organic solvent is too large, the degree of freestanding of the prepared organic gel conductor may be insufficient. Therefore, the volume ratio of the organic solvent and the aqueous solution of the conductive dopant can be adjusted in consideration of this point.

Then, a monomer of the matrix polymer may be further added to the mixture of the organic solvent and the aqueous solution of the conductive dopant. The matrix polymer is as described above with reference to FIG. 1, and the monomers for synthesizing the same are well known to those skilled in the art, so that specific examples are omitted.

The amount of the monomer to be mixed with the mixture of the organic solvent and the aqueous solution of the conductive dopant can be adjusted so that the weight percentage of the monomer after mixing is about 3% to about 15%. If the amount of the monomer is too small, it may not be formed or formed to have a sufficient volume and / or dimension of the matrix polymer. If the amount of the monomer is too large, the mass transfer during the polymerization may be insufficient and the polymerization may be insufficient, or the molecular weight distribution may be excessively widened due to the gel effect.

(Initiator)

The organic solvent, the aqueous solution of the conductive dopant and the mixture of monomers may further comprise an initiator for initiating polymerization of the monomers.

The initiator may be selected from, for example, benzoyl peroxide, dibenzoyl peroxide, monochlorobenzoyl peroxide, dichlorobenzoyl peroxide, p-methylbenzoyl peroxide, octanoyl peroxide, decanoyl peroxide, Tert -butyl hydroperoxide, tert -amyl hydroperoxide, cumene hydroperoxide, dicyclohexyl peroxide, dicyclohexyl peroxide, dicyclohexyl peroxide, cyclohexane peroxide, methyl ethyl ketone peroxide, di- Azobisisobutyronitrile (AIBN), 2,2'-azobis (2-methylbutyronitrile), azo-2-cyanovaleric acid, azobis- (2 , 4-dimethyl) valeronitrile, tert-butyl perbenzoate, di-tert-butylperoxy phthalate, potassium persulfate (potassium persulfate, PPS), ammonium persulfate (ammonium persulfate, APS), However, rhodium or the like persulfate (sodium persulfate, SPS), but is not limited to this.

The initiator is used in an amount effective to initiate polymerization of the monomer, the amount of which will vary depending on, for example, the type of initiator and the desired degree of polymer molecular weight and functionality. The initiator may be used in an amount of about 0.01 part by weight to about 10 parts by weight based on 100 parts by weight of the monomer, preferably about 0.03 part by weight to about 3 parts by weight based on 100 parts by weight of the monomer.

(Accelerator)

The mixture of the organic solvent, the aqueous solution of the conductive dopant and the monomer may further include an accelerator for promoting polymerization of the monomers.

The accelerator may be, for example, N, N, N ', N'-tetramethylethylenediamine (TEMED); An ester of an amino acid such as N-phenylglycine or a bipolar ion compound thereof; Mercapto benzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, -4 (3H) -quinazoline,? -Mercaptonaphthalene, ethylene glycol dithiophosphonate, trimethylolpropane tristyiopropionate, and pentaerythritol tetrakisthiopropionate; Polyfunctional thiol compounds such as hexanedithiol, trimethylolpropane tristhioglyconate and pentaerythritol tetrakisthiopropionate; N, N-dialkylaminobenzoic acid esters, N-phenylglycine or derivatives thereof such as ammonium salts or sodium salts thereof; Phenylalanine, or salts thereof such as ammonium or sodium salts thereof; An amino acid having an aromatic ring such as a derivative of an ester or the like, or an induction residue thereof, but the present invention is not limited thereto. The accelerator is preferably N, N, N ', N'-tetramethylethylenediamine.

The accelerator is used in an amount effective to promote polymerization of the monomer, the amount of which will vary depending on, for example, the type of accelerator and the desired degree of polymer molecular weight and functionality. The accelerator may be used in an amount of about 0.01 part by weight to about 10 parts by weight based on 100 parts by weight of the monomer, and preferably about 0.03 part by weight to about 3 parts by weight based on 100 parts by weight of the monomer.

(Crosslinking agent)

The mixture of the organic solvent, the aqueous solution of the conductive dopant and the monomer may further include a cross-linking agent for causing a cross-linking reaction in the polymerization of the monomers.

The crosslinking agent may be at least one of an isocyanate crosslinking agent, a peroxide crosslinking agent, an epoxy crosslinking agent and an amine crosslinking agent.

Examples of the compound relating to the isocyanate crosslinking agent include isocyanate monomers such as tolylene diisocyanate, chlorophenylene diisocyanate, tetramethylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, and the like; The isocyanate compound, isocyanurate compound, biuret type compound, and further polyurethane polyol, polyester polyol, acrylic polyol, polybutadiene polyol, polyisoprene polyol, etc., added with these isocyanate monomers with trimethylolpropane, Type isocyanate and the like. In particular, it is a polyisocyanate compound, and may be a polyisocyanate compound derived from one kind or a group selected from the group consisting of hexamethylene diisocyanate, hydrogenated xylylene diisocyanate and isophorone diisocyanate.

The peroxide-based crosslinking agent may be, for example, di (2-ethylhexyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, di- T-butyl peroxypivalate, di-lauroyl peroxide, di-n-octanoyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2- Ethylhexanoate, di (4-methylbenzoyl) peroxide, dibenzoyl peroxide, t-butylperoxyisobutyrate, 1,1-di (t-hexylperoxy) cyclohexane and the like.

Examples of the epoxy cross-linking agent include N, N, N ', N'-tetraglycidyl-m-xylenediamine, diglycidyl aniline, 1,3-bis (N, N-glycidylaminomethyl ) Cyclohexane, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, poly Propylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, trimethylol propane Polyglycidyl ether, adipic acid diglycidyl ester, o-phthalic acid diglycidyl ester, triglycidyl-tris (2-hydroxyethyl) isocyanurate, resorcin diglycidyl ether, bisphenol- S-diglycidyl ether, and the like.

As the amine-based crosslinking agent, for example, a compound having a plurality of amino groups such as ethylenediamine can be used. Specific examples of the ethylenediamine include ethylenediamine, 1,2-diaminopropane, 1,2-diamino-2-methylpropane, N-methylethylenediamine, N- ethylethylenediamine, N- N-hexylethylenediamine, N-hexylethylenediamine, N-cyclohexylethylenediamine, N-octylethylenediamine, N-decylethylenediamine, N-dodecylethylenediamine, , N'-diethylethylenediamine, N, N'-diisopropylethylenediamine, N, N, N'-trimethylethylenediamine, diethylenetriamine, N-isopropyldiethylenetriamine, N- Aminoethyl) -1,3-propanediamine, triethylenetetramine, N, N'-bis (3-aminopropyl) ethylenediamine, N, N'- , Tris (2-aminoethyl) amine, tetraethylenepentamine, pentaethylene hexamine, 2- (2-aminoethylamino) ethanol, N, N'-bis (hydroxyethyl) ethylenediamine, N- Hydroxyethyl) triethylene tetramine, piperazine, 1- (2-aminoethyl) piperazine, 4- (2-aminoethyl) morpholine, polyethyleneimine . Specific examples of the diamines and polyamines usable in addition to ethylenediamine include 1,3-diaminopropane, 1,4-diaminobutane, 1,3-diaminopentane, 1,5-diaminopentane, Dimethyl-1,3-propanediamine, hexamethylenediamine, 2-methyl-1,5-diaminopropane, 1,7-diaminoheptane, 1,8-diaminooctane, 2,2,4- 1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 1,9-diaminononane, 1,10-diaminodecane, 1,12-diaminododecane, N 1,3-propanediamine, N, N-dimethyl-1,3-propanediamine, N, N'- 1,3-propanediamine, N, N'-diethyl-1,3-propanediamine, N, N'-diisopropyl- Butyl-2-ethyl-1,5-pentanediamine, N, N'-dimethyl-1,6-hexanediamine, 3,3'-diamino-N-methyldipropylamine , N- (3-aminopropyl) -1,3-propanediamine, N, N ', N'-trimethylbis (hexamethylene) triamine, 4-aminomethyl-1,8-octanediamine, N, -Bis (3-aminopropyl) -1,3-propanediamine, spermine, 4,4'-methylenebis (cyclohexylamine), 1,2- diaminocyclohexane, 1,4-diaminocyclohexane Cyclohexane bis (methylamine), 1,4-cyclohexane bis (methylamine), 1,2-bis (aminoethoxy) ethane, 4,9-dioxa-1,12-dodecane Diamine, 4,7,10-trioxa-1,13-tridecanediamine, 1,3-diaminohydroxypropane, 4,4'-methylene dipiperidine, 4- (aminomethyl) - (4-aminobutyl) piperidine, and polyallylamine, but the present invention is not limited thereto.

In particular, methylene bisacrylamide is preferable as the crosslinking agent.

The amount of the crosslinking agent may be about 0.005 part by weight to about 1 part by weight based on 100 parts by weight of the monomer, and preferably about 0.01 part by weight to about 0.5 part by weight based on 100 parts by weight of the monomer.

Subsequently, the monomer is polymerized to form a matrix polymer (S120). The polymerization of the monomer can be carried out by heating the mixture, that is, the mixture of the aqueous solution of the conductive dopant, the organic solvent and the monomer.

To polymerize the monomer, the mixture may be heated to a temperature of, for example, from about 60 ° C to about 100 ° C. If the temperature is too low, the polymerization may be too slow and uneconomical. If the temperature is too high, some components may be pyrolyzed or water may evaporate, which may adversely affect dialysis for subsequent ion removal.

The heating time may be from about 30 minutes to about 5 hours. If the heating time is too short, the polymerization may not be sufficient and the matrix polymer may be formed insufficiently. If the heating time is too long, the weight average molecular weight of the matrix polymer becomes excessively large, and the stretchability of the organic gel conductor obtained later may be insufficient.

If there is a specific shape of the organic gel conductor obtained later, the mixture may be injected into a mold of a specific shape before performing the polymerization of the monomer, and then the polymerization may be carried out. For example, in the case of molding in the form of a film, the mixture can be spin-coated on a substrate. In some embodiments, the mixture may be injected into a mold in the form of a hexahedral extending in one direction prior to performing the polymerization.

When the polymerization is carried out as described above, a considerable amount of ions are present in the mixture due to reaction byproducts and the like, and these ions may cause ion conduction in the use of the organic gel conductor. Therefore, there is a need to remove unwanted ions and other impurities present in the mixture after polymerization.

In some embodiments, dialysis may be performed to remove the ions and other impurities (S130).

4 is a schematic diagram showing the state of the polymer after polymerization. Referring to FIG. 4, the mixture after polymerization shows that the polymerized matrix polymers 110 are crosslinked by the covalent bond 112 to form a matrix, and conductive dopants 130 are formed on the surfaces of the matrix polymers 110, exist. The solvent 120 'also contains water as well as an organic solvent and fills a space between the conductive dopant 130 and the matrix polymer 110.

In particular, unnecessary ions and other impurities 140 may exist in the solvent 120 'at a predetermined concentration. In order to remove this, a mixture of an organic solvent and water may be prepared in the same ratio as that in the mixture of the organic solvent and the conductive dopant solution prepared in the above-described step S110, and the polymer polymerized in the above may be immersed therein.

Then, the unnecessary ions and other impurities 140 in the polymer are diffused into the mixture of the external organic solvent and the aqueous solution by the osmotic pressure and released. The dialysis can be performed for about 15 hours to about 30 hours. By repeating this process several times, for example, about 2 to 10 times, the unnecessary ions and other impurities 140 in the polymer can be more reliably removed.

Then, the polymer may be heated to remove moisture therein (S140). Moisture can be ionized by the applied voltage, thereby causing ion conduction, so it is necessary to sufficiently remove moisture. To this end, the polymer can be heated to a temperature of from about 50 째 C to about 80 째 C for about 2 hours to about 8 hours. As described above, the polymer is heated to remove water inside, thereby obtaining an organic gel conductor.

5 is a flowchart illustrating a method of fabricating an organic gel conductor according to another embodiment of the present invention. In describing the manufacturing method according to the present embodiment, the same contents as the manufacturing method described with reference to FIG. 3 will be omitted for the sake of simplicity.

Referring to FIG. 5, a mixture of a conductive dopant solution and a monomer of a matrix polymer is prepared (S210). Unlike the embodiment described with reference to FIG. 3, the conductive dopant is directly dissolved in an organic solvent to obtain a conductive dopant solution, which is then mixed with the monomer of the matrix polymer.

The conductive dopant and the organic solvent are the same as those described with reference to Fig. The matrix polymer and the monomer for polymerizing the same are the same as those described with reference to Figs. 1 and 3.

The conductive dopant and the organic solvent may be mixed at a ratio of about 1: 2 to about 1: 70.

Subsequently, the monomer is polymerized to form a matrix polymer (S220). The polymerization of the monomer can be carried out by heating the mixture, that is, the mixture of the conductive dopant solution and the monomer.

To polymerize the monomer, the mixture may be heated to a temperature of, for example, from about 60 ° C to about 120 ° C. If the temperature is too low, the polymerization may be too slow and uneconomical. If the temperature is too high, some of the components may be pyrolyzed.

The heating time may be from about 30 minutes to about 5 hours. If the heating time is too short, the polymerization may not be sufficient and the matrix polymer may be formed insufficiently. If the heating time is too long, the weight average molecular weight of the matrix polymer becomes excessively large, and the stretchability of the organic gel conductor obtained later may be insufficient.

A mold for molding can be used in the polymerization process as described with reference to Fig. In addition, it is necessary to remove unnecessary ions resulting from the polymerization reaction.

Dialysis may be performed to remove the unnecessary ions and other impurities (S230). For the dialysis, the polymer obtained by polymerizing in step S220 may be immersed in an organic solvent. The organic solvent may be the same organic solvent as the organic solvent used for preparing the conductive dopant solution. By immersing the polymer in the organic solvent, undesired ions and other impurities present in the polymer can be osmotically diffused into the organic solvent and removed.

The dialysis can be performed for about 15 hours to about 30 hours. By repeating this process several times, for example, about 2 to 10 times, the unnecessary ions and other impurities 140 in the polymer can be more reliably removed.

Since water is not used in the production of the conductive dopant solution, a process of removing moisture is not necessary. Therefore, the organic gel conductor can be obtained by removing the dialyzed polymer from the organic solvent in which it has been immersed.

Hereinafter, the constitution and effects of the present invention will be described in more detail with reference to specific examples and comparative examples. However, these examples are merely intended to clarify the present invention and are not intended to limit the scope of the present invention.

&Lt; Production example 1 of organic gel conductor >

Commercial PEDOT: PSS was lyophilized and dissolved in deionized water to prepare a uniform PEDOT: PSS aqueous solution having a concentration of 1.3 wt%. The PEDOT: PSS aqueous solution was mixed with ethylene glycol in a volume ratio of 8: 1, and acrylamide was mixed as a monomer for forming a matrix polymer. The amount of acrylamide was adjusted so that the weight of PEDOT: PSS was 5.49 wt% based on the total weight of PEDOT: PSS and acrylamide. Ammonium persulfate as an initiator, methylene bisacrylamide as a crosslinking agent, and N, N, N ', N'-tetramethylethylenediamine as an accelerator were used.

The mixture was reacted at 90 DEG C for 2 hours to polymerize the matrix polymer, and the acidity was measured. As a result, it was found that the pH was 2. These results suggest that a large amount of hydrogen ions are present in the polymerization product, and unnecessary ions (for example, NH ₄ ⁺ , HSO ₄ ⁺ , SO ₄ ^2-, etc.) are generated as a result of the polymerization. These unnecessary ions are undesirable because they cause ionic conduction due to the applied voltage. Therefore, in order to remove the unnecessary ions, dialysis was performed as follows.

First, a mixed solution of deionized water and ethylene glycol was prepared, and the ratio was the same as that in preparing the above mixture solution of PEDOT: PSS aqueous solution and ethylene glycol. Then the polymer polymerized above was immersed in the deionized water / ethylene glycol mixture (pH = 7.4) and allowed to stand for 24 hours. After 24 hours, it was immersed in a fresh deionized water / ethylene glycol mixture and allowed to stand for an additional 24 hours. As a result of repeating this process, the pH of each step was measured to change to 3.75, 6.0, and 7.4 for 72 hours, and it was confirmed that most unnecessary ions were removed.

It was then dried in an oven at 60 DEG C for 4 hours to remove moisture from the polymer. Since the vapor pressure of ethylene glycol at 60 ° C is significantly lower than the vapor pressure of water, most of the water can be selectively removed by drying. Organic gel conductors were prepared by the above method.

&Lt; Preparation Example 2 &

An organic gel conductor was prepared in the same manner as in Preparation Example 1, except that the amount of acrylamide was adjusted so that the weight of PEDOT: PSS was 6.72 wt% based on the total weight of PEDOT: PSS and acrylamide.

&Lt; Preparation Example 3 &

An organic gel conductor was prepared in the same manner as in Preparation Example 1, except that the amount of acrylamide was adjusted so that the weight of PEDOT: PSS was 7.90 wt% based on the total weight of PEDOT: PSS and acrylamide.

&Lt; Preparation Example 4 &

An organic gel conductor was prepared in the same manner as in Preparation Example 1, except that the amount of acrylamide was adjusted so that the weight of PEDOT: PSS was 9.06% by weight based on the total weight of PEDOT: PSS and acrylamide.

&Lt; Production Example 5 &

Except that the amount of acrylamide was adjusted so that the weight of PEDOT: PSS was 6.83% by weight based on the total weight of PEDOT: PSS and acrylamide without performing freeze-drying on commercially available PEDOT: PSS. An organic gel conductor was prepared in the same manner as in Example 1.

<Electrical Conductivity of Organic Gel Conductor>

Using the organic gel prepared in Preparation Example 1, a circuit was constructed as shown in FIG. 6 to confirm whether the LED was lit. As shown in FIG. 6, the LED light emitting devices 201a and 201b and the power source 202 are connected to each other through the organic gel conductor 100 manufactured as described above, thereby forming a closed circuit. As a result, it was confirmed that power was normally supplied to the LED light emitting devices 201a and 201b through the organic gel conductor 100 as shown in FIGS. 7A and 7B. In particular, as shown in FIG. 7B, it was confirmed that the organic gel conductor 100 still conducts electricity well even though the organic gel conductor 100 is considerably deformed (330% from the initial value).

<Comparative Production Example 1>

The matrix polymer was polymerized in the same manner as in Production Example 1, except that ethylene glycol was not mixed. The polymerized matrix polymer was separated from the solvent to obtain a hydrogel. The hydrogel was not dialyzed.

<Nonionic Electrical Conductivity of Organic Gel Conductor>

I-V sweep tests were performed on the gel conductors prepared in Preparative Examples 1 to 5 and Comparative Preparative Example 1 for a predetermined voltage range. FIG. 8A is a graph showing IV sweep test results of the hydrogel conductor manufactured in Comparative Production Example 1, and FIG. 8B is a graph showing IV sweep test results of the organic gel conductor manufactured in Production Examples 1 to 5 .

Referring to FIG. 8A, it can be seen that the slope of the change is rapid in the range of -3 V to -2 V, which is judged to be due to the rapid oxidation / reduction reaction of water. Also, it can be seen that the slope of the change is gentle in the range of -2 V to 0 V, which is considered to be a result of relatively less active oxidation / reduction reaction. The nonlinearity of the change of the current with respect to the change of the voltage is observed through the entire voltage range (-3 V to +4 V) of FIG. 8A, which seems to be due to the difference in oxidation / reduction reaction speed as described above, This means that ion conduction contributes to the electrical conduction.

Referring to FIG. 8B, it can be seen that the change of the current with respect to the voltage change as a whole is almost linear. This means that Faradaic conduction, which is electric conduction by the movement of electrons, is not substantially involved in the conduction of electrons but contributed mainly to conduction.

&Lt; Resistance of Organic Gel Conductor >

The resistance change of the organic gel prepared in Production Examples 1 to 5 was measured and the results are shown in FIG.

Referring to FIG. 9, the values of the resistance (R / R ₀ ) according to the deformation amount (%) are all lower than the theoretical value. Organic gel conductors of Preparation Examples 1 to 4 showed excellent electrical conductivity retention up to over 300% deformation. However, in Production Example 5, an electrical failure occurred at a strain of about 70%.

<Dimensional Stability of Organic Gel Conductor>

The dimensional stability of the organic gel prepared in Preparation Examples 1 to 4 and the hydrogel prepared in Comparative Preparation Example 1 was tested. Using the prepared organic gel and hydrogel, 10 mm ㅧ 10 mm ㅧ 1 mm specimens were prepared. The specimens were weighed under reduced pressure (0.013 bar) and at room temperature, and their weight and shape were observed over time.

FIG. 10A shows the weight change of the solvent with the elapsed time, and FIG. 10B shows images showing the shape changes of the preparation example 1 and the comparative preparation example 1. FIG.

Referring to FIG. 10A, when about 3 hours have elapsed, the weight change of the organic gel in the case of the organic gel was only about 10% to about 15%, but in the case of the hydrogel, almost 95% Could know. In the case of the organic gel, the weight change of the solvent was only about 30% to about 40% even after 22 hours.

Referring to FIG. 10B, in the case of the hydrogel after 24 hours, almost all of the solvent evaporates, thereby causing a dimensional deformation that deviates considerably from the original shape. However, in the case of the organic gel, there is almost no dimensional change and the dimensional stability is excellent Could know.

While the present invention has been particularly shown and described with reference to exemplary 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. The present invention may be modified in various ways. Therefore, modifications of the embodiments of the present invention will not depart from the scope of the present invention.

The present invention can be usefully used in the electronics industry.

100: Organic gel conductor 105: General wiring
110: Matrix polymer 120: Organic solvent
130: Conductive dopant 140: Impurity
200: electronic device 201a, 201b: LED light emitting element
202: power source 210: electronic element
210a, 210b: electrode 220: wiring part

Claims (16)

Matrix polymer;
Conductive dopants dispersed in the matrix polymer; And
An impregnated organic solvent in the matrix polymer to maintain the gel state;
And an organic gel conductor. The method according to claim 1,
Wherein a current flowing when a voltage is applied to both ends is substantially caused by the flow of electrons. 3. The method of claim 2,
Wherein the increase of the current increases substantially linearly with an increase of the voltage applied to both ends. The method according to claim 1,
Wherein the conductive dopant is PEDOT: PSS, and the organic solvent is ethylene glycol, dimethyl sulfoxide, or a mixture thereof. The method according to claim 1,
Wherein the matrix polymer is selected from the group consisting of polyvinyl alcohol, polyvinyl pyrrolidone, polypyrrole, polyvinyl chloride (PVC), poly (alkyl acrylate), poly (ethyl acrylate), poly (ethylene terephthalate), polymethyl methacrylate PMMA), polyaniline, polyvinyl acetate, poly (ethyl vinyl acetate), poly (ethyl-co-vinyl acetate), polyvinyl butyrate, polyacrylate, polyacrylate, polyacrylamide, polymethacrylate, But are not limited to, polyacrylonitrile, polyacrylonitrile (PAN), polycaprolactone (PCL), polyvinylidene fluoride (PVDF), poly (2-vinylpyridine), polyvinyl methyl ether, polyvinyl butyral, Polyether ether ketone, styrene / acrylate ester, vinyl acetate / acrylate ester, ethylene / vinyl acetate copolymer, polybutadiene, Polyimide, polythiophene, polyacetylene, polyetherimide, polysulfone, polyethersulfone, polyimide, polyimide, polyimide, polyimide, polyimide, polyimide, polyimide, polyimide, (PEO), polydimethylsiloxane, CYTOP ( ^TM) , poly (styrene), poly (styrene), poly (styrene), polystyrene sulfonate, polystyrene sulfonyl fluoride, melamine-formaldehyde resin, nylon, epoxy resin, polylactide, polyethylene oxide (styrene-co-butadiene), poly (styrene-co-divinylbenzene), poly (dimethylsiloxane-co-polyethylene oxide), poly Resin, and cellulose. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt; The method according to claim 1,
Wherein the organic solvent is a liquid whose vapor pressure at 20 캜 is from about 0.01% to about 5% of the vapor pressure of water. The method according to claim 1,
Wherein the organic solvent has a boiling point of about 150 캜 to about 400 캜. 8. The method of claim 7,
The organic solvent may be selected from the group consisting of N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylenephosphoramide, But are not limited to, formamide, N-vinyl-acetamide, cresol, phenol, xylenol, ethyleneglycol, diethyleneglycol, triethyleneglycol, propyleneglycol, dipropyleneglycol, But are not limited to, glycols, glycerin, diglycerin, D-glucose, D-glucitol, isoprene glycol, butanediol, 1,5-pentanediol, 1,6- hexanediol, Propylene glycol dialkyl ether, polypropylene glycol dialkyl ether, 3-methyl-2-oxazolidinone, acetonitrile, glutaronitrile, diethylene glycol, diethylene glycol, , Methoxyacet Wherein the organic gel conductor is at least one selected from the group consisting of nitrile, nitrile, propionitrile, and benzonitrile. The method according to claim 1,
Wherein the content of the organic solvent is about 10 wt% to about 60 wt%. The method according to claim 1,
Wherein the organic gel conductor is capable of freestanding and has stretchability. An electronic element having two electrodes;
A power supply for supplying power to the electronic element; And
A wiring part connecting the electronic element and the power supply part;
/ RTI &gt;
Wherein the wiring part comprises the organic gel conductor according to any one of claims 1 to 10. &lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt; Preparing a material mixture comprising a monomer of a conductive dopant, an organic solvent, and a matrix polymer;
Polymerizing the monomer of the matrix polymer to obtain a matrix polymer; And
Performing dialysis against the result of the polymerization;
Wherein the organic gel conductor is a mixture of the organic conductive material and the organic conductive material. 13. The method of claim 12,
Wherein the material mixture further comprises water. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt; 14. The method of claim 13,
And drying the water after the step of performing the dialysis. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt; 13. The method of claim 12,
Wherein the conductive dopant is PEDOT: PSS, and the organic solvent is ethylene glycol, dimethyl sulfoxide, or a mixture thereof. 13. The method of claim 12,
Further comprising drying the conductive dopant prior to preparing the mixture. &Lt; RTI ID = 0.0 &gt; 21. &lt; / RTI &gt;

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