KR101022208B1 - Method for Preparing Organic Solvent Dispersion of Conducting Polymers Using Polymeric Ionic Liquid and the Conducting Polymer by Prepared using the same - Google Patents

Abstract

The present invention relates to a method for producing a conductive polymer that is easy to disperse in an organic solvent using a polymer ionic liquid and has excellent electrical conductivity of about 20 S / cm. More specifically, when a polymer ionic liquid is used, the polymer ionic liquid Instead of making a water-based conductive polymer by mixing a monomer for synthesizing a conductive polymer with an organic solvent and then dispersing the conductive polymer with an organic solvent by ion exchange, the polymer ionic liquid is previously dissolved in an organic solvent through ion exchange and then polymerized. It is a method for synthesizing a conductive polymer dispersed in an organic solvent using as a dispersant. The present invention also relates to a method for synthesizing a conductive polymer in an organic solvent so that the synthesized conductive polymer is uniformly and stably dispersed in an organic solvent. The conductive polymer prepared according to the present invention is characterized by not only excellent dispersibility in organic solvents, but also a simple manufacturing process and high electrical conductivity of about 20 S / cm. Therefore, the conventional water-dispersible conductive polymers can be applied to various application materials that require organic solvent dispersibility, which has been limited in application.

Conductive polymer

Description

Method for Preparing Organic Solvent Dispersion of Conducting Polymers Using Polymeric Ionic Liquid and the Conducting Polymer by Prepared using the same

The present invention relates to a method for preparing a conductive polymer organic solvent dispersion solution using a polymer ionic liquid and a conductive polymer prepared by the method. More specifically, the polymer ionic liquid is prepared to be dissolved in an organic solvent through ion exchange in advance. It relates to a method for synthesizing a conductive polymer dispersed in an organic solvent using this as a polymerization dispersant, and to a conductive polymer produced by the method.

The conductive polymer having a π-conjugated double bond is an organic material exhibiting excellent electrical conductivity, and can be applied to various applications such as an antistatic material, an organic light emitting device, an electrochromic device, and a solar cell. However, the conductive polymer has a problem of poor workability, such as being poorly dissolved in a solvent due to strong attraction between molecules, and many studies have been conducted to improve the processability of the conductive polymer. A typical conductive polymer that is currently commercialized is poly (3,4-ethylenedioxythiophene) / polystyrenesulfonic acid, developed by HC Starck, Germany, and poly (3) is prepared by using polystyrenesulfonic acid dissolved in water as a dopant of the conductive polymer. , 4-ethylenedioxythiophene) was used to stably disperse in water. In fact, poly (3,4-ethylenedioxythiophene) / polystyrenesulfonic acid is a conductive polymer aqueous dispersion, which can be applied to various substrates according to conventional wet coating methods, and is organic because it shows excellent electrical conductivity and high visible light transmittance. Attempts have been made to apply the hole transport layer of a light emitting device and the transparent electrode material of a solar cell.

However, since the conventional poly (3,4-ethylenedioxythiophene) / polystyrenesulfonic acid conductive polymer is dispersed only in water, it requires a separate technique to disperse it in an organic solvent or its application is extremely limited when it is difficult to disperse it in an organic solvent. There is a problem. In addition, since an organic acid such as polystyrene sulfonic acid is used as a dopant, when applied to an organic light emitting device due to its high acidity, indium may be precipitated from ITO, which is a transparent electrode material, to reduce the life of the device. Therefore, there is an urgent need to develop a conductive polymer having low acidity while being stably dispersed in an organic solvent.

An object of the present invention is to solve the above problems, to provide an organic solvent dispersible conductive polymer using a polymer ionic liquid that is easily dissolved in an organic solvent.

It is also an object of the present invention to provide a method for preparing an organic solvent dispersible conductive polymer having a simple manufacturing process, easy dispersing of an organic solvent, and high electrical conductivity.

In order to achieve the object of the present invention, the present invention provides a conductive polymer that is chemically polymerized in an organic solvent using a polymer ionic liquid that is easily dissolved in an organic solvent as a conductive polymer polymerization dispersant. At this time, it is preferable to use an oxidizing agent and a dopant together as a component which can be used in an organic solvent environment.

The conductive polymer prepared according to the present invention is a form in which the conductive polymer is dispersed in an organic solvent by a polymer ionic liquid, and nano-sized conductive polymer particles can be stably dispersed in an organic solvent without formation of a precipitate. do. In addition, the organic solvent dispersible conductive polymer prepared according to the present invention has a simple manufacturing process and high electrical conductivity.

 Therefore, in preparing an organic solvent dispersible conductive polymer using a polymer ionic liquid, the invention of a new technology that can easily disperse the organic solvent, the manufacturing process is simpler, and the electrical conductivity is high need.

The polymer ionic liquid-conductive polymer composite synthesized according to the present invention has the advantage that particles of the conductive polymer composite are stably dispersed in various organic solvents with nano size and have low acidity.

Since the polymer ionic liquid-conductive polymer composite has high electrical conductivity, the polymer ionic liquid-conductive polymer composite can be used in a field where the application of the water-dispersible conductive polymer is limited.

In addition, the manufacturing method of the present invention has the advantage that the manufacturing process is simpler than the conventional method using a polymer ionic liquid.

In addition, since the excellent electrical properties of the conductive polymer final product synthesized in accordance with the present invention is excellent, it can be variously applied to various fields such as an organic light emitting device, a solar cell, including a transparent electrode.

In addition, the electrical conductivity of the conductive polymer finally synthesized according to the present invention is high, and is suitable for applications requiring high electrical conductivity, such as transparent electrodes, and also maintains electrical conductivity of the composition when a separate composition is prepared by mixing binder components later. There is an advantage to this.

Hereinafter, a method for preparing an organic solvent dispersible conductive polymer according to the present invention will be described.

First, a polymer ionic liquid to be used for the conducting polymer polymerization reaction is made, and then ion exchanged to make a polymer ionic liquid that is dissolved in an organic solvent.

Thereafter, the polymerized polymer ionic liquid and the conductive polymer monomer are mixed with the organic solvent and reacted to initiate the chemical polymerization of the conductive polymer. It is preferable to mix and oxidize an oxidizing agent and a dopant here.

The conductive polymer polymerized in the presence of a polymer ionic liquid is obtained in the form of nano-sized particles which are stably dispersed in an organic solvent.

When the polymerization reaction is completed, the washing process is repeated to remove the unreacted material included in the polymerization reaction, and the conductive polymer is dispersed in an organic solvent to prepare a conductive polymer dispersed in an organic solvent. In the washing process, it is preferable to wash with a mixed solvent containing water.

The conductive polymer monomer used in the preparation method is preferably a compound having a conjugated double bond in a cyclic structure containing a hetero atom, as represented by the following formula (1).

Wherein R ₁ and R ₂ are each hydrogen, halogen, or a hydrocarbon of 1 to 15 carbon atoms, consisting of a group optionally containing one or more hetero atoms, or R ₁ and R ₂ together are a 3-8 membered aromatic ring or aliphatic Alkylene, alkenylene, alkenyloxy, alkenyldioxy, alkynyloxy, alkynyldioxy, forming a ring compound, consisting of a group optionally containing one or more heteroatoms. X represents any one selected from NH, NR, S, O, Se, and Te.

Polymerization of the conductive polymer monomer is carried out in the presence of a polymer ionic liquid, the polymer ionic liquid is a polymer form consisting of an organic cation and an organic or inorganic anion containing an imidazolium group as shown in the following formula (2) It is characterized in that the compound.

In Formula 2, R ₁ and R ₃ are the same or different, and each represent hydrogen or 1 to 12 hydrocarbon groups, and may optionally include one or more hetero atoms. In Formula 2, R ₂ is a group containing 0 to 16 carbon atoms and may optionally include one or more hetero atoms. And X ⁻ represents an anion of an ionic liquid.

The polymer ionic liquid can be composed of a polymer ionic liquid having various physical and chemical properties according to a combination of cations and anions. Preferably, the polymer ionic liquid has high solubility in organic solvents and can stably disperse conductive polymers in the organic solvent. It is advantageous to use what is available.

Specific examples of the polymer type ionic liquid cation including the imidazolium group represented by Formula 2 include poly (1-vinyl-3-alkylimidazolium), poly (1-allyl-3-alkylimidazolium), Poly (1- (meth) acryloyloxy-3-alkylimidazolium) and the like. CH ₃ COO as polymeric ionic liquid anions represented by X in the general formula (2) is not particularly limited in solubility side in an organic solvent ^{_{-, CF 3 COO -, CH}} 3 SO 3 -, CF 3 SO 3 -, (CF ^{_{3 SO 2) 2 N -,}} (CF 3 SO 2) 3 C -, (CF 3 CF 2 SO 2) 2 N -, C 4 F 9 SO 3 -, C 3 F 7 COO -, (CF 3 SO 2 (CF ₃ CO) N ^- and the like are preferred.

The polymer ionic liquid may be obtained by first preparing a monomolecular ionic liquid and then subjecting it to a conventional radical polymerization reaction, or using a compound made of a polymer type. After the polymerization reaction is completed, the polymer ionic liquid is prepared to have a suitable anion to impart solubility to the organic solvent through an anion substitution reaction after washing and drying. The compound that can be used for the anion substitution reaction can be used as long as it can give a solubility to the organic solvent of the polymer ionic liquid, preferably an alkali metal salt having an anion represented by X in the formula (2). Do. The polymer ionic liquid obtained through the anion substitution reaction has high solubility in organic solvents and acts as a polymer dispersant for the conductive polymers. Therefore, when the conductive polymers are polymerized in the organic solvent, the conductive polymers are nano-sized particles in the organic solvent. It will serve to ensure stable distribution.

The polymerization of the conductive polymer in the presence of the polymer ionic liquid is preferably initiated by one or more oxidants. The oxidizing agent is not particularly limited as long as it can induce a conductive polymer polymerization reaction in an organic solvent. For example, hydrogen peroxide, organic or inorganic peroxides, persulfates, peracids, and peroxides ( peroxyacids, bromates, chlorates, perchlorates, and iron (III), chromium (IV), chromium (VI), manganese (VII), manganese (V), manganese (IV), And organic or inorganic salts of vanadium (V), ruthenium (IV), and copper (II).

Polymerization of the conductive polymer in the presence of a polymer ionic liquid is carried out in one or more organic solvents, which may include alcohol solvents such as methanol, ethanol, propanol, isopropanol, butanol and isobutanol, and diethyl ether. Ether solvents such as dipropyl ether, dibutyl ether, butyl ethyl ether, tetrahydrofuran, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, etc. Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N-methyl-2-pyridyridone, 2-pyridyridone, N-methylformamide, N, N-dimethylformamide, etc. Sulfoxide solvents such as amide solvents, dimethyl sulfoxide and diethyl sulfoxide, sulfone solvents such as diethyl sulfone and tetramethylene sulfone, aceto Nitrile solvents such as trilyl and benzonitrile, amine solvents such as alkylamines, cyclic amines and aromatic amines, ester solvents such as methyl butyrate, ethyl butyrate and propyl propionate, carboxylic acids such as ethyl acetate and butyl acetate Aromatic hydrocarbon solvents such as ester solvents, benzene, ethylbenzene, chlorobenzene, toluene, xylene, aliphatic hydrocarbon solvents such as hexane, heptane, cyclohexane, chloroform, tetrachloroethylene, carbon tetrachloride, dichloromethane, dichloroethane Halogenated hydrocarbon solvents, propylene carbonate, ethylene carbonate, dimethyl carbonate, dibutyl carbonate, ethyl methyl carbonate, dibutyl carbonate, nitromethane, nitrobenzene and the like can be used. Of these, aprotic polar solvents such as N-methyl-2-pyridyridone, acetonitrile, tetrahydrofuran, dimethylformamide, dimethylsulfoxide and propylene carbonate are particularly preferably used.

The conductive polymer organic solvent dispersion solution prepared by the above method may form a conductive polymer thin film by a conventional wet coating method including spray coating, spin coating, gravure coating, reverse gravure coating, and bar coating. The thin film may have an electrical conductivity in the range of 10 ⁻⁶ to 10 ³ S / cm based on the measurement by the 4-terminal method.

The organic solvent dispersible conductive polymer manufacturing method according to the present invention will be described in more detail through the following examples. However, the following examples are provided only to explain the present invention in more detail, and do not limit the scope of the present invention.

In addition, Examples and Comparative Examples of the present invention discloses a method for synthesizing a conductive polymer composite using mainly 3,4-ethylenedioxythiophene monomer. However, the technique of the present invention is not limited to this monomer, but is applicable to all monomers shown in Formula 1, for example pyrrole, thiophene, or other conductive polymer monomers.

≪ Example 1 >

Example 1 is poly (1-methacryloyloxypropyl-3-methylimidazolium) bis (trifluoromethanesulfonimide) as polymer ionic liquid, 3,4-ethylenedioxythiophene as conductive polymer monomer And a method for producing a conductive polymer dispersed in an organic solvent using iron (III) perchlorate as an oxidizing agent and propylene carbonate as an organic solvent.

Preparation of Polymeric Ionic Liquid, Poly (1-Methacryloyloxypropyl-3-methylimidazolium) Bis (trifluoromethanesulfonimide)

10 g of 1-methacryloyloxypropyl-3-methylimidazolium bromide was dissolved in 100 milliliters of water in a round bottom flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen supply, and then potassium peroxide as a polymerization initiator. 0.2 grams of sulfate was added and reacted at a temperature of 60 degrees Celsius for about 10 hours. Adding excess acetone to the reaction solution separated the liquid poly (1-methacryloyloxypropyl-3-methylimidazolium) bromide, which was dried for 48 hours in a vacuum oven at 40 degrees Celsius. It was confirmed that the poly (1-methacryloyloxypropyl-3-methylimidazolium) bromide obtained through the above process was easily dissolved in water and not in an organic solvent. In order to impart solubility in the organic solvent, a reaction was performed in which an anionic bromide was substituted with bis (trifluoromethanesulfonimide). To this end, poly (1-methacryloyloxypropyl-3-methylimidazolium) bromide is dissolved in water, and separately, an aqueous solution in which lithium-bis (trifluoromethanesulfonimide) is dissolved in water is prepared. When slowly added to the solution, poly (1-methacryloyloxypropyl-3-methylimidazolium) bis (trifluoromethanesulfonimide) substituted with bromide anion is obtained in the form of a precipitate. The precipitate was separated, recovered, washed several times with water and dried for about 48 hours in a vacuum oven at 40 degrees Celsius.

Polymerization Process of Conductive Polymer, Poly (3,4-ethylenedioxythiophene)

1 gram of poly (1-methacryloyloxypropyl-3-methylimidazolium) bis (trifluoromethanesulfonimide) as a polymer ionic liquid in a round bottom flask and 3,4-ethylenedioxane as a conductive polymer monomer 0.3 gram of citofene was dissolved in 20 grams of propylene carbonate, an organic solvent. Separately, 0.7 grams of iron (III) perchlorate as an oxidizing agent was dissolved in 5 grams of propylene carbonate and slowly added to the mixed solution, followed by polymerization at high temperature for about 3 hours at high temperature. As the polymerization reaction proceeded, the color of the reaction solution changed to indigo blue, and after completion of the reaction, an organic solvent dispersion solution in which poly (3,4, -ethylenedioxythiophene) particles were stably dispersed in propylene carbonate at nano size. Was obtained. Thereafter, in order to remove the unreacted substances contained in the reaction solution, the solution was washed several times with excess water, and then only the organic layer was recovered to remove moisture with magnesium sulfate, thereby obtaining a conductive polymer dispersed in the organic solvent.

<Example 2>

Example 2 was the same as Example 1 except that poly (1-vinyl-3-ethylimidazolium) bis (trifluoromethanesulfonimide) was prepared and used according to the following method as a polymer ionic liquid. Do.

Preparation of poly (1-vinyl-3-ethylimidazolium) bis (trifluoromethanesulfonimide)

Dissolve 3 grams of 1-vinyl-3-ethylimidazolium bromide in 50 milliliters of ethyl alcohol in a round-bottomed flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen supply, followed by a temperature of 50 degrees Celsius in a nitrogen atmosphere. Stir in After adding 0.03 grams of azobis (2-methylpropionitrile) as a polymerization initiator to the solution and reacting for about 7 hours, solid poly (1-vinyl-3-ethylimidazolium bromide) in the form of a precipitate Obtained. The obtained product was washed several times with chloroform, and then dried in a vacuum oven at 40 degrees Celsius for 24 hours. The poly (1-vinyl-3-ethylimidazolium bromide) obtained through the above process was dissolved in water, and then lithium-bis (trifluoromethanesulfonimide) was dissolved in water and the solution and When reacted, poly (1-vinyl-3-ethylimidazolium) bis (trifluoromethanesulfonimide) is obtained in the form of a precipitate through an anion substitution reaction. The precipitate was separated, recovered, washed several times with water and dried in a vacuum oven at 40 degrees for 48 hours.

Comparative Example 1

In Comparative Example 1, a conductive polymer was prepared by using 3,4-ethylenedioxythiophene as a conductive polymer monomer, iron perchlorate (III) as an oxidizing agent, and propylene carbonate as an organic solvent, without using a polymer ionic liquid.

0.3 g of 3,4-ethylenedioxythiophene as a monomer was dissolved in 20 g of propylene carbonate in a round bottom flask, and then 0.7 g of iron (III) perchlorate, an oxidizing agent, was dissolved in 5 g of propylene carbonate and slowly added to the mixed solution. Input. After stirring at high temperature for about 10 hours and completing the polymerization reaction, the polymer was dispersed for about 30 minutes using an ultrasonic disperser.

Comparative Example 2

Comparative Example 2 uses poly (1- (meth) acryloyloxy-3-alkylimidazolium) bromide as the polymer ionic liquid, 3,4-ethylenedioxythiophene as the conductive polymer monomer, and ammonium persulfate as the oxidizing agent. After preparing a conductive polymer dispersion in water primarily, the precipitate obtained by reacting the dispersed solution with an aqueous solution of lithium-bis (trifluoromethanesulfonimide) was dispersed in propylene carbonate again to be dispersed in an organic solvent. The conductive polymer is prepared, and its specific manufacturing method is as follows.

To a round bottom flask, 1 gram of poly (1-vinyl-3-ethylimidazolium) bromide and 0.7 grams of 3,4-ethylenedioxythiophene were dissolved in 150 ml of water and 1.1 grams of ammonium persulfate was added while stirring. The polymerization reaction is thereby started. The polymerization reaction is carried out by high-speed stirring at room temperature for 48 hours, and when the reaction is completed, a complex solution of poly (3,4-ethylenedioxythiophene) and poly (1-vinyl-3-ethylimidazolium) bromide dispersed in water Is obtained. Thereafter, a lithium-bis (trifluoromethanesulfonimide) aqueous solution is added to the complex solution dispersed in water, and an anionic substitution reaction can be immediately confirmed to form a precipitate. The precipitate is separated and recovered to propylene carbonate. By dispersing, a poly (3,4-ethylenedioxythiophene) and a poly (1-vinyl-3-ethylimidazolium) bis (trifluoromethanesulfonimide) composite solution dispersed in an organic solvent were prepared.

The evaluation results of the conductive polymers prepared in Examples 1 and 2 and Comparative Examples 1 and 2 are summarized in Table 1 below. In Table 1, the dispersibility evaluation of the organic solvent was left for about 24 hours in a dispersion solution in which the conductive polymer was dispersed in propylene carbonate, and then visually observed whether a precipitate was formed. O was not formed when the precipitate was stably dispersed, and X was used when the precipitate was formed and separated. The size of the conductive polymer particles in the organic solvent was measured using a dynamic optical scattering method, and the measured value was expressed as an average particle size obtained by averaging the diameters of the particles. In order to measure the electrical conductivity, each dispersion solution was coated on a polyester film, dried for 30 minutes at a temperature of 80 degrees, and then dried again in a vacuum oven at 40 degrees Celsius for 3 hours to form a coating film having a thickness of about 1 micron. Thereafter, the electrical conductivity of each coating film was measured using a four-terminal measurement method (Kisley 2400).

Evaluation result of the conductive polymer prepared through the Examples and Comparative Examples Example 1 Example 2 Comparative Example 1 Comparative Example 2 Organic Solvent Dispersibility O O X O Average particle size (μm)  0.05 0.08  > 5 0.10 Conductivity (S / cm) 22.0 10.5 - 0.007

In the results of the conductive polymer organic solvent dispersion solution prepared in Example 1 or Example 2, it can be confirmed that the nano-sized conductive polymer particles are stably dispersed without forming a precipitate, and after forming the coating film The measured conductivity was also found to be excellent. On the other hand, in Comparative Example 1 without using the polymer ionic liquid, the conductive polymer particles were very large in size, and the dispersibility to the organic solvent was significantly decreased, and thus it was difficult to form a coating film for measuring the electrical conductivity itself. In addition, in the case of Comparative Example 2 prepared using a polymer ionic liquid, but the conventional manufacturing method, the dispersibility to the organic solvent is good, but it can be observed that the electrical conductivity is significantly lower than in Example 1.

Comparing the above examples and comparative examples, the electrical conductivity of the conductive polymer-ionic liquid composite solution synthesized by the technique of the present invention is significantly higher than that of the conventional method, and in particular, poly (3,4- Ethylenedioxythiophene) / polystyrenesulfonate shows high electrical conductivity similar to that of the conductive polymer.

The problem to be achieved by the present invention is not limited to the above-mentioned problem, another task that is not mentioned will be clearly understood by those skilled in the art from the following description.

Claims (11)

As a solution in which the conductive polymer monomer represented by the following Chemical Formula 1 and the polymer ionic liquid represented by the following Chemical Formula 2 are dissolved and polymerized in an organic solvent and are easily dispersed in the organic solvent, The polymer ionic liquid is an ionic compound in a polymer form composed of an organic cation including an imidazolium group and an organic or inorganic anion, and the cation includes poly (1-vinyl-3-alkylimidazolium), poly ( 1-allyl-3-alkylimidazolium) and poly (1- (meth) acryloyloxy-3-alkylimidazolium). [Formula 1]

In the above formula, R ₁ and R ₂ are each hydrogen, halogen, or a hydrocarbon group of 1 to 15 carbon atoms, consisting of a group optionally containing one or more hetero atoms, or R ₁ and R ₂ together are a 3 to 8 membered aromatic ring or Alkylene, alkenylene, alkenyloxy, alkenyldioxy, alkynyloxy, alkynyldioxy, forming an aliphatic ring compound, consisting of groups optionally containing one or more heteroatoms. X represents any one selected from NH, NR, S, O, Se, and Te. [Formula 2]

In the above formula, R ₁ and R ₃ are the same as or different from each other, and each represent hydrogen or a hydrocarbon group having 1 to 12 carbon atoms, and may optionally include one or more hetero atoms. In the above formula, R ₂ is a group containing 0 to 16 carbon atoms and may optionally include one or more hetero atoms. And X ⁻ represents an anion of an ionic liquid. The conductive polymer organic solvent dispersion solution according to claim 1, wherein the monomer of the conductive polymer is a monomer compound having a conjugated double bond having a cyclic structure containing a hetero atom. delete delete The method of claim 1, wherein the anion of the polymer ionic liquid is ^{_{CH 3 COO -, CF 3 COO}} -, CH 3 SO 3 -, CF 3 SO 3 -, (CF 3 SO 2) 2 N -, (CF 3 ^{_{SO 2) 3 C -, (}} CF 3 CF 2 SO 2) 2 N -, C 4 F 9 SO 3 -, C 3 F 7 COO -, (CF 3 SO 2) (CF 3 CO) N - containing Polymer organic solvent dispersion solution, characterized in that. 6. The process of claim 5, wherein the polymerization comprises oxidizing agents such as hydrogen peroxide, organic or inorganic peroxides, persulfates, peracids, peroxyacids, bromates, chlorates, Perchlorates, and iron (III), chromium (IV), chromium (VI), manganese (VII), manganese (V), manganese (IV), vanadium (V), ruthenium (IV), copper (II) A conductive polymer organic solvent dispersion solution, characterized in that it comprises at least one organic or inorganic salt. The organic solvent according to any one of claims 1, 2 and 5 to 6, wherein the organic solvent comprises an alcohol solvent including methanol, ethanol, propanol, isopropanol, butanol and isobutanol; Ether solvents including diethyl ether, dipropyl ether, dibutyl ether, butyl ethyl ether, tetrahydrofuran; Alcohol ether solvents including ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether; Ketone solvents including acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Amide solvents including N-methyl-2-pyridyridone, 2-pyridyridone, N-methylformamide, N, N-dimethylformamide; Sulfoxide solvents including dimethyl sulfoxide and diethyl sulfoxide; Sulfone solvents including diethyl sulfone, tetramethylene sulfone; Nitrile solvents including acetonitrile, benzonitrile; Amine solvents including alkylamines, cyclic amines, aromatic amines; Ester solvents including methyl butyrate, ethyl butyrate, and propyl propionate; Carboxylic ester solvents including ethyl acetate, butyl acetate; Aromatic hydrocarbon solvents including benzene, ethylbenzene, chlorobenzene, toluene, xylene; Aliphatic hydrocarbon solvents including hexane, heptane, cyclohexane; Halogenated hydrocarbon solvents including chloroform, tetrachloroethylene, carbon tetrachloride, dichloromethane, dichloroethane; A conductive polymer organic solvent dispersion solution comprising any one or more selected from propylene carbonate, ethylene carbonate, dimethyl carbonate, dibutyl carbonate, ethyl methyl carbonate, dibutyl carbonate, nitromethane and nitrobenzene. The conductive polymer thin film according to any one of claims 1, 2 and 5 to 6, wherein the conductive polymer thin film formed by the conductive polymer organic solvent dispersion solution prepared by the above method is measured by a four-terminal method. The conductive polymer organic solvent dispersion solution, characterized in that the range of 10 ^-6 to 10 ³ S / cm. The non-reacted material in the polymerization reaction according to any one of claims 1, 2 and 5 to 6, wherein the conductive polymer organic solvent dispersion solution is washed with a mixed solvent containing water. A conductive polymer organic solvent dispersion solution. The method of claim 1, 2, 5 to 6, wherein the conductive polymer organic solvent dispersion is conventional, including spray coating, spin coating, gravure coating, reverse gravure coating, bar coating A conductive polymer organic solvent dispersion solution, characterized in that the conductive polymer thin film is formed by a wet coating method. delete