KR20090060110A - Organic solvent dispersible thiophene conductive polymer complex and conductive polymer dispersion - Google Patents

Abstract

A method for manufacturing thiophene-based conductive polymer complex solution is provided to remove impurities such as unreacted materials by additionally washing the complex solution by using solvent of water or alcohol. A method for manufacturing organic solvent-dispersible thiophene-based conductive polymer complex solution comprises the steps of: (a) synthesizing and polymerizing ionic liquid having hydrophilic anions to prepare an ionic liquid polymer; (b) dispersion-polymerizing the thiophene-based conductive polymer by using the ionic liquid polymer as a dispersion stabilizer in a high-speed agitator with the speed of 150~3,000 rpm to prepare hydrophilic conductive polymer-ionic liquid complex solution; (c) exchanging hydrophilic anions of the ionic liquid with hydrophobic anions in the hydrophilic conductive polymer-ionic liquid complex solution to extract hydrophobic conductive polymer-ionic liquid complex; and (d) redistributing the extracted hydrophobic conductive polymer-ionic liquid complex in organic solvent to prepare the conductive polymer-ionic liquid complex solution.

Description

Organic solvent dispersible thiophene conductive polymer complex and conductive polymer dispersion

The present invention relates to a method for preparing a thiophene-based conductive polymer composite having an electrical conductivity of 10 ⁻⁴ S / cm or more while dispersed in an organic solvent, and a thiophene-based conductive polymer composite solution prepared therefrom.

Intrinsically conducting polymers are polymers that are electrically conductive through a doping process, and typical examples thereof include polyaniline, polypyrrole, polythiophene, and derivatives thereof.

Among these, poly (3,4-ethylenedioxythiophene), one of the thiophene conductive polymers commercialized by Bayer, Germany (now HC Starck), is transparent in the visible region and has high electrical conductivity stability in the atmosphere. Due to its characteristics, it is widely used in various display fields and antistatic fields.

The conductive polymer having the trade name Baytron P is obtained by dispersing poly (3,4-ethylenedioxythiophene) using water as a solvent. The conductive polymer film can be obtained by coating and drying on various substrates. Due to its advantages, it has been applied to various applications such as electrostatic protection materials.

However, a lot of efforts have recently been made to develop organic solvent dispersible conductive polymers.

For example, US patent US2003 / 0088032 A1 copolymerizes a thiophene-based conductive polymer block with an ethylene oxide block that can dissolve in an organic solvent, or endcaps a methacrylate or other acrylate group onto the conductive polymer oligomer. The method for producing a conductive polymer dispersed in an organic solvent such as nitromethane and propylene carbonate by -capping) is shown.

The method is a method of changing the bonding structure of the conductive polymer chain itself in order to give dispersibility to the organic solvent, the synthesis and polymerization process is difficult to manufacture in several steps, the physical properties are not easy to control the electrical properties of the synthesized conductive polymer There is a disadvantage that the conductivity is lowered.

In addition, recently, a method of dispersing a conductive polymer in an organic solvent using an ionic liquid as a dispersion medium has been proposed. (Macromolecular Rapid Communications, 26, 1122, 2005, Synth. Met., 156 (2006), 1133).

The method synthesizes poly (1-vinyl-3-ethylimidazolium bromide) as an ionic liquid, and then disperses the conductive polymer in an organic solvent such as N, N-dimethylformamide or acetone using a dispersion medium. As a method, it has been reported that the electrical conductivity is 10 ⁻¹ S / cm in the case of polypyrrole dispersed in the organic solvent by the above method.

On the other hand, when 3,4-ethylenedioxythiophene (EDOT) is used as a monomer to prepare an organic solvent dispersible conductive polymer solution by the same method, the electrical conductivity of the thiophene conductive polymer-ionic liquid composite solution prepared is 10 ^-6. It is reported as very low in S / cm. In addition, when the conductive polymer-ionic liquid composite is prepared with strong stirring in the preparation of the aqueous conductive polymer, which is one of the intermediate steps in the preparation of the thiophene-based conductive polymer-ionic liquid composite solution, the electrical conductivity is 10 ^-2 S / cm. Reported improvement. (Journal of Polymer Science, Part A, Polymer Chemistry, Vol. 46, 3150-3154, 2008).

However, in applying the conductive polymer solution dispersible in these organic solvents to the organic light emitting device, it is necessary to control the work function and the charge mobility of the conductive polymer layer with the removal of impurities. Impurities are a very important factor in improving efficiency or improving long-term reliability in applying the conductive polymer solution to actual products such as organic light emitting devices. For example, when the conductive polymer layer is used as the hole transport layer, the impurity may cause the emission efficiency to be reduced by reducing the charge mobility, and the impurity is injected into the hole by the conductive polymer layer having an appropriate work function. This will interfere with the smooth operation. Therefore, in order to have an appropriate work function and charge mobility, it is important to effectively remove impurities in the conductive polymer and make the electrical conductivity as high as possible.

In addition, in order to apply the finally prepared organic solvent dispersible thiophene conductive polymer-ionic liquid as an antistatic product, a conductive polymer and a binder must be mixed in some cases. It should be as high as possible, and impurities that may harm the dispersibility of the final prepared conductive polymer, that is, unreacted materials such as monomers added during synthesis but not participating in the reaction, should be washed out.

Therefore, when the surface resistance of the synthesized conductive polymer is coated on the surface of the film, at least 10 ^-4 S / cm or more, and impurities such as unreacted substances are removed, the thiophene-based conductive polymer having good dispersibility in an organic solvent or a composite containing the same or There is a need for the invention of an organic solvent dispersible conductive polymer dispersion solution comprising the same.

An object of the present invention is a method for synthesizing a thiophene-based conductive polymer composite having an electrical conductivity of 10 ^-4 S / cm or more and the impurities such as unreacted substances are removed, and has good dispersibility in an organic solvent, and organic solvent dispersibility prepared through the same It is to provide a thiophene-based conductive polymer composite solution.

The objects to be achieved by the present invention are not limited to the above-mentioned objects, and other objects not mentioned will be clearly understood by those skilled in the art from the following description.

Method for producing an organic solvent dispersible thiophene conductive polymer composite solution according to the present invention comprises the steps of (a) synthesizing and polymerizing an ionic liquid having a hydrophilic anion; (b) preparing a solution having a hydrophilic "conductive polymer-ionic liquid composite" (hereinafter referred to as an aqueous conductive polymer) by polymerizing a thiophene conductive polymer represented by the following Chemical Formula 1 using an ionic liquid polymer as a dispersion stabilizer; step; (c) The hydrophobic conductive polymer-ionic liquid composite having hydrophobicity is exchanged by replacing the hydrophilic anion of the ionic liquid with hydrophobic anion in the aqueous conductive polymer solution synthesized in step (b) (hereinafter referred to as hydrophobic or organic solvent dispersible conductive polymer). ) Forming and precipitation; And (d) redispersing the hydrophobic conductive polymer precipitated in step (c) in an organic solvent to produce a conductive polymer solution dispersed in an organic solvent, wherein the thiophene conductive polymer in step (b): The weight ratio of the ionic liquid is 70:30 ~ 30:70, and synthesized in a high speed stirrer when synthesizing the aqueous conductive polymer in step (b), and washing and separating unreacted substances remaining in the solution with a non-aqueous solvent. It is done. In addition, the thiophene-based conductive polymer-ionic liquid composite solution finally prepared by further washing and removing impurities contained in the organic-solvent dispersible conductive polymer composite solution synthesized through the step (d) with water or alcohol. It is characterized by improving the electrical conductivity of.

<Formula 1>

Where R ₁ and R ₂ together may be alkylene, alkenylene, alkenyloxy, alkenyldioxy, alkynyloxy, alkynyldioxy of 3 to 8 membered alicyclic or aromatic structure, optionally hydrogen In addition to carbon, oxygen atoms, it may contain atoms such as nitrogen, sulfur, phosphorus, selenium, and silicon.

Alternatively, R ₁ , R ₂ may be composed of hydrogen, halogen or alkyl having 1 to 10 carbon atoms, alkoxy, carbonyl, hydroxy group, etc.)

The present invention synthesizes a thiophene-based conductive polymer using an ionic liquid as a medium, and then disperses the complex in an organic solvent to adjust the content ratio of the monomer and the ionic liquid for synthesizing the conductive polymer, and the particle size. In order to control, the synthesis is induced in a high speed stirrer and washed and separated using a non-aqueous solvent such as ethyl acetate in the synthesized conductive polymer solution. Further washing using a solvent provides a method for preparing a thiophene-based conductive polymer composite and a conductive polymer solution having excellent dispersibility in an organic solvent and at least 10 ^-4 S / cm in electrical conductivity. The conductive polymer solution of the thiophene-based conductive polymer and the ionic liquid composite of the present invention may be used on its own or mixed with an organic solvent-type binder.

In order to achieve the object of the present invention, in the present invention, a method of causing a reaction with an ionic liquid in synthesizing a thiophene-based conductive polymer was used. In the present invention, the thiophene-based conductive polymer is a compound having a cyclic structure containing sulfur as shown in Formula 1, and substituted with another compound at positions 3 and 4 of the cyclic structure, for example, Formula 2 As shown in, it refers to a conductive polymer such as poly (3,4-ethylenedioxythiophene).

<Formula 2> Structure of poly (3,4-ethylenedioxythiophene)

The reaction of the present invention is largely composed of four steps, (a) a first step of synthesizing a hydrophilic ionic liquid polymer by polymerizing an ionic liquid monomer, and (b) a hydrophilic ionic liquid polymer as a dispersion stabilizer. Step 2 to prepare a hydrophilic aqueous conductive polymer by polymerizing a thiophene-based conductive polymer in water, (c) a hydrophobic conductive polymer by exchanging anions of an ionic liquid with hydrophobic ions in a hydrophilic aqueous conductive polymer (3) a fourth step of forming a thiophene-based conductive polymer solution dispersed in the organic solvent by redispersing the conductive polymer having hydrophobicity in an organic solvent.

The thiophene-based conductive polymer-ionic liquid complex and the composite solution, which consist of four steps, have very low electrical conductivity or poor dispersibility in an organic solvent, as reported in the literature. The inventors of the present invention have found that the steps (b) and (d) of the four steps are the most important steps in the preparation of the organic solvent dispersible conductive polymer having high electrical conductivity without impurities.

That is, the aqueous conductive polymer synthesized in step (b) does not contain unreacted monomers and the particle size of the conductive polymer should not exceed 100 nanometers, and in the process of depositing a hydrophobic conductive polymer in step (c) It was found that impurities mixed in the solution were present in a considerable amount of hydrophobic conductive polymer particles. Therefore, the impurities contained in the hydrophobic conductive polymer precipitate in step (c) must be dispersed in the organic solvent in step (d), and the impurities must be further removed. Finally, the organic solvent dispersible conductive polymer solution having high electrical conductivity and good dispersibility is obtained. It was found that it can be prepared.

Therefore, in the present invention, the water-based conductive polymer synthesis in step (b) during the manufacturing process of the four steps was carried out in a high speed stirrer to adjust the particle size of the synthesized conductive polymer to less than 100 nanometers, and to adjust the unreacted monomers. In step (d), the final conductive polymer dispersion solution prepared by dispersing in an organic solvent was further washed.

Hereinafter, the synthesis method of the organic solvent dispersible thiophene conductive polymer according to the present invention will be described in more detail.

(a) Step 1: Synthesis of Ionic Liquid Polymer

Synthesis of the ionic liquid polymer is roughly divided into (a1) preparing an ionic liquid monomer and (a2) polymerizing an ionic liquid monomer.

(a1) Synthesis of Ionic Liquid Monomer

The ionic liquid monomer synthesized in the present invention is composed of an organic cation and an organic (or inorganic) anion, and characterized in that it has a reactor for polymerization in the cation portion of the ionic liquid so that the polymerization reaction can be performed later.

More specifically, the structure of the cation in the ionic liquid monomer is represented by the following formula (3), imidazolium, pyridinium, pyrrolidinium, pyridazinium, pyrimidinium, pyrazinium, pyrazolium, pipe Ridinium, piperizinium, thiazolium, oxazolium, triazolium, morpholinium, phosphonium, ammonium and derivatives thereof, R ₁ and the hydrogen, alkyl, ether, alkoxy or ester It consists of R <_2>, R <_3> and R <_4> which are reactors containing.

And, to anion (X ^-) in the ionic liquid monomer in the formula (3) ^{Br -, Cl -, I -} , BF 4 -, PF 6 -, ClO 4 -, NO 3 -, AlCl 4 -, Al 2 Cl 7 ^-, AsF ₆ ^- characterized by either is one selected from a ^-, SbF _6.

<Formula 3> Structural formula of the ionic liquid monomer

(Wherein R ₁ represents a vinyl or allyl group, and R ₂ , R ₃ , R ₄ represents a reactor containing hydrogen or an alkyl, ether, alkoxy or ester group consisting of 1 to 15 carbon atoms.)

Representative examples of the ionic liquid monomers include 1-vinyl-3-alkylimidazolium bromide (or chloride), 1-allyl-3-alkylimidazolium bromide (or chloride), and 1-vinyl-4-alkylpyridinium. Bromide (or chloride), 1-allyl-4-alkylpyridinium (or chloride), 2- (meth) acryloyloxyalkyltrialkylammonium bromide (or chloride), including but not limited to inducing subsequent polymerization It includes all the ionic liquid monomer represented by the formula (3) while having a reactor.

Hereinafter, a detailed method for synthesizing the monomer of the ionic liquid will be described.

 In the case of 1-vinyl-3-alkylimidazolium bromide as the ionic liquid monomer of the present invention, it is produced by reacting 1-vinylimidazole and alkyl bromide. Specifically, while stirring a certain amount of 1-vinylimidazole, alkyl bromide in an amount of about 1 to 2 molar ratios is slowly injected to 1-vinylimidazole, and the reaction is performed at a temperature above room temperature for 10 to 100 hours. It starts. At this time, the reaction conditions vary depending on the type of alkyl bromide as the reactant. Usually, the longer the length of the alkyl group of the alkyl bromide, the slower the reaction rate, the higher the reaction temperature and the longer the reaction time. The 1-vinyl-3-alkylimidazolium bromide produced through the synthesis reaction appears to precipitate in a solid form according to the length of the alkyl group or may have a liquid form. The obtained reaction product is washed with a suitable solvent such as chloroform to remove unreacted material, dried in a vacuum oven, and then passed to the next step for polymerization.

(a2) Synthesizing the ionic liquid monomer to synthesize the ionic liquid polymer

Since the ionic liquid monomer synthesized as described above includes a reactor for inducing a polymerization reaction, an ionic liquid polymer can be obtained by adding and reacting a polymerization initiator.

The polymerization reaction is initiated by slowly adding the polymerization initiator while the ionic liquid monomer is dissolved in a suitable solvent and stirred. At this time, the polymerization reaction should proceed in an inert gas atmosphere such as nitrogen or argon to control the side reaction, and adjust the reaction temperature and reaction time according to the type of ionic liquid monomer and the type of initiator. In general, the polymerization of the ionic liquid proceeds by stirring at a temperature of 20 ° C. to 100 ° C. for 1 hour to 48 hours. When the polymerization reaction is completed, unreacted materials are removed with an appropriate solvent such as ethyl acetate and dried in a vacuum oven. To obtain an ionic liquid polymer.

As the initiator used in the polymerization reaction, a conventional initiator for inducing a polymerization reaction may be used. Specific examples thereof include peroxide-based compounds such as benzoyl peroxide, dicumyl peroxide, and acetyl peroxide, and azobis (2-methylpropio). Nitrile), azo compounds such as azobis (2,4-dimethylvalenonitrile), ammonium persulfate or potassium persulfate, and the like, and these may be used alone or in combination of two or more thereof.

Examples of the solvent used for the polymerization reaction include water, alcohol solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol and isobutyl alcohol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and diethyl. Ether solvents such as ether, dipropyl ether, dibutyl ether, butyl ethyl ether, tetrahydrofuran, alcohol ether solvents such as ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol monobutyl ether Amide solvents such as N-methyl-2-pyridyridone, 2-pyridyridone, N-methylformamide, N, N-dimethylformamide, sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, and di Sulfone solvents such as ethyl sulfone and tetramethylene sulfone, nitrile solvents such as acetonitrile, amine solvents such as alkylamine, cyclic amine, aromatic amine, methyl butyrate, Ester solvents such as butylate and propyl propionate, carboxylic acid ester solvents such as ethyl acetate, butyl acetate, aromatic hydrocarbon solvents such as benzene, ethylbenzene, chlorobenzene, toluene, xylene, hexane, heptane, cyclohexane, etc. An aliphatic hydrocarbon solvent, chloroform, tetrachloroethylene, carbon tetrachloride, dichloromethane, dichloromethane, halogenated hydrocarbon solvent such as dichloroethane and the like can be used, and any one or more of these solvents may be used in combination.

In the ionic liquid polymer produced through the present invention, the weight average molecular weight is preferably 1,000 to 1,000,000 g / mol by controlling polymerization conditions. When the weight average molecular weight of the ionic liquid polymer is less than 1,000 g / mol, the dispersibility and durability of the finally formed conductive polymer and the ionic liquid composite may decrease. This is because there is a fear that the coating properties are reduced because the size of the liquid liquid composite particles is large.

The ionic liquid polymer obtained through the polymerization reaction exhibits a property of dissolving in water, and this property can be achieved by appropriately selecting the types of cations and anions of the ionic liquid monomer. The liquid monomer has a hydrophilic anion to prepare a hydrophilic ionic liquid polymer in which the ionic liquid polymer obtained after the polymerization reaction is dissolved in water.

This is because the composite of the thiophene conductive polymer and the ionic liquid of the present invention first prepares a composite solution of the thiophene conductive polymer and the ionic liquid dispersed in water using a hydrophilic ionic liquid, and then the ionic liquid is hydrophobic again. The ionic liquid prepared in the first step exhibits the property of dissolving in water because the ionic liquid prepared in the first step is prepared by the exchange reaction with ions, thereby producing a composite solution of thiophene-based conductive polymer and ionic liquid dispersed in an organic solvent. . For this purpose, it is more preferable to use bromide or chloride as the anion of the ionic liquid.

(b) a second step; Preparation of Aqueous Dispersed Thiophene-based Conductive Polymer and Ionic Liquid

Next, the ionic liquid polymer synthesized as described above is dispersed and polymerized with a thiophene conductive polymer to form a conductive polymer-ionic liquid composite having hydrophilicity.

Method for producing a composite of the water dispersible thiophene-based conductive polymer and the ionic liquid of the present invention is as follows.

First, the ionic liquid polymer prepared in the first step is weighed in an appropriate amount to dissolve in water (H ₂ O), and then the thiophene-based conductive polymer monomer is added and the initiator is slowly added while stirring to initiate the polymerization of the conductive polymer. Done. At this time, the reaction temperature is carried out at -80 ℃ to 80 ℃ and the reaction time is preferably set to 1 hour to 72 hours.

In the reaction of this step is carried out in a high speed stirrer to control the particle size of the composite of the water-dispersible thiophene-based conductive polymer and the ionic liquid synthesized up to 100 nanometers or less.

At this time, the rotation speed of the high speed stirrer is adjusted in the range of 150 to 3,000 rpm. If the stirring speed is less than 150 rpm, since the stirring is not sufficient, the particle size becomes over 100 nanometers. Disturb. If the size of the synthesized conductive polymer particles is 100 nanometers or more, the electrical conductivity of the synthesized conductive polymer is lowered, which is disadvantageous.

The conductive polymer-ionic liquid composite prepared by the above method has a particle size of 100 nm or less and has an aqueous dispersion.

Impurities such as unreacted monomers or initiators remain in the aqueous dispersion solution. These unreacted materials do not significantly affect the electrical conductivity but act as a deterrent to the dispersibility of subsequent processes. Therefore, in order to remove this, it is more effective to go through the washing process using a non-aqueous solvent that can dissolve unreacted monomers without mixing with water.

Organic solvents that can be used for the above purpose include ethyl acetate, toluene, xylene, propylene carbonate, and the like, and any non-aqueous solvent that can dissolve unreacted monomers without being mixed with water can be used.

As the thiophene-based conductive polymer monomer used in the reaction of this step, all conductive polymer monomers represented by Formula 1 may be used. Preferably, 3-methylthiophene, 3-hexylthiophene, 3-octylthiophene, 3-methoxythiophene, dimethoxythiophene, diethoxythiophene, dipropoxythiophene, dibutoxythiophene, methylenedioxythiophene, ethylenedioxythiophene, propylenedioxythiophene, butylenedioxythiophene can be used. have.

In addition, as an initiator used when preparing the conductive polymer, a salt consisting of iron (III) such as FeCl ₃ , Fe (ClO ₄ ) _3, Fe ₂ (SO ₄ ) ₃ , and Fe ₂ (S ₂ O ₈ ) ₃ may be used. Iron (III) -organic acid salts and iron (III) -organic acid salts such as iron (III) -toluenesulfonate, iron (III) -camphorsulfonate, and ammonium persulfate ((NH ₄ ) ₂ S ₂ O _8), sodium persulfate _{(Na 2 S 2 O 8)} , potassium persulfate (K ₂ S ₂ O ₈₎ permanganate persulfate, alkali perborate, potassium, such as carbonate, potassium dichromate, copper salts, hydrogen peroxide, etc. This can be used.

In the composite composed of the water-dispersible thiophene-based conductive polymer and the ionic liquid of the present invention, the weight ratio of the monomer for synthesizing the conductive polymer and the ionic liquid polymer is possible in the whole range of ratios.

However, considering the electrical properties and organic solvent dispersibility of the finally prepared conductive polymer / ionic liquid composite, the weight percent ratio of the monomer for preparing the conductive polymer and the polymerized ionic liquid (hereinafter, referred to as weight ratio) is 70/30 to 30/70 desirable.

This is because the weight ratio of the conductive polymer and the ionic liquid is an important factor in determining the electrical properties and dispersibility of the finally produced conductive composite. When the content of the ionic liquid is less than 30 weight ratio, the particle size of the synthesized conductive polymer composite is It becomes too large or the dispersion in the organic solvent is very low, and it is difficult to obtain a stable conductive solution. In addition, when the content of the ionic liquid exceeds 70 weight ratio, the dispersibility is good, but since the electrical conductivity of the conductive composite is very low, there is a limit to the practical application in various applications.

(c) step 3: ion exchange of hydrophilic anions into hydrophobic anions

Since the conductive polymer prepared in the second step is manufactured using a hydrophilic ionic liquid, the conductive polymer has an aqueous dispersion.

In the third step, the hydrophilic ionic liquid is converted into a hydrophobic ionic liquid through an ion exchange reaction, thereby obtaining a hydrophobic, ie, organic solvent dispersible conductive polymer.

To prepare the hydrophobic conductive polymer, the hydrophilic anion of the ionic liquid is converted into an alkali metal salt by adding an alkali metal salt containing a hydrophobic anion or an organic or inorganic acid containing a hydrophobic anion to the hydrophilic aqueous conductive polymer solution prepared in the second step. The reaction is exchanged with hydrophobic anions.

The alkali metal salt containing the hydrophobic anion is not particularly limited as long as the anion has a hydrophobic group as a lithium salt, sodium salt and potassium salt.

In addition, typical examples of the hydrophobic anions are ^{_{CF 3 COO -, CH 3 COO}} -, CF 3 SO 3 -, (CF 3 SO 2) 2 N -, (CF 3 SO 2) 3 C -, (CF 3 CF 2 SO ^{_{2) 2 N -, (CF}} 3) 2 PF 4 -, (CF 3) 3 PF 3 -, (CF 3) 4 PF 2 -, (CF 3) 5 PF -, (CF 3) 6 P -, SF ^{_{5 CF 2 SO 3 -, SF}} 5 CHFCF 2 SO 3 -, CF 3 CF 2 (CF 3) 2 CO -, (CF 3 SO 2) 2 CH -, (SF 5) 3 C -, (O (CF 3 _{) 2 C 2 (CF 3)} 2 O) 2 PO - , and the _like, and it is also possible to use a mixture of two or more.

When the alkali metal salt containing the hydrophobic anion or the organic or inorganic acid containing the hydrophobic anion is introduced into the aqueous dispersed conductive polymer-ionic liquid complex, the anion of the ionic liquid is replaced with the hydrophobic anion of the alkali metal salt, thereby making it hydrophobic. A conductive polymer precipitates.

At this time, since the conductive polymer precipitated through the ion substitution reaction is rapidly precipitated, impurities such as metal salts mixed in the solution are present in the conductive polymer particles precipitated.

When washing to remove this, impurities on the surface of the particles are removed, but impurities in the particles are not removed. However, this may be removed by further washing after dispersing in the organic solvent in the next step (d).

On the other hand, it is possible to use an organic or inorganic acid compound having a hydrophobic anion even if it is not the metal salt compound specified above. Such organic or inorganic acid compounds are not limited as long as they have a hydrophobic anion, and representative examples of such compounds include bis (2-ethylhexylhydrogen phosphate) or dodecylbenzenesulfonic acid.

(d) 4th step: redispersion and further cleaning of hydrophobic thiophene conductive polymer and ionic liquid composite

The fourth step, which is the final step of synthesizing the organic solvent dispersible conductive polymer of the present invention, is a process of redispersing the conductive polymer precipitate having the hydrophobicity obtained in the third step again in an organic solvent and further washing.

In this case, the organic solvent for dispersing the conductive polymer having hydrophobicity is not particularly limited as all organic solvents except water.

Specific examples of the organic solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, diethyl ether, dipropyl ether, dibutyl ether, butyl ethyl ether, and ether solvents such as tetrahydrofuran, and ethylene. Alcohol ether solvents such as glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, N-methyl-2-pyridyridone, 2-pyridyridone, N-methylformamide, Amide solvents such as N, N-dimethylformamide, sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, sulfone solvents such as diethyl sulfone and tetramethylene sulfone, nitrile solvents such as acetonitrile and benzonitrile and alkylamine Amine solvents such as cyclic amines, aromatic amines, ester solvents such as methyl butyrate, ethyl butyrate, and propyl propionate, ethyl acetate Carboxylic ester solvents such as butyl acetate, aromatic hydrocarbon solvents such as benzene, ethylbenzene, chlorobenzene, toluene and xylene, aliphatic hydrocarbon solvents such as hexane, heptane, cyclohexane, chloroform, tetrachloroethylene, carbon tetrachloride Halogenated hydrocarbon solvents such as dichloromethane, dichloroethane, propylene carbonate, ethylene carbonate, dimethyl carbonate, dibutyl carbonate, ethyl methyl carbonate, dibutyl carbonate, nitromethane, nitrobenzene and the like can be used, and any one of these solvents Or you may mix and use more.

As described above, the conductive polymer particles precipitated in step (c) contain impurities such as metal salts. To remove this, a solvent (eg, water or other polar solvent) that can dissolve impurities such as metal salts without mixing with the organic solvent used to disperse the conductive polymer.

In the process of dispersing the organic solvent dispersible conductive polymer of the present invention in an organic solvent, by using a high speed stirrer, a high pressure homogenizer or a homogenizer, or by performing an ultrasonic treatment selectively or in parallel, the dispersibility is increased and The size can be made small and uniform.

This completes the preparation of the thiophene-based conductive polymer-ionic liquid composite solution dispersed in the organic solvent proposed in the present invention.

Hereinafter, a method of preparing an antistatic coating solution, which is an example of use, using a conductive polymer solution dispersed in the organic solvent prepared above will be described.

※ <Preparation of organic solvent antistatic coating solution using conductive polymer-ionic liquid composite dispersed in organic solvent>

The conductive polymer-ionic liquid composite prepared through the present invention may be dispersed in various organic solvents to prepare an organic solvent-based antistatic coating solution, and may be coated on various substrates and dried to form an antistatic film. At this time, the organic solvent antistatic coating liquid is preferably adjusted to the solids content of the conductive polymer dispersed in the organic solvent at 0.001 to 10% by weight. If the solid content is less than 0.001% by weight, the conductive polymer content is too low to be difficult to impart electrical conductivity. If the content is more than 10% by weight, the conductivity enhancement effect is small despite the large amount of the conductive polymer.

In addition, when preparing the antistatic coating solution, a binder made of an organic or inorganic compound is used for the purpose of controlling the surface resistance of the finally formed coating film, the physical properties of the coating surface, adhesion to the substrate, scratch resistance and durability It is possible to do At this time, as an example of the binder mixed with the conductive polymer, an organic binder such as urethane group, epoxy group, carboxyl group, carbonyl group, acrylic group, hydroxy group, ester group, ether group, amide group, imide group, maleic acid group, vinyl acetate group And inorganic binders including inorganic components such as silicates and titanates, but are not limited thereto and may be used by mixing any one or more selected from organic or inorganic binders commonly used in the art. At this time, the content of the binder can be used by mixing 0.1 to 100 times compared to the content of the conductive polymer-ionic liquid complex.

When the content of the binder exceeds 100 times the content of the conductive polymer-ionic liquid composite, the surface resistance of the finally formed coating film increases, and it is difficult to satisfy the required standard value. It is because it is difficult to implement the improvement of the coating properties.

The above-described technique is a method of dispersing a thiophene-based conductive polymer in an organic solvent using an ionic liquid as a medium to adjust the content ratio of the conductive polymer and the ionic liquid to increase the dispersibility of the organic solvent as well as the electrical conductivity. Therefore, it can be used for various applications.

In particular, the composite of the conductive polymer and the ionic liquid of the present invention is hydrophobic, unlike the conventional thiophene-based conductive polymer is hydrophobic and has good wettability to various polymer films. The coating film properties or solvent resistance to water or alcohol solvents is very good.

In addition, the composite of the conductive polymer and the ionic liquid of the present invention may be mixed with various organic solvent type binders as a form dissolved in an organic solvent rather than in an aqueous dispersed form.

Hereinafter, the conductive polymer-ionic liquid composite of the present invention and an antistatic film prepared by using the same will be described in more detail with reference to Examples and Comparative Examples, but the following examples are only illustrative of the present invention. It does not limit the scope of rights.

1. Examples and Comparative Examples

<Example 1>

As a first step, 1-vinylimidazole 9g was added to a round bottom flask, and while stirring, 20.4 g of bromoethane was added dropwise and reacted at room temperature for 13 hours to thereby react 1-vinyl-3-ethylimidazolium bromide. Is obtained and dried.

After dissolving the 1-vinyl-3-ethylimidazolium bromide in ethyl alcohol, azobis (2-methylpropionitrile), a polymerization initiator, was added to the 1-vinyl-3-ethylimidazolium 2 in a nitrogen atmosphere. Poly (1-vinyl-3-ethylimidazolium bromide) was prepared by adding in mole percent and reacting at a temperature of 50 ° C. for 7 hours, and the obtained product was washed with chloroform and dried in a vacuum oven at a temperature of 40 ° C. It was. The obtained product was measured by gel chromatography (GPC) and found to have a weight average molecular weight of about 170,000 g / mol.

As a second step, 1 g of 3,4-ethylenedioxythiophene and 1 g of poly (1-vinyl-3-ethylimidazolium) bromide were added to 150 ml of water in a round bottom flask, and ammonium peroxide was used as a polymerization initiator. Sulfate is added dropwise at 1.2 molar ratios to 3,4-ethylenedioxythiophene to induce polymerization at room temperature.

When the polymerization reaction was carried out in order to reduce the size of the particles of the conductive polymer was carried out at high speed, the stirring conditions were set to 1,000 rpm. Polymerization reaction through high-speed stirring was performed at room temperature for 48 hours to confirm that a composite solution of aqueous dispersion of poly (3,4-ethylenedioxythiophene) and poly (1-vinyl-3-ethylimidazolium) bromide was prepared. It was. The size of the water-based conductive polymer particles dispersed in the solution was measured using a light scattering particle size meter, and the average particle size was found to be about 40 nm.

Lithium bis, which is an alkali metal salt containing a hydrophobic anion, in a composite solution of the aqueous dispersed poly (3,4-ethylenedioxythiophene) and poly (1-vinyl-3-ethylimidazolium) bromide as a third step (Trifluoromethanesulfonimide) is introduced at 1.2 molar ratio to poly (1-vinyl-3-ethyl imidazolium) bromide to induce anion exchange reaction between bromide and bis (trifluoromethanesulfonimide) .

At this time, as soon as the alkali metal salt is added, a complex of poly (3,4-ethylenedioxythiophene) and poly (1-vinyl-3-ethylimidazolium) bis (trifluoromethanesulfonimide) is formed and dispersed in water. It confirmed that it did not precipitate.

In addition, as a result of measuring the absorption peak of the precipitate through a Fourier transform infrared spectrometer (Avatar, Shinkosa), it was confirmed that the anion of the precipitate was substituted with trifluoromethanesulfonimide at 1054, 1134, 1194, and 1353 cm ^-1 . It was.

As a fourth step, a complex of the poly (3,4-ethylenedioxythiophene) and poly (1-vinyl-3-ethylimidazolium) bis (trifluoromethanesulfonimide) was obtained, which was then organic solvent. The redispersion was carried out so that the solid content was 1.0% by weight in the propylene carbonate to prepare a composite solution of a conductive polymer and an ionic liquid dispersed in an organic solvent.

<Example 2>

Example 2 was prepared in Example 2, except that 1 g of 3,4-ethylenedioxythiophene and 2.2 g of poly (1-vinyl-3-ethylimidazolium) bromide were polymerized in the second step. Is the same as

<Example 3>

Example 3 was polymerized with Example 1 except that 1 g of 3,4-ethylenedioxythiophene and 0.5 g of poly (1-vinyl-3-ethylimidazolium) bromide were polymerized in the second step. same.

Comparative Example 1

Comparative Example 1 was polymerized with Example 1 except that 1 g of 3,4-ethylenedioxythiophene and 9 g of poly (1-vinyl-3-ethylimidazolium) bromide were polymerized in the second step. same.

Comparative Example 2

Comparative Example 2 was polymerized with Example 1 except that 1 g of 3,4-ethylenedioxythiophene and 0.11 g of poly (1-vinyl-3-ethylimidazolium) bromide were polymerized in the second step. same.

Comparative Example 3

Comparative Example 3 is the same as Example 1 except that the magnetic stirring was performed under a stirring condition of 100 rpm without using a high speed stirrer when performing the polymerization reaction in the second step. After the second step, the particle size of the water-based conductive polymer was measured using a light scattering particle size analyzer, and the average particle size was found to be about 400 nm.

2. Formation of coating film

Using the solution prepared by the above Examples and Comparative Examples, a conductive coating film was formed using the casting method and the bar coating method. The conductive film prepared by the casting method was prepared by pouring the solution on a slide glass, drying at about 120 degrees for 5 minutes, and then drying at room temperature for 24 hours in a vacuum oven. The conductive coating film prepared by the bar coating method prepared the poly After pouring into the ester film, it was coated by using a bar coater No. 7 and dried at 150 degrees for 2 minutes.

3. Property measurement

The composite solution of the conductive polymer and the ionic liquid prepared through the above Examples and Comparative Examples was dispersed using propylene carbonate as an organic solvent, and the dispersion solution was allowed to stand for 24 hours at room temperature and then Acidity was evaluated.

○: no precipitation,

△: occurrence of a small amount of precipitation,

X: precipitation

In addition, the dispersion solution was cast on a polyester film, and then the electrical conductivity was measured using a four-terminal measurement method (Kisley's 2400). The surface resistance of the coating film was approximately 100 nm using a bar coater. It measured using the resistance meter (Prostat PRS-801).

The adhesive force was measured by coating the dispersion solution on the polyester film using a bar coater 5 and drying, and then applying the 3M scotch tape and detaching it. The coating film was released (ASTM D3359). Described.

Solvent resistance was evaluated by immersing isopropyl alcohol on a cotton swab, and then reciprocating the coating surface 10 times to determine whether the coating film was peeled off.

4. Property measurement result and analysis

Table 1 shows the results of measuring the physical properties of the conductive polymer-ionic solution and the coating film prepared by the Examples and Comparative Examples of the present invention.

Referring to Table 1, when the content of the ionic liquid is significantly higher than the content of the conductive polymer monomer in Comparative Example 1, the organic solvent dispersibility is good but the electrical conductivity is low, as shown in Comparative Example 2 When the content of the monomer for synthesizing the conductive polymer is high compared to the content of the ionic liquid, the conductive polymer monomers react with each other to cause precipitation, thereby deteriorating the adhesiveness or dispersibility of the organic solvent.

Therefore, in the conductive polymer composite of the present invention, the content ratio of the conductive polymer and the ionic liquid is maintained at an appropriate level at the level suggested by the present invention. It was found to be an important factor in determining the electrical properties of the composite solution.

In addition, in Comparative Example 3, even if the content ratio of the conductive polymer and the ionic liquid is appropriate, when the high speed stirrer is not used in the polymerization reaction, the size of the particles increases, which results in a small amount of precipitation and an electrical conductivity. have.

Hereinafter, a description will be given of a method for providing more excellent physical properties by presenting additional embodiments.

<Example 4>

Example 4 is the same as Example 1, except that dimethylacetamide is used instead of the propylene carbonate used in Example 1 as a dispersed organic solvent.

As a result of measuring the physical properties in the same manner as described above, even when using dimethyl acetamide as an organic solvent, it was confirmed that no precipitation occurred and the dispersibility was excellent, and when coated on a polyester film, the electrical conductivity was 7.9x10 ^-2. Measured in S / cm.

<Example 5>

Example 5 is the same as that of Example 1, except that the conductive polymer composite solution dispersed in the aqueous phase is prepared in the second step, and an additional toluene is poured therein to separate unreacted impurities.

When the aqueous dispersion-conductive polymer composite solution was separated by washing with toluene, it was confirmed that the unreacted EDOT monomer was removed because the color of toluene turned yellow. After the casting of the conductive polymer-ionic liquid composite solution obtained through the process, the measured electrical conductivity was measured as 6.5x10 ^-2 S / cm. Therefore, it was found that when the unreacted metal was removed in step (b), impurities were effectively removed, while the electrical conductivity was not greatly increased.

<Example 6>

In Example 6, a conductive polymer-ionic liquid composite solution was prepared using propylene carbonate as an organic solvent in the same manner as in Example 5. Then, after adding excess water to the solution and stirred and left for a certain time, to separate the organic layer using a separatory funnel to separate the organic layer and the water layer containing the conductive polymer-ionic liquid complex was obtained. The process was repeated three times and the remaining water was completely removed using silica gel. Thereafter, when the dispersibility of the solution was evaluated, no precipitation phenomenon occurred, and the electrical conductivity measured by casting was measured as 3.5 × 10 ⁻¹ S / cm.

As a result, when the process of removing impurities remaining in the water was further performed, a purer ionic liquid-thiophene-based conductive polymer composite was obtained, and it was confirmed that the electrical conductivity of the finally formed coating layer was greatly improved.

<Example 7>

Example 7 dissolves the poly (3,4-ethylenedioxythiophene) / ionic liquid complex obtained in Example 1 in propylene carbonate solvent to 1.0 weight percent, and then adds 20 times more propylene carbonate solvent. After diluting, the polyester surface was coated with a bar coater 7 times and dried to form an antistatic layer on the surface.

As a result of measuring the surface resistance of these films, when the solid content was 1.0% by weight, the surface resistance was 8.4X10 ⁷ Ω / □ and when the diluted solution was coated, the surface resistance was 9.3X10 ⁹ Ω / □.

<Example 8>

Example 8 excludes the use of bis (2-ethylhexyl hydrogen phosphate) when ion displacing the aqueous dispersed poly (3,4-ethylenedioxythiophene) / ionic liquid complex obtained through Example 1 And the same as in Example 1. The composite obtained in Example 1 is dispersible in propylene carbonate but not in ethyl acetate, which is a relatively nonpolar solvent. In this case, by ion exchange using bis (2-ethylhexyl hydrogen phosphate) as in this embodiment, a poly (3,4-ethylenedioxythiophene) / ionic liquid complex dispersed in ethyl acetate can be obtained.

Claims (26)

(a) synthesizing and polymerizing an ionic liquid having a hydrophilic anion to prepare an ionic liquid polymer; (b) A hydrophilic "conductive polymer having a size of 100 nm or less by dispersing-polymerizing a thiophene-based conductive polymer represented by Formula 1 in a high speed stirrer having a speed of 150 to 3,000 rpm using the ionic liquid polymer as a dispersion stabilizer. Preparing an "ionic liquid complex" solution; (c) exchanging the hydrophilic anion of the ionic liquid with a hydrophobic anion in the hydrophilic conductive polymer-ionic liquid complex solution to precipitate a hydrophobic conductive polymer-ionic liquid complex; And (d) redispersing the precipitated hydrophobic "conductive polymer-ionic liquid composite" in an organic solvent to prepare a conductive polymer-ionic liquid composite solution dispersed in the organic solvent; In the step (b), the weight ratio of the thiophene-based conductive polymer monomer: ionic liquid is mixed is 70:30 ~ 30:70 method for producing an organic solvent dispersible conductive polymer-ionic liquid composite solution. <Formula 1>

Wherein R _{1 and} R ₂ together may be alkylene, alkenylene, alkenyloxy, alkenyldioxy, alkynyloxy, alkynyldioxy of 3 to 8 membered alicyclic or aromatic ring structures In some cases, in addition to hydrogen, carbon, and oxygen atoms, atoms such as nitrogen, sulfur, phosphorus, selenium, and silicon may be contained. Alternatively, R ₁ , R ₂ may be composed of hydrogen, halogen or alkyl having 1 to 10 carbon atoms, alkoxy, carbonyl, hydroxy group, etc.) The method of claim 1, wherein step (a) comprises: (a1) imidazolium, pyridinium, pyrrolidinium, pyridazinium, pyrimidinium, pyrazinium, pyrazolium, piperidinium, piperizinium, thiazolium, oxazolium and tria Zolium, morpholinium, phosphonium, ammonium and derivatives thereof consisting of R ₁ , a reactor for inducing subsequent polymerization, and R _2, R ₃ , R _{4 ,} a reactor containing hydrogen, alkyl, ether, alkoxy or ester groups and a material containing a cationic ^{structure, X - (Br -, Cl} -, I -, BF 4 -, PF 6 -, ClO 4 -, NO 3 -, AlCl 4 -, Al 2 Cl 7 -, AsF 6 - , SbF ₆ ^-) by reacting a material containing any selected one or more anion in the step of synthesizing an ionic liquid monomer; (a2) A method for preparing an organic solvent dispersible conductive polymer-ionic liquid composite solution, comprising the step of polymerizing the monomer into a polymer form. <Formula 3>

(Wherein R ₁ represents a vinyl, allyl, acryloyloxy group, and R ₂ , R ₃ , R ₄ represent a reactor containing hydrogen or an alkyl, ether, alkoxy or ester group consisting of 1 to 15 carbon atoms.) The method of claim 2, The ionic liquid monomer synthesized through the reaction (a1) may be 1-vinyl-3-alkylimidazolium bromide (or chloride), 1-allyl-3-alkylimidazolium bromide (or chloride), or 1-vinyl- Characterized by containing all ionic liquid monomers represented by the formula (3) having a 4-alkylpyridinium bromide (or chloride), 1-allyl-4-alkylpyridinium (or chloride) and a reactor to induce subsequent polymerization Method for producing an organic solvent dispersible conductive polymer-ionic liquid composite solution. The method of claim 1, The weight average molecular weight of the ionic liquid polymer polymerized through the step (a) is 1,000 to 1,000,000 g / mole manufacturing method of organic solvent dispersible conductive polymer-ionic liquid composite solution. The method of claim 1, The aqueous dispersed hydrophilic thiophene-based conductive polymer-ionic liquid composite solution prepared in step (b) may be treated with ethyl to remove unreacted monomers contained in the hydrophilic complex solution before the step (c). A method for preparing an organic solvent dispersible conductive polymer-ionic liquid composite solution, further comprising the step of washing and separating using a non-aqueous solvent such as acetate, toluene, xylene and propylene carbonate. The method of claim 1, As the compound used in the ion exchange reaction for replacing the hydrophilic anion of the ionic liquid of step (c) with a hydrophobic anion, an alkali metal salt containing a hydrophobic anion or an organic and inorganic acid containing a hydrophobic anion is used. Method for preparing a dispersible organic polymer-ionic liquid composite solution of an organic solvent. The method of claim 6, An alkali metal salt comprising the hydrophobic anion is a lithium, sodium and potassium as the cation, and a hydrophobic anion is ^{_{CF 3 COO -, CH 3 COO}} -, CF 3 SO 3 -, (CF 3 SO 2) 2 N -, (CF ^{_{3 SO 2) 3 C -,}} (CF 3 CF 2 SO 2) 2 N -, (CF 3) 2 PF 4 -, (CF 3) 3 PF 3 -, (CF 3) 4 PF 2 -, (CF 3 ^{_{) 5 PF -, (CF 3}} ) 6 P -, SF 5 CF 2 SO 3 -, SF 5 CHFCF 2 SO 3 -, CF 3 CF 2 (CF 3) 2 CO -, (CF 3 SO 2) 2 CH - , (SF _{5) 3} C ^- of the ionic liquid solution of a complex _{-, (O (CF 3)} 2 C 2 (CF 3) 2 O) 2 PO - can be selected that the organic solvent component, characterized dispersible conductive polymer, which in Manufacturing method. The method of claim 6, The organic and inorganic acid containing the hydrophobic anion is bis (2-ethylhexyl hydrogen phosphate) or dodecyl benzenesulfonate method of producing an organic solvent dispersible conductive polymer-ionic liquid composite solution. The method of claim 1, The organic solvent used in the step (d) is a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diethyl ether, dipropyl ether, dibutyl ether, butyl ethyl ether, tetrahydro Ether solvents such as furan, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, alcohol ether solvents such as N-methyl-2-pyridyridone and 2-pyridyridone Amide solvents such as N-methylformamide, N, N-dimethylformamide, sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, sulfone solvents such as diethyl sulfone and tetramethylene sulfone, acetonitrile and benzonitrile Amine solvents such as nitrile solvents, alkylamines, cyclic amines, aromatic amines, ester solvents such as methyl butyrate, ethyl butyrate, and propyl propionate Carboxylic ester solvents such as ethyl acetate, butyl acetate, aromatic hydrocarbon solvents such as benzene, ethylbenzene, chlorobenzene, toluene, xylene, aliphatic hydrocarbon solvents such as hexane, heptane, cyclohexane, chloroform, tetrachloroethylene, Halogenated hydrocarbon solvents such as carbon tetrachloride, dichloromethane, dichloroethane, propylene carbonate, ethylene carbonate, dimethyl carbonate, dibutyl carbonate, ethylmethyl carbonate, dibutyl carbonate, nitromethane, nitrobenzene, etc. Method for producing an organic solvent dispersible conductive polymer-ionic liquid composite solution, characterized in that any one or more of them are mixed and used. The method of claim 1, In the step (d) of the organic solvent dispersible conductive polymer-ionic liquid composite solution, characterized in that the addition of a homogenizer, so as to increase the dispersibility and uniformity of the dispersed particles, and to perform the ultrasonic treatment selectively or in parallel Manufacturing method. The method of claim 1, The organic solvent dispersible conductive polymer, characterized in that the solid content of the conductive polymer-ionic liquid complex in the conductive polymer-ionic liquid composite solution dispersed in the organic solvent prepared in step (d) is 0.001 ~ 10% by weight Method for preparing an ionic liquid complex solution. (a) synthesizing and polymerizing an ionic liquid having a hydrophilic anion to prepare an ionic liquid polymer; (b) A hydrophilic "conductive polymer having a size of 100 nm or less by dispersing-polymerizing a thiophene-based conductive polymer represented by Formula 1 in a high speed stirrer having a speed of 150 to 3,000 rpm using the ionic liquid polymer as a dispersion stabilizer. Preparing an "ionic liquid complex" solution; (c) exchanging the hydrophilic anion of the ionic liquid with a hydrophobic anion in the hydrophilic conductive polymer-ionic liquid complex solution to precipitate a hydrophobic conductive polymer-ionic liquid complex; And (d) redispersing the precipitated hydrophobic "conductive polymer-ionic liquid composite" in an organic solvent to prepare a conductive polymer-ionic liquid composite solution dispersed in an organic solvent; (e) Conductive polymer-ionic liquid composite solution and polar solvent dispersed in an organic solvent in order to increase the electrical conductivity of the film prepared by using the composite solution prepared by the steps (a) ~ (d) : Mixing water), stirring until sufficient mixing, and separating the polar solvent again; In the step (b), the weight ratio of the thiophene-based conductive polymer monomer: ionic liquid is mixed is 70:30 ~ 30:70 method for producing an organic solvent dispersible conductive polymer-ionic liquid composite solution. <Formula 1>

Wherein R _{1 and} R ₂ together may be alkylene, alkenylene, alkenyloxy, alkenyldioxy, alkynyloxy, alkynyldioxy of 3 to 8 membered alicyclic or aromatic ring structures In some cases, in addition to hydrogen, carbon, and oxygen atoms, atoms such as nitrogen, sulfur, phosphorus, selenium, and silicon may be contained. Alternatively, R ₁ , R ₂ may be composed of hydrogen, halogen or alkyl having 1 to 10 carbon atoms, alkoxy, carbonyl, hydroxy group, etc.) The method of claim 12, wherein step (a) comprises: (a1) imidazolium, pyridinium, pyrrolidinium, pyridazinium, pyrimidinium, pyrazinium, pyrazolium, piperidinium, piperizinium, thiazolium, oxazolium and tria Zolium, morpholinium, phosphonium, ammonium and derivatives thereof consisting of R ₁ , a reactor for inducing subsequent polymerization, and R _2, R ₃ , R _{4 ,} a reactor containing hydrogen, alkyl, ether, alkoxy or ester groups and a material containing a cationic ^{structure, X - (Br -, Cl} -, I -, BF 4 -, PF 6 -, ClO 4 -, NO 3 -, AlCl 4 -, Al 2 Cl 7 -, AsF 6 - , SbF ₆ ^-) by reacting a material containing any selected one or more anion in the step of synthesizing an ionic liquid monomer; (a2) A method for preparing an organic solvent dispersible conductive polymer-ionic liquid composite solution, comprising the step of polymerizing the monomer into a polymer form. <Formula 3>

(Wherein R ₁ represents a vinyl, allyl, acryloyloxy group, and R ₂ , R ₃ , R ₄ represent a reactor containing hydrogen or an alkyl, ether, alkoxy or ester group consisting of 1 to 15 carbon atoms.) The method of claim 13, The ionic liquid monomer synthesized through the reaction (a1) may be 1-vinyl-3-alkylimidazolium bromide (or chloride), 1-allyl-3-alkylimidazolium bromide (or chloride), or 1-vinyl- Characterized by containing all ionic liquid monomers represented by the formula (3) having a 4-alkylpyridinium bromide (or chloride), 1-allyl-4-alkylpyridinium (or chloride) and a reactor to induce subsequent polymerization Method for producing an organic solvent dispersible conductive polymer-ionic liquid composite solution. The method of claim 12, The weight average molecular weight of the ionic liquid polymer polymerized through the step (a) is 1,000 to 1,000,000 g / mole manufacturing method of organic solvent dispersible conductive polymer-ionic liquid composite solution. The method of claim 12, The aqueous dispersed hydrophilic thiophene-based conductive polymer-ionic liquid composite solution prepared through step (b) is ethyl to remove unreacted monomers contained in the hydrophilic composite solution prior to step (c). A method for preparing an organic solvent dispersible conductive polymer-ionic liquid composite solution, further comprising the step of washing and separating using a non-aqueous solvent such as acetate, toluene, xylene and propylene carbonate. The method of claim 12, As the compound used in the ion exchange reaction for replacing the hydrophilic anion of the ionic liquid of step (c) with a hydrophobic anion, an alkali metal salt containing a hydrophobic anion or an organic and inorganic acid containing a hydrophobic anion is used. Method for preparing a dispersible organic polymer-ionic liquid composite solution of an organic solvent. The method of claim 17, An alkali metal salt comprising the hydrophobic anion is a lithium, sodium and potassium as the cation, and a hydrophobic anion is ^{_{CF 3 COO -, CH 3 COO}} -, CF 3 SO 3 -, (CF 3 SO 2) 2 N -, (CF ^{_{3 SO 2) 3 C -,}} (CF 3 CF 2 SO 2) 2 N -, (CF 3) 2 PF 4 -, (CF 3) 3 PF 3 -, (CF 3) 4 PF 2 -, (CF 3 ^{_{) 5 PF -, (CF 3}} ) 6 P -, SF 5 CF 2 SO 3 -, SF 5 CHFCF 2 SO 3 -, CF 3 CF 2 (CF 3) 2 CO -, (CF 3 SO 2) 2 CH - , (SF _{5) 3} C ^- of the ionic liquid solution of a complex _{-, (O (CF 3)} 2 C 2 (CF 3) 2 O) 2 PO - can be selected that the organic solvent component, characterized dispersible conductive polymer, which in Manufacturing method. The method of claim 17, The organic and inorganic acid containing the hydrophobic anion is bis (2-ethylhexyl hydrogen phosphate) or dodecyl benzenesulfonate method of producing an organic solvent dispersible conductive polymer-ionic liquid composite solution. The method of claim 12, The organic solvent used in the step (d) is a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diethyl ether, dipropyl ether, dibutyl ether, butyl ethyl ether, tetrahydro Ether solvents such as furan, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, alcohol ether solvents such as N-methyl-2-pyridyridone and 2-pyridyridone Amide solvents such as N-methylformamide, N, N-dimethylformamide, sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, sulfone solvents such as diethyl sulfone and tetramethylene sulfone, acetonitrile and benzonitrile Amine solvents such as nitrile solvents such as nitrile solvents, alkylamines, cyclic amines, aromatic amines, ester solvents such as methyl butyrate, ethyl butyrate, and propyl propionate, Carboxylic ester solvents such as ethyl acetate and butyl acetate, aromatic hydrocarbon solvents such as benzene, ethylbenzene, chlorobenzene, toluene, xylene, aliphatic hydrocarbon solvents such as hexane, heptane, cyclohexane, chloroform, tetrachloroethylene, Halogenated hydrocarbon solvents such as carbon tetrachloride, dichloromethane, dichloroethane, propylene carbonate, ethylene carbonate, dimethyl carbonate, dibutyl carbonate, ethylmethyl carbonate, dibutyl carbonate, nitromethane, nitrobenzene, etc. Method for producing an organic solvent dispersible conductive polymer-ionic liquid composite solution, characterized in that any one or more of them are mixed and used. The method of claim 12, In the step (d) of the organic solvent dispersible conductive polymer-ionic liquid composite solution, characterized in that the addition of a homogenizer, so as to increase the dispersibility and uniformity of the dispersed particles, and to perform the ultrasonic treatment selectively or in parallel Manufacturing method. The method of claim 12, The organic solvent dispersible conductive polymer, characterized in that the solid content of the conductive polymer-ionic liquid complex in the conductive polymer-ionic liquid composite solution dispersed in the organic solvent prepared in step (d) is 0.001 ~ 10% by weight Method for preparing an ionic liquid complex solution.  Organic solvent dispersible conductive polymer, characterized in that the composite having a particle size of 100 nm or less and a thiophene conductive polymer dispersed-polymerized in an ionic liquid having a hydrophobic anionic group is uniformly or unevenly dispersed in an organic solvent. Ionic liquid complex solution. The organic or inorganic binder is prepared by adding and mixing an organic or inorganic binder in an amount of 0.1 to 100 times the content of the conductive polymer-ionic liquid composite prepared in the organic solvent dispersible conductive polymer-ionic liquid composite solution prepared by claim 1. Organic Solvent Dispersible Conductive Polymer Composition The method of claim 24, The organic or inorganic binder is an organic binder such as urethane group, epoxy group, carboxyl group, carbonyl group, acrylic group, hydroxy group, ester group, ether group, amide group, imide group, maleic acid group, vinyl acetate group and inorganic such as silicate, titanate, etc. An organic solvent dispersible conductive polymer composition, characterized in that any one or more selected from inorganic binder containing a component. Prepared using the solutions and compositions of claims 24 and 25, Coatings having an electrical conductivity of 1X10 ^-4 S / cm or more.