KR102002722B1 - Manufacturing method of conductive polymer film by semi-continuous process and conductive polymer film manufactured thereby - Google Patents

Abstract

According to the present invention, a conductive polymer film divides a catalyst by a predetermined time and polymerizes through three steps to control a reaction not to explosively proceed in an initial stage of the reaction while maintaining an overall responsivity, thereby maintaining electric conductivity and improving a light transmittance. According to the present invention, the conductive polymer film has an average light transmittance of 81% or higher and a haze of 0.2 or less in a visible light area under a sheet resistance of 60 Ω/sq, and a CIE color coordinate reference b* in -3.5 to -2.5, and has a high transmittance in a low resistance area. In addition, application as a transparent electrode using a conductive polymer film requires a high transmittance in a low resistance area less than 100 Ω/sq. The conductive polymer film of the present invention has a high light transmittance and a low haze value under a sheet resistance of 60 Ω/sq, thereby being applied to a transparent electrode and having an excellent transparent electrode effect.

Description

[0001] The present invention relates to a method for producing a conductive polymer film by a semi-continuous process, and a conductive polymer film produced thereby,

The present invention relates to a method for producing a conductive polymer film through a semi-continuous process and a conductive polymer film produced thereby.

BACKGROUND OF THE INVENTION [0002] As various home appliances and communication devices including computers are digitized and rapidly improved in performance, development of transparent conductive materials for use as electrodes of electronic devices is required. For example, in order to realize a portable display, the electrode material for a display must have transparency and low resistance as well as high flexibility to cope with mechanical impact, and even if the device is overheated and exposed to a high temperature, Should not be large.

ITO (indium-tin oxide) is the most commonly used transparent electrode material for displays. However, when the transparent electrode is formed of ITO, not only is an excessive cost consumed, but also it is difficult to realize a large area. In particular, when the ITO is coated on a large area, the change of the sheet resistance is large, and the luminance and luminous efficiency of the display are reduced. In addition, indium, which is the main raw material of ITO, is a limited minerals and is rapidly depleting as the display market expands.

 In order to overcome the disadvantages of ITO, studies are being conducted to form a transparent electrode using a conductive polymer having excellent flexibility and a simple coating process. However, the batch process for preparing the conductive polymer by mixing all of the reactants, which is a conventional method for producing the conductive polymer, may proceed explosively during the initial reaction, And therefore, high light transmittance can not be achieved in a low sheet resistance. Therefore, the conductive polymer produced according to the conventional batch process can not achieve a high light transmittance at a low sheet resistance of less than 100 Ω / sq, which is a requirement for application to a transparent electrode, and thus it is difficult to apply it as a transparent electrode.

Korean Patent Publication No. 2012-0077112

The present invention relates to a method for producing a conductive polymer film by a semi-continuous process and a conductive polymer film produced by the method. In the production of a conductive polymer film, the catalyst is divided and polymerized at a predetermined time interval, And a method for producing the same.

In order to solve the above problems,

The present invention, in one embodiment,

There is provided a conductive polymer film comprising a repeating unit represented by the following formula (1)

[Chemical Formula 1]

In Formula 1,

X and Y each independently represent O, S, Si or N,

R ₁ and R ₂ each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 3 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms,

n is an integer from 2 to 2000,

Alternatively, R ₁ and R ₂ are bonded to each other to represent a fused ring structure.

Further, the present invention, in one embodiment,

Mixing a solution containing a conductive polymer and an ionic polymer electrolyte and a catalyst amount of 1/4 to 2/5 of the total catalyst amount, and conducting polymerization for 4 to 8 hours;

Mixing the solution and a catalytic amount of 1/4 to 2/5 of the total catalyst amount, and conducting polymerization for 4 to 8 hours; And

Mixing the remaining amount of the catalyst and the amount of the catalyst except for the catalyst used in the polymerization in the solution and the total amount of the catalyst, and allowing the polymerization to proceed for 10 to 14 hours.

In the conductive polymer film according to the present invention, the catalyst is divided at predetermined time intervals and polymerized in three steps, thereby preventing the reaction from proceeding explosively at the beginning of the reaction and maintaining the overall reactivity, Can be improved.

The conductive polymer film according to the present invention has an average light transmittance of not less than 81% and a haze of not more than 0.2 in a visible ray region under a sheet resistance of 60? / Sq, a CIE color coordinate standard b * of not less than -3.5 to -2.5, High transmittance can be exhibited in the low resistance region.

In addition, when the conductive polymer film is used as a transparent electrode, a high transmittance in a low resistance region of less than 100 Ω / sq is essential. The conductive polymer film according to the present invention has high light transmittance and low transmittance at a sheet resistance of 60 Ω / Since the haze value is shown, it can be applied to a transparent electrode to exhibit an excellent transparent electrode effect.

FIG. 1 shows the electrical conductivity measurement results of the conductive polymer films according to Examples and Comparative Examples.
Fig. 2 shows the light transmittance (a) and the light transmittance (b) measurement results in the visible light region according to the sheet resistance of the conductive polymer films according to Examples and Comparative Examples.
3 shows the haze measurement results of the conductive polymer films according to Examples and Comparative Examples.
4 shows the results of measurement of the b * value of the conductive polymer films according to Examples and Comparative Examples.

While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail.

It should be understood, however, that the invention is not intended to be limited to the particular embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

In the present invention, the terms "comprising" or "having ", and the like, specify that the presence of a feature, a number, a step, an operation, an element, a component, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

Hereinafter, the present invention will be described in detail.

The conductive polymer film according to the present invention can provide a conductive polymer film exhibiting high light transmittance under low resistance conditions.

Specifically, the conductive polymer film according to the present invention may include a conductive polymer film containing a repeating unit represented by the following formula (1)

[Chemical Formula 1]

In Formula 1,

X and Y each independently represent O, S, Si or N; R ₁ and R ₂ each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxy group having 3 to 20 carbon atoms An aryl group or a heteroaryl group having 2 to 20 carbon atoms, and n is an integer of 2 to 2000, and optionally, R ₁ and R ₂ are bonded to each other to form a fused ring structure.

At this time, the alkyl group may mean a functional group derived from a linear or branched saturated hydrocarbon.

Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a 1,1-dimethylpropyl group, Ethylpropyl group, 2-ethylpropyl group, n-hexyl group, 1-methyl-2-ethylpropyl group, 1-ethyl- Methylbutyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, Dimethylbutyl group, 2,3-dimethylbutyl group, 2-ethylbutyl group, 2-methylpentyl group, 3-methylpentyl group and the like.

In addition, the aryl group may mean a monovalent substituent derived from an aromatic hydrocarbon.

Specific examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a naphthacenyl group, a pyrenyl group, A tolyl group, a biphenylyl group, a terphenyl group, a chrycenyl group, a spirobifluorenyl group, a fluoranthenyl group, a fluorine group, A perfluoroalkyl group, a fluorenyl group, a perylenyl group, an indenyl group, an azulenyl group, a heptalenyl group, a phenalenyl group, a phenanthrenyl group phenanthrenyl group).

Further, the heteroaryl group represents an aromatic heterocycle or a heterocyclic group derived from a monocyclic or condensed ring. The heteroaryl group may include at least one of nitrogen (N), sulfur (S), oxygen (O), phosphorus (P), selenium (Se), and silicon (Si) as a heteroatom.

Specific examples of the heteroaryl group include pyrrolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazolyl, tetrazolyl, benzotriazolyl, pyrazolyl, imidazolyl, An imidazolyl group, an imidazolyl group, a thiazolyl group, an isothiazolyl group, a benzothiazolyl group, a benzothiadiazolyl group, a phenothiazyl group, an isoxazolyl group, a furazanyl group, a phenoxazinyl group, , A benzooxazolyl group, an oxadiazolyl group, a pyrazoloxazolyl group, an imidazothiazolyl group, a thienopuranyl group, a furopyrrolyl group, and a pyridoxazinyl group.

As an example, the conductive polymer may be represented by the following formula (1): K (K is an arbitrary integer between 2 and 2000) repeating structure, X, Y, R ₁ and R < ₂ > may be different from each other. For example, the conductive polymer having the structure of Formula 1 may include at least one selected from the structures represented by Chemical Formulas 2 to 4 below.

(2)

(3)

[Chemical Formula 4]

In the above Chemical Formulas 2 to 4,

and n is an integer of 2 to 2000.

Specifically, the conductive polymer may be at least one selected from the group consisting of poly (3,4-ethylenedioxythiophene): polystyrene sulfonic acid, polypyrrole: polystyrene sulfonic acid, and polythiophene: polystyrene sulfonic acid.

The conductive polymer film according to the present invention is a conductive polymer film comprising PEDOT: PSS. The conductive polymer film has an average light transmittance of 81% or more in a visible light region at a sheet resistance of 60 Ω / sq, b * may include a conductive polymer film in the range of -3.5 to -2.5. For example, the polymer film may have an average light transmittance of 81 to 85%, 81 to 84%, 81 to 83%, or 81 to 82% in the visible light region at a sheet resistance of 60? / Sq, The CIE color coordinate criterion b * may be in the range of -3.4 to -2.6, -3.3 to -2.7, -3.2 to -2.8, or -3.1 to -2.9.

In addition, the conductive polymer film according to the present invention may have a haze of 0.2 or less at a sheet resistance of 60 Ω / sq. For example, the conductive polymer film may have a haze of 0.18 or less, 0.16 or less, 0.14 or less, 0.12 or less, or 0.1 or less at a sheet resistance of 60 Ω / sq.

When the conductive polymer film is used as a transparent electrode, a high transmittance in a low resistance region of less than 100 Ω / sq is essential. The conductive polymer film of the present invention has high light transmittance and low haze value at a sheet resistance of 60 Ω / sq Therefore, it can be applied to a transparent electrode and exhibit an excellent transparent electrode effect.

The present invention can provide a method for producing a conductive polymer film.

In the batch process for preparing conductive polymer by mixing all of the existing reactants at one time, the reaction may explosively proceed during the initial reaction, but the overall reactivity decreases sharply as the reaction progresses, High light transmittance can not be achieved. Therefore, the conductive polymer produced according to the conventional batch process can not achieve a high light transmittance at a low sheet resistance of less than 100 Ω / sq, which is a requirement for application to a transparent electrode, and thus it is difficult to apply it as a transparent electrode.

However, in the method for producing a conductive polymer film according to the present invention, it is possible to control the reaction so that the reaction does not proceed explosively at the beginning of the reaction and to maintain the overall reactivity by polymerizing the catalyst in three steps, The physical properties such as haze and b * can be improved. In particular, since it exhibits a high light transmittance and a low haze value at a sheet resistance of 60 Ω / sq, it can be applied to a transparent electrode to exhibit an excellent transparent electrode effect.

Specifically, the present invention relates to a method for preparing a polymer electrolyte membrane, comprising: a first step of mixing a solution containing a conductive polymer and an ionic polymer electrolyte and a catalyst amount of 1/4 to 2/5 of the total catalyst amount for 4 to 8 hours; A second step of mixing the reactants of the first step and a catalytic amount of 1/4 to 2/5 of the total amount of the catalyst to proceed the polymerization for 4 to 8 hours; And the second stage catalyst, and the remaining catalyst amount except for the catalysts used in the first and second stages, and conducting the polymerization for 10 to 14 hours.

In the first step, the amount of catalyst may be in the range of 1/4 to 2/5, 1/4 to 1/3, or 1/3 to 2/5 of the total catalyst amount. The polymerization time may be from 5 to 7 hours, from 4 to 6 hours, or from 5 to 6 hours.

In the second step, the amount of catalyst may be in the range of 1/4 to 2/5, 1/4 to 1/3, or 1/3 to 2/5 of the total amount of catalyst. The polymerization time may be from 5 to 7 hours, from 4 to 6 hours, or from 5 to 6 hours.

In the third step, the polymerization time may be from 11 to 13 hours, from 10 to 12 hours, or from 11 to 12 hours.

In the second and third steps, the catalyst may be degassed using Ar gas before the mixing of the catalyst, and the deaeration may prevent the inflow of oxygen into the solution.

The polymerization temperature in the first, second and third steps may be 5 to 15 캜, for example, the polymerization temperature may be 8 to 12 캜, 8 to 10 캜, or 10 to 12 캜.

In the first step, the second step and the third step, the stirring speed of the solution may be 200 to 400 rpm, 250 to 350 rpm, 200 to 300 rpm, or 300 to 400 rpm.

After the completion of the polymerization, the solution can be used in the form of a conductive polymer film by coating on a glass substrate. The coating thickness may be 50 to 200 nm, 50 to 150 nm, 50 to 100 nm, or 50 to 80 nm.

The coating may be one or more wet coatings selected from spin coating, flow coating, spray coating, dip coating, slit die coating, roll coating and bar coating.

The conductive polymer may include a structure represented by the following Formula 1:

[Chemical Formula 1]

In Formula 1,

X and Y each independently represent O, S, Si or N; R ₁ and R ₂ each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxy group having 3 to 20 carbon atoms An aryl group or a heteroaryl group having 2 to 20 carbon atoms, and n is an integer of 2 to 2000, and optionally, R ₁ and R ₂ are bonded to each other to form a fused ring structure.

At this time, the alkyl group may mean a functional group derived from a linear or branched saturated hydrocarbon.

Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a 1,1-dimethylpropyl group, Ethylpropyl group, 2-ethylpropyl group, n-hexyl group, 1-methyl-2-ethylpropyl group, 1-ethyl- Methylbutyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, Dimethylbutyl group, 2,3-dimethylbutyl group, 2-ethylbutyl group, 2-methylpentyl group, 3-methylpentyl group and the like.

In addition, the aryl group may mean a monovalent substituent derived from an aromatic hydrocarbon.

Specific examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a naphthacenyl group, a pyrenyl group, A tolyl group, a biphenylyl group, a terphenyl group, a chrycenyl group, a spirobifluorenyl group, a fluoranthenyl group, a fluorine group, A perfluoroalkyl group, a fluorenyl group, a perylenyl group, an indenyl group, an azulenyl group, a heptalenyl group, a phenalenyl group, a phenanthrenyl group phenanthrenyl group).

Further, the heteroaryl group represents an aromatic heterocycle or a heterocyclic group derived from a monocyclic or condensed ring. The heteroaryl group may include at least one of nitrogen (N), sulfur (S), oxygen (O), phosphorus (P), selenium (Se), and silicon (Si) as a heteroatom.

Specific examples of the heteroaryl group include pyrrolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazolyl, tetrazolyl, benzotriazolyl, pyrazolyl, imidazolyl, An imidazolyl group, an imidazolyl group, a thiazolyl group, an isothiazolyl group, a benzothiazolyl group, a benzothiadiazolyl group, a phenothiazyl group, an isoxazolyl group, a furazanyl group, a phenoxazinyl group, , A benzooxazolyl group, an oxadiazolyl group, a pyrazoloxazolyl group, an imidazothiazolyl group, a thienopuranyl group, a furopyrrolyl group, and a pyridoxazinyl group.

As an example, the conductive polymer may be represented by the following formula (1): K (K is an arbitrary integer between 2 and 2000) repeating structure, X, Y, R ₁ and R < ₂ > may be different from each other. For example, the conductive polymer having the structure of Formula 1 may include at least one selected from the structures represented by Chemical Formulas 2 to 4 below.

(2)

(3)

[Chemical Formula 4]

In the above Chemical Formulas 2 to 4,

and n is an integer of 2 to 2000.

Specifically, the conductive polymer may be at least one selected from the group consisting of poly (3,4-ethylenedioxythiophene): polystyrene sulfonic acid, polypyrrole: polystyrene sulfonic acid, and polythiophene: polystyrene sulfonic acid.

The solution containing the conductive polymer and the ionic polymer electrolyte may further contain a dopant.

For example, the dopant may include at least one of an ammonium salt electrolyte, a sodium salt electrolyte, a lithium salt electrolyte, an iron salt electrolyte, a sulfonic acid compound, and sulfuric acid. For example, the dopant is not particularly limited, but may include organic compounds containing oxygen and nitrogen.

The ammonium salt electrolyte may include at least one of tetra-n-Bu ₄ NClO ₄ , n-Bu ₄ NPF ₆ , n-Bu ₄ NBF ₄ and n-Et ₄ NClO ₄ .

The sodium salt electrolyte may include, for example, at least one of NaPF ₆ , NaBF _4, and NaClO ₄ .

The lithium salt electrolyte, for _{example, LiClO 4, LiPF 6, LiBF} 4, LiN (SO 2 CF 3) 2, LiN (SO 2 C 2 F 5) 2, LiCF 3 SO 3, LiC (SO 2 CF 3 _{) 3, LiPF 4 (CF 3} ) 2, LiPF 3 (C 2 F 5) 3, LiPF 3 (CF 3) 3, LiPF 3 (iso-C 3 F 7) 3, LiPF 5 (iso-C 3 F 7 ) And a lithium salt electrolyte having a cyclic alkylene group.

For example, the lithium salt having a cyclic alkylene group may include (CF ₂ ) ₂ (SO ₂ ) ₂ NLi and (CF ₂ ) ₃ (SO ₂ ) ₂ NLi.

The iron salt electrolyte may include, for example, iron (III) oxide p-toluenesulfonic acid.

The sulfonic acid compound is, for example, an alkanesulfonic acid having 1 to 20 carbon atoms, a perfluoroalkanesulfonic acid having 1 to 20 carbon atoms, an alkylhexylcarboxylic acid having 1 to 20 carbon atoms, a purple having 1 to 20 carbon atoms An aromatic sulfonic acid substituted or unsubstituted by an alkyl group having 1 to 20 carbon atoms, and a cycloalkanesulfonic acid (e.g., camphorsulfonic acid).

Specifically, the sulfonic acid compound may be selected from the group consisting of methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, dodecanesulfonic acid, octadecanesulfonic acid, nonadecanesulfonic acid, trifluoromethanesulfonic acid, perfluorobutane Sulfonic acid, perfluorooctanesulfonic acid, ethylhexylcarboxylic acid, benzenesulfonic acid, o -toluenesulfonic acid, p -toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, P-toluenesulfonic acid and p-toluenesulfonic acid.

The dopant may be discontinued or a mixture of two or more dopants may be used.

For example, the dopant may be either a sulfuric acid or a sulfonic acid compound, or two or more thereof.

The dopant may be dissolved and mixed in a solvent.

The solvent used in mixing the dopant is not particularly limited as long as it can dissolve the dopant and can be mixed with water. For example, the solvent may include at least one of water, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), acetonitrile, and an alcohol-based solvent.

In one example, the conductive polymer may be uncharged or cationic. Where "cation" may relate only to the charge present on the main chain.

Therefore, the conductive polymer may require anion to compensate for the positive charge.

That is, the conductive polymer may be doped with an ionic polymer electrolyte which provides an anion.

The ionic polymer electrolyte has a molecular weight of 20,000 to 1,000,000, and may include at least one or more of, for example, a monomer anion and a polyanion.

The monomeric anions are selected, for example, by C ₁ -C ₂₀ -alkanesulfonic acids, aliphatic perfluorosulfonic acids, aliphatic C ₁ -C ₂₀ -carboxylic acids, aliphatic perfluorocarboxylic acids, C ₁ -C ₂₀ -alkyl groups Such as aromatic sulfonic acid, cycloalkanesulfonic acid, iron sulfate, sodium persulfate, tetrafluoroborate, hexafluorophosphate, perchlorates, hexafluoroantimonate, hexafluoroarsenate, Hexafluoroarsenates or hexachloroantimonates, and the like.

The polyanion may be an anion of, for example, a polymeric carboxylic acid (e.g., polyacrylic acid, polymethacrylic acid or polymaleic acid), a polymeric sulfonic acid (e.g., polystyrene sulfonic acid and polyvinyl sulfonic acid) Styrene sulfonic acid-co-maleic acid), and the like. Specifically, the ionic polymer electrolyte may be polystyrene sulfonic acid having a molecular weight of 20,000 to 1,000,000.

As one example, the conductive polymer according to the present invention may be poly-3,4-ethylenedioxythiophene / polystyrenesulfonate (PEDOT / PSS).

In particular, among the conductive polymers, polythiophene has attracted much attention among conductive polymers due to its high electrical conductivity and thermal stability. Particularly, poly-3,4-ethylenedioxythiophene (PEDOT) having an ethylenedioxy group in the polythiophene has an electron donating effect of an ethylene dioxy group, (band gap) is low, not only has transparency in the visible light region but also has high antistatic function and high chemical stability and electrical stability.

The catalyst may be an iron sulfate and a persulfate series, for example, potassium persulfate. The iron sulfate catalyst is present in the form of iron (III) ions in solution, which serves to oxidize the monomers in the oxidation polymerization reaction to produce a conductive polymer solution. The persulfate ion of the persulfate catalyst oxidizes the reduced iron (II) ion to the iron (III) ion, and plays a role in sustaining the reaction.

Hereinafter, the present invention will be described in more detail with reference to the following Examples. However, the scope of the present invention is not limited by the following Examples.

Example : Semicontinuous  Preparation of Conductive Polymer Film by Synthesis Method

8.75 g of polystyrene sulfonic acid (PSS, Mw 75,000) was dissolved in 750 g of distilled water, and 0.108 g of iron sulfate as a catalyst was added to the reaction vessel. After degassing and stirring at 10 ° C for 1 hour, 3.5 g of 3,4-ethylenedioxythiophene (EDOT) monomer and 10 g of an aqueous solution containing 1.368 g of persulfate were placed and polymerization was carried out for 6 hours. After 6 hours, 10 g of aqueous solution having dissolved therein 1.368 g of persulfate was deaerated for 10 minutes, further mixed slowly, and the reaction was continued with stirring at 10 DEG C for 6 hours. 10 g of an aqueous solution containing 1.368 g of persulfate while stirring was continuously degassed was degassed for 10 minutes and then further mixed slowly and further stirred at 10 DEG C for 12 hours to conduct the reaction. After the completion of the reaction, 500 mL of a mixed ion exchange resin in which a cation exchange resin and an anion exchange resin were mixed at a ratio of 1: 1 was added to remove unnecessary ions to prepare a conductive polymer solution.

Then, the prepared conductive polymer solution and dimethyl sulfoxide (DMSO) were mixed at a weight ratio of 95: 5, coated on a glass substrate using a spin coater, and dried at 150 ° C for 2 minutes to obtain a conductive polymer A film was prepared.

Comparative Example : Batch batch ) Preparation of Conductive Polymer Film by Synthesis Method

8.75 g of polystyrene sulfonic acid (PSS, Mw 75,000) was dissolved in 750 g of distilled water, and 0.108 g of iron sulfate as a catalyst was mixed and deaerated and stirred at 10 ° C for 1 hour, 3.5 g of 3,4-ethylenedioxythiophene (EDOT) monomer and 30 g of an aqueous solution in which 4.103 g of persulfate was dissolved were placed and polymerization was carried out for 24 hours. After the completion of the reaction, 500 mL of a mixed ion exchange resin in which a cation exchange resin and an anion exchange resin were mixed at a ratio of 1: 1 was added to remove unnecessary ions to prepare a conductive polymer solution.

Then, the prepared conductive polymer solution and dimethyl sulfoxide (DMSO) were mixed at a weight ratio of 95: 5, coated on a glass substrate using a spin coater, and dried at 150 ° C for 2 minutes to obtain a conductive polymer A film was prepared.

Experimental Example  1: Electrical conductivity measurement

The electrical conductivity of the films prepared by curing the conductive polymer solution prepared in the above Examples and Comparative Examples was measured. The results are shown in Fig.

1, it can be seen that the conductive polymer film prepared by the present invention maintains the same electric conductivity as the conductive polymer film prepared by the comparative example.

Experimental Example  2: Light transmittance  And Sheet resistance  Measure

The transmittance and sheet resistance of the film prepared by curing the conductive polymer solution prepared in Examples and Comparative Examples were measured in the visible light region. The results are shown in FIG.

2 (a), it can be seen that the light transmittance of the conductive polymer film prepared by the present invention at a wavelength of 550 nm is 81% or more at a sheet resistance of 60 Ω / sq, and the conductivity High light transmittance can be confirmed at a low resistance compared with a polymer film.

Also, FIG. 2 (b) shows that the light transmittance of the conductive polymer film prepared in Examples is higher than that of the conductive polymer film at the range of the sheet resistance of 50? / Sq.

Experimental Example  3: Hayes  Measure

The haze of the films prepared by curing the conductive polymer solution prepared in the above Examples and Comparative Examples was measured. The results are shown in FIG.

It can be confirmed that the conductive polymer film produced by the present invention has a haze of 0.2 or less.

Experimental Example  4: Measurement of b * value

With respect to the film prepared by curing the conductive polymer solution prepared in the above Examples and Comparative Examples, the measurement area of 2.5 x 2.5 cm was measured by using a haze meter (color difference meter) and a b * value at a visible light wavelength of 550 nm Respectively. The results are shown in FIG.

It can be seen that the conductive polymer film produced by the present invention has a low b * absolute value in the low resistance range as compared with the comparative example, which means that the film is less distinctive in color and improved in visibility.

Claims (9)

A conductive polymer solution comprising a conductive polymer coated on a substrate,
Wherein the conductive polymer is a conductive polymer film comprising a repeating unit represented by the following formula (1)
The conductive polymer film had an average light transmittance of 81% or more in a visible light region at a sheet resistance of 60? / Sq,
CIE color coordinate reference, b * is in the range of -3.5 to -2.5,
Conducting polymer film having a haze of 0.2 or less at a sheet resistance of 60 Ω / sq:
[Chemical Formula 1]

In Formula 1,
X and Y each independently represent O, S, Si or N,
R ₁ and R ₂ each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 3 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms,
n is an integer from 2 to 2000,
Alternatively, R ₁ and R ₂ are bonded to each other to represent a fused ring structure.
The method according to claim 1,
The conductive polymer is a conductive polymer film containing PEDOT: PSS.
delete A first step of mixing the solution containing the conductive polymer and the ionic polymer electrolyte and a catalyst amount of 1/4 to 2/5 of the total amount of the catalyst to proceed the polymerization for 4 to 8 hours;
A second step of mixing the reactants of the first step and a catalytic amount of 1/4 to 2/5 of the total amount of the catalyst to proceed the polymerization for 4 to 8 hours; And
Mixing the reactants of the second step and the catalyst amount excluding the catalysts used in the first step and the second step at a total amount of the catalyst, and allowing the polymerization to proceed for 10 to 14 hours.
5. The method of claim 4,
Wherein the polymerization temperature is 5 to 15 占 폚.
5. The method of claim 4,
Further comprising degassing the catalyst using Ar gas before mixing the catalyst in the second and third steps.
5. The method of claim 4,
Wherein the conductive polymer comprises a repeating unit represented by the following formula (1): < EMI ID =
[Chemical Formula 1]

In Formula 1,
X and Y each independently represent O, S, Si or N,
R ₁ and R ₂ each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 3 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms,
n is an integer from 2 to 2000,
Alternatively, R ₁ and R ₂ are bonded to each other to represent a fused ring structure.
5. The method of claim 4,
Wherein the conductive polymer is PEDOT: PSS.
5. The method of claim 4,
Wherein the ionic polymer electrolyte comprises a monomeric anion or a polyanion.

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