TW201305273A - Electrically conductive polymer suspension and film having high ductility and high transparency - Google Patents

Abstract

The present invention relates to electrically conductive polymer suspension and film having high ductility and high transparency prepared from the same. The electrically conductive polymer suspension consists of a suspension of poly(3, 4-ethylenedioxythiophene) and a dispersion of soft polymer with Tg ≤ 25 DEG C. The film prepared from the polymer suspension comprises 1 to 44 wt.% of poly(3, 4-ethylenedioxythiophene) and 56 to 99 wt.% of soft polymer. The conductive film exhibits high ductility, high transparency and conductivity, and it is useful in the application of flexible display, clothes, packaging material for semiconductor, touch panel, electrode for solar cell etc.

Description

Conductive polymer suspension and conductive film made of the same with high ductility and high transparency

The present invention relates to a conductive polymer dispersion and a conductive film made of the same having high ductility and transparency.

Since 1977, conductive polymers have been discovered (Shirakawa, H., et al., Synthesis of Electrically Conducting Organic Polymers-Halogen Derivatives of Polyacetylene, (Ch) X. Journal of the Chemical Society-Chemical Communications, 1977 (16): p After 578-580.), research on this field has increased rapidly, and a series of organic polymers with good conductivity have been developed, including polyacetylene (PA) and heterocyclic polymers of unsaturated hydrocarbons. Polypyrrole (PPy), polythiophene (PT), polyfuran (PF), poly(3,4-ethylenedioxythiophene) (PEDOT), polyaniline (PAN) of aromatic polymers, unsaturated hydrocarbons and Poly(extended benzene) (PPV) of aromatic coexisting polymers.

While PEDOT was successfully developed by Bayer AG (Bayer, AG, Bayer AG , in European Patent. 1988. p. 339 340.) in early 1990, it has been highly experienced in the past decade due to its high electrical conductivity and stability. Attention. PEDOT itself is a polythiophene derivative, which has a lower oxidation potential and a smaller energy level difference, and since ethylenedioxythiophene (EDOT) does not generate a bond of α, β position like thiophene during polymerization, It can effectively control the structure of the polymer. In addition, PEDOT has a higher conductivity and its film also shows higher penetration and color contrast. PEDOT and its derivatives have many industrial applications, such as antistatic materials, light-emitting diodes (Rannou, P. and M. Nechtschein, Aging studies on polyaniline: Conductivity and thermal stability. Synthetic Metals, 1997. 84 ( 1-3): p. 755-756.), electrochromic element (Armelao, L., et al., High-Purity Wo3 Sol-Gel Coatings-Synthesis and Characterization. Journal of Materials Chemistry, 1994. 4 (3 ): p. 407-411.) and so on.

There are three main methods for the synthesis of PEDOT: Oxidative Chemical Polymerization, Electrochemical Polymerization, and Transition Metal-mediated coupling.

(1) Chemical oxidation polymerization

EDOT is a thiophene derivative, so EDOT can be polymerized by oxidative polymerization like thiophene. There are many oxidants to choose from, and FeCl ₃ and Fe(OTs) ₃ are typical. Upon completion of the reaction, PEDOT which is black, insoluble in a general organic solvent and having a high melting point is obtained. When FeCl ₃ is used as the oxidant, Kumer and Reynolds (Kumar, A. and JR Reynolds, Soluble alkyl-substituted poly(ethylenedioxythiophenes) as electrochromic materials. Macromolecules, 1996. 29 (23): p. 7629-7630.) [FeCl] ₃ /[EDOT] ratio is greater than 2, PEDOT is not easily soluble in organic solvents, and when the ratio is greater than or equal to 5, it will become completely insoluble. If Fe(OTs) ₃ is used as the oxidant, Deleeuw et al. (Deleeuw, DM, et al., Electroplating of Conductive Polymers for the Metallization of Insulators. Synthetic Metals, 1994. 66 (3): p. 263-273.) The addition of imidazole as a base at elevated temperatures (as shown in Figure 1) produces a black insoluble material which, after purification with water and butanol, has a conductivity of 550 S/cm.

At present, the most practical value is the "BAYTRON P." developed by Bayer AG, which uses a liquid polymer electrolyte (usually polystyrene sulfonate, PSS) and Na ₂ S ₂ O ₈ as an oxidant. Reaction at room temperature to obtain a dark blue PEDOT/PSS suspension (as shown in Figure 2), with very high conductivity (400-600 S/cm), high penetration, electrochemical stability, heat after proper doping Stability (Aleshin, AN, SR Williams, and AJ Heeger, Transport properties of poly(3,4-ethylenedioxythiophene)/poly(styrene-sulfonate) . Synthetic Metals, 1998. 94 (2): p. 173-177; Kirchmeyer , S. and K. Reuter, Scientific importance, properties and growing applications of poly(3,4-ethylenedioxythiophene) (vol 15, pg 2077 , 2005 ) . Journal of Materials Chemistry, 2005. 15 (23): p. 2338- 2338.). When dried, PEDOT/PSS becomes a transparent conductive film which is mechanically strong and insoluble in a general solvent.

(2) Electrochemical polymerization

Electroenergetic polymerization (Groenendaal, L., et al., Electrochemistry of poly(3,4-alkylenedioxythiophene) derivatives . Advanced Materials, 2003. 15 (11): p. 855-879.) for EDOT with multiple electrons and Its derivatives are a very useful polymerization method, mainly by the application of voltage to cause the transfer of electrons to produce further polymerization. Only a small amount of monomer and a very short reaction time can be used to obtain a high-transparency, conductive, sky-blue PEDOT film at the cathode, and the electrochemically polymerized film can quickly and easily measure its electrochemical properties. With optical properties. The main disadvantage is that the obtained polymer yield is small, and most of them are insoluble, so that the polymer produced by electrochemical polymerization cannot be structurally analyzed such as NMR and GPC. Different electrolytes are also compatible for the polymerization of EDOT derivatives, such as Wernet et al. (Yamato, H., et al., Synthesis of free-standing poly(3,4 - ethylenedioxythiophene) conducting polymer films on a pilot scale Synthetic Metals, 1996. 83 (2): p. 125-130.) Using a polymer solution as an electrolyte and Lacaze et al. (Sakmeche, N., et al., Application of sodium dodecylsulfate (SDS) micellar solution as an Organic medium for electropolymerization of thiophene derivatives in water . Synthetic Metals, 1997. 84 (1-3): p. 191-192.) The use of a microcell solution as a electrolyte has good results.

(3) Transition metal-mediated coupling

Since EDOT is a derivative of thiophene, EDOT can also be polymerized into PEDOT by a coupling reaction using a metal complex as a catalyst, such as NiCl ₂ or PdC ₂ as a catalyst (as shown in Reaction Scheme 3). Many monomers with thiophene functional groups are suitable for polymerization in this way, Yamamoto et al. (Yamamoto, T., et al., Temperature dependent electrical conductivity of p-doped poly(3,4-ethylenedioxythiophene) and poly( 3-alkylthiophene)s . Polymer Bulletin, 1999. 42 (3): p. 321-327.) Low molecular weight neutral PEDOT is directly produced by this method.

Although the film produced by PEDOT described above is electrically conductive, it also has the disadvantage of being brittle and having poor transparency. The present inventors conducted extensive research based on the shortcomings of the PEDOT, and found that by incorporating a soft polymer into the PEDOT, not only the original conductivity of the PEDOT can be retained, but also the film made from the mixture is highly malleable and transparent. Luminosity, thus completing the present invention.

The present invention relates to a conductive polymer suspension, which is based poly (3,4-ethylenedioxy thiophene) suspensions and glass transition temperature T _g of less than or equal to 25 deg.] C of the soft polymer dispersion formed, and After the conductive suspension is formed into a film, it comprises 1 to 44% by weight of poly(3,4-ethylenedioxythiophene) and 56 to 99% by weight of a soft polymer.

The conductive polymer suspension according to the present invention, wherein the poly(3,4-ethylenedioxythiophene) suspension further contains a dispersing agent in an amount of 0.1 to 10% by weight based on the total weight of the suspension.

A conductive polymer suspension according to the present invention, wherein the soft polymer is selected from the group consisting of styrene, vinyl acetate (VAc), methyl methacrylate (MMA), methoxyethyl acrylate (MEA), N , N-methylenebisacrylamide (MBA), methacrylic acid (MAA), acrylic acid (AA), methyl acrylate (MA), butyl acrylate (BA), ethyl acrylate (EA), ethyl acrylate A monomer of a group consisting of hexyl ester (EHA), aniline (AN), and urethane is a soft copolymer having a _Tg of 25 ° C or less obtained by copolymerization of two or more.

The conductive polymer suspension according to the present invention, wherein the soft polymer dispersion comprises 0.1 to 10% by weight, based on the total weight of the dispersion, of at least one emulsifier selected from the group consisting of an anionic type, a nonionic emulsifier, and a polymeric emulsifier.

The conductive polymer suspension according to the present invention, wherein the emulsifier used in the soft polymer dispersion is a nonionic emulsifier and is selected from the group consisting of ester type, ether type, amine type, guanamine type and polyol type emulsifier. At least one of them.

The conductive polymer suspension according to the present invention, wherein the emulsifier used in the soft polymer dispersion is a nonionic emulsifier selected from the group consisting of propylene glycol fatty acid esters, glycerin fatty acid esters, sucrose fatty acid esters, and polyoxyethylene oxides. At least one of a group ether, a polyoxyethylene alkylamine, an alkanolamine, a polyoxyethylene alkylguanamine, a lauric acid monoglyceride, and a sorbitan fatty acid sodium.

The conductive polymer suspension according to the present invention, wherein the emulsifier used in the soft polymer dispersion is an anionic emulsifier and is selected from the group consisting of fatty acid salts, sulfates, sulfonates, and phosphate ester emulsifiers. At least one of them.

The conductive polymer suspension according to the present invention, wherein the emulsifier used in the soft polymer dispersion is an anionic emulsifier selected from the group consisting of sodium stearate, sodium laurate, sodium oleate, sodium lauryl sulfate, At least one of sodium cetylbenzenesulfonate and dodecylbenzenesulfonic acid.

The conductive polymer suspension according to the present invention, wherein the emulsifier used in the soft polymer dispersion is a polymeric emulsifier, and is selected from the group consisting of poly(vinylpyrrolidone) (PVP) and polyvinyl alcohol (PVA). At least one of a group consisting of polystyrene sulfonate (PPS), poly(ethylene oxide) (PEO), and poly(propylene oxide) (PPO).

The invention further relates to a conductive film having high ductility and transparency, which is obtained by forming a film of the conductive polymer suspension, and has a conductivity of 0.03 to 235 S/cm and a visible light of 400 to 700 nm. The penetration within the range is ≧75%, and the surface resistance is 100~1,000,000 Ω/□, and the ductility is 1~97%.

The film formation of the conductive polymer suspension can be carried out on a substrate (for example, a glass substrate) by various film formation methods such as a dip coating method or a spin coating method.

The highly ductile and transparent conductive film of the present invention can be used for a folding display, a clothing, a semiconductor packaging material, a touch panel, a solar cell electrode, and the like.

The aqueous conductive polymer suspension of the present invention is prepared by separately preparing a suspension of poly(3,4-ethylenedioxythiophene) and a latex dispersion of a soft polymer, and then adding dimethyl hydrazine (DMSO). Mix. The aqueous conductive polymer suspension thus obtained can be subsequently subjected to a process film such as a spin coating method or a dip coating method to obtain a conductive film having high ductility and transparency.

The preparation of the latex dispersion of the suspension of poly(3,4-ethylenedioxythiophene) and the soft polymer is described as follows.

(A) Preparation of poly(3,4-ethylenedioxythiophene) suspension

The poly(3,4-ethylenedioxythiophene) used in the aqueous suspension of the conductive polymer of the present invention is prepared by making the 3,4-ethylenedioxythiophene monomer 0.1 to 10% by weight in the suspension. In the presence of a dispersing agent, 0.1 to 10% by weight of the first oxidizing agent and 0.01% to 10% by weight of the second oxidizing agent are used in the presence of a solvent to react in a nitrogen atmosphere. The dispersant may, for example, be, for example, polystyrene sulfonate (PSS) having a molecular weight of 1000 to 100,000, etc., and the first oxidizing agent may, for example, be potassium persulfate (KPS, K ₂ S ₂ O ₈ ) or sodium persulfate ( SPS, Na ₂ S ₂ O ₈ ), ammonium persulfate (APS, (NH ₄ ) ₂ S ₂ O ₈ ), sodium metabisulfite (Na ₂ S ₂ O ₅ ), sodium hydrogen sulfite (NaHSO ₃ ), second oxidant For example, it is iron sulfate (Fe ₂ (SO ₄ ) ₃ ) hydrate, iron chloride (FeCl ₃ ), or the like. As the solvent, water, a water-miscible alcohol such as a C _1-4 alkanol or the like can be used. The reaction system firstly disperses the 3,4-ethylenedioxythiophene monomer and the dispersant by ultrasonic vibration at room temperature, and then stirs the first and second oxidants, and then, after 7 hours, the mixture is stirred. The first oxidizing agent is further reacted at room temperature to obtain a stable conductive suspension of poly(3,4-ethylenedioxythiophene) and a dispersing agent.

(B) Preparation of soft polymer dispersion (B1) emulsion polymerization

The monomer is present in the presence of an anionic emulsifier or a nonionic emulsifier at a concentration of 0.1 to 10 wt.% and under acidic conditions in the presence of a polymerization initiator of 0.01 to 20 mol.% relative to the monomer. First, stirring at 0 to 100 ° C for 1 minute to 24 hours, followed by polymerization at 50 to 120 ° C for 30 minutes to 24 hours to obtain a latex particle dispersion.

In order to disperse the oil droplets during the reaction, a homogenizer or an ultrasonic oscillator may be used before the polymerization reaction.

Examples of the monomer which can be used in the reaction are, for example, styrene, vinyl acetate, methyl methacrylate, methoxyethyl acrylate, N,N-methylenebisacrylamide, methacrylic acid, acrylic acid, acrylic acid. At least one of a group consisting of methyl ester, butyl acrylate, ethyl acrylate, ethyl hexyl acrylate, polyaniline, and polyurethane, and the obtained polymer may be a homopolymer of the monomers. The copolymer is a soft copolymer having a _{Tg of} less than or equal to 25 ° C obtained by copolymerization. .

The nonionic emulsifier usable in the reaction is selected from at least one of an ester type, an ether type, an amine type, a guanamine type, and a polyol type emulsifier, and examples thereof include propylene glycol fatty acid esters and glycerin fatty acid esters. At least one of sucrose fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkylamine, alkanolamine, polyoxyethylene alkylguanamine, lauric acid monoglyceride, and sorbitan fatty acid sodium. For example, the Tween series and the SPAN series are marketed.

The anionic emulsifier usable in the reaction is at least one selected from the group consisting of fatty acid salts, sulfates, sulfonates, and phosphate ester emulsifiers, and examples thereof include sodium stearate, sodium laurate, and oleic acid. At least one of sodium, sodium lauryl sulfate (DBSA), sodium cetylbenzenesulfonate, and dodecylbenzenesulfonic acid.

The initiator used in the reaction may be, for example, azobisisobutyronitrile (AIBN), benzammonium peroxide (BPO), potassium persulfate (KPS, K ₂ S ₂ O ₈ ), sodium persulfate (SPS, Na ₂ S ₂ O ₈ ), ammonium persulfate (APS, (NH ₄ ) ₂ S ₂ O ₈ ), sodium metabisulfite (Na ₂ S ₂ O ₅ ), sodium hydrogen sulfite (NaHSO ₃ ), and the like.

(B2) Dispersion polymerization

In the presence of a polymer type emulsifier having a concentration of the monomer in the dispersion of 0.1 to 10% by weight, in the presence of a polymerization initiator of 0.01 to 20 mol.% relative to the monomer, under a nitrogen atmosphere, The mixture was stirred at 0 to 100 ° C for 1 minute to 24 hours, and then further polymerized at 50 to 120 ° C for 30 minutes to 24 hours to obtain a latex particle dispersion.

This dispersion polymerization is preferably carried out in a solvent mixture of water and a C _1-6 alkanol.

The monomer usable in the reaction is the same as the above (B1) emulsion polymerization method, and the polymer type emulsifier can be exemplified by, for example, poly(vinylpyrrolidone) (PVP), polyvinyl alcohol (PVA), polystyrene sulfonate. Acid salt (PSS), poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO), and the like.

The initiator used in the reaction may be, for example, azobisisobutyronitrile (AIBN), 1,1'-azobis(cyclohexanecarbonitrile) (ABCN), benzammonium peroxide (BPO), Potassium sulfate (KPS), ammonium persulfate (APS), sodium persulfate (SPS), sodium metabisulfite, and the like.

The invention will be specifically described by the following examples, but these examples are for illustrative purposes only and are not intended to limit the scope of the invention.

[Examples] Preparation example (1) Preparation of PEDOT:PSS stable conductive suspension

This preparation example employs an emulsion polymerization reaction. First, 1.736 g of polystyrenesulfonic acid (PSS) (Mw = 75,000) was dissolved in 11.698 g of water, and after stirring, monomer 3,4-ethylenedioxythiophene (EDOT) 0.125 g was added and stirred for 1 minute. Ultrasonic vibration was used for 15 minutes, at which time the emulsion showed yellow turbidity. Then, the mixture was stirred under nitrogen for 10 minutes at room temperature, and an oxidizing agent potassium persulfate (KPS) and an aqueous solution of Fe ₂ (SO ₄ ) ₃ ‧5H ₂ O (0.2835 g KPS dissolved in 5 g of water/0.0019 g Fe ₂ (SO ₄ ) were added. ₃ ‧5H ₂ O is dissolved in 1 g of water), and the reaction is fully filled with nitrogen and maintained under stirring. After 7 hours, an aqueous KPS solution (0.0473 g KPS dissolved in 2 g water) was added. The reaction was then carried out for 17 hours to obtain a PEDOT:PSS conductive suspension.

(2) Preparation of soft polymer (P(BA-St)) latex particle dispersion (emulsification polymerization method)

1 g of an anionic emulsifier (such as dodecylbenzenesulfonic acid, DBSA) or 3.761 g of a nonionic emulsifier (Tween 20, n=20 of the structure shown below) is dissolved in 100 g of water in a reaction flask. Stir well. The pre-dissolved starter and monomer mixture was added to the reaction flask (0.168 g AIBN/8.4 g butyl acrylate (BA) / 2.8 g styrene (St)), and stirred at room temperature for one hour. The homogenizer oscillates for 30 minutes. The turbulent suspension was reacted at 80 ° C for two hours, and the whole process was filled with nitrogen and stirred to obtain a P (BA-St) latex particle dispersion.

(3) Preparation of soft polymer (P(BA-MMA)) latex particle dispersion (dispersion polymerization method)

An appropriate amount of a polymeric emulsifier (for example, poly(vinylpyrrolidone), PVP, molecular weight: 360,000) of the following formula was dissolved in a reaction flask in a methanol aqueous solution (44.6 g of methanol + 44.6 g of water) and stirred uniformly. A mixture of the pre-dissolved starter and the monomer shown in Table 1 below was added to the reaction flask (0.1 g AIBN/xg BA/yg MMA), and reacted at 70 ° C for six hours, and the whole process was filled with nitrogen gas. After stirring, a P(BA-MMA) latex particle dispersion can be obtained.

Note: The numbers in parentheses above indicate the weight percentage in the monomer. For example, P(BA50-MMA) means that the BA monomer accounts for 50 wt.% of all monomers.

Example Preparation of PEDOT:PSS/soft polymer stable conductive suspension

The PEDOT:PSS/soft polymer stable conductive suspension prepared in this embodiment is a PEDOT:PSS conductive suspension synthesized and purified in part (1) of the preparation example by using a mixing method, and the preparation example (2) or (3) The soft latex particle dispersion prepared in the section was mixed and doped with a little dimethyl hydrazine (DMSO). The mixing ratio is shown in Table 2 and Table 3 below:

Note: sample number PECO indicates a mixture of PEDOT only: PSS conductive suspension and DMSO, PEB indicates a mixture of PEDOT:PSS conductive suspension and soft latex particle dispersion, and D indicates that the soft polymer is DBSA as emulsifier and based on Prepared in the preparation of part (2), T indicates that the soft polymer was selected from Tween 20 as an emulsifier and prepared according to the preparation of the part (2).

Note: Sample No. PEB indicates a mixture of PEDOT:PSS conductive suspension and soft latex particle dispersion. The number shown after PV indicates the proportion of monomer BA in soft polymer. For example, PV50 means BA accounts for BA and MMA. The total body weight is 50 wt.%.

Comparative example 1 Preparation of soft polymer (P(BA-St)) latex particle dispersion (emulsion polymerization method)

In a reaction flask, 1.12 g of a cationic emulsifier CTAB (Cetyl trimethylammonium bromide) was dissolved in 100 g of water and stirred well. The pre-dissolved starter and monomer mixture was added to the reaction flask (0.168 g AIBN/8.4 g butyl acrylate (BA) / 2.8 g styrene (St)), and stirred at room temperature for one hour. The homogenizer oscillates for 30 minutes. The turbulent suspension was reacted at 80 ° C for two hours to obtain a P(BA-St)_CTAB latex particle dispersion. When the PEDOT:PSS conductive suspension is mixed with the P(BA-St)_CTAB dispersion, agglomeration occurs and agglomeration occurs, and a uniform dispersion cannot be obtained.

Test case PEDOT: PSS/soft polymer stable conductive suspension properties and its conductive film properties test (1) Thermal property test

The mixing ratio of the different formulations PEDOT configured: PSS / soft polymer stabilized conductive suspension, which was dried into a powder, the thermal analysis using DSC properties T _g. Its T _g point is shown in Table 4 below.

(2) Conductivity and transparency test

A small amount of conductive suspension was taken, a conductive film was formed on the glass slide by spin coating, the resistance value was measured with a three-meter electric meter, and the thickness was measured by a surface profile meter (α-step), thereby converting the film conductivity. The transparency of the conductive film in the visible light range was measured by an ultraviolet-visible spectrometer (UV-vis).

(3) ductility test

Another part of the obtained conductive suspension was dropped into a Teflon mold, dried at 50 ° C for 1 day, and cut into a ductile film of 6 cm * 1 cm. The thickness was set to be about 0.06 mm, and the tension was pulled using a universal tension machine. Tests can include mechanical properties such as elongation and maximum tensile strength. The ductility test results measured for PEB_D1, PEB_D2 and PEB_D3 are shown in Fig. 1.

As can be seen from Figure 1, the electrically conductive suspension of the present invention is malleable, especially PEB_D3 has a ductility of up to 97%.

The operating conditions of the instruments used in each of the above tests are shown in Table 5 below:

The test results are described in Tables 6 to 9 below.

It can be seen from the above data that the film made of the conductive polymer suspension of the present invention has good conductivity and transparency, and has a transmittance of about 80% even at a thickness of up to 1000 nm, and is in the second column of Table 9. And in the eighth column, it can be seen that the PEDOT:PSS addition amount is as low as 1 wt.%, and the conductivity can also be exhibited. Therefore, the conductive property can be obtained by adding a small amount of PEDOT:PSS, and thus the conductive polymer suspension is prepared. The film, as shown by the ductile results in Figure 1, is ductile, especially for PEB_D3, with a ductility of up to 97%, which can be used in a variety of films that require both conductivity and ductility, such as touch For folding displays, clothing, semiconductor packaging materials, touch panels, solar cell electrodes, etc.

Figure 1 shows the ductility results of a film made from the conductive polymer suspension of the present invention.

Claims (11)

A conductive polymer suspension composed of a poly(3,4-ethylenedioxythiophene) suspension and a soft polymer dispersion having a glass transition temperature _{Tg of} less than or equal to 25 ° C, and when the conductive The polymer suspension is prepared into a film comprising 1 to 44% by weight of poly(3,4-ethylenedioxythiophene) and 56 to 99% by weight of a soft polymer. The conductive polymer suspension of claim 1, wherein the poly(3,4-ethylenedioxythiophene) suspension further comprises a dispersant in an amount of from 0.1 to 10% by weight based on the total weight of the suspension. The conductive polymer suspension according to claim 1, wherein the soft polymer is selected from the group consisting of styrene, vinyl acetate (VAc), methyl methacrylate (MMA), and methoxyethyl acrylate ( MEA), N,N-methylenebisacrylamide (MBA), methacrylic acid (MAA), acrylic acid (AA), methyl acrylate (MA), butyl acrylate (BA), ethyl acrylate (EA) a monomer composed of a group consisting of ethyl hexyl acrylate (EHA), aniline (AN), and urethane, which is homopolymerized or copolymerized by two or more to obtain a soft copolymer having a T _g of 25 ° C or lower. Things. The conductive polymer suspension according to claim 1, wherein the soft polymer dispersion comprises at least 0.1 to 10% by weight of the total weight of the dispersion selected from the group consisting of an anionic type, a nonionic emulsifier and a high molecular emulsifier. An emulsifier. The conductive polymer suspension according to claim 4, wherein the emulsifier used in the soft polymer dispersion is a nonionic emulsifier and is selected from the group consisting of ester type, ether type, amine type, guanamine type and plural At least one of alcohol type emulsifiers. The conductive polymer suspension according to claim 5, wherein the nonionic emulsifier is selected from the group consisting of propylene glycol fatty acid esters, glycerin fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene oxides. At least one of a base amine, an alkanolamine, a polyoxyethylene alkylguanamine, a lauric acid monoglyceride, and a sorbitan fatty acid sodium. The conductive polymer suspension according to claim 4, wherein the emulsifier used in the soft polymer dispersion is an anionic emulsifier and is selected from the group consisting of fatty acid salts, sulfates, sulfonates, and phosphate esters. At least one of a salt emulsifier. The conductive polymer suspension according to claim 7, wherein the anionic emulsifier is selected from the group consisting of sodium stearate, sodium laurate, sodium oleate, sodium lauryl sulfate, and cetylbenzenesulfonate. At least one of sodium acid and dodecylbenzenesulfonic acid. An aqueous suspension of a conductive polymer according to claim 4, wherein the emulsifier used in the soft polymer dispersion is a polymeric emulsifier and is selected from the group consisting of poly(vinylpyrrolidone) and polyvinyl alcohol. At least one of a group consisting of polystyrene sulfonate, poly(ethylene oxide), and poly(propylene oxide). A conductive film having high ductility and transparency, which is obtained by forming a film of an aqueous conductive polymer suspension according to any one of claims 1 to 9 and having a conductivity of 0.03 to 235 s. /cm, the transmittance in the visible range of 400 to 700 nm is ≧75%, and the surface resistance is 100~1,000,000 Ω/□. The ductile film having high ductility and transparency, as in claim 10, has a ductility of 1 to 97%.