JP7151065B2 - Conductive polymer aqueous solution and its use - Google Patents

Description

The present invention provides a novel conductive polymer aqueous solution capable of producing a conductive polymer film having both good hole transportability and durability, and an organic electronic element excellent in durability using the same. An object of the present invention is to provide an organic photoelectric light-emitting device or an organic electroluminescence device. Specifically, it is an aqueous solution of a novel conductive composition characterized by containing a specific self-doping type conductive polymer having high conductivity and a specific water-soluble resin, and further obtained by drying them. The present invention relates to a conductive polymer film and its use.

Conductive polymer materials have been developed by doping π-conjugated polymers such as polyacetylene, polythiophene, polyaniline, and polypyrrole with electron-accepting compounds as dopants. Applications to paints, electromagnetic wave shields, electrochromic devices, electrode materials, hole injection materials, thermoelectric conversion materials, transparent conductive films, chemical sensors, actuators, etc. are being investigated. Among these conductive polymer materials, polythiophene-based conductive polymer materials are practically useful in terms of chemical stability.

As a polythiophene-based conductive polymer material, (i) PEDOT/PSS aqueous dispersion obtained by polymerizing 3,4-ethylenedioxythiophene (EDOT) in an aqueous solution of polystyrene sulfonic acid (PSS) as a dopant. and (ii) a so-called self-doping conductive polymer (ii) having a substituent group (sulfo group, sulfonate group, etc.) that has both water-solubility and doping action in the polymer main chain directly or via a spacer ( For example, sulfonated polyaniline, PEDOT-S, etc.) are known (see, for example, Non-Patent Documents 1 and 2).

In recent years, the applications of conductive polymers are not limited to conventional antistatic agents and solid electrolytes in solid electrolytic capacitors, but also transparent conductive films ( transparent electrode, etc.) (for example, Patent Document 1). For example, in applications such as organic EL devices, a conductive polymer is used to coat the cathode ITO to form a smooth anode layer. It is known that PEDOT/PSS can be applied for this purpose, but with regard to PEDOT/PSS, the sulfonate ions decomposed and released from PSS migrate to the anode interface of the organic EL, causing a quenching phenomenon. It has been found that this has been a problem for practical use (Non-Patent Document 3). Therefore, in particular, from the viewpoint of extending the life of the device, the conductive polymer composition itself used should have high durability of the compound or composition itself (heat resistance, moisture resistance, withstand voltage in a solid or coating state) characteristics) are becoming necessary.

Japanese Patent Publication No. 2000-514590

Journal of American Chemical Society, 112, 2801-2803 (1990) Advanced Materials, Vol. 23 (38) 4403-4408 (2011) Characteristics of PEDOT, synthesis method and device application (information mechanism)

As described above, PEDOT/PSS has a durability problem such as gradual decomposition to generate sulfonate ions from PSS. For this reason, there is an increasing demand for highly durable conductive polymer membranes that are capable of suppressing decomposition such as liberation of sulfonate ions, are resistant to quenching phenomena, and exhibit little increase in surface resistance. At the same time, there is also a demand for a conductive polymer aqueous solution that has good applicability to conductive metal oxides, low damage properties, and high smoothing ability.

Further, an object of the present invention is to provide a conductive polymer film having both hole transportability and durability that can extend the life of organic electronic devices, organic photoelectric conversion devices, organic electroluminescence devices, and the like, and the film. It is to provide a conductive polymer aqueous solution for production.

The present inventors have made intensive studies to solve the above problems, and found that a self-doping conductive polymer having a repeating unit represented by the general formula described later, a polyacrylic acid-based water-soluble resin, and a glycol ether A conductive polymer film produced from an aqueous conductive polymer solution comprising The inventors have found that an organic photoelectric conversion element or an organic electroluminescence element has excellent durability, and completed the present invention.

That is, the present invention relates to a conductive polymer aqueous solution composition, a conductive polymer film, and an organic electronic device, organic photoelectric conversion device, and organic electroluminescence device using the same, as shown below.

That is, the present invention relates to a conductive polymer aqueous solution composition, a conductive polymer film, and an organic electronic device, organic photoelectric conversion device, and organic electroluminescence device using the same, as shown below.
[1] Polythiophene (A ), 0.001 to 20% by weight of polyacrylic acid-based water-soluble resin (B), and 0.5 to 60% by weight of glycol ether (C).

[In the above formulas (1) and (2), L represents the following formula (3) or (4), and M represents a hydrogen ion, an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium cation. show. ]

[In the above formula (3), l represents an integer of 6 to 12. ]

[In the above formula (4), m represents an integer of 1 to 6. R2 represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a fluorine atom. ]
[2] The aqueous conductive polymer solution according to [1], which has a viscosity of 20 mPa·s or less at 20° C. and a surface tension of 20 to 50 mN/m.
[3] Polyacrylic acid-based water-soluble resin is polyacrylic acid water-soluble resin or polymethacrylic acid water-soluble resin (B), the conductive high according to [1] or [2] Molecular aqueous solution.
[4] The aqueous conductive polymer solution according to any one of [1] to [3], wherein the polyacrylic acid-based water-soluble resin (B) has a weight average molecular weight of 1,000 to 1,000,000.
[5] A method for producing a conductive film, comprising drying the aqueous conductive polymer solution according to [1].

The conductive polymer film produced from the novel conductive polymer aqueous solution of the present invention has an unexpectedly remarkable effect of having higher hole transport performance and durability than conventionally known conductive polymers. play. Therefore, the conductive polymer aqueous solution and the conductive polymer film using the aqueous solution of the present invention are expected to significantly improve the durability and performance of organic electronic devices, organic photoelectric conversion devices, and organic electronic devices. effect. In addition, the aqueous conductive polymer solution of the present invention and the conductive polymer film using the same can be organically dispersed at a lower temperature and/or for a shorter time than conventionally known conductive polymer aqueous solutions. Since it exhibits good performance as a hole-injecting layer for EL devices, it has the effect of being excellent in operability and productivity in the production of organic EL devices.

The present invention will be described in detail below.

The present invention provides 0.01 to 10% by weight of a polythiophene ( A), 0.001 to 20% by weight of polyacrylic acid-based water-soluble resin (B), and 0.5 to 60% by weight of glycol ether (C).

[In the above formulas (1) and (2), L represents the following formula (3) or (4), and M represents a hydrogen ion, an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium cation. show. ]

[In the above formula (3), l represents an integer of 6 to 12. ]

[In the above formula (4), m represents an integer of 1 to 6. R ² represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a fluorine atom. ]
In formula (1) or (2) above, M represents a hydrogen ion, an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium cation.

Li ions, Na ions, and K ions are preferable as the alkali metal ions.

The conjugate acid of the amine compound may be any amine compound that forms a conjugate acid by reacting with a sulfonic acid group to form a cationic species by addition of hydron (H ⁺ ) to the amine compound. An amine compound represented by N(R ¹ ) ₃ having an sp3 hybrid orbital [represented by [NH(R ¹ ) ₃ ] ⁺ as a conjugate acid. ], or an amine compound having an sp2 hybrid orbital (for example, a pyridine compound, an imidazole compound), or the like.

Each substituent R ¹ independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms having a substituent.

The alkyl group having 1 to 6 carbon atoms is not particularly limited, but examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, 2-ethylbutyl group, cyclohexyl group and the like.

Examples of the substituted alkyl group having 1 to 6 carbon atoms include a halogen atom, an alkyl group having 1 to 6 carbon atoms, an amino group, or an alkyl group having 1 to 6 carbon atoms and having a hydroxy group. Specific examples include a trifluoromethyl group, a 2-hydroxyethyl group and the like.

Among these, the substituent R ¹ is independently preferably a hydrogen atom, a methyl group, an ethyl group, or a 2-hydroxyethyl group.

The amine compound having an sp2 hybrid orbital is not particularly limited, but examples thereof include ammonia, methylamine, dimethylamine, ethylamine, triethylamine, normal-propylamine, isopropylamine, normal-butylamine, tertiary-butylamine, and hexylamine. , ethanolamine compounds (e.g., aminoethanol, dimethylaminoethanol, methylaminoethanol, diethanolamine, N-methyldiethanolamine, triethanolamine), 3-amino-1,2-propanediol, 3-methylamino-1,2- propanediol, 3-dimethylamino-1,2-propanediol, 1,4-butanediamine and the like.

The amine compound having the sp2 hybrid orbital is not particularly limited, but examples thereof include imidazole compounds (eg, imidazole, N-methylimidazole, 1,2-dimethylimidazole), pyridinepicoline, lutidine, and the like. be done. Among these, ethanolamine compounds and imidazole compounds are preferred.

That is, the conjugate acid of the amine compound is preferably ammonium, the conjugate acid of monoethanolamine, the conjugate acid of diethanolamine, the conjugate acid of triethanolamine, or the conjugate acid of imidazole in terms of excellent conductivity.

Examples of the quaternary ammonium cations include tetramethylammonium cations, tetraethylammonium cations, tetra-normal propylammonium cations, tetra-normal butylammonium cations, and tetra-normal hexylammonium cations. Tetramethylammonium cations and tetraethylammonium cations are preferred from the standpoint of availability.

In the above formula (3), l represents an integer of 6-12, preferably an integer of 6-8.

In formula (4) above, R ² represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a fluorine atom.

The linear or branched alkyl group having 1 to 6 carbon atoms is not particularly limited, but examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec -butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, 2-ethylbutyl group, cyclohexyl group and the like.

R ² in formula (4) is preferably a hydrogen atom, a methyl group, an ethyl group, or a fluorine atom from the viewpoint of film-forming properties.

In the above formula (4), m represents an integer of 1 to 6, preferably m is an integer of 1 to 4, more preferably 2.

The structural unit represented by the above formula (2) represents the doping state of the structural unit represented by the above formula (1).

Dopants that cause an insulator-metal transition upon doping can be divided into acceptors and donors. The former enters the vicinity of the polymer chain of the conductive polymer by doping and deprives the conjugated system of the main chain of π electrons. As a result, positive charges (holes, holes) are injected onto the main chain, so they are also called p-type dopants. The latter, on the contrary, gives electrons to the conjugated system of the main chain, and since these electrons move in the conjugated system of the main chain, it is also called an n-type dopant.

The dopant in the present invention is a sulfo or sulfonate group covalently attached within the polymer molecule and is a p-type dopant. Polymers that exhibit conductivity without the addition of dopants from the outside are called self-doping polymers.

The polythiophene (A) of the present invention can be produced by polymerizing a thiophene monomer represented by the following formula (5) in water or an alcohol solvent in the presence of an oxidizing agent.

[In the above formula (5), L has the same definition as above. M represents a metal ion. ]
Metal ions represented by M in formula (5) are not particularly limited, but transition metal ions, noble metal ions, nonferrous metal ions, alkali metal ions (e.g., Li ions, Na ions, and K ions). , alkaline earth metal ions, and the like.

Since the polymer after polymerization is a metal salt, M can be converted to a hydrogen ion by subjecting the obtained polymer to an acid treatment, if necessary. It can be converted to the conjugate acid of the compound.

Specifically, the thiophene monomer for obtaining the polythiophene of the present invention, in which L is represented by the above formula (3) in the above formula (1) or (2), is 6-(2,3-dihydro -thieno[3,4-b][1,4]dioxin-2-yl)hexane-1-sulfonic acid, 6-(2,3-dihydro-thieno[3,4-b][1,4]dioxin -2-yl)sodium hexane-1-sulfonate, 6-(2,3-dihydro-thieno[3,4-b][1,4]dioxin-2-yl)lithium-hexane-1-sulfonate, 6 Potassium -(2,3-dihydro-thieno[3,4-b][1,4]dioxin-2-yl)hexane-1-sulfonate, 8-(2,3-dihydro-thieno[3,4- b][1,4]dioxin-2-yl)octane-1-sulfonic acid, 8-(2,3-dihydro-thieno[3,4-b][1,4]dioxin-2-yl)octane- Examples include sodium 1-sulfonate and potassium 8-(2,3-dihydro-thieno[3,4-b][1,4]dioxin-2-yl)octane-1-sulfonate.

Specifically, the thiophene monomer for obtaining the polythiophene of the present invention, in which L is represented by the above formula (4) in the above formula (1) or (2), is 3-[(2,3- Sodium dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-propanesulfonate, 3-[(2,3-dihydrothieno[3,4-b]-[1, 4]dioxin-2-yl)methoxy]-1-potassium propanesulfonate, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1 - sodium methyl-1-propanesulfonate, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-ethyl-1-propanesulfonic acid sodium, sodium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-propyl-1-propanesulfonate, 3-[(2, Sodium 3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-butyl-1-propanesulfonate, 3-[(2,3-dihydrothieno[3,4- Sodium b]-[1,4]dioxin-2-yl)methoxy]-1-pentyl-1-propanesulfonate, 3-[(2,3-dihydrothieno[3,4-b]-[1,4] Dioxin-2-yl)methoxy]-1-hexyl-1-propanesulfonate, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy] Sodium 1-isopropyl-1-propanesulfonate, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-isobutyl-1-propane sodium sulfonate, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-isopentyl-1-propanesulfonate, 3-[( Sodium 2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-fluoro-1-propanesulfonate, 3-[(2,3-dihydrothieno[3, 4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonic acid potassium, 3-[(2,3-dihydrothieno[3,4-b]-[1, 4]dioxin-2-yl)methoxy]-1-methyl -1-propanesulfonic acid, 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonic acid ammonium, 3 -[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonic acid triethylammonium, 4-[(2,3- Sodium dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-butanesulfonate, 4-[(2,3-dihydrothieno[3,4-b]-[1, 4]dioxin-2-yl)methoxy]-1-butanesulfonic acid potassium, 4-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1 -sodium methyl-1-butanesulfonate, 4-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-butanesulfonic acid potassium, sodium 4-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-fluoro-1-butanesulfonate, and 4-[(2 ,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-fluoro-1-butanesulfonic acid potassium and the like.

In the present invention, the conductivity of the polythiophene (A) is not particularly limited, but it is preferably 10 S/cm or more as the conductivity (electrical conductivity) in the film state.

The present invention provides polythiophene (A) containing at least one structural unit selected from the group consisting of structural units represented by formula (1) and structural units represented by formula (2), in an amount of 0.01 to 10 % by weight. The concentration of the polythiophene (A) is preferably 0.02% by weight and 5.0% by weight, and 0.05% by weight and 3.0% by weight, from the viewpoint of exhibiting excellent performance as a hole injection material. more preferably 0.05% by weight and 2.0% by weight.

The polyacrylic acid-based water-soluble resin (B) in the present invention is not particularly limited, but may be a homopolymer or copolymer of an αβ unsaturated carboxylic acid compound such as acrylic acid, methacrylic acid and maleic acid. can be mentioned. Examples of the homopolymer include, but are not limited to, polyacrylic acid and polymethacrylic acid. The above-mentioned copolymer is obtained by copolymerizing at least one αβ-unsaturated carboxylic acid monomer, and the comonomer may be a monomer that can be copolymerized with the αβ-unsaturated carboxylic acid monomer. can. The copolymer is not particularly limited, but for example, poly(acrylic acid-methacrylic acid) copolymer, poly(acrylic acid-hydroxyethyl acrylate) copolymer, poly(acrylic acid-maleic acid) Copolymer, poly(acrylic acid-vinylsulfonic acid) copolymer, poly(acrylic acid-styrenesulfonic acid) copolymer, poly(methacrylic acid-styrenesulfonic acid) copolymer, poly(hydroxyethyl methacrylate-styrene) sulfonic acid) copolymers, and the like. The copolymer may be a block copolymer, a random copolymer, or an alternating polymer.

As the polyacrylic acid-based water-soluble resin (B), a polyacrylic acid water-soluble resin, a polymethacrylic acid water-soluble resin, or an acrylic acid copolymer water-soluble resin (B ), more preferably a polyacrylic acid water-soluble resin or a polymethacrylic acid water-soluble (B) resin.

Although the molecular weight of the polyacrylic acid-based water-soluble resin (B) of the present invention is not particularly limited, it is preferably 1,000 to 1,000,000, more preferably 150,000 to 500,000.

The present invention is characterized by containing 0.001 to 20% by weight of a polyacrylic acid-based water-soluble resin (B). The concentration of the polyacrylic acid-based water-soluble resin (B) is more preferably 0.1 to 10% by weight, more preferably 0.5% to 5% by weight, in terms of exhibiting excellent performance as a hole injection material. 0% by weight is more preferred.

In the conductive polymer aqueous solution of the present invention, from the group consisting of the polyacrylic acid-based water-soluble resin (B), the structural unit represented by the above formula (1), and the structural unit represented by the above formula (2) The weight ratio of the selected polythiophene (A) containing at least one structural unit is not particularly limited, but the weight ratio represented by (B)/(A) satisfies 0.05 to 40. It is preferably 0.1 to 30, more preferably 3 to 20.

The present invention is characterized by containing 0.5 to 60% by weight of glycol ether (C). The concentration of the glycol ether (C) is preferably 3.0 to 40% by weight, more preferably 5.0 to 30% by weight, in order to maintain smoothness during film formation.

Examples of the glycol ether (C) include, but are not particularly limited to, ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, or dipropylene glycol monoalkyl ether.

Examples of the ethylene glycol monoalkyl ether include, but are not limited to, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol mono iso-propyl ether, ethylene glycol mono n-butyl ether, ethylene glycol mono iso-butyl ether, ethylene glycol mono sec-butyl ether, ethylene glycol mono tert-butyl ether, ethylene glycol mono n-pentyl ether, ethylene glycol mono iso-pentyl ether, ethylene glycol mono neo-pentyl ether, ethylene Glycol mono-tert-pentyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol mono-iso-hexyl ether and the like can be mentioned.

Examples of the diethylene glycol monoalkyl ether include, but are not limited to, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono n-propyl ether, diethylene glycol mono iso-propyl ether, diethylene glycol mono n-butyl ether, diethylene glycol mono iso-butyl ether, diethylene glycol mono sec-butyl ether, diethylene glycol mono tert-butyl ether, diethylene glycol mono n-pentyl ether, diethylene glycol mono iso-pentyl ether, diethylene glycol mono neo-pentyl ether, diethylene glycol mono tert-pentyl ether, diethylene glycol mono n-hexyl ether , or diethylene glycol mono-iso-hexyl ether.

The propylene glycol monoalkyl ether is not particularly limited, but examples include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-propyl ether, propylene glycol mono iso-propyl ether, propylene glycol mono n-butyl ether, propylene glycol mono iso-butyl ether, propylene glycol mono sec-butyl ether, propylene glycol mono tert-butyl ether, propylene glycol mono n-pentyl ether, propylene glycol mono iso-pentyl ether, propylene glycol mono neo-pentyl ether, propylene Glycol mono-tert-pentyl ether, propylene glycol mono-n-hexyl ether, propylene glycol mono-iso-hexyl ether and the like can be mentioned.

Examples of the dipropylene glycol monoalkyl ether include, but are not limited to, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, and dipropylene glycol mono-iso-propyl. Ether, dipropylene glycol mono n-butyl ether, dipropylene glycol mono iso-butyl ether, dipropylene glycol mono sec-butyl ether, dipropylene glycol mono tert-butyl ether, dipropylene glycol mono n-pentyl ether, dipropylene glycol mono iso-pentyl ether, dipropylene glycol mono neo-pentyl ether, dipropylene glycol mono tert-pentyl ether, dipropylene glycol mono n-hexyl ether, dipropylene glycol mono iso-hexyl ether and the like.

Glycol ether (C) is preferably ethylene glycol monoalkyl ether or diethylene glycol monoalkyl ether from the viewpoint of excellent element life, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol. mono iso-propyl ether, ethylene glycol mono n-butyl ether, ethylene glycol mono iso-butyl ether, ethylene glycol mono sec-butyl ether, ethylene glycol mono tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono n-propyl ether, More preferred are diethylene glycol mono iso-propyl ether, diethylene glycol mono n-butyl ether, diethylene glycol mono iso-butyl ether, diethylene glycol mono sec-butyl ether, or diethylene glycol mono tert-butyl ether.

Glycol ether (C) may also be a mixture of the compounds exemplified above.

The conductive polymer aqueous solution of the present invention is an aqueous solution containing polythiophene (A), polyacrylic acid (B) and glycol ether (C), and the viscosity and surface tension of the aqueous solution at 20° C. are each 20 mPa·s or less. , and preferably 25 to 50 mN/m. From the viewpoint of wettability with the substrate, the viscosity and surface tension are more preferably 15 mPa·s or less and 20 to 35 mN/m.

A surfactant may be added to the conductive polymer aqueous solution of the present invention, if necessary. Examples of surfactants include molecular nonionic surfactants, amphoteric surfactants, fluorine-based surfactants, silicone-based surfactants, and the like.

Examples of the polymeric nonionic surfactant include, but are not particularly limited to, polyvinylpyrrolidone and a copolymer of polyvinylpyrrolidone. The average molecular weight of the polyvinylpyrrolidone used in the present invention is preferably 1,000 to 2,000,000, preferably 10,000 to 1,500,000. The copolymer of polyvinylpyrrolidone is not particularly limited, but preferably has both a hydrophilic portion and a hydrophobic portion in the polymer chain. -vinyl acetate] block copolymer, [vinylpyrrolidone-methyl methacrylate] copolymer, [vinylpyrrolidone-n-butyl methacrylate] copolymer, [vinylpyrrolidone-acrylamide] copolymer and the like.

Examples of the amphoteric surfactant include, but are not limited to, betaine-type amphoteric surfactants. Examples of betaine type amphoteric surfactants include, but are not limited to, alkyldimethylbetaine, lauryldimethylbetaine, stearyldimethylbetaine, lauryldihydroxyethylbetaine, and the like.

The fluorosurfactant is not particularly limited as long as it has a perfluoroalkyl group, and perfluoroalkane, perfluoroalkylcarboxylic acid, perfluoroalkylsulfonic acid, perfluoroalkylethylene oxide adduct, and the like. mentioned.

The silicone surfactant is not particularly limited, but polyether-modified polydimethylsiloxane, polyetherester-modified polydimethylsiloxane, hydroxyl group-containing polyether-modified polydimethylsiloxane, acrylic group-containing polyether-modified polydimethylsiloxane, acrylic group Containing polyester-modified polydimethylsiloxane, perfluoropolyether-modified polydimethylsiloxane, perfluoropolyester-modified polydimethylsiloxane, silicone-modified acrylic compound, and the like.

Fluorine-based surfactants and silicone-based surfactants are effective as leveling agents to improve the flatness of coating films.

Surfactants other than those described above include, but are not particularly limited to, acetylene glycol-type surfactants.

The method for preparing the aqueous conductive polymer solution of the present invention is not particularly limited. Glycol ether (C), optionally water, and optionally other additives can be used. By mixing these in any order, the conductive polymer aqueous solution of the present invention can be prepared.

Here, the temperature for mixing is not particularly limited, but for example, it can be carried out at room temperature to under heating. The temperature is preferably 0° C. or higher and 100° C. or lower.

The atmosphere during mixing is not particularly limited, but may be air or an inert gas.

When mixing the conductive polymer aqueous solution of the present invention, in addition to a general mixing and dissolving operation using a stirrer tip, stirring blade, etc., ultrasonic irradiation, homogenization treatment (e.g., mechanical homogenizer, ultrasonic homogenizer, high pressure homogenizer, etc.) etc.) may be performed. When the homogenization treatment is performed, it is preferable to perform the treatment while keeping the temperature cold in order to prevent thermal deterioration of the polymer.

The concentration of the conductive polymer aqueous solution of the present invention may be adjusted by adjusting the compounding ratio, or by concentration after compounding. The method of concentration may be a method of distilling off the solvent under reduced pressure or a method of using an ultrafiltration membrane.

The concentration of polythiophene (A) in the aqueous conductive polymer solution of the present invention is not particularly limited as long as it is 0.001% by weight or more, but is preferably in the range of 0.01% by weight to 10% by weight. . Since the conductive polymer aqueous solution containing polythiophene (A), polyacrylic acid-based water-soluble resin (B) and glycol ether (C) of the present invention is dried and dehydrated after application, A good uniform film can be obtained.

The particle size of the solid content in the conductive polymer aqueous solution of the present invention is not particularly limited, but the smaller the particle size, the better the water solubility, which is desirable from the viewpoint of conductivity and uniform film formation during film formation. . For example, when the solid content concentration of the conductive polymer aqueous solution prepared at room temperature or under heating is 10% by weight or less, the water solubility is better if the particle diameter (D50) of the solid content is 0.02 μm or less. Become.

The method for forming a conductive polymer film from the aqueous conductive polymer solution of the present invention is not particularly limited. A conductive polymer film can be easily obtained on the support.

The support is not particularly limited as long as it can be coated with the conductive polymer aqueous solution of the present invention, and examples thereof include polymer substrates and inorganic substrates. Polymer substrates include, for example, thermoplastic resins, nonwoven fabrics, paper, resist film substrates, and the like. Examples of thermoplastic resins include polyethylene, polypropylene, polyethylene terephthalate, polyacrylate, polycarbonate and the like. The nonwoven fabric may be made of, for example, natural fibers, synthetic fibers, or glass fibers. As the paper, general cellulose-based paper may be used. Examples of inorganic substrates include glass, metal oxides such as ITO, ceramics, aluminum oxide, and tantalum oxide.

Examples of the method of applying the conductive polymer aqueous solution include casting method, dipping method, bar coating method, dispenser method, roll coating method, gravure coating method, flexographic printing method, spray coating method, spin coating method, inkjet method, and the like. mentioned. A bar coating method, a spin coating method and an inkjet method are preferred.

The drying temperature of the coating film is not particularly limited as long as it is equal to or lower than the temperature at which a uniform conductive polymer film can be obtained and the heat resistance temperature of the substrate. °C, more preferably room temperature to 200°C.

The drying atmosphere may be air, inert gas, vacuum, or reduced pressure. From the viewpoint of suppressing deterioration of the polymer film, it is preferable to be in an inert gas such as nitrogen or argon.

The film thickness of the resulting conductive polymer film is not particularly limited, but is preferably in the range of 10 ⁻³ to 10 ² μm. It is more preferably 10 ⁻³ to 10 ⁻¹ μm. Although the conductivity of the conductive polymer film is not particularly limited, it is preferably high. In addition, the conductivity of the conductive polymer film varies depending on the type and amount of surfactant or water-soluble resin added, so it cannot be unambiguously determined, but the surface resistance value of the resulting conductive polymer film is is not particularly limited, but is preferably 1.0E+11 Ω/□ or less, more preferably 1.0E+9 Ω/□ or less, and still more preferably 1.0E+7 Ω/□ or less. Although the applied voltage when measuring the surface resistance value is not particularly limited, it is measured at 10V or 500V.

The conductive polymer film of the present invention is used as, for example, organic electronic devices, organic photoelectric conversion devices, and organic electroluminescence devices. In particular, it is extremely useful as a hole-injecting material, a hole-transporting material, and a buffer layer for organic electroluminescence devices. As for the organic electroluminescence device, the conductive polymer film of the present invention can be applied not only to a fluorescent organic EL device but also to a phosphorescent organic EL device that consumes less power.

The structure of the organic electroluminescence device of the present invention is not particularly limited as long as it includes the conductive polymer film.

Regarding the conductive polymer film of the present invention, from the viewpoint of excellent film durability, The weight ratio of the polythiophene (A) containing at least one structural unit selected from the group consisting of the structural units represented by (B)/(A) satisfies 0.05 to 40. It is preferably 0.1 to 30, more preferably 3 to 20.

Examples relating to the present invention are shown below.

Analytical instruments and measuring methods used in this example are listed below.
[NMR measurement]
Apparatus: Gemini-200 manufactured by VARIAN
[Surface resistivity measurement]
Apparatus: Loresta GP MCP-T600 manufactured by Mitsubishi Chemical Corporation
Apparatus: Hiresta UX MCP-HT8000 manufactured by Mitsubishi Chemical Corporation
[Film thickness measurement]
Device: DEKTAK XT manufactured by BRUKER
[Viscosity measurement]
Complete type viscometer/BROOKFIELD VISCOMETER DV-1 Prime
Conductivity [S/cm]=10 ⁴ /(Surface resistivity [Ω/□]×Film thickness [μm])
[Conductivity measurement of self-doping conductive polymer]
0.5 ml of the conductive polymer aqueous solution of the present invention is applied to a 25 mm square non-alkali glass plate, dried at room temperature overnight, heated on a hot plate at 120° C. for 20 minutes, and further heated at 160° C. for 10 minutes. Then, a conductive polymer film was obtained. It was calculated based on the following formula from the film thickness and the surface resistance value.

Synthesis example 1.
Sodium 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1-propanesulfonate [represented by the following formula (6) compound].
In a nitrogen atmosphere, 0.437 g (10.9 mmol) of 60% sodium hydride and 37 ml of toluene were charged in a 100 ml eggplant-shaped flask, and then (2,3-dihydrothieno[3,4-b][1,4]dioxin- 2-yl)methanol 1.52 g (8.84 ml) was added. Thereafter, the reaction solution was heated to the reflux temperature and stirred at the same temperature for 1 hour. After that, a mixture of 1.21 g (8.89 mmol) of 2,4-butanesultone and 10 ml of toluene was added dropwise, and the mixture was stirred at the same temperature for 2 hours. After cooling, the resulting reaction liquid was dropped into 160 ml of acetone for reprecipitation. The obtained powder was filtered and vacuum dried to obtain 1.82 g of pale yellow powder with a yield of 62%. From NMR measurement, this is 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1 represented by the following formula (6) - Confirmed to be sodium propane sulfonate.

1H-NMR (D ₂ O) δ (ppm); 6.67 (s, 2H), 4.54-4.60 (m, 1H), 4.45 (dd, 1H, J = 12.0, 2 .2Hz), 4.26 (dd, 1H, J = 12.0, 6.8Hz), 3.90-3.81 (m, 4H), 3.10-3.18 (m, 1H), 2 .30-2.47 (m, 1H), 1.77-1.92 (m, 1H), 1.45 (d, 3H)
13C-NMR (D2O) δ (ppm); , 141.06
Synthesis example 2.
Synthesis of polythiophene (A) [polymer containing structural unit represented by formula (7) or (8) below].
3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1 synthesized according to Synthesis Example 1 was placed in a 500 ml separable flask. - 10 g (30 mmol) of sodium propanesulfonate and 150 g of water were added. After dissolution, 2.94 g (18.1 mmol) of anhydrous iron (III) chloride was added at room temperature and stirred for 20 minutes. Thereafter, a mixed solution of 14.5 g (60.4 mmol) of sodium persulfate and 100 g of water was added dropwise while maintaining the temperature of the reaction solution at 30° C. or lower. After stirring at room temperature for 3 hours, the reaction solution was dropped into 800 g of acetone to precipitate a black Na-type polymer. Filtration and vacuum drying of the polymer gave 18.0 g of 3-[(2,3-dihydrothieno[3,4-b]-[1,4]dioxin-2-yl)methoxy]-1-methyl-1 - A crude polymer of sodium propanesulfonate was obtained.

Next, 700 g of an aqueous solution prepared by adding water to 14.5 g of this crude polymer to prepare a 2% by weight solution is passed through a column packed with 200 ml of a cation exchange resin Lewatit MonoPlus S100 (H type) (space velocity = 1.1 ) to obtain 738 g of an H-type polymer aqueous solution. Furthermore, by purifying the present polymer aqueous solution by cross-flow ultrafiltration (filter = Vivaflow 200, molecular weight cut off = 5,000, permeability = 5), it is represented by the following formula (7) or formula (8) 698 g of a deep ultramarine blue aqueous solution of a polymer containing a structural unit was obtained. The amount of polymer contained in this aqueous polymer solution was 0.74% by weight. It also contained 44 ppm and 12 ppm (relative to the polymer) of iron ions and sodium ions, respectively.

Synthesis example 3.
Synthesis of polythiophene (A) [polymer containing a structural unit represented by the following formula (9) or (10)].
An aqueous solution of polythiophene (A) [a polymer containing a structural unit represented by the above formula (7) or the above formula (8)] obtained according to Synthesis Example 2 was stirred while adding 50% by weight of N,N-dimethyl. An aqueous aminoethanol solution was added until the pH of the aqueous solution reached 7.8, and then the water was evaporated to a solids content of 2% by weight to obtain an aqueous polymer solution. The electrical conductivity of this aqueous polymer solution was 119 S/cm.

Example 1.
An aqueous solution containing 2.1% by weight of the polythiophene (A) obtained in Synthesis Example 2 [a polymer containing a structural unit represented by the above formula (7) or the above formula (8)] [conductivity 54 S/cm] 0 To .965 g, 4.01 g of a 5.0% by weight polyacrylic acid (molecular weight: 250,000) aqueous solution, 1.00 g of ethylene glycol mono-iso-butyl ether, and 4.02 g of water were added and mixed well with stirring to form an aqueous solution HIM-01. and The composition of the aqueous solution HIM-01 is 0.20% by weight of the conductive polymer (A), 2.01% by weight of the polyacrylic acid-based water-soluble resin (B), and 10.0% by weight of the glycol ether (C). %, and the viscosity and surface tension were 4.7 mPa·s and 28 mN/m, respectively.

Example 2.
An aqueous solution containing 2.1% by weight of the polythiophene (A) obtained in Synthesis Example 2 [a polymer containing a structural unit represented by the above formula (7) or the above formula (8)] [conductivity 54 S/cm] 0 To .965 g, 4.01 g of 5.0% by weight polyacrylic acid (molecular weight 250,000) aqueous solution, 4.00 gg of ethylene glycol mono-iso-butyl ether, and 1.03 g of water were added and mixed well with stirring to form an aqueous solution HIM-02. and The composition of the aqueous solution HIM-02 is 0.20% by weight of the conductive polymer (A), 2.01% by weight of the polyacrylic acid-based water-soluble resin (B), and 30.0% by weight of the glycol ether (C). %, and the viscosity and surface tension were 8.5 mPa·s and 27 mN/m, respectively.

Example 3.
An aqueous solution containing 2.1% by weight of the polythiophene (A) obtained in Synthesis Example 2 [a polymer containing a structural unit represented by the above formula (7) or the above formula (8)] [conductivity 54 S/cm] 0 To .965 g, 4.02 g of a 5.0% by weight polyacrylic acid (molecular weight 250,000) aqueous solution, 4.99 g of ethylene glycol mono-iso-butyl ether, and 0.063 of water are added and stirred well to mix and form an aqueous solution HIM-03. and The composition of the aqueous solution HIM-03 is 0.20% by weight of the conductive polymer (A), 2.00% by weight of the polyacrylic acid-based water-soluble resin (B), and 49.7% by weight of the glycol ether (C). %, and the viscosity and surface tension were 12.6 mPa·s and 27 mN/m, respectively.

Example 4.
An aqueous solution containing 2.1% by weight of the polythiophene (A) obtained in Synthesis Example 2 [a polymer containing a structural unit represented by the above formula (7) or the above formula (8)] [conductivity 54 S/cm] 0 To .965 g, 8.01 g of a 5.0% by weight polyacrylic acid (molecular weight 250,000) aqueous solution, 2.01 g of ethylene glycol mono-n-butyl ether, and 9.04 g of water are added and stirred well to mix and form an aqueous solution HIM-04. and The composition of the aqueous solution HIM-04 is 0.10% by weight of the conductive polymer (A), 2.00% by weight of the polyacrylic acid-based water-soluble resin (B), and 10.0% by weight of the glycol ether (C). %, and the viscosity and surface tension were 4.6 mPa·s and 28 mN/m, respectively.

Example 5.
An aqueous solution HIM-05 was obtained in the same manner as in Example 4, except that the molecular weight of polyacrylic acid was changed to 345,000 (manufactured by Polysciences). The composition of HIM-05 is 0.10% by weight of conductive polymer (A), 2.00% by weight of polyacrylic acid-based water-soluble resin (B), and 10.0% by weight of glycol ether (C). , and the viscosity and surface tension were 4.9 mPa·s and 28 mN/m, respectively.

Example 6.
An aqueous solution containing 2.1% by weight of the polythiophene (A) obtained in Synthesis Example 2 [a polymer containing a structural unit represented by the above formula (7) or the above formula (8)] [conductivity 54 S/cm] 0 Add 8.01 g of 5.0% by weight polyacrylic acid (molecular weight 250,000) aqueous solution, 2.01 g of ethylene glycol mono n-butyl ether, 0.5 g of diethylene glycol mono n-butyl ether, and 8.51 g of water to 965 g. The mixture was well stirred and mixed to obtain an aqueous solution HIM-06. The composition of the aqueous solution HIM-06 is 0.10% by weight of the conductive polymer (A), 2.00% by weight of the polyacrylic acid-based water-soluble resin (B), and 12.5% by weight of the glycol ether (C). % (breakdown: ethylene glycol mono-n-butyl ether = 10% by weight, diethylene glycol mono-n-butyl ether = 2.5% by weight), and the viscosity and surface tension were 5.8 mPa·s and 29 mN/m, respectively.

Example 7. (conductivity measurement)
The aqueous solution HIM-01 containing the polythiophene-based compound prepared in Example 1 was filtered through a filter with a pore size of 0.4 μm, applied to a 233 mm square non-alkali glass plate by spin coating (1500 rpm, 120 seconds), and heated at 180 ° C. and dried for 20 minutes to obtain a thin film having a thickness of 50 nm. From the film thickness and surface resistivity, conductivity was calculated based on the following formula. The surface efficiency was measured using Hiresta UP MCP-HT450 manufactured by Mitsubishi Chemical Corporation.
Conductivity [S/cm]=10^4/(surface resistivity [Ω/□]×film thickness [μm]).

As a result, the electrical conductivity of the thin film obtained as shown in Table 1 was 9×10 ⁻⁵ S/cm.

Example 8. (conductivity measurement)
A thin film was prepared in the same manner as in Example 7, except that the aqueous solution HIM-02 prepared in Example 2 was used instead of the aqueous solution HIM-01, and the electrical conductivity was calculated. The evaluation results are shown in Table 1.

Example 9. (conductivity measurement)
A thin film was prepared in the same manner as in Example 7, except that the aqueous solution HIM-03 prepared in Example 3 was used instead of the aqueous solution HIM-01, and the conductivity was calculated. The evaluation results are shown in Table 1.

Example 10. (conductivity measurement)
A thin film was prepared in the same manner as in Example 7, except that the aqueous solution HIM-04 prepared in Example 4 was used instead of the aqueous solution HIM-01, and the electrical conductivity was calculated. The evaluation results are shown in Table 1.

Example 11. (conductivity measurement)
A thin film was prepared in the same manner as in Example 7, except that the aqueous solution HIM-05 prepared in Example 5 was used instead of the aqueous solution HIM-01, and the conductivity was calculated. The evaluation results are shown in Table 1.

Example 12. (conductivity measurement)
A thin film was prepared in the same manner as in Example 7, except that the aqueous solution HIM-06 prepared in Example 6 was used instead of the aqueous solution HIM-01, and the electrical conductivity was calculated. The evaluation results are shown in Table 1.

Comparative example 1. (conductivity measurement)
A thin film was prepared in the same manner as in Example 7, except that a PEDOT:PSS solution (Clevios PVP AI4083 manufactured by Heraeus) was used instead of the aqueous solution HIM-01, and the electrical conductivity was calculated. The evaluation results are shown in Table 1.

Example 13. (Fabrication and evaluation of element)
A glass substrate laminated with an ITO transparent electrode (anode) having a thickness of 200 nm was subjected to ultrasonic cleaning with acetone and pure water and boiling cleaning with isopropyl alcohol. Furthermore, ultraviolet ozone cleaning was performed.

The aqueous solution HIM-01 containing the polythiophene-based compound prepared in Example 1 was filtered through a filter with a pore size of 0.4 μm, applied by spin coating (1000 rpm, 120 seconds), and dried at 180° C. for 30 minutes. As a result, a hole injection layer of 64 nm was deposited.

Next, after being placed in a vacuum deposition apparatus, it was evacuated with a vacuum pump until the pressure became 1.0×10 ⁻⁴ Pa or less. Subsequently, a film of N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine (α-NPD), which is a material for the hole transport layer, was formed with a thickness of 50 nm by a vacuum evaporation method. A pore transport layer was formed. Further, a film of tris(8-quinolinolato)aluminum (Alq3) was formed with a thickness of 50 nm by a vacuum evaporation method to form a light-emitting layer and an electron-transporting layer.

Subsequently, a 1 nm LiF film and a 100 nm aluminum film were formed as a cathode to form a metal electrode. In addition, each film thickness was measured with a stylus type film thickness meter (DEKTAK).

Furthermore, in a nitrogen atmosphere, a glass plate for sealing was adhered with a UV curable resin to obtain an organic EL element for evaluation.

A current of 10 mA/cm ² was applied to the device thus produced, and the drive voltage was measured. Also, a constant current was applied, the initial luminance was set to 1000 cd/m ² , and the time until the luminance decreased to 70% of the initial luminance was evaluated as LT70. In addition, it means that durability is so favorable that the value of LT70 is large. Table 2 shows the evaluation results.

Example 14. (Fabrication and evaluation of element)
A device was fabricated in the same manner as in Example 13, except that the drying temperature of the spin-coated film was changed from 180° C. to 200° C., and the drive voltage and LT70 were measured. Table 2 shows the evaluation results.

Example 15. (Fabrication and evaluation of element)
A device was fabricated in the same manner as in Example 13, except that the drying temperature of the spin-coated film was changed from 180° C. to 220° C., and the drive voltage and LT70 were measured. Table 2 shows the evaluation results.

Example 16. (Fabrication and evaluation of element)
A device was fabricated in the same manner as in Example 14, except that the aqueous solution HIM-02 prepared in Example 2 was used instead of the aqueous solution HIM-01, and the drive voltage and LT70 were measured. Table 2 shows the evaluation results.

Example 17. (Fabrication and evaluation of element)
A device was fabricated in the same manner as in Example 14, except that the aqueous solution HIM-03 prepared in Example 3 was used instead of the aqueous solution HIM-01, and the drive voltage and LT70 were measured. Table 2 shows the evaluation results.

Example 18. (Fabrication and evaluation of element)
A device was fabricated in the same manner as in Example 14, except that the aqueous solution HIM-04 prepared in Example 4 was used instead of the aqueous solution HIM-01, and the drive voltage and LT70 were measured. Table 2 shows the evaluation results.

Example 19. (Fabrication and evaluation of element)
A device was fabricated in the same manner as in Example 14, except that the aqueous solution HIM-05 prepared in Example 5 was used instead of the aqueous solution HIM-01, and the drive voltage and LT70 were measured. Table 2 shows the evaluation results.

Example 20. (Fabrication and evaluation of element)
A device was fabricated in the same manner as in Example 14 except that the aqueous solution HIM-06 prepared in Example 6 was used instead of the aqueous solution HIM-01, and the drive voltage and LT70 were measured. Table 2 shows the evaluation results.

Example 21. (Fabrication and evaluation of element)
A device was produced in the same manner as in Example 20, except that the drying temperature of the spin-coated film was changed from 200° C. to 220° C., and the drive voltage and LT70 were measured. Table 2 shows the evaluation results.

Comparative example 2. (Fabrication and evaluation of element)
In Example 13, a PEDOT:PSS solution (Clevios P VP AI4083 manufactured by Heraeus) was used instead of the aqueous solution HIM-01. . Table 2 shows the evaluation results.

The measurement results of Examples 13 to 21 were normalized by setting the measurement value of Comparative Example 2 to 100 and displayed. The drive voltage represents the voltage required for light emission, and the lower the drive voltage, the better the industrial application. LT70 represents the lifetime of the light-emitting element, and the higher the LT70, the longer the lifetime and the better for industrial use.

The conductive polymer aqueous solution of the present invention is capable of forming a polymer film having good hole transportability (injectability) and durability, and an organic electronic device using the same. , an organic photoelectric conversion element, and an organic electroluminescence element can be manufactured as a durable element with an improved element life. In particular, in organic electroluminescence devices, not only fluorescent organic EL devices but also phosphorescent organic EL devices with low power consumption can be provided.

This aqueous solution also has good wettability to polymeric substrates in addition to substrates such as glass and metal, and can be applied without cissing or spots. Therefore, it can be used as a conductive coating agent (antistatic agent) for various substrates, a solid electrolyte (cathode material) for solid electrolytic capacitors, and the like. Coated articles made of a polymer substrate coated with this conductive polymer film can also be used as antistatic films, solid electrolytes for solid electrolytic capacitors, and separators for wound aluminum electrolytic capacitors. In addition, electrochromic elements, transparent electrodes, transparent conductive films, thermoelectric conversion materials, chemical sensors, actuators, electromagnetic shielding materials, surface coating materials of metal oxides such as ITO, which is an electrode material for organic EL and solar cells, etc. Applications are also expected.

Claims (3)

0.01 to 10% by weight of a polythiophene (A) containing at least one structural unit selected from the group consisting of structural units represented by the following formula (1) and structural units represented by the following formula (2); 0.001 to 20% by weight of polyacrylic acid water-soluble resin (B) having a weight average molecular weight of 1,000 to 1,000,000 and 0.5 to 60% by weight of glycol ether (C), An aqueous conductive polymer solution, wherein the weight ratio represented by "weight of acrylic acid water-soluble resin (B)"/"weight of said polythiophene (A)" is 10 or 20 .

[In the above formulas (1) and (2), L represents the following formula (3) or (4), and M represents a hydrogen ion, an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium cation. show. ]

[In the above formula (3), l represents an integer of 6 to 12. ]

[In the above formula (4), m represents an integer of 1 to 6. R2 represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a fluorine atom. ] A method for producing a conductive film, comprising drying the aqueous conductive polymer solution according to claim 1 . According to claim 1, wherein the polyacrylic acid water-soluble resin (B) having a weight average molecular weight of 1,000 to 1,000,000 is a polyacrylic acid water-soluble resin (B) having a molecular weight of 150,000 to 500,000. The conductive polymer aqueous solution described above.