JP2020026490A - Conductive polymer-containing ink and use therefor - Google Patents

Abstract

To provide a polythiophene conductive polymer-containing composition (ink) that is improved in the probability of occurrence of dark spots, the durability of elements and the yield in making devices.SOLUTION: The present invention provides a composition containing polythiophene containing a specific structural unit containing SOM group (A), polyacrylic acid water-soluble resin (B), glycol (C), glycol ether (D), and aprotic polar solvent (E). The contents of (A), (B), (C) and (D) are 0.01-1.0 wt.%, 0.1-10 wt.%, and 0.01-30 wt.%, and 0.01-30 wt.%, and the total of (C), (D) and (E) is 60-99 wt.%.SELECTED DRAWING: None

Description

  The present invention relates to a novel conductive polymer-containing ink capable of producing a conductive polymer film having both good hole transportability and durability.

  Conductive polymer materials have been developed in which a π-conjugated polymer represented by polyacetylene, polythiophene, polyaniline, polypyrrole, etc. is doped with an electron-accepting compound as a dopant, for example, an antistatic material, a solid electrolyte of a capacitor, and a conductive polymer. 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 studied. Among these conductive polymer materials, a polythiophene-based conductive polymer material is practically useful from the viewpoint of chemical stability.

  The polythiophene-based conductive polymer material is obtained by polymerizing 3,4-ethylenedioxythiophene (EDOT) in an aqueous solution of (i) polystyrenesulfonic acid (PSS) or perfluoroethylenesulfonic acid as a dopant. Aqueous dispersion containing PEDOT / PSS, PEDOT / perfluoroethylene sulfonic acid, or (ii) a polymer having a substituent (sulfo group, sulfonate group, etc.) having both water solubility and doping function directly or via a spacer A so-called self-doping type conductive polymer having in the main chain (for example, sulfonated polyaniline, PEDOT-S, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2) -Yl) methoxy] -1-methyl-1-propanesulfonic acid polymer and the like are known. (E.g., Non-Patent Documents 1 and 2, Patent Document 1).

  The use of conductive polymers is being developed not only as conventional antistatic agents and solid electrolytes for solid electrolytic capacitors, but also as hole injection layers for organic electroluminescent devices and organic thin-film solar cells. .

The hole injection layer is an organic thin film having a thickness of several tens to one hundred and several tens nm obtained by applying and drying the ink containing the conductive polymer on a transparent electrode, and having an appropriate conductivity (10 ⁻³ S / cm) and smoothness is required. Examples of reports of inks containing the conductive polymer include, for example, in the case of PEDOT / PSS, a solvent having a higher boiling point than water, such as ethylene glycol, containing 10 to 50% by weight, typically 30% by weight. An ink that is an aqueous dispersion has been reported (Patent Document 2). Further, an aqueous dispersion containing 5 to 50% by weight of an alcohol solvent such as methanol, ethanol and 1-propanol and an alcohol ether solvent such as 2-butoxyethanol has been reported (Patent Document 3). Further, in the case of PEDOT / perfluoroethylenesulfonic acid, an aqueous dispersion containing an alcohol such as isopropanol and containing at least 40% by weight of H ₂ O has been reported (Patent Document 4).

  As an application example of the hole injection layer of the self-doping type polythiophene-based conductive polymer, although there is no specific example, it contains 0.001 to 10% by weight of a 1-value or 2-value alcohol. A description of a good water-soluble ink is described in the specification (Patent Document 5).

  As described above, the conventional polythiophene-based conductive polymer-containing ink used for the hole injection layer contains 50% by weight or more of water.

  On the other hand, as a method of applying the conductive polymer-containing ink on the transparent electrode, a spin coating method or the like is usually frequently used. However, in consideration of material use efficiency and application to a large substrate, an ink jet method is used. Is preferred. The ink jet method uniformly spreads ink dropped on a target pixel in a pixel to form a thin film having a uniform film thickness. However, the peripheral film thickness often becomes large (Coffee Strain Effect). This causes problems such as blockage. Therefore, it is necessary to have an appropriate ink viscosity (25 mPa · s or less) and a surface tension (40 mN / m or less) and to be capable of continuous ejection by an inkjet method, which is not satisfactory at present.

WO 2014/007299 pamphlet Japanese Patent No. 5235660 JP 2006-520994 A JP 2006-500463 A JP 2017-222831 A

Journal of American Chemical Society, 112, 2801-2803 (1990). Advanced Materials, Vol. 23 (38) 4403-4408 (2011)

  As described above, conventionally known inks containing a polythiophene-based conductive polymer (for example, PEDOT: PSS) contain 50% by weight or more of water, but water is used in an organic device such as an organic EL. It is also a deterioration factor and increases the probability of occurrence of so-called dark spots (non-light-emitting regions). As a result, there is a problem that the durability and the product yield of the organic device are reduced. In addition, conventionally known polythiophene-based conductive polymers have a problem that they are easily blocked at the nozzle tip due to the dispersion liquid. Therefore, there is a need for a composition (ink) containing a polythiophene-based conductive polymer having a water content of less than 50% and having no problem of nozzle clogging in an ink jet method.

  The present inventors have conducted intensive studies in order to solve the above-mentioned problems. As a result, the conductive polymer-containing composition (ink) described below has a water content of less than 50% by weight, and the nozzle blockage by the inkjet method has been suppressed. It has been found that the above problem can be solved, and the present invention has been completed.

That is, the present invention resides in the following [1] to [16].
[1] Polythiophene (A) containing at least one structural unit selected from the group consisting of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2), a polyacrylic acid-based water-soluble A composition comprising a resin (B), a glycol (C), a glycol ether (D) represented by the following general formula (3), and an aprotic polar solvent (E), wherein (A) and (B) , (C) and (D) are 0.005 to 1.0% by weight, 0.1 to 10% by weight, 0.01 to 30% by weight, and 0.01 to 30% by weight, respectively. A composition, wherein the total of (C), (D) and (E) is 60 to 99% by weight.

[In the formula (1), M represents a hydrogen ion, an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium cation. In the formulas (1) and (2), R ¹ represents a hydrogen atom, a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms having a substituent. Represents a group or a fluorine atom, m represents an integer of 1 to 10, and n represents 0 or 1. ]

(Wherein, R ² represents a straight-chain or branched alkyl group having 3 to 6 carbon atoms. R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group. P represents 1 or 2) .)
[2] The composition according to [1], wherein the total of (C), (D) and (E) is 70 to 98% by weight.
[3] The composition according to [1], wherein the total of (C), (D) and (E) is 80 to 98% by weight.
[4] Any one of [1] to [3], wherein the polyacrylic acid-based water-soluble resin (B) is contained in an amount of 5 to 40 parts by weight based on 1 part by weight of the polythiophene (A). A composition according to claim 1.
[5] Glycol (C) is a group consisting of ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butylene glycol, 2,3-butanediol, and 2-methyl-2,4-pentanediol. The composition according to any one of [1] to [4], which is at least one member selected from the group consisting of:
[6] The composition according to any one of [1] to [5], wherein the content of the glycol (C) is 0.1 to 15% by weight.
[7] The glycol ether (D) is ethylene glycol mono n-propyl ether, ethylene glycol mono n-butyl ether, propylene glycol mono n-propyl ether, propylene glycol mono n-butyl ether, diethylene glycol mono n-propyl ether, diethylene glycol mono n The composition according to any one of [1] to [6], which is -butyl ether, dipropylene glycol mono n-propyl ether, or dipropylene glycol mono n-butyl ether.
[8] The composition according to any one of [1] to [7], wherein the content of the glycol ether (D) is 0.1 to 15% by weight.
[9] The aprotic polar solvent (E) is at least one selected from the group consisting of dimethylformamide, dimethylacetamide, diethylacetamide, N-methylpyrrolidone, and N-ethylpyrrolidone. ] The composition according to any one of [8] to [8].
[10] The polyacrylic acid-based water-soluble resin (B) is polyacrylic acid, polymethacrylic acid, a poly (acrylic acid-styrenesulfonic acid) copolymer, or a poly (methacrylic acid-styrenesulfonic acid) copolymer. The composition according to any one of [1] to [9], wherein:
[11] The composition according to any one of [1] to [10], wherein the polyacrylic acid-based water-soluble resin (B) has a weight average molecular weight of 1,000 to 500,000.
[12] The composition according to any one of [1] to [11], further comprising water.
[13] The composition according to any one of [1] to [12], which has a viscosity at 20 ° C. of 20 mPa · s or less and a surface tension of 20 to 40 mN / m. .
[14] An ink containing a conductive polymer, comprising the composition according to any one of [1] to [13].
[15] A method for producing a film, comprising applying the composition according to any one of [1] to [13] and drying the composition.
[16] An organic electronic device of any one of an organic electroluminescence device and an organic photoelectric conversion device, comprising the film obtained by the production method according to [15].

  The conductive polymer film prepared from the novel conductive polymer-containing composition (ink) of the present invention has a more adverse effect on the device life than that prepared from a conventionally known conductive polymer-containing composition. Since the content of water in the ink is small, a remarkable effect of high durability and high performance is achieved.

  In addition, the novel conductive polymer-containing composition (ink) of the present invention has an appropriate ink viscosity and surface tension, and thus has ink characteristics suitable for an inkjet method which is advantageous in process as a printing method for a large substrate.

  The conductive polymer-containing composition (ink) of the present invention can be adjusted to have a lower surface tension by controlling the water content to be lower. Therefore, the conductive polymer-containing composition (ink) is produced by an inkjet method as compared with the conductive ink containing PEDOT / PSS. Has the effect of improving the uniformity of the coating film.

  The conductive polymer-containing composition (ink) of the present invention has effects such as higher heat resistance and decomposition resistance and excellent storage stability as compared to the conductive ink containing PEDOT / PSS. In addition, based on such durability, the conductive polymer-containing composition (ink) of the present invention is remarkably less likely to cause clogging at the tip of the inkjet nozzle than the conductive ink containing PEDOT / PSS. Effect.

  Hereinafter, the present invention will be described in detail.

  The present invention provides a polythiophene (A) containing at least one structural unit selected from the group consisting of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2), and a polyacrylic acid-based aqueous solution. A composition comprising an aprotic resin (B), a glycol (C), a glycol ether (D) represented by the following general formula (3), and an aprotic polar solvent (E), wherein (A), (B) ), (C) and (D) are 0.005 to 1.0% by weight, 0.1 to 10% by weight, 0.01 to 30% by weight, and 0.01 to 30% by weight, respectively. Wherein the total of (C), (D) and (E) is 60 to 99% by weight.

[In the formula (1), M represents a hydrogen ion, an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium cation. In the formulas (1) and (2), R ¹ represents a hydrogen atom, a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms having a substituent. Represents a group or a fluorine atom, m represents an integer of 1 to 10, and n represents 0 or 1. ]

(Wherein, R ² represents a straight-chain or branched alkyl group having 3 to 6 carbon atoms. R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group. P represents 1 or 2) .)
In the above formula (1), M represents a hydrogen ion, an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium cation.

  Although it does not specifically limit as said alkali metal ion, For example, Li ion, Na ion, K ion, Rb ion, or Cs ion is mentioned, Among these, Li ion, Na ion, or K ion Ions are practically preferred.

As the conjugate acid of the above-mentioned amine compound, a conjugate acid obtained by adding hydron (H +) to the amine compound is shown. The amine compound is not particularly limited as long as it is an amine compound which reacts with a sulfonic acid group to form a conjugate acid, and is not particularly limited. For example, the amine compound is represented by N (R ⁵ ) ₃ having an sp3 hybrid orbital. An amine compound [a conjugate acid is represented by [NH (R ⁵ ) ₃ ] ⁺ . Or an amine compound having an sp2 hybrid orbital (for example, a pyridine compound or an imidazole compound).

The substituent R ⁵ is not particularly limited, but each independently represents a hydrogen atom, a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 6 carbon atoms, or a substituent. Represents an alkyl group having 1 to 6 carbon atoms.

  The straight-chain or branched alkyl group having 3 to 6 carbon atoms is not particularly limited, and examples thereof include an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a sec-butyl group. Tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, 2-ethylbutyl group, and cyclohexyl group.

  The alkyl group having 1 to 6 carbon atoms having a substituent is not particularly limited, and examples thereof include a methyl group having a substituent, an ethyl group having a substituent, and a 3 to 6 carbon atoms having a substituent. Linear or branched alkyl group of 3 to 6 carbon atoms having the substituent is not particularly limited, for example, the substituent N-propyl group having, isopropyl group having a substituent, n-butyl group having a substituent, isobutyl group having a substituent, sec-butyl group having a substituent, tert-butyl group having a substituent, N-pentyl group having a substituent, isopentyl group having a substituent, neopentyl group having a substituent, tert-pentyl group having a substituent, cyclopentyl group having a substituent, having a substituent - hexyl, 2-ethylbutyl group having a substituent group, or a cyclohexyl group having a substituent.

  The substituent in the alkyl group having 1 to 6 carbon atoms having the above substituent is not particularly limited, and examples thereof include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom) and an amino group. Group, and a group selected from the group consisting of a hydroxy group. Examples of the alkyl group having 1 to 6 carbon atoms having the substituent include, but are not particularly limited to, a trifluoromethyl group, Examples thereof include a 2-hydroxyethyl group and a 2-hydroxypropyl group.

Among these, the substituent R ^5, independently, a hydrogen atom, a methyl group, an ethyl group, or a 2-hydroxyethyl group is preferred.

The amine compound represented by N (R ⁵ ) ₃ that forms the conjugate acid of the above amine compound is not particularly limited, and examples thereof include ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, and triethylamine. , Normal-propylamine, isopropylamine, normal butylamine, tertiary butylamine, hexylamine, ethanolamine compounds (eg, 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 And the like.

  The amine compound having a sp2 hybrid orbital that forms a conjugate acid of the above amine compound is not particularly limited. For example, an imidazole compound (for example, imidazole, N-methylimidazole, or 1,2-dimethyl) Imidazole, etc.), pyridine, picoline, lutidine and the like.

  Of these, the amine compound used for the conjugate acid of the amine compound is preferably ammonia, monoethanolamine, diethanolamine, triethanolamine, or imidazole.

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

  Although it does not specifically limit as said quaternary ammonium cation, For example, a tetramethyl ammonium cation, a tetraethyl ammonium cation, a tetra normal propyl ammonium cation, a tetra normal butyl ammonium cation, or a tetra normal hexyl ammonium cation is mentioned. Can be Of these, from the viewpoint of availability, a tetramethylammonium cation or a tetraethylammonium cation is preferred.

In the formulas (1) and (2), R ¹ represents a hydrogen atom, a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 6 carbon atoms, or a C ¹ to C 6 group having a substituent. Represents an alkyl group or a fluorine atom.

  The straight-chain or branched alkyl group having 3 to 6 carbon atoms is not particularly limited. For example, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, Examples include a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a cyclopentyl group, an n-hexyl group, a 2-ethylbutyl group, and a cyclohexyl group.

  The alkyl group having 1 to 6 carbon atoms having a substituent is not particularly limited, and examples thereof include a methyl group having a substituent, an ethyl group having a substituent, and a carbon atom having 3 to 6 carbon atoms having a substituent. Linear or branched alkyl group of 3 to 6 carbon atoms having the substituent is not particularly limited, for example, the substituent N-propyl group having, isopropyl group having a substituent, n-butyl group having a substituent, isobutyl group having a substituent, sec-butyl group having a substituent, tert-butyl group having a substituent, N-pentyl group having a substituent, isopentyl group having a substituent, neopentyl group having a substituent, tert-pentyl group having a substituent, cyclopentyl group having a substituent, having a substituent n- hexyl, 2-ethylbutyl group having a substituent group, or a cyclohexyl group having a substituent.

  The substituent in the alkyl group having 1 to 6 carbon atoms having the above substituent is not particularly limited, and examples thereof include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom) and an amino group. Group, and a group selected from the group consisting of a hydroxy group. Examples of the alkyl group having 1 to 6 carbon atoms having the substituent include, but are not particularly limited to, a trifluoromethyl group, Examples thereof include a 2-hydroxyethyl group and a 2-hydroxypropyl group.

R ^{1 in the} above formulas (1) and (2) is preferably a hydrogen atom, a methyl group, an ethyl group, or a fluorine atom from the viewpoint of film formability.

  In the above formulas (1) and (2), m represents an integer of 1 to 10, preferably an integer of 1 to 4, and more preferably 2.

  In the above formulas (1) and (2), n represents 0 or 1, and is preferably 1.

  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 by doping are divided into acceptors and donors. The former enters near the polymer chain of the conductive polymer by doping and removes π electrons from the conjugate system of the main chain. As a result, positive charges (holes, holes) are injected on the main chain, and thus are also called p-type dopants. In the latter, on the other hand, electrons are given to the conjugate system of the main chain, and the electrons move in the conjugate system of the main chain.

  The dopant in the present invention is a sulfo group or a sulfonate group covalently bonded to the polymer main chain, and is a p-type dopant. Such a polymer exhibiting conductivity without adding a dopant from the outside is called a self-doping type conductive polymer.

  The polythiophene (A) of the present invention can be produced by polymerizing a thiophene monomer represented by the following formula (4) in water or an alcohol solvent in the presence of an oxidizing agent.

In [the formula ^{(4), R} 1, m, and n are the same definition as ^R 1, m, and n in the formula (1) and (2). M represents a metal ion. ]
The metal ion represented by M in the formula (4) is not particularly limited, but may be a transition metal ion, a noble metal ion, a non-ferrous metal ion, or an alkali metal ion (eg, Li ion, Na ion, and K ion). And alkaline earth metal ions.

  Polythiophene (A) obtained by polymerizing the thiophene monomer represented by the above formula (4) becomes a metal salt. With regard to the metal salt, if necessary, M can be converted to a hydrogen ion by treating with an acid, and by treating this (hydrogen ion conversion product) with an amine compound, M can be conjugated with the amine compound. Polythiophene (A) which is an acid is obtained.

  As the thiophene monomer represented by the above formula (4), specifically, 6- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) hexane-1 -Sulfonic acid, sodium 6- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) hexane-1-sulfonate, 6- (2,3-dihydro-thieno Lithium [3,4-b] [1,4] dioxin-2-yl) hexane-1-sulfonate, 6- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin- 2- (yl) hexane-1-sulfonic acid potassium, 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) sodium octane-1-sulfonate, and potassium 8- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) octane-1-sulfonate, 3- [ Sodium (2,3-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-propanesulfonic acid potassium salt, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) ) Methoxy] -1-methyl-1-propanesulfonic acid sodium salt, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-ethyl- 1-propanesulfonic acid sodium Lithium, 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- b]-[1,4] dioxin-2-yl) methoxy] -1-pentyl-1-propanesulfonic acid sodium salt, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] Dioxin-2-yl) methoxy] sodium 1-hexyl-1-propanesulfonate, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-isopropyl- Sodium 1-propanesulfonate, sodium 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-isobutyl-1-propanesulfonate, 3 -[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-isopentyl-1-propanesulfonate, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-fluoro-1-propanesulfonic acid sodium salt, 3-[(2,3-dihydrothieno [3,4-b]- Potassium [1,4] dioxin-2-yl) methoxy] -1-methyl-1-propanesulfonate, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2 -Ill) Toxy] -1-methyl-1-propanesulfonic acid, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-methyl-1- Ammonium propanesulfonate, triethylammonium 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-methyl-1-propanesulfonate, 4- Sodium [(2,3-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-butanesulfonate, 4-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2- Yl) methoxy]- -Methyl-1-butanesulfonic acid sodium salt, 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, or 4-[(2 And potassium 3-, 3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-fluoro-1-butanesulfonate.

In the glycol ether represented by the general formula (3) (D), R 2 represents a linear or branched alkyl group having 3 to 6 carbon atoms. R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group.

Wherein the linear or branched alkyl group having 3 to 6 carbon atoms in R ^2, is not particularly limited, for example, n- propyl group, an isopropyl group, n- butyl group, isobutyl group, sec- butyl group, Examples include a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a cyclopentyl group, an n-hexyl group, a 2-ethylbutyl group, and a cyclohexyl group.

R ² is preferably a linear or branched alkyl group having 3 or 4 carbon atoms from the viewpoint of excellent solubility and dispersibility of the polythiophene (A) and the polyacrylic acid-based water-soluble resin (B). More preferably, they are an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group.

R ³ and R ⁴ are both hydrogen atoms or one is a methyl group and the other is a hydrogen atom, because the polythiophene (A) and the polyacrylic acid-based water-soluble resin (B) are excellent in solubility and dispersibility. It is preferably an atom.

  In the glycol ether (D) represented by the general formula (3), p represents 1 or 2, and it is preferable that p is 1 from the viewpoint of film formability.

  The glycol ether (D) represented by the general formula (3) is not particularly limited. For example, ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, or dipropylene glycol monoalkyl Ethers.

  Examples of the ethylene glycol monoalkyl ether include, but are not particularly limited to, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol mono iso-propyl ether, and ethylene glycol monoethyl ether. 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 or ethylene glycol mono-iso-hexyl ether is exemplified.

  The diethylene glycol monoalkyl ether is not particularly limited. For example, 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 Ether, diethylene glycol mono-n- hexyl ether, or diethylene glycol iso- hexyl ether.

  The propylene glycol monoalkyl ether is not particularly limited, but includes, for example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-propyl ether, propylene glycol monoiso-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-pentylue Ether, propylene glycol mono-n- hexyl ether, or propylene glycol monomethyl iso- hexyl ether.

  The dipropylene glycol monoalkyl ether is not particularly limited. For example, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono n-propyl ether, 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 monotert-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 can be mentioned.

  Regarding the glycol ether (D) represented by the general formula (3), ethylene glycol mono-n-propyl ether and ethylene glycol mono-iso-propyl are preferred in that the organic thin film produced from the composition of the present invention has excellent flatness. 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 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, 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 monotert-butyl ether, dipropylene Glycol mono-n-propyl ether, dipropylene glycol mono-iso-propyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol mono-iso-butyl ether, dipropylene glycol mono-sec-butyl ether, or dipropylene glycol mono-tert-butyl ether More preferably, ethylene glycol Mono n-propyl ether, ethylene glycol mono n-butyl ether, propylene glycol mono n-propyl ether, propylene glycol mono n-butyl ether, diethylene glycol mono n-propyl ether, diethylene glycol mono n-butyl ether, dipropylene glycol mono n-propyl More preferably, it is ether or dipropylene glycol mono n-butyl ether.

  As for the glycol ether (D) represented by the general formula (3), a pure product may be used alone, or a plurality of glycol ethers may be used in combination.

  The content of the glycol ether (D) represented by the general formula (3) in the present invention is 0.01 to 30% by weight, but the flatness of a coating film produced by a method such as an ink jet method or a spin coating method. In terms of excellent properties, the content is preferably 0.1 to 20% by weight, more preferably 0.1% by weight or more and 15% by weight or less.

  The composition of the present invention is characterized by containing glycol (C).

  The glycol (C) is not particularly limited. For example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butylene glycol, 2,3-butanediol, 1,4-butane Diol, 1,5-pentanediol, 2-butene-1,4-diol, 2-methyl-2,4-pentanediol, diethylene glycol, dipropylene glycol, triethylene glycol, glycerin, or 1,2,6-hexane Triol and the like.

  Among these, glycol (C) having a boiling point of 220 ° C. or less is preferred from the viewpoint that the drying rate from the composition of the present invention is high. Specifically, ethylene glycol (boiling point 197 ° C.) ° C), 1,3-propanediol (boiling point 210 ° C), 1,3-butylene glycol (boiling point 207 ° C), 2,3-butanediol (boiling point 182 ° C), or 2-methyl-2,4-pentanediol (Boiling point 197 ° C.).

  The content of the glycol (C) in the composition of the present invention is 0.01 to 30% by weight. The content of the glycol (C) is preferably from 0.1 to 20% by weight, and more preferably from 0.1 to 15% by weight, since the composition of the present invention has low smoothness and low viscosity during film formation. % Is more preferable.

  The polythiophene (A) used in the present invention is not particularly limited, but preferably has a conductivity of 10 S / cm or more as a conductivity (electric conductivity) in a film state. .

  The content (composition) of polythiophene (A) in the composition of the present invention is 0.005 to 1.0% by weight. The content (composition) of the polythiophene (A) is preferably from 0.01% by weight to 0.5% by weight, and more preferably from 0.02% by weight, from the viewpoint of exhibiting excellent performance as a hole injection material. More preferably, it is 0.3% by weight.

  The polyacrylic acid-based water-soluble resin (B) in the composition of the present invention is not particularly limited, but a homopolymer of an αβ unsaturated carboxylic acid compound such as acrylic acid, methacrylic acid, and maleic acid, or a homopolymer thereof. Can be mentioned. The homopolymer is not particularly limited, and examples thereof include polyacrylic acid and polymethacrylic acid. Examples of the copolymer include those obtained by copolymerizing at least one kind of αβ unsaturated carboxylic acid monomer and a comonomer, and the comonomer may be copolymerized with the αβ unsaturated carboxylic acid monomer. Anything possible can be used. The copolymer is not particularly limited. For example, poly (acrylic acid-methacrylic acid) copolymer, poly (acrylic acid-hydroxyethyl acrylate) copolymer, poly (acrylic acid-maleic acid) Copolymer, poly (acrylic acid-vinyl sulfonic acid) copolymer, poly (acrylic acid-styrene sulfonic acid) copolymer, poly (methacrylic acid-styrene sulfonic acid) copolymer, or poly (hydroxyethyl methacrylate) (Styrene sulfonic acid) copolymer. The copolymer may be a block copolymer, a random copolymer, or an alternating polymer.

  As the polyacrylic acid-based water-soluble resin (B), polyacrylic acid, polymethacrylic acid, poly (acrylic acid-styrenesulfonic acid) copolymer, or poly ( Methacrylic acid-styrenesulfonic acid) copolymer is preferred.

  The polyacrylic acid-based water-soluble resin (B) of the present invention is not particularly limited, but preferably has a molecular weight of 1,000 to 5,000,000, more preferably 1,000 to 500,000, and more preferably 10,000 to 500,000. More preferably, it is 300,000.

  The content (composition) of the polyacrylic acid-based water-soluble resin (B) in the composition of the present invention is 0.1 to 10% by weight. The content (composition) of the polyacrylic acid-based water-soluble resin (B) is preferably 0.3 to 5.0% by weight from the viewpoint that the viscosity of the composition of the present invention can be appropriately controlled. , 0.5 to 3.0% by weight.

  In the composition of the present invention, the weight ratio of the polyacrylic acid-based water-soluble resin (B) to the polythiophene (A) is such that conductivity can be appropriately controlled as a hole injecting material for an organic electric element. It is preferable that the weight ratio (weight / weight) represented by (B) / (A) satisfies 1 to 40, more preferably satisfies 5 to 40, more preferably satisfies 15 to 40, and 20 to 20. Those satisfying 40 are more preferable.

  The aprotic polar solvent (E) is not particularly limited, but is preferably an aprotic polar solvent having a boiling point of 150 to 240 ° C. For example, dimethylformamide, dimethylacetamide, diethylacetamide, It is preferably at least one selected from the group consisting of N-methylpyrrolidone and N-ethylpyrrolidone.

  In the composition of the present invention, the content (composition) of the aprotic polar solvent (E) is preferably from 30 to 95% by weight and from 40 to 90% by weight from the viewpoint of the solubility of the polythiophene (A). Is more preferable, and more preferably 50 to 85% by weight.

  The composition of the present invention comprises the above polythiophene (A), polyacrylic acid-based water-soluble resin (B), glycol (C), glycol ether (D) represented by the above general formula (3), and aprotic It is a composition containing a polar solvent (E), wherein the content of (A), (B), (C) and (D) is 0.005 to 1.0% by weight, % By weight, 0.01 to 30% by weight, and 0.01 to 30% by weight, and the total content of (C), (D), and (E) is 60 to 99% by weight. It is characterized by. The total content of (C), (D), and (E) is preferably from 70 to 98% by weight, and more preferably from 80 to 98% by weight.

  The composition of the present invention preferably further contains water as a component thereof. The water content is preferably from 0.01 to 30% by weight, more preferably from 0.01 to 20% by weight, even more preferably from 0.01 to 15% by weight. More preferably, it is 0.01 to 10% by weight.

  Further, with respect to the composition of the present invention, the viscosity at 20 ° C. and the surface tension are preferably 25 mPa · s or less, and 15 to 50 mN / m, respectively, from the viewpoint of excellent wettability to the substrate, More preferably, they are respectively 20 mPa · s or less, and 20 to 40 mN / m.

  The composition of the present invention may contain a surfactant, if necessary. Examples of the surfactant include, but are not particularly limited to, a polymer type nonionic surfactant, an amphoteric surfactant, a fluorine-based surfactant, and a silicone-based surfactant.

  Examples of the polymer type nonionic surfactant include, but are not particularly limited to, polyvinylpyrrolidone, a copolymer of polyvinylpyrrolidone, and a polyalkylene glycol. The average molecular weight of the polyvinylpyrrolidone used in the present invention is preferably from 1,000 to 2,000,000, and more preferably from 10,000 to 1.5,000,000. The copolymer of polyvinylpyrrolidone is not particularly limited, but a copolymer having both a hydrophilic part and a hydrophobic part in a polymer chain is preferable. For example, a copolymer in which polyvinylpyrrolidone is grafted on polyvinyl alcohol or [vinyl Examples thereof include a [pyrrolidone-vinyl acetate] block copolymer, a [vinyl pyrrolidone-methyl methacrylate] copolymer, a [vinyl pyrrolidone-normal butyl methacrylate] copolymer, and a [vinyl pyrrolidone-acrylamide] copolymer.

  The polyalkylene glycol is not particularly limited, but may be, for example, Sanyo Kasei Kogyo Co., Ltd., trade names: Newpol PE-61, PE-62, PE-64, PE-68, PE-71. , PE-74, PE-75, PE-78, PE-108, PE-128, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade names: Epan 450, 750, 785, U-103, U-105, U108, etc. Polyethylene glycol / polypropylene glycol block polymers, manufactured by Sanyo Chemical Industry Co., Ltd., trade name: Polyoxy such as Sanix GP-250, GP-400, GP-600, GP-1000, GP-3000, GP-4000 An example is propylated glycerin.

  The amphoteric surfactant is not particularly limited, and examples thereof include a betaine-type amphoteric surfactant. The betaine-type amphoteric surfactant is not particularly limited, and examples thereof include alkyl dimethyl betaine, lauryl dimethyl betaine, stearyl dimethyl betaine, and lauryl dihydroxyethyl betaine.

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

  Examples of the silicone surfactant include, but are not particularly limited to, polyether-modified polydimethylsiloxane, polyetherester-modified polydimethylsiloxane, hydroxyl group-containing polyether-modified polydimethylsiloxane, and acryl group-containing polyether-modified polydimethylsiloxane. And acrylic group-containing polyester-modified polydimethylsiloxane, perfluoropolyether-modified polydimethylsiloxane, perfluoropolyester-modified polydimethylsiloxane, and silicone-modified acrylic compound.

  Fluorine surfactants and silicone surfactants are effective as leveling agents for improving the flatness of the coating film of the composition of the present invention.

  In addition, the surfactant other than the above is not particularly limited, and examples thereof include an acetylene glycol-type surfactant.

  The method for preparing the composition of the present invention is not particularly limited. For example, an aqueous solution or solid of the polythiophene (A) and an aqueous solution or solid of the polyacrylic acid-based water-soluble resin (B) may be used. Glycol (C), glycol ether (D) represented by the above general formula (3) and aprotic polar solvent (E), water as required, and other additives as required Arbitrary mixing methods can be mentioned within the range. The order of mixing the components is not particularly limited, and the composition of the present invention can be prepared by mixing the components in any order.

  Here, the temperature at which the respective components are mixed is not particularly limited, but, for example, the mixing can be performed at room temperature to under heating, and preferably from 0 ° C to 100 ° C.

  The atmosphere at the time of mixing is not particularly limited, but may be air or an inert gas.

  When mixing the composition of the present invention, in addition to a general mixing and dissolving operation using a stirrer chip, a stirring blade, and the like, ultrasonic irradiation and homogenization treatment (for example, use of a mechanical homogenizer, an ultrasonic homogenizer, a high-pressure homogenizer, or the like) ) May be performed.

  In the case of performing the homogenization treatment, it is preferable to perform the homogenization treatment at a low temperature in order to prevent the thermal degradation of the polythiophene (A).

  The concentration of the composition of the present invention may be adjusted by a compounding ratio or may be adjusted 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.

  Since the composition of the present invention contains a conductive polymer and has excellent ink properties, it is preferably a conductive ink containing a conductive polymer.

  A film having conductivity can be produced from the composition of the present invention (or conductive ink containing a conductive polymer). For example, a film having conductivity can be produced on a support by applying the composition (or the conductive ink containing a conductive polymer) of the present invention to the support and drying the composition.

  The support is not particularly limited as long as the composition of the present invention can be applied, and examples thereof include a polymer substrate and an inorganic substrate. The polymer substrate is not particularly limited, and examples thereof include a thermoplastic resin, a nonwoven fabric, paper, and a resist film substrate. Although it does not specifically limit as a thermoplastic resin, For example, polyethylene, polypropylene, polyethylene terephthalate, polyacrylate, polycarbonate, etc. are mentioned. The nonwoven fabric is not particularly limited, and examples thereof include a natural fiber nonwoven fabric, a synthetic fiber nonwoven fabric, and a glass fiber nonwoven fabric. The paper may be a paper containing general cellulose as a main component. Examples of the inorganic substrate include, but are not particularly limited to, glass, metal oxides such as ITO, ceramics, aluminum oxide, and tantalum oxide.

  The method for applying the composition (or conductive polymer-containing conductive ink) of the present invention is not particularly limited, and examples thereof include a casting method, a dipping method, a bar coating method, a dispenser method, a roll coating method, and gravure. Examples include a coating method, a flexographic printing method, a spray coating method, a spin coating method, and an inkjet method. Preferably, a bar coating method, a spin coating method, or an ink jet method is used.

  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 is obtained and the heat-resistant temperature of the substrate, and is in the range of room temperature to 300 ° C., preferably room temperature to 240 ° C. ° C, more preferably from room temperature to 220 ° C.

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

  The thickness of the obtained conductive film is not particularly limited, but is preferably in the range of 20 to 200 nm. More preferably, it is 30 to 80 nm.

  The conductive film of the present invention produced by the above method can be used as a conductor in an organic electronic device such as an organic electroluminescent device or an organic photoelectric light emitting device.

The conductivity of the conductive film is preferably 10 ⁻² S / cm or less. For example, when the film is used as a hole injection agent for an organic electronic element, an organic photoelectric conversion element, or the like, 10 ⁻⁸ S / cm. / Cm to 10 ⁻³ S / cm, more preferably 10 ⁻⁷ to 10 ⁻⁴ S / cm.

  The conductive film obtained by drying the composition of the present invention is not particularly limited. For example, it can be used as a hole injection material for blocking organic electrons, or a hole transport material. . For this reason, the conductive film is not particularly limited, but is preferably used by being included in, for example, an organic electronic element such as an organic electroluminescence element or an organic photoelectric conversion element.

  Examples of the present invention will be described below.

The analytical instruments and measuring methods used in this example are listed below.
[Surface resistivity measurement]
Apparatus: Mitsubishi Chemical Corporation Loresta GP MCP-T600
Apparatus: Mitsubishi Chemical Corporation Hiresta UX MCP-HT8000
[Thickness measurement]
Equipment: DEKTAK XT manufactured by BRUKER
[Conductivity measurement of conductive polymer]
About 0.4 ml of the conductive polymer-containing ink of the present invention was applied to a non-alkali glass plate having a length of 33 mm and a width of 33 mm, and then a film was formed using a spin coater MS-A150 manufactured by MIKASA (condition = 1000 rpm (20 seconds)). Then, it heated on a hot plate at 200 degreeC for 20 minutes, and obtained the conductive polymer film. It was calculated from the film thickness and the surface resistance value based on the following formula.
Conductivity [S / cm] = 10 ⁴ / (surface resistivity [Ω / □] × film thickness [μm])
[Surface tension measurement]
Apparatus: Capillary rise type surface tensiometer DG-1 (manufactured by surface side unit)
[Smoothness evaluation]
After applying a conductive polymer-containing composition (ink) to a glass substrate of 33 mm each in length and width washed with isopropanol and O ₃ , spin-coating was performed at 1000 rpm (20 seconds) (using a spin coater MS-A150 manufactured by MIKASA). The state of the obtained thin film of several tens nm (non-uniformity or presence or absence of irregularities) was visually observed.
[Viscosity measurement]
Complete Viscometer / BROOKFIELD VISCOMETER DV-1 Prime
[GPC measurement of polyacrylic acid-based water-soluble resin]
Apparatus: Build-up GPC system Column: TSKgel GMPWXL (7.8 mm ID × 30 cm) × 2 Detector: RI detector Eluent: 0.2 M-phosphate buffer (pH = 7.0) / acetonitrile = 9/1
Flow rate: 1.0 ml / min
Concentration: 0.05wt%
Injection volume: 100 μl
Column temperature: 40 ° C
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 (5) Compound].
Under a nitrogen atmosphere, 4.4 g (109 mmol) of 60% sodium hydride and 400 ml of toluene were charged into a 1000 ml eggplant-shaped flask, and then (2,3-dihydrothieno [3,4-b] [1,4] dioxin-2- Il) Methanol 15.2 g (88.4 ml) was added. Thereafter, the reaction solution was heated to the reflux temperature and stirred at the same temperature for 1 hour. Thereafter, a mixed solution comprising 12.1 g (89 mmol) of 2,4-butanesultone and 100 ml of toluene was added dropwise, and the mixture was stirred at the same temperature for 2 hours. After cooling, the obtained reaction solution was dropped into 1500 ml of acetone to perform reprecipitation. The obtained powder was filtered and dried under vacuum to obtain 18.0 g of a pale yellow powder in a yield of 62%. From NMR measurement, this was 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-methyl-1 represented by the following formula (5). -It was confirmed to be sodium propanesulfonate.

1H-NMR (D ₂ O) δ (ppm); 6.67 (s, 2H), 4.54 to 4.60 (m, 1H), 4.45 (dd, 1H, J = 12.0, 2) .2 Hz), 4.26 (dd, 1H, J = 12.0, 6.8 Hz), 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 (D ₂ O) δ (ppm); 14.91, 31.22, 53.13, 66.18, 69.18, 73.29, 73.36, 100.81, 100.94, 140 .88, 141.06.

Synthesis Example 2.
Synthesis of polythiophene (A) [polymer containing structural units represented by the following formulas (6) and (7)].
In a 500 ml separable flask, 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-methyl-1 synthesized according to Synthesis Example 1. -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 the mixture was stirred for 20 minutes. Thereafter, a mixed solution consisting 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. The polymer was filtered and dried under vacuum to obtain 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, 1450 g of the crude polymer was mixed with water to prepare a 1% by weight aqueous solution (1450 g), and then passed through a column packed with 350 ml of cation exchange resin Lewatit MonoPlus S100 (H type) (space velocity = 1.1). ) To obtain 1550 g of an H-type polymer aqueous solution. Further, the polymer aqueous solution is purified by a cross-flow type ultrafiltration (fraction molecular weight = 10,000, transmission factor = 20) to obtain a polymer containing structural units represented by the following formulas (6) and (7). As a result, 579 g of a deep ultramarine blue aqueous solution of the combination (polythiophene (A)) was obtained.

  The amount of polymer contained in the aqueous solution of polythiophene (A) was 1.51% by weight. Further, they contained 44 ppm and 12 ppm (based on polymer) of iron ion and sodium ion, respectively. When a thin film was formed using the present polymer aqueous solution and the electrical conductivity was measured, it was 230 S / cm.

Synthesis Example 3 (Synthesis of styrene sulfonic acid / methacrylic acid copolymer (molar ratio 10/90))
To a 300 ml eggplant-shaped flask, 2.50 g (10.7 mmol) of sodium styrenesulfonate (manufactured by Tosoh Finechem, pure content = 88.2 wt%), 10.5 g (97.2 mmol) of sodium methacrylate, and 142 g of water were added. Thereafter, the mixture was stirred at room temperature under a nitrogen atmosphere until the mixture became uniform. Thereafter, 59 mg (0.21 mmol) of 2,2′-azobis (2-methylpropionamidine) dihydrochloride was added, and the mixture was stirred at 80 ° C. for 20 hours. After cooling, the obtained reaction solution was reprecipitated in 2 L of acetone. After filtration and drying, 12.5 g of a sodium polystyreneate / sodium methacrylate copolymer (molar ratio 10/90) was obtained. As a result of GPC measurement, the weight average molecular weight of the copolymer was 170,000 (Mw / Mn = 1.8).

  The obtained copolymer was diluted with water, passed through 120 ml of ion exchange resin Lewatit S108H, and ion-exchanged to obtain a styrene sulfonic acid / methacrylic acid copolymer (molar ratio 10/90) (copolymer A and copolymer A). 298 g was obtained as a 2.7 wt% aqueous solution (yield = 76%, viscosity = 8.3 mPa · s (20 ° C.)).

Synthesis Example 4 (Synthesis of styrene sulfonic acid / methacrylic acid copolymer (molar ratio 25/75))
The same operation as in Synthesis Example 3 was performed except that sodium styrenesulfonate and sodium methacrylate were changed to 6.57 g (28.1 mmol) and 9.10 g (84.2 mmol), respectively, to thereby obtain 15.5 g of sodium styrenesulfonate. / Sodium methacrylate copolymer (molar ratio 25/75) was obtained. As a result of GPC measurement, the weight average molecular weight of the copolymer was 220,000 (Mw / Mn = 2.0).

  By performing ion exchange treatment in the same manner as in Synthesis Example 3, 301 g of a 2.5 wt% aqueous solution of a styrenesulfonic acid / methacrylic acid copolymer (molar ratio: 25/75) (abbreviated as copolymer B) was obtained. Rate = 77%, viscosity = 9.3 mPa · s (20 ° C.).

Embodiment 1 FIG.
To a 30 ml sample bottle, 1.52 g of a 20% by weight aqueous solution of polyacrylic acid (molecular weight 250,000), 2.00 g of propylene glycol n-propyl ether, 11.49 g of dimethylacetamide, and 4.44 g of ethylene glycol were added, and a homogeneous solution was added. (Solution-1) was obtained. To 19.45 g of the homogeneous solution, the polythiophene (A) obtained in Synthesis Example 2 [the polymer containing the structural units represented by the formulas (6) and (7)] [conductivity 230 S / cm] was added. 0.57 g of an aqueous solution containing 1.51% by weight was added and stirred overnight at room temperature to obtain a conductive polymer-containing ink (HIMOl). The concentrations of polythiophene (A), polyacrylic acid-based water-soluble resin (B), ethylene glycol (C), propylene glycol n-propyl ether (D), and dimethylacetamide (E) in the obtained HIM01 were respectively , 0.043%, 1.5%, 22.1%, 10.0% and 57.5% by weight.

  The viscosity and surface tension of HIM01 were 11.3 mPa · s and 35 mN / m, respectively.

Example 2
The same operation as in Example 1 was performed except that ethylene glycol was changed to propylene glycol, to obtain a conductive polymer-containing ink HIM02. Table 1 shows the measurement results of the viscosity and surface tension of HIM02.

Example 3
The same operation as in Example 1 was performed, except that propylene glycol n-propyl ether was changed to ethylene glycol n-butyl ether, to obtain a conductive polymer-containing ink HIM03. Table 1 shows the measurement results of the viscosity and surface tension of HIM03.

Example 4
To a 30 ml sample bottle, 1.52 g of a 20% by weight aqueous solution of polyacrylic acid (molecular weight: 250,000), 2.00 g of ethylene glycol n-butyl ether, 14.93 g of dimethylacetamide and 1.00 g of propylene glycol were added, and a homogeneous solution ( Solution-1) was obtained. To 19.45 g of the homogeneous solution, the polythiophene (A) obtained in Synthesis Example 2 [the polymer containing the structural unit represented by the formula (6) or (7)] [conductivity 230 S / cm] was added. 0.57 g of an aqueous solution containing 1.51% by weight was added and stirred overnight at room temperature to obtain a conductive polymer-containing ink (HIM04). The concentrations of polythiophene (A), polyacrylic acid-based water-soluble resin (B), propylene glycol (C), ethylene glycol n-butyl ether (D), and dimethylacetamide (E) in the obtained HIM04 were respectively 0.043%, 1.5%, 5.0%, 10.0% and 74.6% by weight.

  The viscosity and surface tension of HIM04 were 6.7 mPa · s and 37 mN / m, respectively.

Example 5
The same operation as in Example 4 was performed except that the amounts of ethylene glycol n-butyl ether and propylene glycol were changed to 1.00 g and 2.00 g, respectively, to obtain a conductive polymer-containing ink HIM5. Table 1 shows the measurement results of the viscosity and surface tension of HIM05.

Example 6
The same operation as in Example 4 was performed, except that 2.0 g of ethylene glycol n-butyl ether was changed to 1.0 g of propylene glycol n-butyl ether, and the amount of propylene glycol was changed from 1.0 g to 2.0 g. Polymer-containing ink HIM06 was obtained. Table 1 shows the measurement results of the viscosity and surface tension of HIM06.

Example 7
Same as Example 4 except that 2.0 g of ethylene glycol n-butyl ether was changed to 1.0 g of diethylene glycol mono-n-butyl ether, the amount of propylene glycol was changed from 1.0 g to 2.0 g, and dimethylacetamide was changed to diethylacetamide. By performing various operations, a conductive polymer-containing ink HIM07 was obtained. Table 1 shows the measurement results of the viscosity and surface tension of HIM07.

Example 8
The same operation as in Example 4 was performed, except that dimethylacetamide was changed to diethylacetamide, to obtain a conductive polymer-containing ink HIM08. Table 1 shows the measurement results of the viscosity and surface tension of HIM08.

Example 9
The same operation as in Example 4 was performed, except that 2.0 g of ethylene glycol n-butyl ether was changed to 1.0 g, and 14.93 g of dimethylacetamide was changed to 15.93 g of diethylacetamide, to prepare the conductive polymer-containing ink HIM09. Obtained. Table 1 shows the measurement results of the viscosity and surface tension of HIM09.

Example 10
1.52 g of a 20% by weight aqueous solution of polyacrylic acid (molecular weight 250,000) was changed to 1.51 g of a 20% by weight aqueous solution of polyacrylic acid (molecular weight 100,000), and propylene glycol was changed to ethylene glycol. Conductive polymer-containing ink HIM10 was obtained in the same manner as in Example 4, except that ethylene glycol mono n-butyl ether was changed to propylene glycol n-butyl ether and dimethylacetamide was changed to diethylacetamide. Table 1 shows the measurement results of the viscosity and surface tension of HIM10.

Example 11
50 g of a 20% by weight aqueous solution of polyacrylic acid (molecular weight 100,000) was concentrated under reduced pressure to obtain 33.2 g of a 30.0% by weight aqueous solution of polyacrylic acid. Except that 1.51 g of the 20 wt% polyacrylic acid (molecular weight 100,000) aqueous solution in Example 10 was changed to 1.00 g of the 30.0 wt polyacrylic acid (molecular weight 100,000) aqueous solution obtained above. The same operation as in Example 10 was performed to obtain a conductive polymer ink HIM11. Table 1 shows the measurement results of the viscosity and surface tension of HIM11.

Example 12
0.57 g of an aqueous solution containing 1.51% by weight of polythiophene (A) [a polymer containing a structural unit represented by the formula (6) or the formula (7)] [conductivity of 230 S / cm] is reduced to 0.67 g. A conductive polymer ink HIM12 was obtained in the same manner as in Example 4, except that the dimethylacetamide was changed to diethylacetamide. Table 1 shows the measurement results of the viscosity and surface tension of HIM12.

Example 13
0.57 g of an aqueous solution containing 1.51% by weight of polythiophene (A) [a polymer containing a structural unit represented by the formula (6) or (7)] [conductivity of 230 S / cm] is reduced to 0.80 g. A conductive polymer ink HIM13 was obtained in the same manner as in Example 4, except that the dimethylacetamide was changed to diethylacetamide. Table 1 shows the measurement results of the viscosity and surface tension of HIM13.

Example 14
250 g of the aqueous solution containing 2.7% by weight of copolymer A obtained in Synthesis Example 3 was concentrated under reduced pressure to obtain 45.1 g of an aqueous solution containing 15.0% by weight of copolymer A as a viscous aqueous solution. Was.

  Same as Example 4 except that 1.52 g of a 20% by weight aqueous solution of polyacrylic acid (molecular weight 250,000) was changed to 1.52 g of an aqueous solution containing 15.0% by weight of copolymer A obtained above. The operation was performed to obtain a conductive polymer ink HIM14. Table 1 shows the measurement results of the viscosity and surface tension of HIM14.

Example 15
250 g of the aqueous solution containing 2.5% by weight of copolymer B obtained in Synthesis Example 4 was concentrated under reduced pressure to obtain an aqueous solution containing 15.0% by weight of copolymer B as a viscous aqueous solution.

  Same as Example 4 except that 1.52 g of a 20% by weight aqueous solution of polyacrylic acid (molecular weight 250,000) was changed to 1.52 g of an aqueous solution containing 15.0% by weight of copolymer B obtained above. The operation was performed to obtain a conductive polymer ink HIM15. Table 1 shows the measurement results of the viscosity and surface tension of HIM15.

Example 16 (Smoothness, film thickness and conductivity measurement)
With respect to the conductive polymer-containing ink HIM01 prepared in Example 1, the smoothness was evaluated and the conductivity of the conductive polymer was measured.

As a result, as shown in Table 2, the smoothness of the obtained thin film was good (represented by “○” in the table), and the conductivity was 6.7 × 10 ⁻⁶ S / cm.

Examples 17 to 30 (Smoothness, film thickness and conductivity measurement)
For the conductive polymer-containing inks HIM02 to HIM15 prepared in Examples 2 to 15, the smoothness was evaluated and the conductivity of the conductive polymer was measured. Table 2 shows the results. The results of the smoothness evaluation were all good.

Comparative Example 1
The same operation as in Example 1 was performed except that ethylene glycol mono-n-butyl ether was changed to ethanol, to obtain a conductive polymer-containing ink (REF01). The concentrations of polythiophene (A), polyacrylic acid-based water-soluble resin (B), propylene glycol, ethanol, and dimethylacetamide in the obtained REF01 were 0.043% by weight, 1.5% by weight, and 22%, respectively. 0.2 wt%, 10.0 wt%, and 57.6 wt%.

  The viscosity and surface tension of REF01 were 7.7 mPa · s and 32 mN / m, respectively. However, the spin coat film obtained from REF01 had unevenness and no smoothness.

Comparative Examples 2-3
The same operation as in Example 1 was performed except that ethylene glycol mono-n-butyl ether was changed to propylene glycol monomethyl ether or diethylene glycol monomethyl ether, to obtain conductive polymer-containing inks (REF02 and 03).

  The viscosity and surface tension of REF02 were 12.7 mPa · s and 33 mN / m, respectively, and the viscosity and surface tension of REF03 were 13.0 mPa · s and 33 mPa · s, respectively. However, as in Comparative Example 1, neither REF 02 nor 03 had smoothness of the spin-coated film.

Embodiment 31 FIG. (Device fabrication and evaluation)
A glass substrate on which a 200-nm-thick ITO transparent electrode (anode) was laminated was subjected to ultrasonic cleaning with acetone and pure water and boiling cleaning with isopropyl alcohol. Further, ultraviolet ozone cleaning was performed.

  The conductive polymer-containing ink HIM01 prepared in Example 1 was filtered through a filter having a pore size of 0.4 μm, applied by a spin coating method (700 rpm, 20 seconds), and dried at 200 ° C. for 30 minutes. As a result, a hole injection layer having a thickness of 63 nm was formed.

Next, after installing in a vacuum evaporation apparatus, the inside of the apparatus was evacuated with a vacuum pump until the pressure became 1.0 × 10 ⁻⁴ Pa or less. Subsequently, N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine (α-NPD), which is a material for a hole transport layer, is formed to a thickness of 50 nm by a vacuum evaporation method. A hole transport layer was formed. Further, tris (8-quinolinolato) aluminum (Alq ₃ ) was formed to a thickness of 50 nm by a vacuum evaporation method to form a light emitting layer and an electron transport layer.

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

  Further, a glass plate for sealing was bonded with a UV curing resin under a nitrogen atmosphere to obtain an organic EL element for evaluation.

A current of 10 mA / cm ² was applied to the device thus fabricated, and the driving voltage was measured. The initial luminance was set to 1000 cd / m ² by applying a constant current, and the time during which 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 3 shows the evaluation results.

Examples 32 to 45 (Production and Evaluation of Element)
In Example 31, an organic EL element was prepared in the same manner as in Example 31 except that HIM02 to HIM15 prepared in Examples 2 to 15 were used instead of the conductive polymer-containing ink HIM01, and the driving voltage and LT70 was measured. Table 3 shows the evaluation results.

Comparative Example 4. (Device fabrication and evaluation)
A device was prepared in the same manner as in Example 31 except that a PEDOT: PSS solution (Clebios PVP AI4083 manufactured by Heraeus) was used in place of the conductive polymer-containing ink HIM01 in Example 31, and the driving voltage and LT70 were used. Was measured. Table 3 shows the evaluation results.

  In addition, about the measurement result in Examples 31-45, the measured value of Comparative Example 4 was set as 100 and it was normalized and displayed. The drive voltage indicates a voltage required for light emission, and the lower the drive voltage, the better the industrial use. LT70 indicates the life of the light emitting element, and the longer the LT70, the longer the life and the better the industrial use.

Example 46 (Examination of dischargeability using inkjet printer)
Diethylacetamide was added to each of the conductive polymer-containing inks (HIM01 to 15) prepared above, and the solid content concentration (total concentration of component (A) and component (B)) was 1.2% by weight. To obtain an inkjet composition. The following ejection studies were conducted using an inkjet printer DMP-2831 manufactured by Fuji Film Dimatix.

  In the examination of ejection, a state in which each of the above-described inkjet compositions was continuously ejected for 15 minutes using a head cartridge having a droplet ejection amount of 10 pl was observed. As a result, it was confirmed that continuous ejection was possible without observing non-ejection during ejection or ejection disorder in all the inkjet compositions.

  In addition, the discharge stability after pausing was also evaluated. For the evaluation of the ejection stability after pausing, discharging was performed for 5 minutes under the above conditions, and after the pausing overnight, the state when discharging was started again under the same conditions was observed. As a result, it was confirmed that all the ink jet compositions can be ejected without any problem at the same time as the droplet ejection instruction.

  The conductive polymer-containing ink of the present invention can form a polymer film having good hole transporting property (injection property) and durability, and an organic electroluminescent element and an organic photoelectric conversion element using the same can be used as an element. A durable element with improved life can be manufactured. In particular, in the organic electroluminescence element, not only a fluorescent organic EL element but also a phosphorescent organic EL element with low power consumption can be provided.

  This conductive polymer-containing ink has good wettability to a polymer base material other than a base material such as glass or metal, and can be applied without repelling or spotting. Therefore, it can be used as a conductive coating agent (antistatic agent) for various substrates, a solid electrolyte (cathode material) of a solid electrolytic capacitor, and the like. The coated article comprising the polymer substrate coated with the conductive polymer film can be used as an antistatic film, a solid electrolyte of a solid electrolytic capacitor, and a separator for a wound aluminum electrolytic capacitor. In addition, electrochromic devices, transparent electrodes, transparent conductive films, thermoelectric conversion materials, chemical sensors, actuators, electromagnetic wave shielding materials, surface coating materials of metal oxides such as ITO, which are electrode materials for organic EL and solar cells, etc. Applications can also be expected.

Claims (16)

Polythiophene (A) containing at least one structural unit selected from the group consisting of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2), a polyacrylic acid-based water-soluble resin (B ), Glycol (C), glycol ether (D) represented by the following general formula (3), and aprotic polar solvent (E), wherein (A), (B), (C) ) And (D) are 0.005 to 1.0% by weight, 0.1 to 10% by weight, 0.01 to 30% by weight, and 0.01 to 30% by weight, respectively. A composition, wherein the sum of (C), (D) and (E) is 60 to 99% by weight.

[In the formula (1), M represents a hydrogen ion, an alkali metal ion, a conjugate acid of an amine compound, or a quaternary ammonium cation. In the formulas (1) and (2), R ¹ represents a hydrogen atom, a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms having a substituent. Represents a group or a fluorine atom, m represents an integer of 1 to 10, and n represents 0 or 1. ]

(Wherein, R ² represents a straight-chain or branched alkyl group having 3 to 6 carbon atoms. R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group. P represents 1 or 2) .)   The composition according to claim 1, wherein the total of (C), (D) and (E) is 70 to 98% by weight.   The composition according to claim 1, wherein the total of (C), (D) and (E) is 80 to 98% by weight.   The polyacrylic acid-based water-soluble resin (B) is contained in an amount of 5 to 40 parts by weight based on 1 part by weight of the polythiophene (A). Composition.   The glycol (C) is selected from the group consisting of ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butylene glycol, 2,3-butanediol, and 2-methyl-2,4-pentanediol. The composition according to any one of claims 1 to 4, wherein the composition is at least one kind.   The composition according to any one of claims 1 to 5, wherein the content of the glycol (C) is 0.1 to 15% by weight.   The glycol ether (D) is ethylene glycol mono n-propyl ether, ethylene glycol mono n-butyl ether, propylene glycol mono n-propyl ether, propylene glycol mono n-butyl ether, diethylene glycol mono n-propyl ether, diethylene glycol mono n-butyl ether, The composition according to any one of claims 1 to 6, wherein the composition is dipropylene glycol mono n-propyl ether or dipropylene glycol mono n-butyl ether.   The composition according to any one of claims 1 to 7, wherein the content of the glycol ether (D) is 0.1 to 15% by weight.   9. The aprotic polar solvent (E) is at least one selected from the group consisting of dimethylformamide, dimethylacetamide, diethylacetamide, N-methylpyrrolidone, and N-ethylpyrrolidone. The composition according to any one of the above.   The polyacrylic acid-based water-soluble resin (B) is a polyacrylic acid, polymethacrylic acid, poly (acrylic acid-styrenesulfonic acid) copolymer, or poly (methacrylic acid-styrenesulfonic acid) copolymer. A composition according to any one of claims 1 to 9, characterized in that:   The composition according to any one of claims 1 to 10, wherein the polyacrylic acid-based water-soluble resin (B) has a weight average molecular weight of 1,000 to 500,000.   The composition according to any one of claims 1 to 11, further comprising water.   The composition according to any one of claims 1 to 12, wherein the composition has a viscosity at 20 ° C of 20 mPa · s or less and a surface tension of 20 to 40 mN / m.   An ink containing a conductive polymer, comprising the composition according to claim 1.   A method for producing a film, comprising applying the composition according to claim 1 and drying the composition.   An organic electronic device, comprising an organic electroluminescent device or an organic photoelectric conversion device, comprising a film obtained by the method according to claim 15.