JP2019131778A - Conductive polymer aqueous solution, and conductive polymer film - Google Patents

Abstract

To provide a conductive polymer aqueous solution in a high viscosity region that can be used for screen printing or the like, and a conductive polymer film obtained from the same.SOLUTION: A conductive polymer aqueous solution contains a polythiophene (A) containing a structural unit represented by formula (1) or the like of 0.01-10 wt.%, and a thickener (B) of 0.001-10 wt.%. -(CH)-(3) [In formula (1), L represents formula 3 or formula 4, M represents an H ion, an alkali metal ion, a conjugated acid of an amine compound, or a quaternary ammonium cation. In the formula 3, 4, l represents an integer of 6-12, m represents an integer of 1-6, Rrepresents H, a C1-6 linear or branched alkyl group, or F].SELECTED DRAWING: None

Description

  The present invention was made to develop an aqueous conductive polymer solution having a high viscosity that can be used in a screen printing method and the like and capable of providing a conductive polymer film having high conductivity by printing and drying. Specifically, an aqueous solution of a novel conductive composition containing a specific self-doped conductive polymer having a high conductivity and a specific water-soluble resin, etc., and conductivity obtained by drying them Relates to a conductive polymer membrane.

  Conductive polymer materials have been developed by doping π-conjugated polymers such as polyacetylene, polythiophene, polyaniline, and polypyrrole with electron-accepting compounds as dopants. For example, antistatic agents, capacitor solid electrolytes, conductivity Applications to paints, electromagnetic shielding, electrochromic elements, electrode materials, thermoelectric conversion materials, transparent conductive films, chemical sensors, actuators, etc. are being studied. Among these conductive polymer materials, polythiophene-based conductive polymer materials are practically useful from the viewpoint of chemical stability.

  As a polythiophene-based conductive polymer material, a PEDOT / PSS aqueous dispersion solution obtained by polymerizing 3,4-ethylenedioxythiophene (EDOT) in an aqueous solution of polystyrene sulfonic acid (PSS) serving as a dopant, There are so-called self-doped conductive polymers having substituents (sulfo groups, sulfonate groups, etc.) having water solubility and doping action, either directly or via spacers in the polymer main chain, such as sulfonation Polyaniline, PEDOT-S, and the like are known (see, for example, Non-Patent Documents 1 and 2).

  In recent years, a method for applying or printing a conductive polymer dispersion in a predetermined pattern when applying a conductive polymer to a transparent conductive laminate or the like has been studied. For example, Patent Document 3 describes a method in which a PEDOT / PSS aqueous dispersion solution is made into a paste as a conductive polymer dispersion and printed on the surface of an insulating substrate using a screen printer.

  Similarly, as an example of the conductive polymer laminate obtained by the screen printing method, a resin composition using a PEDOT / PSS aqueous dispersion solution with increased viscosity as a conductive polymer is disclosed (for example, (See Patent Document 4).

  Such screen printing is attracting attention because it can be applied to the surface of a substrate with a relatively small amount of coating liquid. However, in this method, in order to achieve a good printing result that maintains the mold separation and the printing pattern shape, the printing material to be used has a characteristic of having a high viscosity. In the screen printing method, the printing material is required to have a high viscosity of 1,000 to 100,000 mPa · s.

JP 2011-199089 A International Publication No. 2014/007299 Special table 2002-500408 gazette Japanese Patent Laying-Open No. 2015-117366

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

  Cited Document 4 discloses an invention having a conductivity improver as an essential constituent requirement as a conductive resin composition having excellent printing characteristics. The conductivity improver in the invention has a drawback of aggregating and crystallizing a conductive polymer, and therefore a conductive resin composition for printing applications not containing the conductivity improver has been demanded.

  The present invention has been made in view of the background art described above, and has the object of (1) having a high viscosity that can be applied to screen printing or the like without using a conductivity improver, and by a printing-drying operation. Providing a conductive polymer solution capable of forming a conductive polymer film, and (2) providing a conductive polymer film having high conductivity using the conductive polymer aqueous solution, It is.

  As a result of intensive studies to solve the above problems, the present inventors have at least selected from the group consisting of a structural unit represented by the following general formula (1) and a structural unit represented by the following formula (2). The following conductive composition containing polythiophene (A) containing a kind of structural unit exhibits good high-viscosity characteristics without containing a conductivity improver, and forms a significantly good conductive polymer film. As a result, the present invention has been completed.

That is, this invention relates to the composition of the conductive polymer aqueous solution as shown below, and a conductive polymer film. The conductive polymer film obtained from the composition can be used as, for example, a film having an antistatic function, a transparent conductive film, or a solid electrolyte of a solid electrolytic capacitor.
[1] 0.01 to 10 weight of 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 conductive polymer aqueous solution containing 0.001 to 10% by weight of the thickener (B).

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

[In said formula (3), l represents the integer of 6-12. ]

[In said formula (4), m represents the integer of 1-6. R ² represents a hydrogen atom, a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 6 carbon atoms, or a fluorine atom. ]
[2] The conductive polymer aqueous solution according to [1], wherein the thickener (B) is a polyvinyl resin.
[3] The thickener (B) is at least one selected from the group consisting of polyvinyl alcohol, polyvinyl pyrrolidone, poly-N-vinylacetamide, and their respective copolymers, [1] ] The conductive polymer aqueous solution of description.
[4] The conductive polymer aqueous solution according to [1], wherein the thickener (B) is poly-N-vinylacetamide or a copolymer thereof.
[5] The thickener (B) is poly N-vinylacetamide having an average molecular weight of about 1,000 to 3,000,000 or a copolymer thereof, according to any one of [1] to [4]. Conductive polymer aqueous solution.
[6] The conductive polymer aqueous solution according to any one of [1] to [5], which contains a surfactant (C).
[7] The conductive polymer aqueous solution according to any one of [1] to [6], which contains a saccharide (E).
[8] The conductive polymer aqueous solution according to any one of [1] to [7], wherein the conductive polymer aqueous solution has a viscosity of 1,000 to 100,000 mPa · s.
[9] The solid content (all components other than water) concentration in the aqueous conductive polymer solution is in the range of 0.1 to 30% by weight, according to any one of [1] to [8] The conductive polymer aqueous solution as described.
[10] The conductive polymer aqueous solution according to any one of [1] to [9], which does not contain a conductivity improver.
[11] A method for producing a film, comprising drying the aqueous conductive polymer solution according to any one of [1] to [10].
[12] A polythiophene (A) and a thickener (B) 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) Containing membrane.

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

[In said formula (3), l represents the integer of 6-12. ]

[In said formula (4), m represents the integer of 1-6. R ² represents a hydrogen atom, a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 6 carbon atoms, or a fluorine atom. ]

  According to the present invention, it is possible to provide a high-viscosity novel aqueous electropolymer solution that can be applied to screen printing or the like without using a conventional conductivity improver, and the produced electroconductive polymer. The film exhibits the effect that high conductivity can be maintained. In addition, the aqueous conductive polymer solution of the present invention exhibits an effect of excellent screen printing transferability.

  Moreover, it discovered that the conductive polymer film obtained by this invention was excellent in heat resistance, and also improved adhesiveness with a polymer or a metal base material.

  Since the conductive polymer film and the coated article formed from this aqueous solution have high conductivity, it can be expected to be used for an antistatic film, a transparent conductive film and the like.

  Hereinafter, the present invention will be described in detail.

  The aqueous polymer solution of the present invention contains 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): A conductive polymer aqueous solution containing 0.01 to 10% by weight and 0.001 to 10% by weight of the thickener (B).

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

[In said formula (3), l represents the integer of 6-12. ]

[In said formula (4), m represents the integer of 1-6. R ² represents a hydrogen atom, a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 6 carbon atoms, or a fluorine atom. ]
In the above formula (1) or (2), 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, or K ion is preferable.

As the conjugate acid of the amine compound, one obtained by adding hydrone (H ⁺ ) to the amine compound to become a cationic species. The amine compound that becomes a conjugate acid group of the amine compound is not particularly limited as long as it reacts with a sulfonic acid group to form a conjugate acid. For example, N (having sp3 hybrid orbitals ( An amine compound represented by R ¹ ) ₃ [the conjugate acid is represented by [NH (R ¹ ) ₃ ] ⁺ . Or amine compounds having sp2 hybrid orbitals (for example, pyridine compounds, imidazole compounds, etc.).

Each of the substituents R ¹ independently 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. .

  Although it does not specifically limit as a C3-C6 linear or branched alkyl group, For example, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- A 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 can be mentioned.

  Examples of the alkyl group having 1 to 6 carbon atoms having a substituent include a halogen atom, an amino group, or an alkyl group having 1 to 6 carbon atoms having a hydroxy group, specifically, a trifluoromethyl group, Or 2-hydroxyethyl group etc. are illustrated.

Of 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 represented by N (R ¹ ) ₃ is not particularly limited, and examples thereof include ammonia, methylamine, dimethylamine, ethylamine, triethylamine, normal-propylamine, isopropylamine, normal butylamine, and tarsha. Libutylamine, hexylamine, ethanolamine compounds (for example, 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, and examples thereof include imidazole compounds (for example, imidazole, N-methylimidazole, 1,2-dimethylimidazole), pyridine picoline, and lutidine. It is done. Of these, ethanolamine compounds and imidazole compounds are preferred.

  That is, the amine compound conjugate acid is preferably ammonium, monoethanolamine conjugate acid, diethanolamine conjugate acid, triethanolamine conjugate acid, imidazole conjugate acid, or the like from the viewpoint of excellent conductivity.

  The quaternary ammonium cation is not particularly limited, and examples thereof include a tetramethylammonium cation, a tetraethylammonium cation, a tetranormalpropylammonium cation, a tetranormalbutylammonium cation, and a tetranormalhexylammonium cation. . From the viewpoint of availability, a tetramethylammonium cation or a tetraethylammonium cation is preferable.

  In said formula (3), l represents the integer of 6-12, Preferably, it is an integer of 6-8.

In the formula (4), R ² represents a hydrogen atom, a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 6 carbon atoms, or a fluorine atom.

  Although it does not specifically limit as a C3-C6 linear or branched alkyl group, For example, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- Examples thereof include a 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 in the} formula (4) is preferably a hydrogen atom, a methyl group, an ethyl group, or a fluorine atom from the viewpoint of film formability.

  In said formula (4), m represents the integer of 1-6, Preferably, m is an integer of 1-4, More preferably, it is 2.

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

  The dopant causing the insulator-metal transition by doping is divided into an acceptor and a donor. The former enters near the polymer chain of the conductive polymer by doping and takes π electrons from the conjugated system of the main chain. As a result, since positive charges (holes, holes) are injected onto the main chain, it is also called a p-type dopant. The latter is also referred to as an n-type dopant because it gives electrons to the conjugated system of the main chain, which moves in the conjugated system of the main chain.

  The dopant in the present invention is a sulfo group or a sulfonate group that is covalently bonded in the polymer molecule, and is a p-type dopant. Such a polymer that exhibits conductivity without adding a dopant from the outside is called a self-doped polymer.

  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. ]
Although it does not specifically limit as a metal ion represented by M in Formula (5), A transition metal ion, a noble metal ion, a nonferrous metal ion, an alkali metal ion (for example, Li ion, Na ion, and K ion) Or alkaline earth metal ions.

  Since the polymer after polymerization is a metal salt, M can be converted to a hydrogen ion by acid treatment of the obtained polymer, if necessary, and further reacted with an amine compound, whereby M is converted to an amine. The compound can be converted to a conjugate acid.

  As 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), specifically, 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) hexane-1-sodium sulfonate, 6- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) hexane-1-sulfonate lithium, 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-sulfo Acid, sodium 8- (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl) octane-1-sulfonate, and 8- (2,3-dihydro-thieno [ 3,4-b] [1,4] dioxin-2-yl) octane-1-sulfonate potassium and the like.

  As 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), specifically, 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-propanesulfonic acid potassium, 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, 3-[(2, -Dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-propyl-1-propanesulfonate sodium, 3-[(2,3-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, 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-1-propanesulfone Sodium, 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 sodium, 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]-[1,4] Dioxin-2-yl) methoxy] -1-methyl-1-propanesulfonate, 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-propanesulfonate, 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] Potassium dioxin-2-yl) methoxy] -1-butanesulfonate, 4-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1 -Methyl-1-butane Sodium sulfonate, potassium 4-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-methyl-1-butanesulfonate, 4-[( 2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-fluoro-1-butanesulfonate sodium, and 4-[(2,3-dihydrothieno [3] , 4-b]-[1,4] dioxin-2-yl) methoxy] -1-fluoro-1-butanesulfonate and the like.

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

  Although the thickener (B) in this invention will not be specifically limited if it is water-soluble, For example, it can select from an existing polymer suitably and can be used. For example, polyacrylic acid resins (polyacrylic acid, polymethacrylic acid, or copolymers thereof), cellulose ether resins (methyl cellulose, ethyl cellulose), and polyvinyl resins (eg, polyvinylpyrrolidone, carboxyvinyl polymer, polyvinyl) It is preferably at least one selected from the group consisting of an alcohol and poly-N-vinylacetamide or a copolymer thereof. These may be used alone or in combination of two or more as required.

  The thickener (B) is preferably a polyvinyl resin from the viewpoint that it is highly compatible with the conductive polymer and can maintain a high conductivity, and is preferably a polyvinyl pyrrolidone or carboxyvinyl. It is preferably at least one selected from the group consisting of a polymer, polyvinyl alcohol, or poly-N-vinylacetamide, and their respective copolymers, and is poly-N-vinylacetamide or a copolymer thereof. It is more preferable.

  Regarding the thickener (B), among the above examples, the average molecular weight is about 1,000 in that the compatibility with the conductive polymer is high and the effect of being able to maintain high conductivity is excellent. Poly-N-vinylacetamide having a molecular weight of about 2,000 to 2,000,000 is more preferable.

  As for the thickener (B) (for example, poly-N-vinylacetamide), a solid, powder, semi-solid, liquid, or solution can be used. From the viewpoint, a solution is preferable, and an aqueous solution is more preferable. About the thing of aqueous solution, that whose density | concentration is 0.1-40 mass% is preferable, and what is about 1-20 mass% is more preferable. In addition, although it is preferable to use water as the solvent in the poly-N-vinylacetamide aqueous solution, it is also possible to use a mixture of one or several kinds of alcohols such as ethanol, glycerols, glycol ethers, etc. with water. it can.

  Specific examples of the poly-N-vinylacetamide aqueous solution include poly-N-vinylacetamide (PNVA [registered trademark]) manufactured by Showa Denko KK, for example, N-vinylacetamide homopolymer (trade name GE-191). -103, GE-191-104, GE-191-107, GE-191-108, GE-191-053), N-vinylacetamide-sodium acrylate copolymer (trade name GE-167-000), etc. 1 type or 2 types or more selected from can be used.

  Although the conductive polymer aqueous solution of the present invention is not particularly limited, it contains 0.001 to 10% by weight of the thickener (B) (referring to solid content). When the amount is less than 0.001% by weight, a sufficient thickening effect tends not to be obtained. When the amount exceeds 10% by weight, a precipitate is generated, which tends to cause plate clogging.

  The content of the thickener (B) (which refers to the solid content) is preferably 0.01 to from the viewpoint that the compatibility with the conductive polymer is high and high conductivity can be maintained. It is 8% by weight, more preferably 0.1 to 5% by weight.

  The saccharide (E) is not particularly limited, and examples thereof include erythritol, pentaerythritol, inmitol, lactitol, maltitol, mannitol, sorbitol, xylitol, and sucrose. More preferred are erythritol, pentaerythritol, and sorbitol.

  Although it does not specifically limit as addition amount of saccharide | sugar (E), For example, it is preferable that it is 0.01-50 times weight with respect to the weight of conductive polymer solid content, More preferably, it is 0.05. ~ 5 times weight.

  The viscosity (20 ° C.) of the conductive polymer aqueous solution of the present invention is not particularly limited, but is preferably 1,000 to 100,000 mPa · s in that it is suitable for printing.

  In the present invention, it is preferable not to include a conductivity improver. The conductivity improver generally has a boiling point higher than a specific temperature and gradually volatilizes by heating during the formation of the conductive film, and in the process, the orientation of the conductive polymer becomes conductive. This means an additive that controls the orientation advantageous for the film, and as a result, improves the conductivity of the formed conductive film by one digit (10 times) or more as compared with the case of no addition.

Specific examples of the conductivity improver include compounds such as (i) to (vii) below. However, among these compounds, as described above, those that do not have the effect of improving the conductivity by one digit (10 times) or more as compared with the case of no addition are not regarded as conductivity improvers.
(I) a compound having a boiling point of 60 ° C. or more and having at least one ketone group in the molecule (ii) a compound having a boiling point of 100 ° C. or more and having at least one ether group in the molecule (iii) a molecule having a boiling point of 100 ° C. or more Compound (iv) having at least one sulfinyl group in it (iv) Compound having a boiling point of 100 ° C. or more and at least one amide group in the molecule (v) Compound having a boiling point of 50 ° C. or more and having at least one carboxyl group in the molecule (Vi) a compound having a boiling point of 100 ° C. or more and having two or more hydroxyl groups in the molecule (vii) a compound having a boiling point of 100 ° C. or more and having at least one lactam group in the molecule; Examples of the compound (i) having at least one ketone group include isophorone, propylene carbonate, and γ-butyrolas. Tons, beta-butyrolactone, 1,3-dimethyl-2-imidazolidinone. However, among these compounds, as described above, those that do not have the effect of improving the conductivity by one digit (10 times) or more as compared with the case of no addition are not regarded as conductivity improvers.

  Examples of the compound (ii) having a boiling point of 100 ° C. or higher and having at least one ether group in the molecule include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, 2-phenoxyethanol, dioxane, morpholine, 4-acryloylmorpholine, N-methylmorpholine N-oxide, 4-ethylmorpholine, 2-methoxyfuran and the like can be mentioned. However, among these compounds, as described above, those that do not have the effect of improving the conductivity by one digit (10 times) or more as compared with the case of no addition are not regarded as conductivity improvers.

  Examples of the compound (iii) having a boiling point of 100 ° C. or higher and having at least one sulfinyl group in the molecule include dimethyl sulfoxide and the like. However, among these compounds, as described above, those that do not have the effect of improving the conductivity by one digit (10 times) or more as compared with the case of no addition are not regarded as conductivity improvers.

  Examples of the compound (iv) having a boiling point of 100 ° C. or more and having at least one amide group in the molecule include N, N-dimethylacetamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-ethylacetamide. N-phenyl-N-propylacetamide, benzamide and the like. However, among these compounds, as described above, those that do not have the effect of improving the conductivity by one digit (10 times) or more as compared with the case of no addition are not regarded as conductivity improvers.

  Examples of the compound (v) having a boiling point of 50 ° C. or more and having at least one carboxyl group in the molecule include acrylic acid, methacrylic acid, methanoic acid, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, and octane. Acid, decanoic acid, dodecanoic acid, benzoic acid, p-toluic acid, p-chlorobenzoic acid, p-nitrobenzoic acid, 1-naphthoic acid, 2-naphthoic acid, phthalic acid, isophthalic acid, oxalic acid, malonic acid, Examples include succinic acid, adipic acid, maleic acid, fumaric acid and the like. However, among these compounds, as described above, those that do not have the effect of improving the conductivity by one digit (10 times) or more as compared with the case of no addition are not regarded as conductivity improvers.

  Examples of the compound (vi) having a boiling point of 100 ° C. or more and having two or more hydroxyl groups in the molecule include ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, β-thiodiglycol, triethylene glycol, and tripropylene. Glycol, 1,4-butanediol, 1,5-pentanediol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, catechol, cyclohexanediol, cyclohexanedimethanol, glycerin, erythritol, inmitol, lactitol , Maltitol, mannitol, sorbitol, xylitol, sucrose and the like. However, among these compounds, as described above, those that do not have the effect of improving the conductivity by one digit (10 times) or more as compared with the case of no addition are not regarded as conductivity improvers.

  Examples of the compound (vii) having a boiling point of 100 ° C. or higher and having at least one lactam group in the molecule include N-methylpyrrolidone, β-lactam, γ-lactam, δ-lactam, ε-caprolactam, laurolactam and the like. Can be mentioned. However, among these compounds, as described above, those that do not have the effect of improving the conductivity by one digit (10 times) or more as compared with the case of no addition are not regarded as conductivity improvers.

  The aqueous conductive polymer solution of the present invention may further contain at least one surfactant (C) selected from the group consisting of a nonionic surfactant and an amphoteric surfactant. As content of the said surfactant (C), 0.001 to 10 weight% is preferable and 0.1 to 5 weight% is more preferable.

  Examples of the surfactant (C) include anionic surfactants (for example, sodium lauryl alcohol sulfate ester and sodium dodecylbenzenesulfonate), cationic surfactants (for example, dodecyltrimethylammonium chloride), nonionic surfactants, and the like. An agent, an amphoteric surfactant, a fluorine-based surfactant, a silicone-based surfactant, or the like can be used, but more preferably at least one selected from the group consisting of a nonionic surfactant and an amphoteric surfactant.

  Although it does not specifically limit as a nonionic surfactant, For example, a polyethyleneglycol type surfactant, an acetylene glycol type surfactant, a polyhydric alcohol type surfactant, a polymeric nonionic surfactant etc. are mentioned. It is done.

  Examples of the polyethylene glycol surfactant include higher alcohol ethylene oxide adduct, alkylphenol ethylene oxide adduct, fatty acid ethylene oxide adduct, polyhydric alcohol fatty acid ester ethylene oxide adduct, higher alkylamine ethylene oxide adduct, Examples thereof include an ethylene oxide adduct of fats and oils or a polypropylene glycol ethylene oxide adduct.

  Examples of the acetylene glycol type surfactant include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, Surfynol (manufactured by Air Products), orphine (manufactured by Nissin Chemical Industry Co., Ltd.). Etc.

  Examples of the polyhydric alcohol surfactant include glycerol fatty acid ester, pentaerythritol fatty acid ester, sorbitol and sorbitan fatty acid ester, sucrose fatty acid ester, high alcohol alkyl ether, alkanolamine fatty acid amide and the like. Can be mentioned.

  Although it does not specifically limit as an amphoteric surfactant, For example, a betaine type | mold amphoteric surfactant is mentioned. The betaine-type amphoteric surfactant is not particularly limited, and examples thereof include alkyldimethylbetaine, lauryldimethylbetaine, stearyldimethylbetaine, and lauryldihydroxyethylbetaine.

  The fluorosurfactant is not particularly limited as long as it has a perfluoroalkyl group, but plus coat RY-2, perfluoroalkane, perfluoroalkylcarboxylic acid, perfluoroalkylsulfonic acid, or perfluoroalkylethylene. And oxide adducts.

  The silicone-based 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 Examples thereof include polyester-modified polydimethylsiloxane, perfluoropolyether-modified polydimethylsiloxane, perfluoropolyester-modified polydimethylsiloxane, and silicone-modified acrylic compound.

  Fluorine-based surfactants and silicone-based surfactants are effective for improving the flatness of the coating film as leveling agents.

  In the present invention, the surfactant (C) is preferably a surfactant having a water solubility of 0.01% by weight or more and an HLB in the range of 7-20.

  The Griffin method HLB (Hydrophile-Lipophile Balance) is a numerical value representing the hydrophilicity of the surfactant. It shows that hydrophilic property is so large that a value is large, and it represents with following Formula.

Griffin method HLB of nonionic surfactant
= (Molecular weight of hydrophilic group part) / (Molecular weight of surfactant) × 100/5
= (Weight of hydrophilic group) / (weight of hydrophobic group + weight of hydrophilic group) × 100/5
= (Weight% of hydrophilic group) / 5
As a method for adding the surfactant (C) to the aqueous conductive polymer solution, it may be added as a solid, or a solution prepared in advance as an aqueous solution may be added. In that case, you may add independently to a conductive polymer aqueous solution, and may mix and add 2 or more types.

  When the conductive polymer aqueous solution of the present invention contains a surfactant (C), the conductive polymer aqueous solution contains 0.1 to 10% by weight of polythiophene (A) and 0.001 of the thickener (B). It is preferable to contain 10 to 10 weight% and surfactant (C) 0.001 to 10 weight%.

  The method for preparing the aqueous conductive polymer solution of the present invention is not particularly limited. For example, the aqueous solution or solid of the polythiophene (A) of the present invention, the thickener (B), and as necessary. Surfactant (C) Water and other additives can be used as necessary. By mixing these in any order, the conductive polymer aqueous solution of the present invention can be prepared.

  The method for preparing the aqueous conductive polymer solution of the present invention is not particularly limited and can be carried out by mixing with a known stirrer or disperser. For example, a preparation method using a magnetic stirrer, a mechanical stirrer, an impeller stirrer, a stirrer with a propeller, a homomixer, a homodisper, a high-pressure homogenizer, or the like may be mentioned, and several methods may be combined.

  Moreover, the preferable rotation conditions (rotation speed) when using a stirrer with a propeller, a homomixer, a homodisper, etc. are 500 rpm or more, More preferably, it is 1000 rpm or more. The upper limit of the rotation speed is not particularly limited, but is preferably 50000 rpm, for example.

  Here, the temperature at the time of mixing is not particularly limited, but can be performed, for example, from room temperature to warming. Preferably it is 0 degreeC or more and 100 degrees C or less.

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

  The pH of the aqueous conductive polymer solution of the present invention is preferably 10 or less, and more preferably 9 or less. Furthermore, the pH of the aqueous conductive polymer solution of the present invention is preferably in the range of 1.5 or more and 9.5 or less, and more preferably in the range of 1.5 or more and 9 or less. Here, the procedure for adjusting the pH is not particularly limited. For example, the pH is adjusted by adding the amine compound (D) after mixing the polythiophene (A) and the thickener (B). be able to. Moreover, pH can be adjusted by adding an amine compound (D) to the aqueous solution of polythiophene (A) previously. Moreover, when using in the acidic region whose pH is 2 or less, it is not always necessary to add an amine.

  The amine compound (F) is not particularly limited. For example, ammonia, methylamine, dimethylamine, ethylamine, triethylamine, normal-propylamine, isopropylamine, normal butylamine, tertiary butylamine, hexylamine, aminoethanol. , Dimethylaminoethanol, methylaminoethanol, diethanolamine, N, N-dimethylethanolamine, N-methyldiethanolamine, triethanolamine, 3-amino-1,2-propanediol, 3-methylamino-1,2-propanediol 3-dimethylamino-1,2-propanediol, 1,4-butanediamine, imidazole, N-methylimidazole, 1,2-dimethylimidazole, pyridine, picoline, rutile Emissions, and the like. When adding, it may be neat or an aqueous solution.

  Alcohol may be added to the conductive polymer aqueous solution of the present invention as necessary for viscosity adjustment or the like. Although it does not specifically limit as said alcohol, For example, methanol, ethanol, propanol, butanol, methoxyethanol, ethoxyethanol, or butoxyethanol etc. are preferable. More preferably, it is ethanol, propanol, or butoxyethanol.

  The amount of alcohol added to the aqueous conductive polymer solution of the present invention is not particularly limited as long as the amount of the component dissolved in the aqueous solution before the addition does not precipitate due to the addition of alcohol. In the molecular aqueous solution, the content is preferably 0.1% by weight to 60% by weight, and more preferably 1% by weight to 40% by weight.

  When mixing the aqueous conductive polymer solution of the present invention, in addition to general mixing and dissolving operations using a stirrer chip, a stirring blade, etc., ultrasonic irradiation, homogenization treatment (for example, mechanical homogenizer, ultrasonic homogenizer, high-pressure homogenizer) May be used). In the case of homogenizing treatment, it is preferable to carry out the treatment while cooling in order to prevent thermal degradation of the polymer.

  The concentration adjustment of the aqueous conductive polymer solution of the present invention may be adjusted by the mixing ratio, or may be adjusted by concentration after mixing. The concentration method may be a method of distilling off the solvent under reduced pressure, or a method 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. . In addition, since the conductive polymer aqueous solution containing the polythiophene (A) and the thickener (B) of the present invention is dried and dehydrated after coating, a good uniform film can be obtained in the above concentration range.

  Although it does not specifically limit about the electroconductive aqueous solution of this invention shown above, Specific composition like the following (composition (X-1)-composition (X-700)) may be illustrated. it can.

  In addition, about each component of a composition (X-1)-a composition (X-700), it is as follows.

  (A) A polythiophene comprising at least one structural unit selected from the group consisting of the structural unit represented by the formula (1) and the structural unit represented by the following formula (2).

(B-1) Polyacrylic acid (B-2) Polymethacrylic acid (B-3) Copolymer of acrylic acid (B-4) Copolymer of methacrylic acid (B-5) Methylcellulose (B-6) ) Ethyl cellulose (B-7) Polyvinylpyrrolidone (B-8) Copolymer of vinylpyrrolidone (B-9) Carboxyvinyl polymer (B-10) Copolymer of carboxyvinyl (B-11) Polyvinyl alcohol (B-12) ) Copolymer of vinyl alcohol (B-13) Poly-N-vinylacetamide (B-14) Copolymer of N-vinylacetamide (C-1) 2,4,7,9-tetramethyl-5-decyne -4,7-diol (C-2) Surfynol (C-3) Orphine (C-4) Lauryldimethylbetaine (C-5) Stearyldimethylbetaine (C-6) Plus Coat RY-2
(C-7) Dodecylbenzenesulfonic acid (D-1) Triethylamine (D-2) Monoethanolamine (D-3) Diethanolamine (D-4) Triethanolamine (E-1) Erythritol (E-2) Sorbitol

  About the electroconductive polymer aqueous solution of this invention, it is preferable that the density | concentration of all the components other than water is the range of 0.1 to 30 weight%.

  The particle size of the solid content in the aqueous conductive polymer 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 aqueous conductive polymer solution prepared at room temperature or under heating is 10% by weight or less, the water solubility is better if the particle size (D50) of the solid content is 0.02 μm or less. Become.

  The method for forming the conductive polymer film from the conductive polymer aqueous solution of the present invention is not particularly limited. For example, the conductive polymer aqueous solution of the present invention is applied to a support and dried. A conductive polymer film can be easily obtained on the support.

  The support is not particularly limited as long as the conductive polymer aqueous solution of the present invention can be applied, and examples thereof include a polymer substrate and an inorganic substrate. Examples of the polymer substrate include thermoplastic resins, nonwoven fabrics, paper, resist film substrates, and the like. Examples of the thermoplastic resin include polyethylene, polypropylene, polyethylene terephthalate, polyacrylate, polycarbonate, and the like. As a nonwoven fabric, any of a natural fiber, a synthetic fiber, or glass fiber may be sufficient, for example. The paper may be composed mainly of general cellulose. Examples of the inorganic base material include glass, ceramics, aluminum oxide, and tantalum oxide.

  Examples of the coating method of the conductive polymer aqueous solution include casting method, dipping method, bar coating method, dispenser method, roll coating method, gravure coating method, flexographic printing, screen printing method, offset printing method, and the like.

  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, but it is in the range of room temperature to 300 ° C, preferably room temperature to 250. It is the range of ° C, and more preferably in the range of room temperature to 200 ° C.

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

Although it does not specifically limit as a film thickness of the conductive polymer film obtained, The range of 10 < ^-3 > ^-10 < ² > micrometer is preferable. More preferably, it is 10 ⁻³ to 10 ⁻¹ μm.

  The coated article of the present invention is used, for example, as a transparent conductive film in addition to an antistatic film and a solid electrolyte for a solid electrolytic capacitor.

  Examples relating to the present invention will be described below.

  The analytical instruments and measurement methods used in this example are listed below.

[GC measurement]
Apparatus: manufactured by Shimadzu, GC-2014.

[NMR measurement]
Apparatus: VARIAN, Gemini-200.

[Surface resistivity measurement]
Apparatus: Loresta GP MCP-T600 manufactured by Mitsubishi Chemical Corporation.

[Film thickness measurement]
Apparatus: DEKTAK XT manufactured by BRUKER.

[Viscosity measurement]
Complete viscometer / BROOKFIELD VISCOMETER DV-1 Prime.

[Particle size measurement]
Apparatus: Nikkiso Co., Ltd. Microtrac Nanotrac UPA-UT151.

[Measurement of conductivity of self-doped conductive polymer]
0.5 ml of an aqueous solution containing a self-doped conductive polymer was applied to a 25 mm square alkali-free glass plate, dried overnight at room temperature, and then heated at 150 ° C. for 30 minutes to obtain a conductive polymer film. It calculated based on the following formula | equation from the film thickness and the surface resistance value.

Electrical conductivity [S / cm] = 104 / (surface resistivity [Ω / □] × film thickness [μm]).
[Contact angle measurement]
Apparatus: Kyowa Interface Science Co., Ltd., FACE contact angle meter CA-X150 type.

Using an Al foil having a thickness of 100 μm, contact angles of various conductive polymer aqueous solutions were measured.
[Transferability evaluation: Screen printing]
Using a screen plate (34 cm × 44 cm, pattern size 12 cm × 15 cm) and a squeegee, screen printing was performed on a 15 cm × 15 cm blue plate glass.

  The evaluation indices are as follows: ◎ = Able to be clearly transferred without blurring, rubbing, spots, etc., ○ = Slightly blurred but can be clearly transferred, Δ = Blurred, etc. conspicuous, × = No transfer at all.

  Synthesis Example 1 (Synthesis of sodium 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-methyl-1-propanesulfonate)

  Under a nitrogen atmosphere, 0.437 g (10.9 mmol) of 60% sodium hydride and 37 mL of toluene were charged into 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 temperature was raised to the reflux temperature while stirring, and the mixture was stirred at the reflux temperature for 1 hour. Thereafter, while continuing the reflux, a mixed solution consisting of 1.21 g (8.89 mmol) of 2,4-butane sultone and 10 mL of toluene was dropped, and then the mixture was further stirred at the reflux temperature for 2 hours. After cooling, the resulting reaction solution was added dropwise to 160 mL of acetone for reprecipitation. The obtained powder was filtered and vacuum-dried to obtain 1.82 g of a pale yellow powder with a yield of 62%. From NMR measurement, this is represented by the above formula (6) 3-[(2,3-dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-methyl- It was confirmed that it was sodium 1-propanesulfonate.

  1H-NMR (D2O) 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 (D2O) 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 (7) and (8)].

  3-[(2,3-Dihydrothieno [3,4-b]-[1,4] dioxin-2-yl) methoxy] -1-methyl-1 synthesized according to Synthesis Example 1 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 consisting of 14.5 g (60.4 mmol) of sodium persulfate and 100 g of water was added dropwise while maintaining the reaction solution temperature at 30 ° C. or lower. Next, after stirring at room temperature for 3 hours, the reaction solution was dropped into 800 g of acetone to deposit a black Na-type polymer. The polymer was filtered and vacuum-dried 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, 700 g of 725 g of an aqueous solution prepared by adding water to 14.5 g of this crude polymer to a solid content of 2% by weight was passed through a column packed with 200 mL of the cation exchange resin Lewatit MonoPlus S100 (H type) (space velocity). = 1.1), 738 g of an H-type polymer aqueous solution was obtained. Furthermore, this polymer aqueous solution is expressed by the above formulas (7) and (8) by purifying the polymer aqueous solution by cross flow ultrafiltration (filter = Vivaflow 200, fractional molecular weight = 5,000, permeation rate = 5). 698 g of a deep blue aqueous solution of a polymer containing structural units was obtained. The polymer amount (solid content) contained in the polymer aqueous solution was 0.74% by weight. Further, when ICP-MS analysis was performed, the polymer aqueous solution contained 44 ppm of iron ions and 12 ppm of sodium ions based on the solid amount.

Example 1.
To 285.00 g of a conductive aqueous solution containing 2.0% by weight of polythiophene (A) obtained by the method of Synthesis Example 2, poly-N-vinylacetamide (manufactured by Showa Denko KK, GE191-104) was added as a thickener (B). , Molecular weight 300,000, hereinafter referred to as PNVA (104).) 6.25 g of a 13% by mass aqueous solution (0.8125 g as a solid content) and 8.78 g of water for adjusting the concentration were added, and a magnetic stirrer was added. The mixture was stirred and mixed to obtain a conductive polymer aqueous solution having a solid content concentration of 2.17% by weight. The viscosity of this aqueous conductive polymer solution was 10,340 mPa · s (20 ° C.). 0.5 mL of this aqueous conductive polymer solution is cast on glass in the air, dried in the air at room temperature overnight, and then heated in air at 150 ° C. for 30 minutes on the hot plate to form a conductive polymer film. Got. The conductivity of this conductive polymer film was 204 S / cm. The results are shown in Table 28.

Examples 2-3.
Table 28 shows the results of experiments and measurements performed in accordance with the method of Example 1 except that the amount of poly-N-vinylacetamide added was changed in Example 1.

Example 12
To 285.00 g of a conductive aqueous solution containing 2.0% by weight of polythiophene (A) obtained by the method of Synthesis Example 2, poly-N-vinylacetamide (manufactured by Showa Denko KK, GE191-053) was added as a thickener (B). , Molecular weight 1,500,000, hereinafter referred to as PNVA (053)) 15.0 g of a 5% by mass aqueous solution (0.75 g as a solid content) was added, and the mixture was stirred and mixed (3000 rpm) using a homomixer. A conductive polymer aqueous solution having a concentration of 2.15% by weight was obtained. The viscosity of this aqueous conductive polymer solution was 7,200 mPa · s (20 ° C.). 0.5 mL of this aqueous conductive polymer solution is cast on glass in the air, dried in the air at room temperature overnight, and then heated in air at 150 ° C. for 30 minutes on the hot plate to form a conductive polymer film. Got. The conductivity of this conductive polymer film was 180 S / cm. The results are shown in Table 28.

Example 13
Table 28 shows the results of experiments and measurements performed in accordance with the method of Example 12, except that the amount of poly-N-vinylacetamide added was changed in Example 12.

  These conductive polymer aqueous solutions have high viscosity that can be applied to screen printing, and maintain high conductivity.

  The evaluation results of screen printing transferability of Example 3 are shown in Table 31.

Comparative Example 1
Regarding the conductive aqueous solution containing 2.0% by weight of polythiophene (A) obtained by the method of Synthesis Example 2, the viscosity of the conductive polymer aqueous solution was 73 mPa · s. Using the aqueous conductive polymer solution, the same operation as in Example 1 was performed to obtain a conductive polymer film. The conductivity of the conductive polymer film was 244 S / cm. The results are shown in Table 28.

Comparative Example 2
To 287.50 g of a conductive aqueous solution containing 1.2% by weight of poly (3,4-ethylenedioxythiophene) polystyrenesulfonic acid, poly-N-vinylacetamide (GE191-, manufactured by Showa Denko KK) as a thickener (B) was added. 104) and 6.731 g of water for adjusting the concentration were added and mixed well with stirring to obtain a conductive polymer aqueous solution having a solid content of 1.40% by weight. The viscosity of the conductive polymer aqueous solution was 874 mPa · s. Using the aqueous conductive polymer solution, the same operation as in Example 1 was performed to obtain a conductive polymer film. The conductivity of the conductive polymer film was 0.2 S / cm. The results are shown in Table 28.

Example 4
A conductive polymer aqueous solution 0.5 g obtained in Example 3 was cast on an aluminum substrate (2 cm × 5 cm × thickness 0.1 μm), and a heat drying moisture meter (MS-70 manufactured by A & D Co., Ltd.) was used. Used to dry at 120 ° C. until constant weight. The obtained coating film was treated for 300 hours at 125 ° C. in a heating furnace (EOP-450B manufactured by ETTAS), then allowed to cool, and a simple peel test was performed using a cellophane tape at room temperature to evaluate adhesion. . When the conductive film was peeled off from the substrate, it was marked as x, and when it was not peeled off, it was marked as o. The results are shown in Table 29. Compared with the following comparative examples 3-4, in Example 4, the electrically conductive film did not peel and adhesiveness improved.

Example 5
270.00 g of a conductive polymer aqueous solution containing 2.0% by weight of polythiophene (A) obtained by the method of Synthesis Example 2, 3.00 g of sorbitol as a saccharide (E), and poly-as a thickener (B) 14.32 g of N-vinylacetamide (manufactured by Showa Denko KK, GE191-104) and 12.68 g of water for concentration adjustment were added and mixed well with stirring, and adjusted to pH 5 with 50% monoethanolamine. 0.5 mL of this aqueous conductive polymer solution is cast on glass in the air, dried in the air at room temperature overnight, and then heated in air at 150 ° C. for 30 minutes on the hot plate to form a conductive polymer film. Got. The conductivity of this conductive polymer film was 64 S / cm.

Example 6
Table 29 shows the results of evaluating the adhesion of the aqueous conductive polymer solution obtained in Example 5 according to Example 4. As in Example 4, the adhesion was improved.

Comparative Examples 3-4
Table 29 shows the results of investigation based on Example 4 except that the conductive polymer aqueous solution was changed to that used in Synthesis Example 2 or Comparative Example 2.

Example 7
1.0 g of a solution diluted with water so that the content of the conductive polymer in the aqueous conductive polymer solution obtained in Example 3 was 1.0% by weight was cast on a 3 cm square glass substrate. Dried overnight at room temperature. Then, it processed at 150 degreeC x 30 minutes-> 200 degreeC x 30 minutes with the hotplate, and produced the coating film. The obtained coating film was treated for 300 hours at 125 ° C. in EOP-450B manufactured by ETTAS, and then the surface resistance value (SR) was measured to determine the change rate (SR / SR0) from the initial value (SR0). The results are shown in Table 30. Compared with the following comparative example 5, in Example 7, the change magnification was small and heat resistance improved.

Example 8
Table 30 shows the results of evaluating the aqueous conductive polymer solution obtained in Example 5 according to Example 7. The heat resistance was improved in the same manner as in Example 7.

Comparative Example 5
Table 30 shows the results of investigation based on Example 7 except that the conductive polymer aqueous solution was changed to that used in Synthesis Example 2 or Comparative Example 2.

Example 9
1 g of an aqueous solution obtained by diluting 1% of acetylene glycol type surfactant Olfine (manufactured by Nissin Chemical Industry Co., Ltd., Olphine EXP4200) as a surfactant (C) to 10 g of the conductive polymer aqueous solution obtained in Example 3 In addition, the mixture was well stirred and mixed to obtain a conductive polymer aqueous solution composed of polythiophene (A), thickener (B), and surfactant (C). 0.5 mL of this aqueous conductive polymer solution is cast on glass in the air, dried in the air at room temperature overnight, and then heated in air at 150 ° C. for 30 minutes on the hot plate to form a conductive polymer film. Got. The conductivity of this conductive polymer film was 175 S / cm. The conductive polymer aqueous solution had a viscosity of 18,191 mPa · s and a contact angle with respect to the Al foil of 75 °.

  The transferability of screen printing was very good.

Examples 10-11
According to the method of Example 9, except that the surfactant (C) acetylene glycol type surfactant orphine was changed to Fluorosurfactant Plus Coat RY-2 (manufactured by Kanayo Chemical Co., Ltd.). Results of experiment and measurement (Example 10), and in Example 9, surfactant (C) acetylene glycol type surfactant orphine, anionic surfactant dodecylbenzenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) Table 31 shows the results (Example 11) of the experiment and measurement performed in accordance with the method of Example 9 except that is changed.

  The screen printability was very good.

  Since the conductive polymer aqueous solution of the present invention forms a good conductive polymer film, it can be used as a conductive coating agent (antistatic agent), a solid electrolyte (cathode material) of a solid electrolytic capacitor, and the like. Furthermore, since the conductive polymer aqueous solution has a high viscosity, a laminate having a conductive polymer is produced by a method with extremely high productivity such as screen printing that can be easily patterned at low cost. It can be applied to transparent conductive laminates used as transparent electrodes in touch panels and display elements of various electronic devices.

  Further, the aqueous conductive polymer solution of the present invention is very industrially useful in that it does not require the addition of a conductivity improver, and is superior in storage stability compared to conventionally known conductive polymer compositions. is there.

Claims (12)

0.01 to 10% by weight of 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 conductive polymer aqueous solution containing 0.001 to 10% by weight of the thickener (B).

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

[In said formula (3), l represents the integer of 6-12. ]

[In said formula (4), m represents the integer of 1-6. R ² represents a hydrogen atom, a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 6 carbon atoms, or a fluorine atom. ]   The conductive polymer aqueous solution according to claim 1, wherein the thickener (B) is a polyvinyl resin.   The thickener (B) is at least one selected from the group consisting of polyvinyl alcohol, polyvinyl pyrrolidone, poly-N-vinylacetamide, and their respective copolymers. Conductive polymer aqueous solution.   The conductive polymer aqueous solution according to claim 1, wherein the thickener (B) is poly-N-vinylacetamide or a copolymer thereof.   5. The highly conductive material according to claim 1, wherein the thickener (B) is poly N-vinylacetamide having an average molecular weight of about 1,000 to 3,000,000 or a copolymer thereof. Molecular aqueous solution.   The aqueous conductive polymer solution according to claim 1, comprising a surfactant (C).   The conductive polymer aqueous solution according to any one of claims 1 to 6, comprising a saccharide (E).   The conductive polymer aqueous solution according to any one of claims 1 to 7, wherein the viscosity of the conductive polymer aqueous solution is 1,000 to 100,000 mPa · s.   9. The conductive material according to claim 1, wherein the concentration of solids (all components other than water) in the aqueous conductive polymer solution is in the range of 0.1 to 30% by weight. Aqueous polymer solution.   The conductive polymer aqueous solution according to claim 1, which does not contain a conductivity improver.   The manufacturing method of the film | membrane characterized by drying the electrically conductive polymer aqueous solution in any one of Claim 1 thru | or 10. Film containing polythiophene (A) and at least one thickener (B) 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) .

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

[In said formula (3), l represents the integer of 6-12. ]

[In said formula (4), m represents the integer of 1-6. R ² represents a hydrogen atom, a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 6 carbon atoms, or a fluorine atom. ]