JP2014065870A - Nanocarbon-containing conductive compositions, and conductors comprising said compositions - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide nanocarbon-containing conductive compositions having heat resistance and crack resistance, and conductors having coatings made thereof.SOLUTION: Provided are: conductive compositions which comprise a conductive polymer (A) with a repeating unit represented by the specified general formula (1), nanocarbon (B), and a water-soluble polymer (D) having a specific structure; conductive compositions further comprising a basic compound (C); and conductors obtained from the conductive compositions. In the formula (1), Rto Reach independently represent a hydrogen atom, a C1-C24 linear or branched alkyl group, a C1-C24 linear or branched alkoxy group, an acidic group, a hydroxy group, a nitro group or a halogen atom, where at least one of Rto Ris an acidic group or a salt thereof.

Description

  The present invention relates to a nanocarbon-containing conductive composition and a conductor composed of the composition.

In recent years, in various industrial fields, nanotechnology that handles nanometer-sized nanomaterials has attracted attention. By combining nanomaterials with other materials at the nanometer level, materials with new functions that have never existed have been developed. Highly dispersed nanomaterials exhibit properties that are different from the bulk state, and therefore a highly dispersed technology in the composite is indispensable.
However, in general, nanomaterials have a large surface area and a strong interaction due to intermolecular forces, etc., and therefore, there is a problem that the nanomaterials aggregate when composited and cannot exhibit functions specific to nanomaterials.

  Among the nanomaterials, carbon nanotubes have been evaluated for their physical properties and elucidated their functions since they were discovered in 1991, and research and development related to their application has been actively conducted. In addition, the carbon nanotubes in a tangled state at the time of production are further aggregated, and there is a problem that the original characteristics cannot be exhibited. For this reason, attempts have been made to disperse or dissolve the carbon nanotubes uniformly in a solvent or resin by physically treating the carbon nanotubes or chemically modifying the carbon nanotubes. For example, a method has been proposed in which single-walled carbon nanotubes are ultrasonically treated in a strong acid to cut and disperse the single-walled carbon nanotubes. However, since the treatment is carried out in a strong acid, the operation becomes complicated, which is not an industrially suitable method, and defects are introduced into the carbon nanotubes, so that the original characteristics cannot be fully utilized.

  Further, a method using a specific conductive polymer is disclosed as a method for dispersing carbon nanotubes without performing physical treatment or chemical treatment (Patent Document 1). According to this method, it is possible to disperse the carbon nanotubes in a solvent such as water, an organic solvent, or a water-containing organic solvent without impairing the characteristics of the carbon nanotubes themselves. It is excellent in conductivity, film formation, and moldability, and can be applied and coated on a substrate by a simple method.

JP-A-2005-97499

However, the method described in Patent Document 1 has a problem that the strength as a coating film is insufficient and the coating film is easily cracked.
Moreover, the entanglement of electroconductive polymers reduced by containing a basic compound, and the subject that a coating film tends to crack also occurred.

An object of the present invention is to provide a conductive composition excellent in solubility, dispersibility and long-term storage stability, and a conductive coating film excellent in conductivity and durability.
In other words, without impairing the conductivity of the nanocarbon itself, improving the solubility and dispersibility and maintaining long-term storage stability, without cracking by heating the coating film of the nanocarbon-containing conductive composition Another object is to provide a conductive coating film having durability and high conductivity.

  As a result of intensive research to solve these problems, the present inventor has excellent conductivity and durability without impairing the dispersibility / solubility of nanocarbon by coexisting a polymer having a specific structure. It was found that a coated film can be obtained.

  That is, the first aspect of the present invention is a conductive polymer (A) having a repeating unit represented by the following general formula (1), nanocarbon (B), and water-soluble represented by the following general formula (2). The present invention relates to a conductive composition containing a polymer (D).

In formula (1), R ^{1 to} R ⁴ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxy group having 1 to 24 carbon atoms, or an acidic group. , A hydroxy group, a nitro group or a halogen atom. Further, at least one of R ^{1 to} R ⁴ is an acidic group or a salt thereof.

  In formula (2), X is a 5-membered or 6-membered cyclic structure containing a nitrogen atom and / or a carbon atom, and n represents the degree of polymerization.

  Moreover, the 2nd viewpoint of this invention is the water-soluble property represented by the conductive polymer (S) which has a repeating unit represented by following General formula (3), nanocarbon (B), and the following general formula (2). The present invention relates to a conductive composition containing a polymer (D).

In Formula (3), R ^{5 to} R ⁷ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxy group having 1 to 24 carbon atoms, or an acidic group. Or its salt, a hydroxyl group, a nitro group, or a halogen atom, A is an acidic group or its salt, and m is an integer of 1-20.

  In formula (2), X is a 5-membered or 6-membered cyclic structure containing a nitrogen atom and / or a carbon atom, and n represents the degree of polymerization.

  Furthermore, the third aspect of the present invention further includes the conductive composition containing a basic compound (C), and the fourth aspect is that the basic compound (C) is an alkali metal hydroxide and / or Alkaline earth metal hydroxide (C-1) or the conductive composition which is a basic compound (C-2) containing a hydroxy group and a basic group in the same molecule, the fifth aspect is The present invention relates to a conductor formed from the conductive composition.

  According to the present invention, the conductive composition capable of suppressing degassing and preventing cracking of the conductive coating film when the coating film of the nanocarbon-containing conductive composition is heated, the composition A conductor made of can be obtained.

Hereinafter, the present invention will be described in detail.
In the present invention, “soluble” means water, water containing a base and a basic salt, water containing an acid, a solvent such as methyl alcohol, ethyl alcohol, isopropyl alcohol, or a mixture thereof (10 g (liquid temperature 25). ℃) means that 0.1 g or more is uniformly dissolved.
“Conductivity” means having an electric conductivity of 10 ⁻⁹ S / cm or more.

<Conductive polymer (A)>
The conductive polymer (A) used in the present invention has a repeating unit represented by the following general formula (1).

In formula (1), R ^{1 to} R ⁴ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxy group having 1 to 24 carbon atoms, or an acidic group. , A hydroxy group, a nitro group or a halogen atom (-F, -Cl, -Br or -I), and at least one of R ^{1 to} R ⁴ is an acidic group or a salt thereof.

Here, the “acidic group” is a sulfonic acid group or a carboxy group. The sulfonic acid group and the carboxy group may each be included in an acid state (—SO ₃ H, —COOH) or may be included in an ionic state (—SO ₃ ^— , —COO ⁻ ).
The “salt” refers to at least one of an alkali metal salt, an ammonium salt, and a substituted ammonium salt.

As the repeating unit represented by the general formula (1), one of R ^{1 to} R ⁴ is a linear or branched alkoxy group having 1 to 4 carbon atoms in terms of easy production, It is preferable that any other one is a sulfonic acid group and the rest is hydrogen.

  The conductive polymer preferably contains 10 to 100 mol% of the repeating unit represented by the general formula (1) among all repeating units (100 mol%) constituting the conductive polymer, It is more preferable to contain 100 mol%, and it is especially preferable to contain 100 mol% at the point which is excellent in the solubility to water and an organic solvent irrespective of pH.

  Moreover, it is preferable that the said conductive polymer contains 10 or more repeating units represented by the said General formula (1) in 1 molecule from a viewpoint which is excellent in electroconductivity.

  Further, the conductive polymer is preferably a compound having a structure represented by the following general formula (2).

In formula (4), R ^{8 to} R ²³ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxy group having 1 to 4 carbon atoms, or an acidic group. , A hydroxy group, a nitro group or a halogen atom (—F, —Cl, —Br or —I), and at least one of R ^{8 to} R ²³ is an acidic group. N represents the degree of polymerization.

  Among the compounds having the structure represented by the general formula (4), poly (2-sulfo-5-methoxy-1,4-iminophenylene) is particularly preferable in terms of excellent solubility.

The weight average molecular weight of the conductive polymer is preferably 3,000 to 1,000,000, more preferably 5,000 to 100,000, from the viewpoints of conductivity, film formability, and film strength.
Here, the mass average molecular weight of the conductive polymer is a mass average molecular weight (in terms of sodium polystyrene sulfonate) measured by gel permeation chromatography (GPC).

<Method for producing conductive polymer (A)>
The conductive polymer (A) is, for example, at least one compound (monomer) selected from the group consisting of an acidic group-substituted aniline represented by the following general formula (5), an alkali metal salt thereof, an ammonium salt, and a substituted ammonium salt. Can be obtained by polymerization using an oxidizing agent in the presence of a basic compound.

In formula (5), R ^{24 to} R ²⁸ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxy group having 1 to 24 carbon atoms, or an acidic group. , A hydroxy group, a nitro group, or a halogen atom, and at least one of R ^{24 to} R ²⁸ is an acidic group or a salt thereof.

  Examples of the acidic group-substituted aniline represented by the general formula (5) include a sulfonic acid group-substituted aniline having a sulfonic acid group as an acidic group and a carboxy group-substituted aniline having a carboxy group as an acidic group.

  Typical examples of the sulfone group-substituted aniline are aminobenzenesulfonic acids, specifically, o-, m-, p-aminobenzenesulfonic acid, aniline-2,6-disulfonic acid, aniline-2,5- Disulfonic acid, aniline-3,5-disulfonic acid, aniline-2,4-disulfonic acid, aniline-3,4-disulfonic acid and the like are preferably used.

Examples of sulfone group-substituted anilines other than aminobenzenesulfonic acids include methylaminobenzenesulfonic acid, ethylaminobenzenesulfonic acid, n-propylaminobenzenesulfonic acid, iso-propylaminobenzenesulfonic acid, and n-butylaminobenzenesulfonic acid. Alkyl group-substituted aminobenzene sulfonic acids such as sec-butylaminobenzenesulfonic acid and t-butylaminobenzenesulfonic acid; alkoxy group-substituted aminobenzenes such as methoxyaminobenzenesulfonic acid, ethoxyaminobenzenesulfonic acid and propoxyaminobenzenesulfonic acid Hydroxy group-substituted aminobenzene sulfonic acids; Nitro group-substituted aminobenzene sulfonic acids; Fluoroaminobenzene sulfonic acid, Chloroaminobenzene sulfone Acid, and halogen-substituted aminobenzenesulfonic acids such as bromo aminobenzenesulfonic acid.
Among these, an alkyl group-substituted aminobenzene sulfonic acid, an alkoxy group-substituted aminobenzene sulfonic acid, a hydroxy group-substituted aminobenzene sulfonic acid, or a halogen-substituted one is obtained in that a conductive polymer having excellent conductivity and solubility is obtained. Aminobenzenesulfonic acids are preferred.
These sulfonic acid group-substituted anilines may be used alone or in a mixture of two or more at any ratio.

  Representative examples of carboxyl group-substituted anilines are aminobenzene carboxylic acids, specifically o-, m-, p-aminobenzene carboxylic acid, aniline-2,6-dicarboxylic acid, aniline-2,5-dicarboxylic acid. Acid, aniline-3,5-dicarboxylic acid, aniline-2,4-dicarboxylic acid, aniline-3,4-dicarboxylic acid and the like are preferably used.

Examples of carboxyl group-substituted anilines other than aminobenzenecarboxylic acids include methylaminobenzenecarboxylic acid, ethylaminobenzenecarboxylic acid, n-propylaminobenzenecarboxylic acid, iso-propylaminobenzenecarboxylic acid, and n-butylaminobenzenecarboxylic acid. Alkyl group-substituted aminobenzene carboxylic acids such as sec-butylaminobenzenecarboxylic acid and t-butylaminobenzenecarboxylic acid; alkoxy group-substituted aminobenzenes such as methoxyaminobenzenecarboxylic acid, ethoxyaminobenzenecarboxylic acid and propoxyaminobenzenecarboxylic acid Carboxylic acids; Hydroxy group-substituted aminobenzene carboxylic acids; Nitro group-substituted aminobenzene carboxylic acids; Fluoroaminobenzene carboxylic acid, Chloroaminobenzene carbon Bon acid, such as a halogen group-substituted aminobenzenesulfonic acids such as bromo aminobenzene carboxylic acid. Among other carboxyl group-substituted anilines, alkyl group-substituted aminobenzene carboxylic acids, alkoxy group-substituted aminobenzene carboxylic acids or halogen group-substituted aminobenzene sulfonic acids are obtained in that conductive polymers having particularly excellent conductivity and solubility can be obtained. Is practically preferable.
Each of these carboxyl group-substituted anilines may be used alone, or two or more (including isomers) may be mixed and used in an arbitrary ratio.
Among these acidic group-substituted anilines represented by the general formula (5), at least selected from the group consisting of alkoxy group-substituted aminobenzenesulfonic acids, alkali metal salts, ammonium salts, and substituted ammonium salts in terms of easy production. One compound is particularly preferred.

As the basic compound, inorganic base, ammonia, fatty amines, cyclic saturated amines, cyclic unsaturated amines and the like are used.
Examples of inorganic bases include hydroxide salts such as sodium hydroxide, potassium hydroxide, and lithium hydroxide.

  Examples of the fatty amines include compounds represented by the following general formula (4), ammonium hydroxide compounds represented by the following general formula (5), and the like.

In formula (6), R < ²⁹ > -R < ³⁰ > is a C1-C4 alkyl group each independently.

In formula (7), R < ³² > -R < ³⁵ > is a hydrogen atom or a C1-C4 alkyl group each independently.

  Examples of the cyclic saturated amines include piperidine, pyrrolidine, morpholine, piperazine and derivatives having these skeletons, and ammonium hydroxide compounds thereof.

  Examples of the cyclic unsaturated amines include pyridine, α-picoline, β-picoline, γ-picoline, quinoline, isoquinoline, pyrroline, derivatives having these skeletons, and ammonium hydroxide compounds thereof.

As the basic compound, an inorganic base is preferable. Among basic compounds other than inorganic bases, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylmethylamine, ethyldimethylamine, diethylmethylamine, pyridine, α-picoline, β-picoline, γ -Picoline and the like are preferably used.
If inorganic salts or these basic compounds are used, a highly conductive and highly pure conductive polymer can be obtained.
Each of these basic compounds may be used alone or in admixture of two or more at any ratio.

  The concentration of the basic compound is preferably 0.1 mol / L or more, more preferably 0.1 to 10.0 mol / L, and particularly preferably 0.2 to 8 from the viewpoints of reactivity and conductivity. 0.0 mol / L.

  The mass ratio of the monomer to the basic compound is preferably monomer: basic compound = 1: 100 to 100: 1, more preferably 10:90 to 90:10, from the viewpoint of reactivity and conductivity. is there.

The oxidizing agent is not particularly limited as long as the standard electrode potential is 0.6 V or more. For example, peroxodisulfuric acids such as peroxodisulfuric acid, ammonium peroxodisulfate, sodium peroxodisulfate, and potassium peroxodisulfate; It is preferable to use hydrogen peroxide or the like.
These oxidizing agents may be used alone or in a combination of two or more at any ratio.

1-5 mol is preferable with respect to 1 mol of said monomers, and, as for the usage-amount of an oxidizing agent, More preferably, it is 1-3 mol.
In the present invention, it is important to carry out the polymerization in a system in which the oxidant is present in an equimolar amount or more with respect to the monomer.
It is also effective to use a transition metal compound such as iron or copper in combination with an oxidizing agent as a catalyst.

  Examples of the polymerization method include, for example, a method in which a mixed solution of a monomer and a basic compound is dropped into an oxidizing agent solution, a method in which an oxidizing agent solution is dropped into a mixed solution of a monomer and a basic compound, and a monomer and a base in a reaction vessel. And a method in which a mixed solution of an ionic compound and an oxidizing agent solution are added dropwise simultaneously.

Examples of the solvent used for the polymerization include water or a mixed solvent of water and a water-soluble organic solvent. The water-soluble organic solvent is not limited as long as it is mixed with water. For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-butanol, 3-butanol, t-butanol, Such as 1-pentanol, 3-methyl-1-butanol, 2-pentanol, n-hexanol, 4-methyl-2-pentanol, 2-ethylbutynol, benzyl alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, etc. Alcohols; polyhydric alcohol derivatives such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methoxymethoxyethanol, propylene glycol monoethyl ether, glyceryl monoacetate; acetone, acetonitrile, dimethylform Amides, such as dimethylacetamide.
In addition, when using a mixed solvent as a solvent, although the mixing ratio of water and a water-soluble organic solvent is arbitrary, water: water-soluble organic solvent = 1: 100-100: 1 is preferable.

After polymerization, the solvent is usually filtered off with a filter such as a centrifugal separator. Furthermore, after filtering a filtrate with a washing | cleaning liquid as needed, it is made to dry and a polymer (electroconductive polymer) is obtained.
Examples of the cleaning liquid include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-butanol, 3-butanol, t-butanol, 1-pentanol, 3-methyl-1-butanol, 2- Alcohols such as pentanol, n-hexanol, 4-methyl-2-pentanol, 2-ethylbutynol, benzyl alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methoxy Polyhydric alcohol derivatives such as methoxyethanol, propylene glycol monoethyl ether, glyceryl monoacetate; acetone, acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, dimethyl Rusuruhokishido like are preferable because of high purity can be obtained. In particular, methanol, ethanol, isopropanol, acetone, and acetonitrile are effective.

  The basic compound which forms the salt in the conductive polymer (A) obtained by the production method can reduce the content of the basic compound by performing purification as described later. From the viewpoint of conductivity and heat resistance, the content of the basic compound is preferably 0.1% by mass or less.

(Purification process)
The conductive polymer (A) obtained by the production method may contain unreacted monomers, low molecular weight substances, impurities, and the like, which are factors that impede conductivity. It is desirable to remove.
In order to remove impurities such as unreacted monomers and low molecular weight substances, a method in which the conductive polymer dispersion or solution is subjected to membrane filtration is preferable. As a solvent used for membrane filtration, a solvent such as water, water containing a basic salt, water containing an acid, water containing an alcohol, or a mixture thereof can be used. As a separation membrane used for membrane filtration, an ultrafiltration membrane is preferable in consideration of removal efficiency of unreacted monomers, low molecular weight substances and impurities.

  As a material for the separation membrane, an organic membrane using a polymer such as cellulose, cellulose acetate, polysulfone, polypropylene, polyester, polyethersulfone, or polyvinylidene fluoride, or an inorganic membrane using an inorganic material typified by ceramics may be used. In general, there is no particular limitation as long as it is used as a material for the ultrafiltration membrane.

Furthermore, the conductive polymer (A) obtained by the above production method forms a salt with a cation derived from an oxidant, which is a factor inhibiting conductivity. The conductivity can be improved by removing these cations.
In order to remove impurities such as cations, a method in which a dispersion or solution of a conductive polymer is brought into contact with a cation exchange resin is preferable.
When impurities are removed from the conductive polymer (A) with a cation exchange resin, the conductive polymer (A) is used in a state dispersed or dissolved in a solvent.

  Solvents include alcohols such as water, methanol, ethanol, isopropanol, propanol, and butanol; ketones such as acetone, methyl ethyl ketone, ethyl isobutyl ketone, and methyl isobutyl ketone; ethylene glycol, ethylene glycol methyl ether, ethylene glycol mono-n- Ethylene glycols such as propyl ether; propylene glycols such as propylene glycol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether and propylene glycol propyl ether; amides such as dimethylformamide and dimethylacetamide; N-methylpyrrolidone, Pyrrolidones such as N-ethylpyrrolidone; methyl lactate, ethyl lactate, β-methoxyiso Methyl acid, hydroxy esters such as α- hydroxy methyl isobutyrate, or a mixture of these are preferred.

  As a density | concentration at the time of disperse | distributing or dissolving a conductive polymer in the said solvent, 0.1-20 mass% is preferable from a viewpoint of industrial property or refinement | purification efficiency, and 0.1-10 mass% is more preferable.

Commercially available products can be used as the cation exchange resin, and for example, strong acid type cation exchange resins such as “Amberlite” manufactured by Organo Corporation are preferred.
The form of the cation exchange resin is not particularly limited, and various forms can be used. Examples thereof include spherical fine particles, membranes, and fibers.
100-2000 mass parts is preferable with respect to 100 mass parts of conductive polymers, and, as for the quantity of the cation exchange resin with respect to a conductive polymer, 500-1500 mass parts is more preferable. When the amount of the cation exchange resin is less than 1 part by mass, impurities such as cations are not easily removed. On the other hand, when the amount of the cation exchange resin exceeds 1500 parts by mass, the amount becomes excessive with respect to the dispersion or solution of the conductive polymer, so that the separation after contact with the cation exchange resin and the cation exchange treatment is performed. Recovery of the liquid or eluent becomes difficult.

As a method of contacting the dispersion or solution of the conductive polymer with the cation exchange resin, the dispersion or solution of the conductive polymer and the cation exchange resin are placed in a container, and the mixture is stirred or rotated to exchange the cation. The method of making it contact with resin is mentioned.
In addition, the column is filled with a cation exchange resin, and the dispersion or solution of the conductive polymer is preferably passed at a flow rate of SV = 0.01 to 20, more preferably SV = 0.2 to 10, A method of performing cation exchange treatment may be used.
Here, space velocity SV (1 / hr) = flow rate (m ³ / hr) / filter medium amount (volume: m ³ ).

From the viewpoint of purification efficiency, the time for which the conductive polymer dispersion or solution is brought into contact with the cation exchange resin is preferably 0.1 hour or longer, and more preferably 0.5 hour or longer.
The upper limit of the contact time is not particularly limited, and may be appropriately set in accordance with conditions such as the concentration of the dispersion or eluent of the conductive polymer, the amount of the cation exchange resin, and the contact temperature described later.

  From the industrial viewpoint, the temperature at which the conductive polymer dispersion or solution is brought into contact with the cation exchange resin is preferably 10 to 50 ° C, more preferably 10 to 30 ° C.

  The conductive polymer purified in this manner exhibits a more excellent conductivity because low molecular weight substances such as oligomers and monomers and impurities such as cations are sufficiently removed.

<Conductive polymer (S)>
The conductive polymer (S) has a repeating unit represented by the following general formula (3).

In Formula (3), R ^{5 to} R ⁷ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxy group having 1 to 24 carbon atoms, or an acidic group. Or its salt, a hydroxyl group, a nitro group, or a halogen atom, A is an acidic group or its salt, and m is an integer of 1-20.
In particular, from the viewpoint of conductivity and solubility, m is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3.

  The “acidic group” in the formula (3) is the same as the “acidic group” in the formula (1), and the “salt” in the formula (3) is the “salt” in the formula (1) and the alkaline earth metal. At least one selected from the group consisting of salts.

  As the conductive polymer (S), substituted or unsubstituted aniline, thiophene, pyrrole, phenylene as structural units other than those represented by the general formula (3), as long as they do not affect the solubility, conductivity and properties , Vinylene, other divalent unsaturated groups and divalent saturated groups may be included.

  The conductive polymer (S) according to the embodiment of the present invention preferably contains 70% or more, more preferably 80% or more, particularly 90% of the repeating unit of the general formula (3) from the viewpoint of improving solubility. % Or more is preferable. Here, those having an acidic group content of 70% or less with respect to the aromatic ring are not preferable because of insufficient solubility in water. Further, the higher the content of acidic groups with respect to the aromatic ring, the better the solubility, which is suitable for capacitor production.

  In addition, it is thought that the conductive polymer which concerns on the aspect of this invention has the phenylenediamine structure (reduction type) and quinodiimine structure (oxidation type) represented by the following general formula (8).

In formula (8), R ^{36 to} R ⁵¹ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxy group having 1 to 24 carbon atoms, an acidic group. A group or a salt thereof, a hydroxyl group, a nitro group or a halogen atom, and at least one of R ³⁸ , R ⁴² , R ⁴⁶ and R ⁵⁰ is — (CH ₂ ) _n —A. Here, A is an acidic group or a salt thereof, and n is an integer of 1 to 20. Y represents the degree of polymerization.

  This phenylenediamine structure (reduced type) and quinodiimine structure (oxidized type) can be reversibly converted at an arbitrary ratio by oxidation or reduction. The ratio (x) of the phenylenediamine structure to the quinodiimine structure is preferably in the range of 0.2 <x <0.8 from the viewpoint of conductivity and solubility, and more preferably 0.3 <x <0.7.

The weight average molecular weight of the conductive polymer is preferably 3000 or more, more preferably 5000 to 500,000 in terms of polyethylene glycol, from the viewpoint of conductivity, film formability and film strength. Here, when the weight average molecular weight is 3000 or less, the solubility is excellent but the film formability and conductivity are insufficient. When the weight average molecular weight is 500,000 or more, the solubility and impregnation into the porous molded body are inferior. It is enough.
In addition, as the solid electrolytic capacitor has better performance such as frequency characteristics, a soluble conductive polymer having a conductivity of 0.01 S / cm or more, preferably 0.05 S / cm or more is used.

<Method for producing conductive polymer (S)>
The conductive polymer (S) can be obtained by polymerizing the aniline monomer component in a solvent using an oxidizing agent.
The aniline monomer component used in the present invention has a sulfone group and / or a carboxyl group, and as such an acidic group-substituted aniline derivative, an acidic group-substituted aniline, its alkali metal salt, alkaline earth metal salt, ammonium A compound selected from the group consisting of a salt and a substituted ammonium salt is preferred.

The monomer component according to the embodiment of the present invention is a monomer in which an acidic group or a salt thereof is bonded to an aromatic ring via an alkylene group, and the acidic group or a salt thereof is difficult to be removed even by heat treatment.
Therefore, the conductive polymer according to the embodiment of the present invention has high conductivity and is excellent in thermal stability. Therefore, conductivity can be maintained even after heat treatment.
As the acidic group-substituted aniline, a compound represented by the following general formula (8) is preferable in consideration of expressing excellent conductivity and improving water solubility.

In formula (9), R ^{52 to} R ⁵⁵ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxy group having 1 to 24 carbon atoms, an acidic group. A group or a salt thereof, a hydroxyl group, a nitro group or a halogen atom, A is an acidic group or a salt thereof, and n is an integer of 1 to 20.

It does not specifically limit as a manufacturing method of the conductive polymer (S) which concerns on the aspect of this invention, Well-known manufacturing methods, such as the chemical polymerization method and electrolytic polymerization method by an oxidizing agent, can be used.
Hereinafter, an example of the manufacturing method of the conductive polymer which concerns on the aspect of this invention is demonstrated concretely.

  The conductive polymer (S) according to the embodiment of the present invention can be obtained, for example, by polymerizing the above aniline monomer component with an oxidizing agent in a polymerization solvent.

<Oxidizing agent>
Examples of the oxidizing agent include peroxodisulfuric acids such as peroxodisulfuric acid, ammonium peroxodisulfate, sodium peroxodisulfate, and potassium peroxodisulfate; hydrogen peroxide.
These oxidizing agents may be used individually by 1 type, and 2 or more types may be mixed and used for them in arbitrary ratios.

1-5 mol is preferable with respect to 1 mol of aniline-type monomer components, and, as for the usage-amount of an oxidizing agent, More preferably, it is 1-3 mol. When the amount of the oxidizing agent used is within the above range, the conductive polymer can be sufficiently polymerized and the main chain can be oxidized sufficiently.
It is also effective to use a transition metal compound such as iron or copper in combination with an oxidizing agent as a catalyst.

<Polymerization solvent>
Examples of the polymerization solvent include water and organic solvents. Examples of the organic solvent include alcohols such as methanol, ethanol, isopropyl alcohol, propyl alcohol and butanol; ketones such as acetone and ethyl isobutyl ketone; ethylene glycols such as ethylene glycol and ethylene glycol methyl ether; propylene glycol and propylene glycol Propylene glycols such as methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether and propylene glycol propyl ether; Amides such as N, N-dimethylformamide and N, N-dimethylacetamide; N-methylpyrrolidone, N-ethylpyrrolidone and the like Pyrrolidones and the like.
As the polymerization solvent, water or a mixed solvent of water and an organic solvent is preferable.

(Polymerization process)
A conductive polymer is obtained by chemically oxidatively polymerizing the above aniline monomer component with an oxidizing agent in a polymerization solvent (polymerization step).
Specifically, a method of dropping an aniline monomer component solution (monomer solution) into an oxidizer solution, a method of dropping an oxidizer solution into an aniline monomer component solution, an aniline monomer in a reaction vessel, etc. Conductive conductivity is achieved by various methods, such as a method in which a body component solution and an oxidant solution are dropped simultaneously, a method in which an aniline monomer component solution and an oxidant solution are continuously supplied to a reactor or the like, and polymerization is performed by extrusion flow. A functional polymer is obtained.
In the polymerization, the above-described polymerization solvent can be used.

In the polymerization, a protonic acid may be added to the reaction system.
Examples of the protic acid include mineral acids such as hydrochloric acid, nitric acid, sulfuric acid, and borofluoric acid, super strong acids such as trifluoromethanesulfonic acid, and organic substances such as methanesulfonic acid, dodecylbenzenesulfonic acid, toluenesulfonic acid, and camphorsulfonic acid. Examples thereof include sulfonic acids, and polymer acids such as polystyrene sulfonic acid, polyacrylic acid, polyvinyl sulfonic acid, poly-2-methylpropane-2-acrylamide sulfonic acid, and the like.

  The internal temperature of the polymerization reaction is preferably 50 ° C. or lower, more preferably −15 to 50 ° C., and further preferably −10 to 20 ° C. In particular, if the internal temperature of the polymerization reaction is 20 ° C. or lower, it is possible to suppress a decrease in conductivity due to the progress of side reactions and changes in the redox structure of the main chain. Moreover, if the internal temperature of a polymerization reaction is -15 degreeC or more, sufficient reaction rate can be maintained and reaction time can be shortened.

(Purification process)
The conductive polymer (S) is obtained in the state of a conductive polymer solution dissolved or dispersed in a solvent. The conductive polymer may be used for various purposes as it is after the solvent is removed, but the polymer solution may contain unreacted monomers (aniline monomer components), oligomers, impurities, etc. It is a factor that inhibits sex. Therefore, it is preferable to use the conductive polymer after purification (purification step).
As a method for purifying the conductive polymer (S), a cleaning method using a solvent described in the conductive polymer (A), a membrane filtration method, a cation exchange method, or the like can be used.

  The content of the conductive polymer (A) or (S) in the composition is 0.01% by mass to 20% by mass based on 100% by mass of the entire composition, preferably from the viewpoint of solubility. It is 01 mass%-10 mass%, More preferably, it is 0.01 mass%-5 mass%.

  The conductive polymer (A) or (S) according to the embodiment of the present invention is simply water, water containing a base and a basic salt, water containing an acid, or a solvent such as methanol, ethanol, or isopropanol, or It can be dissolved in a mixture of them and has excellent processability.

  The conductive polymer (A) or (S) according to the embodiment of the present invention includes spray coating, dip coating, roll coating, gravure coating, reverse coating, roll brushing, air knife coating, and curtain coating. A conductor can be formed by a simple method such as the above.

<Nanocarbon (B)>
The nanocarbon (B) of the present invention is mainly composed of carbon such as activated carbon, carbon black, graphite, graphene, graphene, single-walled carbon nanotube, multi-walled carbon nanotube, carbon fiber, carbon nanohorn, carbon nanowall, fullerene. Materials.
From the viewpoint of conductivity, carbon nanotubes are preferable, and single-walled carbon nanotubes and multi-walled carbon nanotubes are particularly preferable.

[carbon nanotube]
A carbon nanotube is a tube having an outer diameter of the order of nm, which is formed by stacking 1 to several tens of layers of graphitic carbon.
Examples of the carbon nanotube include ordinary carbon nanotubes, that is, single-walled carbon nanotubes, multi-walled carbon nanotubes in which single-walled carbon nanotubes are concentrically stacked in a multilayer shape, and those in a coil shape.
In addition, carbon nanotubes include carbon nanohorns with closed carbon nanotubes, cup-shaped nanocarbon materials with holes in the head, fullerenes that are analogs of carbon nanotubes, and carbon nanofibers. .
Among these, single-walled carbon nanotubes and multi-walled carbon nanotubes are preferable in terms of higher conductivity.

Carbon nanotube production methods include, for example, catalytic hydrogen reduction of carbon dioxide, arc discharge method, laser evaporation method, chemical vapor deposition method (CVD method), vapor phase growth method, carbon monoxide at high temperature and high pressure and iron catalyst For example, the HiPco method in which the reaction is performed together with the gas and grown in a gas phase. Moreover, when manufacturing a carbon nanotube, it is preferable to refine | purify by various purification methods, such as the washing | cleaning method, the centrifugation method, the filtration method, the oxidation method, and the chromatographic method.
The carbon nanotubes may be pulverized by a ball-type kneader such as a ball mill, a vibration mill, a sand mill, or a roll mill. The carbon nanotube (a) may be cut short by chemical and physical treatment.
Commercially available carbon nanotubes include, for example, HiPco single-walled carbon nanotubes and double-walled carbon nanotubes manufactured by Unidim, USA; SWNT and MWNT manufactured by Korea Irjin Nanotech; C-100 and C-200 manufactured by Korea CNT; And carbon nanotubes manufactured by China Shenzhen Nanotechport Co., Ltd .; and NC7100 manufactured by Belgian Nanosil Co., Ltd.

  Examples of the carbon nanotube production method include carbon dioxide catalytic hydrogen reduction method, arc discharge method, laser evaporation method, chemical vapor deposition method (CVD method), vapor phase growth method and carbon monoxide at high temperature and high pressure. A HiPco method in which a reaction is performed with a catalyst and grown in a gas phase can be mentioned.

[Activated carbon]
Activated carbon is a porous carbon material, and examples of commercially available activated carbon include activated carbon (Shirakaba) manufactured by Nippon Enviro Chemicals and activated carbon (Kuraray Coal) manufactured by Kuraray Chemical.

(Nanocarbon dispersion)
After mixing the dispersion or solution of the conductive polymer and the nanocarbon, a treatment for accelerating the contact between the conductive polymer and the carbon material may be performed using stirring, ultrasonic irradiation, or the like. The timing of adding the basic compound may be before or after mixing the conductive polymer and nanocarbon. Preferably, in order to improve the dispersibility of nanocarbon, it is preferable to add a basic compound before mixing the conductive polymer and nanocarbon.

<Basic compound (C)>
As the basic compound (C), inorganic bases, ammonia, fatty amines, cyclic saturated amines, cyclic unsaturated amines and the like are used.
In particular, from the viewpoint of conductivity, heat resistance, degassing suppression, and improvement in dispersion stability of the nanocarbon material, alkali metal hydroxide and / or alkaline earth metal hydroxide (C-1) or hydroxy in the same molecule A basic compound (C-2) containing a group and a basic group is preferred.
Addition of the compound (C-1) and / or (C-2) to the conductive polymer (A) or (S) obtained by purification suppresses a decrease in conductivity after heat treatment. be able to.
The reason is that the side groups of the conductive polymer (A) or (S) are desorbed by heating with the basic group contained in the compound (C) and / or the conductive polymer (A ) Or (S), it is considered that the hydroxy group contained in the compound (C) acts as a dopant to improve conductivity.

<Alkali metal hydroxide and / or alkaline earth metal hydroxide (C-1)>
Examples of the compound (C-1) include alkali metal salts and alkaline earth metal salts such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide. Examples of the oxide include hydroxide salts such as beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, and calcium hydroxide. Any one of these hydroxides may be used alone, or two or more thereof may be mixed and used.
The addition amount of the alkali metal hydroxide and / or alkaline earth metal hydroxide (C-1) is 1 mol of the monomer unit of the conductive polymer (A) or (S) from the viewpoints of heat resistance and conductivity. On the other hand, 0.1-5.0 mol is preferable and 0.5-2.0 mol is more preferable.

<Basic compound (C-2) containing hydroxy group and basic group in the same molecule>
Here, the compound (C-2) has a chemical structure represented by the following general formula (6).

式（１０）中、Ａ^１は、ヒドロキシ基であり、Ｂ^１は塩基性基であり、Ｒ^５６は有機基である。

In formula (10), A ¹ is a hydroxy group, B ¹ is a basic group, and R ⁵⁶ is an organic group.

  The hydroxy group may be in a hydroxy group state or a protected state with a protecting group. Examples of the protective group include acetyl groups, silyl groups such as trimethylsilyl group and t-butyldimethylsilyl group, acetal type protective groups (for example, methoxymethyl group, ethoxymethyl group, methoxyethoxymethyl group, etc.), benzoyl group, and the like. Can be mentioned. Moreover, an alkoxide group may be sufficient.

Examples of the basic group include basic groups defined by Arrhenius base, Bronsted base, Lewis base, and the like.
Examples of the organic group include aliphatic, alicyclic, aromatic, straight chain or branched chain, saturated and / or unsaturated organic groups.

Examples of the compound (C-2) containing one or more hydroxy groups and basic groups in the same molecule include 2-aminoethanol, 3-amino-1-propanol, 2-amino-1,3-propanediol, 3-amino-1,2-propanediol, tris (hydroxymethyl) aminomethane, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, diethanolamine, Triethanolamine, 2-amino-1-butanol, L-prolinol, tyramine, L-serine, 2- (4-hydroxyphenyl) glycine, L-threonine, L-isoserine, N, N-di (2-hydroxy) Ethyl) glycine, 3- [N-tris (hydroxymethyl) methylamino] -2-hydroxypropanesulfonic acid N-tris (hydroxymethyl) methyl-2-aminoethanesulfonic acid, L-homoserine, tyrosine, 3- (3,4-dihydroxyphenyl) -L-alanine, N, N-bis (2-hydroxyethyl) -2 -Aminoethanesulfonic acid, N-tris (hydroxymethyl) methyl-3-aminopropanesulfonic acid, 4-amino-3-hydroxybutyric acid, 3-pyrrolidinol, 2-piperidineethanol, 1,3-diamino-2-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 2- (methylamino) ethanol, 3-amino-2,2-dimethyl-1-propanol, 3- (methylamino) -1-propanol, 1- Amino-2-butanol, 4-amino-1-butanol, 4-amino-2-methyl-1-butanol , Valinol, hydroxypiperidine, 4-amino-cyclohexanol, 4- (2-aminoethyl) cyclohexanol, 4-amino-cyclohexane ethanol, and the like.
Some of the compounds (C-2) have L-form and D-form geometric isomers, and either L-form or D-form may be used. You may use it as a mixture of various ratios.
Further, some of the compounds (C-2) have substituent position isomers at the ortho position, the meta position, and the para position, but any one of the ortho position, the meta position, and the para position may be used. It may be used as a mixture of various ratios.
Among these, from the viewpoint of conductivity and heat resistance, 3-amino-1-propanol, 2-amino-1,3-propanediol, tris (hydroxymethyl) aminomethane, 2-amino-2-methyl-1,3-propane Diol, 2-amino-2-ethyl-1,3-propanediol, diethanolamine, triethanolamine, L-prolinol, L-serine, 3- [N-tris (hydroxymethyl) methylamino] -2-hydroxypropane More preferred are sulfonic acid and N-tris (hydroxymethyl) methyl-2-aminoethanesulfonic acid. Any one of these compounds (C-2) may be used alone, or two or more thereof may be mixed and used.
Furthermore, from the viewpoint of conductivity and heat resistance, the compound (C-2) preferably has two or more hydroxy groups in the same molecule.

<Water-soluble polymer (D)>
Here, the water-soluble polymer (D) has a polyvinyl structure and is a structure represented by the following general formula (2).
From the viewpoint of improving the dispersibility and durability of nanocarbon, the polymer (D) preferably contains 10% by mass or more, more preferably 30% by mass or more, in the polymer (D). More preferably, it is contained at 50% by mass or more, particularly preferably 80% by mass or more.

  In formula (2), X is a 5-membered or 6-membered cyclic structure containing a nitrogen atom and / or a carbon atom, and n represents the degree of polymerization.

  The addition amount of the water-soluble polymer (D) is from 0 to 1 part by mass with respect to 1 part by mass of the conductive polymer (A) or (S) from the viewpoints of conductivity, nanocarbon dispersibility, and coating film durability. 1-5.0 mass parts is preferable and 0.1-1.0 mass part is preferable.

Examples of the water-soluble polymer include polyvinyl pyrrolidine and derivatives thereof, polyvinyl pyrrole and derivatives thereof, polyvinyl pyrrolidone and derivatives thereof, polyvinyl piperidine and derivatives thereof, polyvinyl pyridine and derivatives thereof, polyvinyl imidazole and derivatives thereof, polyvinyl lactone and derivatives thereof. , Polyvinylprazole and its derivatives, polystyrene and its derivatives, and the like.
Among these, from the viewpoint of durability of the coating film, polyvinyl pyrrolidone and its derivatives or polystyrene and its derivatives are preferable, and polyvinyl pyrrolidone or polystyrene sulfonic acid is more preferable.

By blending the water-soluble polymer into the conductive composition, the water-soluble polymer (D) is a binder (binder) between the conductive particles comprising the conductive polymer (A) or (S) and the nanocarbon (B). It is considered that the strength of the conductive film made of the conductive composition is increased.
In addition, the structure of the water-soluble polymer (D) is considered to increase the affinity with the nanocarbon (B) and suppress aggregation.

<Solvent (E)>
The solvent (E) may be any solvent that dissolves the conductive polymer (A), the conductive polymer (S), the basic compound (C), and the water-soluble polymer (D). For example, water or water and water-soluble A mixed solvent with an organic solvent is mentioned.

  When the mixed solvent is used, the mixing ratio of water and the water-soluble organic solvent is not particularly limited, but a mixed solvent of water: water-soluble organic solvent = 1: 100 to 100: 1 is preferable.

The water-soluble organic solvent is not particularly limited as long as it is mixed with water. Specific examples of water-soluble organic solvents include water or alcohols such as methanol, ethanol, isopropanol, n-propanol, and n-butanol; ketones such as acetone, methyl ethyl ketone, ethyl isobutyl ketone, and methyl isobutyl ketone; ethylene glycol, Ethylene glycols such as ethylene glycol methyl ether and ethylene glycol mono-n-propyl ether; propylene glycols such as propylene glycol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether and propylene glycol propyl ether; dimethylformamide and dimethyl Amides such as acetamide; Pyrrolidones such as N-methylpyrrolidone and N-ethylpyrrolidone; N-methyl Pyrrolidone, pyrrolidones such as N- ethyl-pyrrolidone; methyl lactate, ethyl lactate, beta-methoxyisobutyrate methyl butyrate, hydroxypropyl esters such as α- hydroxy methyl isobutyrate and the like.
Among these, alcohols, acetone, acetonitrile, dimethylformamide, dimethylacetamide and the like are preferable from the viewpoint of solubility, and alcohols are particularly preferable. As alcohols, methanol, ethanol, isopropanol and the like are preferable.

  As the solvent (E), water or a mixed solvent of water and alcohols is particularly preferable from the viewpoints of solubility and film formability. Moreover, it is preferable that this mixed solvent contains 50 mass% or more of water.

Since the conductive polymer after the cation exchange is in a state of being dispersed or dissolved in a solvent such as water, a solid conductive polymer can be obtained by removing the solvent with an evaporator or the like. It may be used in a dissolved state.
In the conductive composition, the content of the conductive polymer (A) or (S) is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the solvent (E) from the viewpoint of conductivity and workability. 0.5-5.0 mass parts is more preferable.

<Conductor manufacture>
In the present invention, a conductor is produced by sequentially performing a step of applying the conductive composition to a substrate to form a coating film and, if necessary, a step of performing a heat treatment on the coating film. can do.

The base material to which the conductive composition is applied is not particularly limited, and polymer compounds, wood, paper materials, metals, metal oxides, ceramics, and films or glass plates thereof are used.
For example, as a base material made of a polymer compound, polyethylene, polyvinyl chloride, polypropylene, polystyrene, ABS resin, AS resin, methacrylic resin, polybutadiene, polycarbonate, polyarylate, polyvinylidene fluoride, polyamide, polyimide, polyaramid, polyphenylene sulfide , Polymer films containing any one or more of polyether ether ketone, polyphenylene ether, polyether nitrile, polyamide imide, polyether sulfone, polysulfone, polyether imide, polybutylene terephthalate, etc. .
For example, aluminum, tantalum, niobium, etc. are raised as a base material made of a metal oxide.

  Since these polymer films form a conductive film made of the conductive composition on at least one surface thereof, the film surface is subjected to corona surface treatment or plasma treatment for the purpose of improving the adhesion of the conductive film. Or it is preferable that the ultraviolet ozone treatment is performed.

  As a method for coating the conductive composition, a method generally used for coating a paint can be used. For example, gravure coater, roll coater, curtain flow coater, spin coater, bar coater, reverse coater, kiss coater, phanten coater, rod coater, air doctor coater, knife coater, blade coater, cast coater, screen coater, etc. A spraying method such as spray coating, a dipping method such as dipping under normal pressure, pressurization, or reduced pressure is used.

[Production Example 1]
<Polymerization of conductive polymer (A)>
1 mol of 2-aminoanisole-4-sulfonic acid was dissolved in 300 ml of 4 mol / L triethylamine aqueous solution (water: acetonitrile = 3: 7) at 0 ° C. to obtain a monomer solution.
Separately, 1 mol of ammonium peroxodisulfate was dissolved in 1 L of a solution of water / acetonitrile = 3: 7 to obtain an oxidant solution.
Subsequently, the monomer solution was dropped into the oxidant solution while the oxidant solution was cooled to 5 ° C. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 12 hours, and then the reaction product was separated by a centrifugal filter.
Further, the reaction product is washed with methanol and then dried, and the repeating unit represented by the formula (1) (in the formula (1), R ¹ is a sulfonic acid group and R ^{2 to} R ³ are hydrogen atoms). 185 g of a conductive polymer powder having atoms and R ⁴ is a methoxy group.
Content of the basic compound (triethylamine and ammonia) which forms the salt contained in the obtained conductive polymer was 16.7 mass%.

<Preparation of conductive composition>
5 parts by mass of the obtained conductive polymer was dissolved in 95 parts by mass of water at room temperature to obtain a conductive polymer solution (A-1).
“Room temperature” means 25 ° C.
An acidic cation exchange resin (manufactured by Organo Corporation, “Amberlite”) is packed into a column so as to be 50 parts by mass with respect to 100 parts by mass of the obtained aqueous conductive polymer solution (A-1). Then, the conductive polymer solution (A-1) was passed at a flow rate of SV = 8 to perform a cation exchange treatment to obtain a purified conductive polymer solution (A-2).
In the obtained conductive polymer solution (A-2), the proportion of the conductive polymer was 4.5% by mass (4.7 parts by mass with respect to 100 parts by mass of the solvent). Moreover, content of the basic compound (triethylamine and ammonia) which forms the salt contained in a conductive polymer (A-2) was 0.1 mass% or less.

[Production Example 2]
<Polymerization of conductive polymer (S)>
1 mol of (3-amino-4-methoxyphenyl) -methanesulfonic acid was dissolved in 300 ml of 4 mol / L triethylamine aqueous solution (water: acetonitrile = 3: 7) at 0 ° C. to obtain a monomer solution.
Separately, 1 mol of ammonium peroxodisulfate was dissolved in 1 L of a solution of water / acetonitrile = 3: 7 to obtain an oxidant solution.
Subsequently, the monomer solution was dropped into the oxidant solution while the oxidant solution was cooled to 5 ° C. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 12 hours, and then the reaction product was separated by a centrifugal filter.
Furthermore, the reaction product is washed with methanol and then dried, and the repeating unit represented by the formula (1) (in the formula (2), A is a sulfonic acid group, and R ⁵ and R ⁷ are hydrogen atoms. , And R ⁶ is a methoxy group).
Content of the basic compound (triethylamine and ammonia) which forms the salt contained in the obtained conductive polymer was 16.7 mass%.

<Preparation of conductive composition>
5 parts by mass of the obtained conductive polymer was dissolved in 95 parts by mass of water at room temperature to obtain a conductive polymer solution (S-1).
“Room temperature” means 25 ° C.
An acidic cation exchange resin (manufactured by Organo Corporation, “Amberlite”) is packed into a column so as to be 50 parts by mass with respect to 100 parts by mass of the obtained aqueous conductive polymer solution (S-1). Then, the conductive polymer solution (S-1) was passed at a flow rate of SV = 8 to perform cation exchange treatment to obtain a purified conductive polymer solution (S-2).
In the obtained conductive polymer solution (S-2), the proportion of the conductive polymer was 4.5% by mass (4.7 parts by mass with respect to 100 parts by mass of the solvent). Moreover, content of the basic compound (triethylamine and ammonia) which forms the salt contained in a conductive polymer (S-2) was 0.1 mass% or less.
The following water-soluble resin solution used was adjusted to a 5% aqueous solution.

[Example]
20 parts by mass of the conductive polymer (A-1) obtained in Production Example 1, 1 part by mass of a multi-walled carbon nanotube (VGCF-X manufactured by Showa Denko), 0.2 part by mass of sodium hydroxide, polyvinyl pyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd., K15) ) (Hereinafter PVP) 20 parts by mass was mixed with 60 parts by mass of water at room temperature to prepare a conductive composition 1.

[Example 2]
21 parts by mass of the conductive polymer (A-2) obtained in Production Example 1, 1 part by mass of multi-walled carbon nanotube (VGCF-X manufactured by Showa Denko), 0.2 part by mass of sodium hydroxide, polystyrene sulfonic acid (Tosoh Organic Chemical Co., Ltd.) PS-5) (hereinafter referred to as PSS) 20 parts by mass was mixed with 59 parts by mass of water at room temperature to prepare a conductive composition 2.

[Example 3]
21 parts by mass of the conductive polymer (A-2) obtained in Production Example 1, 1 part by mass of a multi-walled carbon nanotube (VGCF-X manufactured by Showa Denko), 0.2 part by mass of lithium hydroxide, and 20 parts by mass of PVP are 59 parts by mass of water. The electrically conductive composition 3 was prepared by mixing the resultant at room temperature.

[Example 4]
20 parts by mass of the conductive polymer (A-1) obtained in Production Example 1, 1 part by mass of a multi-walled carbon nanotube (VGCF-X manufactured by Showa Denko), 0.2 part by mass of lithium hydroxide, and 20 parts by mass of PSS are 60 parts by mass of water. The electrically conductive composition 4 was prepared by mixing the resultant at room temperature.

[Example 5]
21 parts by mass of the conductive polymer (A-2) obtained in Production Example 1, 1 part by mass of a multi-walled carbon nanotube (VGCF-X manufactured by Showa Denko), 0.6 part by mass of trishydroxymethylaminomethane (hereinafter, THMA), PSS 20 parts by mass was mixed with 59 parts by mass of water at room temperature to prepare a conductive composition 5.

[Example 6]
21 parts by mass of the conductive polymer (S-2) obtained in Production Example 2, 1 part by mass of a multi-walled carbon nanotube (VGCF-X manufactured by Showa Denko), 0.2 part by mass of lithium hydroxide, 20 parts by mass of PSS and 59 parts by mass of water The electrically conductive composition 6 was prepared by mixing with the part at room temperature.

[Comparative Example 1]
A conductive composition 7 was prepared by mixing 21 parts by weight of the conductive polymer (A-2) obtained in Production Example 1, 1 part by weight of multi-walled carbon nanotubes (VGCF-X manufactured by Showa Denko) and 79 parts by weight of water at room temperature. did.

[Comparative Example 2]
20 parts by mass of the conductive polymer (A-1) obtained in Production Example 1, 1 part by mass of a multi-walled carbon nanotube (VGCF-X, manufactured by Showa Denko), 0.1 part by mass of ammonia, acrylic resin (Dianal MX1845, manufactured by Mitsubishi Rayon Co., Ltd.) The conductive composition 8 was prepared by mixing 20 parts by weight with 60 parts by weight of water at room temperature.

[Comparative Example 3]
21 parts by mass of the conductive polymer (A-2) obtained in Production Example 1, 1 part by mass of a multi-walled carbon nanotube (VGCF-X manufactured by Showa Denko), 0.1 part by mass of triethylamine, acrylic resin (Dynar MX MX1845 manufactured by Mitsubishi Rayon Co., Ltd.) The conductive composition 9 was prepared by mixing 20 parts by weight with 59 parts by weight of water at room temperature.

[Comparative Example 4]
21 parts by mass of the conductive polymer (A-2) obtained in Production Example 1, 1 part by mass of multi-walled carbon nanotube (VGCF-X manufactured by Showa Denko), 0.2 part by mass of sodium hydroxide, poly N vinylacetamide (Showa Denko) (Made) (hereinafter referred to as PNVA) 20 parts by mass with water (59 parts by mass) at room temperature to prepare a conductive composition 10.

[Comparative Example 5]
20 parts by mass of the conductive polymer (A-1) obtained in Production Example 1, 1 part by mass of multi-walled carbon nanotubes (VGCF-X manufactured by Showa Denko), 0.2 parts by mass of sodium hydroxide, polyvinyl alcohol (Poval 207 manufactured by Kuraray Co., Ltd.) ) (Hereinafter PVA) 10 parts by mass was mixed with 70 parts by mass of water at room temperature to prepare a conductive composition 11.

[Comparative Example 6]
20 parts by mass of the conductive polymer (A-1) obtained in Production Example 1, 1 part by mass of a multi-walled carbon nanotube (VGCF-X made by Showa Denko), 0.2 part by mass of sodium hydroxide, acrylic resin (Made by Mitsubishi Rayon, Dianal) MX1845) 20 parts by mass of water was mixed with 60 parts by mass of water at room temperature to prepare a conductive composition 12.

<Evaluation 1 (dispersed state)>
The conductive compositions 1 to 12 were subjected to ultrasonic treatment for 30 minutes while being cooled using an ultrasonic homogenizer (vibra cell 20 kHz manufactured by SONIC). The dispersion state of the nanocarbon was observed visually. The evaluation criteria are as follows.
○: Uniformly dispersed or dissolved ×: Nonuniformly dispersed or agglomerated

<Evaluation 2 (Durability Evaluation)>
0.5 g of the conductive compositions 1 to 12 was dropped on a glass watch glass having a diameter of 9 cm, heated with a dryer at 160 ° C. for 30 minutes, and the state of the film was visually observed. The evaluation criteria are as follows.
○: No crack occurred in the film ×: Crack occurred in the film

<Evaluation 3 (Evaluation of degassing by heating)>
Conductive compositions 1 to 12 are applied to a diameter of about 1 cm on a 5 cm square glass substrate and dried at 80 ° C. for 1 hour. Then, it sealed with the silver paste so that the coating film of an electroconductive composition might be covered, it dried at 150 degreeC for 1 hour, and the interface peeling by degassing was observed.
○: No holes or bulges occurred in the silver pace film ×: Holes or bulges occurred in the silver pace film

  The results of the evaluations 1 to 3 are shown in Table 1.

From Table 1, Examples 1-6 which used the electrically conductive composition of this invention were excellent in the dispersion stability of a nanocarbon material, durability of a coating film, and a degassing suppression effect.
On the other hand, in Comparative Examples 1 to 6 that do not use the specific water-soluble polymer (D), film cracking occurred during heating, and the durability of the coating film was reduced as compared with the Examples. In particular, in Comparative Example 4, nanocarbon was not dispersed and film formation was not possible.
Moreover, Examples 1-6 containing a basic compound (C) were also favorable in the degassing suppression effect at the time of a heating.

  The nanocarbon-containing conductive composition of the present invention can be applied to various antistatic agents, capacitors, batteries, fuel cells, polymer electrolytes thereof, and electrode layers by using simple coating techniques such as coating, spraying, casting, and dipping. , Catalyst layer, gas diffusion layer, gas diffusion electrode layer, etc. and conductive auxiliary agent in each layer, EMI shield, chemical sensor, display element, nonlinear material, anticorrosive, adhesive, fiber, spinning material, plating primer, etc. It is applicable to.

Claims (5)

A conductive composition comprising a conductive polymer (A) having a repeating unit represented by the following general formula (1), nanocarbon (B) and a water-soluble polymer (D) represented by the following general formula (2).

In formula (1), R ^{1 to} R ⁴ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxy group having 1 to 24 carbon atoms, or an acidic group. , A hydroxy group, a nitro group or a halogen atom. At least one of R ^{1 to} R ⁴ is an acidic group or a salt thereof.

In formula (2), X is a 5-membered or 6-membered cyclic structure containing a nitrogen atom and / or a carbon atom, and n represents the degree of polymerization. A conductive composition comprising a conductive polymer (S) having a repeating unit represented by the following general formula (3), nanocarbon (B), and a water-soluble polymer (D) represented by the following general formula (2).

In Formula (3), R ^{5 to} R ⁷ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxy group having 1 to 24 carbon atoms, or an acidic group. Or its salt, a hydroxyl group, a nitro group, or a halogen atom, A is an acidic group or its salt, and m is an integer of 1-20.

In formula (2), X is a 5-membered or 6-membered cyclic structure containing a nitrogen atom and a carbon atom, and n represents the degree of polymerization.   Furthermore, the electroconductive composition of Claim 1 or 2 containing a basic compound (C).   The basic compound (C) is an alkali metal hydroxide and / or alkaline earth metal hydroxide (C-1) or a basic compound (C-2) containing a hydroxy group and a basic group in the same molecule. The conductive composition according to claim 3, wherein   The conductor formed from the electrically conductive composition as described in any one of Claims 1-4.