JPH10158395A - Production of soluble conductive polymer having acidic group - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a soluble conductive polymer exhibiting high conductivity and solubility and having a high mol.wt. SOLUTION: This method for producing a soluble conductive polymer having acidic groups comprises subjecting at least one kind of compound selected from the group consisting of an acidic group-substituted aniline, an acidic group-substituted pyrrole, an acidic group-substituted thiophene, an acidic group-substituted furan, an acidic group-substituted selenophene, an acidic group-substituted tellurophene, an acidic group-substituted isothianaphthene, an acidic group-substituted isobenzofuran, an acidic group-substituted isoindoline, an acidic group-substituted isobenzoselenophene, an acidic group-substituted isobenzotellurophene, their alkali metal salts, ammonium salts and substituted ammonium salts, or the compound and at least one kind of compound selected from the group consisting of an aniline derivative, a pyrrole derivative, a thiophene derivative, a furan derivative, a selenophene derivative, a tellurophene derivative, an isothianaphthene derivative, an isobenzofuran derivative, an isoindoline derivative, an isobenzoselenophene derivative and an isobenzotellurophene derivative to an electrolytic oxidation polymerization in a solution containing a basic compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a soluble conductive polymer soluble in a solvent. The solution containing the soluble conductive polymer as a main component is applied onto various substrates by spray coating, dip coating, roll coating, gravure coating, reverse coating, roll coating, air knife coating, curtain coating, etc. The conductor can be formed by the simple method described above. Further, in order to increase the adhesiveness of the conductive film and the strength of the coating film, an appropriate binder polymer may be mixed and used.

[0002] As a coating substrate, polyester resin such as PET, polyethylene naphthalate (PEN), polyethylene, polypropylene, vinyl chloride, nylon, polystyrene, polycarbonate, epoxy resin, fluororesin, polysulfone, polyimide, silicone resin, polyurethane, Examples include various plastics and films such as phenolic resin and synthetic paper, paper, iron, aluminum, copper, zinc, nickel, and stainless steel. The application step may be performed before or during the steps of manufacturing these substrates, for example, a uniaxial stretching method, a biaxial stretching method, a molding process, an embossing process, or the like. You can do it too.

[0003] Compositions containing the polymer as a main component include various kinds of antistatic, antistatic, capacitors, batteries, EMI
It can be applied to shields, chemical sensors, display elements, non-linear materials, anticorrosives, adhesives, fibers, antistatic paints, electrodeposition paints, plating primers, bases for electrostatic painting, anticorrosion, improvement of battery storage capacity, etc. is there. Further, the polymer does not have humidity dependence of conductivity, has high transparency, and can be stretched, molded, embossed, etc., and thus has excellent suitability for various antistatic applications.

[0004] Antistatic applications include packaging materials, magnetic cards, magnetic tapes, magnetic disks, photographic films, printing substrates, release films, heat seal tape films,
There are an IC tray, an IC carrier tape, a cover tape, and the like.

[0005]

2. Description of the Related Art Although doped polyaniline (soluble conductive polymer) is well known, it is insoluble in almost all common solvents except for some aprotic polar solvents, and has difficulty in molding and processing. is there. Further, a method of electrolytic oxidation polymerization of aniline [JP-A-60-235831,
J. Polymer Sci. Polymer Ch
em. Ed. , 26, 1531 (1988)], it is possible to form a polyaniline film on an electrode, but there is a problem that the isolation operation is complicated and mass synthesis is difficult.

In recent years, alkali-soluble sulfonated polyanilines exhibiting conductivity without adding a dopant and a method for synthesizing the same, and carboxylated polyanilines and a method for synthesizing the same have been proposed.

As a method of synthesizing a sulfonated polyaniline, for example, a method of electrochemically polymerizing aniline and m-aminobenzenesulfonic acid to synthesize a sulfonated polyaniline (Journal of the Chemical Society of Japan, 1985, 1124, Japanese Patent Application Laid-Open No. No. 166165), a method of synthesizing a sulfonated polyaniline by electrochemically polymerizing o-, m-, and p-aminobenzenesulfonic acid alone [The 64th Annual Meeting of the Chemical Society of Japan, Proceedings II, 706 (199
2)], a method of chemically polymerizing aniline and o-, m-aminobenzenesulfonic acid to synthesize a sulfonated polyaniline (Japanese Patent Application Laid-Open No. 01-301714), an aminobenzenesulfonic acid-based compound or aminobenzenesulfonic acid A method of chemically oxidizing and polymerizing a monomer containing an aniline compound and a monomer containing an aniline compound (Japanese Patent Application Laid-Open No. 6-56987), using an emeraldine-type polymer (polyaniline) obtained by polymerizing chemically or electrochemically. A method of sulfonating with concentrated sulfuric acid (JP-A-58-210902), a method of sulfonating using sulfuric anhydride / triethyl phosphate complex (JP-A-61-197633), and a method of sulfonating with fuming sulfuric acid [J. Am. Chem. Soc. ,
(1991) 113, 2665-2671; Am.
Chem. Soc. , (1990) 112, 2800,
WO91-06887], a method of chemically polymerizing diphenylamine-4-sulfonic acid (sodium salt) to synthesize an N-substituted sulfonated polyaniline [Polyme]
r, (1993) 34, 158-162] and the like.

[0008] Am. Chem. Soc. , (199
1) According to 113, 2665-2671, it is stated that polymerization of o-, m-aminobenzenesulfonic acid was attempted chemically and electrochemically but was not successful.

Further, Japanese Patent Application Laid-Open No. 6-56987 discloses that
Aminobenzenesulfonic acid-based compound or aminobenzenesulfonic acid-based compound and aniline-based compound can be water-soluble soluble conductive polymer by chemical oxidative polymerization in acidic, neutral and alkaline solutions. Although it is shown in the polymerization example in a sulfuric acid solution, there is no description about the molecular weight of the polymer and other physical properties, and it is not clear what kind of physical properties of the polymer were obtained. According to the follow-up test of the present inventors, a polymer having a molecular weight sufficient for forming a film could not be obtained.

Further, when the present inventors attempted polymerization in an aqueous solution containing a protonic acid using ammonium peroxodisulfate as an oxidizing agent, a water-soluble polymer was obtained. A practical polymer as formed could not be obtained.

The present inventors have also disclosed in Japanese Patent Application Laid-Open No. 01-301.
No. 714, a method of chemically polymerizing aniline and m-aminobenzenesulfonic acid with ammonium peroxodisulfate, and a method of converting aniline and m-aminobenzenesulfonic acid described in JP-A-6-56987. When a follow-up test was conducted on the method of chemically polymerizing with potassium manganate, only one sulfonic acid group was introduced into five aromatic rings, showing high conductivity, but completely in neutral and acidic water. And almost insoluble in an alkaline aqueous solution such as ammonia. Also,
In the case of sulfonation by the method of JP-A-61-197633, as described on page 7 of the same publication, the solubility of polyaniline in the sulfonation solvent is not sufficient, and the sulfonation reaction in the dispersion state of the polymer is not sufficient. As a result, only about one sulfonic acid group is introduced into five aromatic rings. The thus obtained sulfonated polyaniline having a small sulfonic acid group introduction ratio has a problem that the conductivity and the solubility are not sufficient.

Further, J. J. Am. Chem. Soc. ,
(1991) 113, 2665-2671; Am.
Chem. Soc. , (1990) 112, 2800, it is stated that when polyaniline is sulfonated with fuming sulfuric acid, about one sulfonic acid group is introduced into two aromatic rings. However, when polyaniline is sufficiently sulfonated by the present method, a large excess of fuming sulfuric acid is required because the solubility of polyaniline in fuming sulfuric acid is not sufficient. Further, when polyaniline is added to fuming sulfuric acid, there is a problem that the polymer is easily solidified. Further, a polymer synthesized by the above method and a sulfonated product thereof,
There is also a problem that it is soluble in an aqueous solution containing a base such as ammonia and alkylamine, but not in water alone.

Further, Polymer (1993) 34,
According to 158 to 162, when diphenylamine-4-sulfonic acid (sodium salt) is polymerized, an N-substituted sulfonated polyaniline having one benzenesulfonic acid group introduced into the aniline skeleton is obtained, and water alone is used. Are dissolved, but the isolation of the polymer requires an ultracentrifugation operation. When the present inventors performed additional tests, the yield of the polymer obtained from the polymerization solvent was low due to high solubility, and the polymer could not be isolated without high-speed centrifugation. Was. In addition, because of the N-substitution type, J. Am. Chem. Soc. , (199
1) The conductivity was lower than that of the polymer synthesized by the method of 113, 2665 to 2671.

As a method for synthesizing a carboxylated polyaniline, for example, 2- or 3-carboxylic acid group-substituted aniline or a salt thereof is oxidatively polymerized and then treated with a basic substance to obtain a carboxylic acid group in a salt form. Method (JP-A-4-
268331) has been proposed, but the amount of the oxidizing agent to be used is twice or more the amount of the raw material, and the conductivity is low. From this, it is considered that the reactivity of the monomer was low and a low molecular weight polymer was formed.

Also, a synthesis method in which methyl anthranilate (anthranilic acid methyl ester) is polymerized in an aqueous acidic medium in the presence of ammonium peroxodisulfate, and then the methyl ester is saponified with alcoholic potassium hydroxide (Japanese Patent Laid-Open No. Japanese Patent Application Laid-Open No. 5-226238) has been proposed, but the operation is very complicated because the reaction has two steps.

Further, the present inventors attempted polymerization in an aqueous solution containing a protonic acid by using 2-carboxylic acid group-substituted aniline as an oxidizing agent and using ammonium peroxodisulfate as an oxidizing agent. As a result, a product was obtained. Did not. Further, when polymerization was performed in an aqueous solution containing a protonic acid using aniline and ammonium peroxodisulfate as an oxidizing agent using aniline and 2-carboxylic acid group-substituted aniline, a copolymer was obtained. Both were low. It is considered that the obtained copolymer has a low copolymerization ratio of 2-carboxylic acid group-substituted aniline.

In consideration of moldability such as film formation by coating, in order to be able to apply to both hydrophilic and hydrophobic substrates, it is necessary to have solubility in both water and an organic solvent. Is desired. However, the sulfonated polyaniline has solubility in alkaline water, but is insoluble in neutral to acidic aqueous solutions, and is not sufficiently soluble in organic solvents.

As a method of solving these various problems,
The present inventors developed a polymer without adding a doping agent, and in order to improve solubility, more acidic groups such as sulfonic acid groups or carboxylic acid groups were added to the aromatic ring of the main chain. Considering that it is necessary to introduce, aniline, N-alkyl aniline and at least one compound selected from the group consisting of phenylenediamines, and aminobenzenesulfonic acid are copolymerized using an oxidizing agent in an acidic solvent, Furthermore, a method for producing a sulfonated aniline copolymer which is sulfonated with a sulfonating agent has been proposed (JP-A-5-17889). However, in this method, the operation of sulfonating in concentrated sulfuric acid is performed, so that there is a problem of waste acid treatment. In addition, it is presumed that each of the copolymers synthesized by the above method has a structure represented by the following formula (7).

[0019]

Embedded image (Wherein, R _{11 to} R ₁₄ are each a group selected from the group consisting of hydrogen and a sulfonic acid group, and R ′ is a group selected from the group consisting of hydrogen or an alkyl group having 1 to 4 carbon atoms. And the proportion of sulfonic acid groups is 40 to 80 with respect to the aromatic ring.
X is an arbitrary number from 0 to 1;
Is a number of 2 to 1500 indicating the degree of polymerization)

Further, the present inventors have proposed aniline, N-
By copolymerizing at least one compound selected from the group consisting of alkylanilines and phenylenediamines with an alkoxy-substituted aminobenzenesulfonic acid, a sulfonation operation that generates a large amount of waste is omitted. (Japanese Patent Application Laid-Open No. 6-293828). In addition,
It is presumed that each of the copolymers synthesized by the above method has the structure of the following formula (8).

[0021]

Embedded image (Wherein, R _{15 to} R ₂₂ are each a group selected from the group consisting of hydrogen, an alkoxy group and a sulfonic acid group, and the proportion of the sulfonic acid group is such that the sulfonic acid group is 25 to the aromatic ring.
The same aromatic ring contains an alkoxy group and a sulfonic acid group, and R 'is a group selected from the group consisting of hydrogen and an alkyl group having 1 to 4 carbon atoms; Represents an arbitrary number of 0 to 1, and n is a number of 2 to 1500 indicating the degree of polymerization.)

Further, the present inventors have proposed a soluble aniline-based soluble conductive polymer which polymerizes an acid group-substituted aniline such as a sulfonic acid group-substituted aniline or a carboxylic acid group-substituted aniline in a solution containing a basic compound, and a method for producing the same. JP-A-7-196791, JP-A-7-324132) have been proposed. This method can produce a high molecular weight polymer, contrary to the conventional belief that anilines having a sulfonic acid group or a carboxylic acid group are not easily polymerized by themselves. Moreover, the obtained soluble conductive polymer exhibits high conductivity and excellent dissolution in any of acidic to alkaline aqueous solutions. However, when isolating the soluble conductive polymer and the by-product salt of the oxidizing agent used in the oxidative polymerization,
Since the solubility of the soluble conductive polymer itself is very excellent, there is a problem that its operation is not easy in industrial practice. In addition, it is presumed that each of the copolymers synthesized by the above method has a structure represented by the following formula (9).

[0023]

Embedded image (Wherein, A _{1 to} A ₄ represent a sulfonic acid group, a carboxylic acid group,
B _{1 to} B ₄ are one group selected from the group consisting of an alkali metal salt, a ammonium salt, and a substituted ammonium salt;
A linear or branched alkyl group having 1 to 4 carbon atoms, 1 carbon atom
1 to 4 represent one group selected from the group consisting of a linear or branched alkoxy group, an acidic group, a hydroxyl group, a nitro group and a halogen group. x represents an arbitrary number of 0 to 1, and n is a number of 2 to 5,000 indicating the degree of polymerization.)

On the other hand, a method of synthesizing a sulfonated polyaniline by electrochemically polymerizing aniline and m-aminobenzenesulfonic acid (Journal of the Chemical Society of Japan, 1985, 1124;
JP-A-02-166165), a method of electrochemically polymerizing aminobenzenesulfonic acid (The Chemical Society of Japan No. 6)
Proceedings of the 4th Annual Meeting II 706 (1992) have been reported. However, these methods have a problem that since an inorganic salt is added as an electrolyte, the operation of isolating the soluble conductive polymer and the electrolyte after polymerization becomes complicated, and it is very difficult to apply the method to industrial mass synthesis.

[0025]

SUMMARY OF THE INVENTION The object of the present invention is to
An object of the present invention is to provide a soluble conductive polymer having high conductivity and solubility and a high molecular weight and a method useful as an industrial production method thereof.

[0026]

Means for Solving the Problems The present inventors have proposed, as polyanilines having high conductivity and solubility, sulfonated polyanilines having a high ratio of introducing sulfonic acid groups to aromatic rings and carboxylated polyanilines having a high ratio of introducing carboxylic acid groups. As a result of intensive studies on a method for producing an acidic group-substituted polyaniline having a large ratio of introduction of an acidic group, an acidic group-substituted aniline such as a sulfonic acid group-substituted aniline or a carboxylic acid group-substituted aniline, or the acid group-substituted aniline and an aniline derivative are used as monomers. It has been found that, when electrolytically oxidized and polymerized in a solution containing a basic compound, a highly conductive, highly soluble and high molecular weight soluble conductive polymer which cannot be obtained by chemical oxidative polymerization can be obtained. In addition, since the monomer and the polymer work as electrolytes, the electrolyte usually required for electrolytic oxidation polymerization is unnecessary, and the operation of separating the electrolyte and the soluble conductive polymer can be omitted.
Therefore, the polymerization solution can be used as it is as a product such as a coating agent, which is industrially convenient. Further, since the polymerized polymer is soluble in the reaction solution, it can be applied to a continuous electrolysis system such as a flow system. A flow-through system is a method in which a reaction solution is circulated through a cell between a working electrode and a cathode by a liquid sending pump to carry out polymerization.By connecting these cells in series or in parallel, polymerization under optimal conditions is performed. It is possible to carry out the reaction. In addition, the knowledge of electrolytic polymerization with these acidic group-substituted anilines is exactly the same as that of the acidic group-substituted pyrrole, thiophene, furan, selenophene, tellurophen, isothianaphthene, isobenzofuran, isoindoline, isobenzoselenophene, and isobenzoselenophene. It has been found that it can also be applied to benzotellurophen.
The present invention has been achieved based on such findings.

That is, the present invention relates to an acid group-substituted aniline, an acid group-substituted pyrrole, an acid group-substituted thiophene, an acid group-substituted furan, an acid group-substituted selenophene, an acid group-substituted tellurophen, an acid group-substituted isothianaphthene, and an acid group-substituted isothianaphthene. At least one compound (a) selected from the group consisting of benzofuran, acid-substituted isoindoline, acid-substituted isobenzoselenophene, acid-substituted isobenzotellurophen, metal salts thereof, ammonium salt and substituted ammonium salt The present invention relates to a method for producing a soluble conductive polymer having an acidic group, which is characterized by carrying out electrolytic polymerization in a solution containing a basic compound (ii).

Another one of the present invention is an acid-substituted aniline, an acid-substituted pyrrole, an acid-substituted thiophene, an acid-substituted furan, an acid-substituted selenophene, an acid-substituted tellurophen, an acid-substituted isothianaphthene, an acid-substituted isothianaphthene, At least one compound selected from the group consisting of group-substituted isobenzofuran, acid-substituted isoindoline, acid-substituted isobenzoselenophene, acid-substituted isobenzotellurophen, and metal salts, ammonium salts and substituted ammonium salts thereof ( A) and an aniline derivative, a pyrrole derivative, a thiophene derivative, a furan derivative, a selenophene derivative, a tellurophen derivative, an isothianaphthene derivative,
Electrolytically polymerizing at least one compound (c) selected from the group consisting of an isobenzofuran derivative, an isoindoline derivative, an isobenzoselenophene derivative and an isobenzotellurophen derivative in a solution containing a basic compound (b) And a method for producing a soluble conductive polymer having an acidic group.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to an acid group-substituted aniline system which is the most preferred example.
The same is true for selenophene, tellurophen, isothianaphthene, isobenzofuran, isoindoline, isobenzoselenophene and isobenzotellurophen. The acid group-substituted aniline has a general formula (1)

Embedded image (Wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are hydrogen,
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 hydroxyl group, a substituent selected from the group consisting of a nitro group and a halogen group, At least one of them represents an acidic group.
Here, the acidic group represents a sulfonic acid group or a carboxylic acid group), and represents at least one compound selected from the group consisting of an acidic group-substituted aniline represented by the formula: metal salt, ammonium salt and substituted ammonium salt. The compound of the general formula (1) in which the acidic group is bonded to the o-position or the m-position with respect to the amino group has better performance such as conductivity and solubility of the obtained polymer.

The most typical aniline substituted with an acidic group is aniline substituted with a sulfonic acid group or aniline substituted with a carboxylic acid group. Preferred is aniline-substituted aniline, which tends to have higher conductivity than carboxylic acid-substituted aniline.

The most typical sulfonic acid group-substituted anilines 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 are preferably used.

Other aniline-substituted anilines include methylaminobenzenesulfonic acid, ethylaminobenzenesulfonic acid, n-propylaminobenzenesulfonic acid, iso-propylaminobenzenesulfonic acid, n
Alkyl-substituted aminobenzenesulfonic acids such as -butylaminobenzenesulfonic acid, sec-butylaminobenzenesulfonic acid, t-butylaminobenzenesulfonic acid, methoxyaminobenzenesulfonic acid, ethoxyaminobenzenesulfonic acid, and n-propoxyaminobenzenesulfonic acid Acid, iso-propoxyaminobenzenesulfonic acid, n-butoxyaminobenzenesulfonic acid, se
Alkoxy-substituted aminobenzenesulfonic acids such as c-butoxyaminobenzenesulfonic acid and t-butoxyaminobenzenesulfonic acid, hydroxy-substituted aminobenzenesulfonic acids, nitro-substituted aminobenzenesulfonic acids, fluoroaminobenzenesulfonic acid, chloroaminobenzene Examples thereof include halogen-substituted aminobenzenesulfonic acids such as sulfonic acid and bromoaminobenzenesulfonic acid. Among them, alkyl-substituted aminobenzenesulfonic acids, alkoxy-substituted aminobenzenesulfonic acids, or hydroxy-substituted aminobenzenesulfonic acids are most practically preferable. In addition, these sulfonic acid group-substituted anilines may be used alone or may be mixed in an isomer at an arbitrary ratio.

The most typical aniline-substituted anilines are aminobenzenecarboxylic acids, specifically, o-, m-, p-aminobenzenecarboxylic acid, aniline-2,6-dicarboxylic acid, aniline -2,5-dicarboxylic acid, aniline-3,5-dicarboxylic acid, aniline-2,4-dicarboxylic acid, aniline-3,4-dicarboxylic acid are preferably used.

Other aniline-substituted anilines include methylaminobenzenecarboxylic acid, ethylaminobenzenecarboxylic acid, n-propylaminobenzenecarboxylic acid, iso-propylaminobenzenecarboxylic acid, and n-propylaminobenzenecarboxylic acid.
Alkyl-substituted aminobenzenecarboxylic acids such as -butylaminobenzenecarboxylic acid, sec-butylaminobenzenecarboxylic acid, t-butylaminobenzenecarboxylic acid, methoxyaminobenzenecarboxylic acid, ethoxyaminobenzenecarboxylic acid, n-propoxyaminobenzenecarboxylic acid Acid, iso-propoxyaminobenzenecarboxylic acid, n-butoxyaminobenzenecarboxylic acid, se
Alkoxy-substituted aminobenzenecarboxylic acids such as c-butoxyaminobenzenecarboxylic acid and t-butoxyaminobenzenecarboxylic acid, hydroxy-substituted aminobenzenecarboxylic acids, nitro-substituted aminobenzenecarboxylic acids, fluoroaminobenzenecarboxylic acid, chloroaminobenzene Examples thereof include halogen-substituted aminobenzenecarboxylic acids such as carboxylic acid and bromoaminobenzenecarboxylic acid. Of these, alkyl-substituted aminobenzenecarboxylic acids, alkoxy-substituted aminobenzenecarboxylic acids or hydroxy-substituted aminobenzenecarboxylic acids are most practically preferable. Each of these carboxylic acid group-substituted anilines may be used alone, or the isomers may be mixed at an arbitrary ratio.

More specifically, specific examples of the acid group-substituted aniline represented by the general formula (1) include: sulfonic acid group-substituted alkylaniline carboxylic acid group-substituted alkylaniline sulfonic acid group-substituted alkoxyaniline carboxylic acid group-substituted alkoxyaniline sulfonic acid group-substituted Hydroxyaniline Carboxylic acid-substituted hydroxyaniline Sulfonic acid-substituted nitroaniline Carboxylic acid-substituted nitroaniline Sulfonic acid-substituted fluoroaniline Carboxylic acid-substituted fluoroaniline Sulfonic-acid-substituted chloroaniline And carboxylic acid group-substituted bromoaniline. Specific examples of the positions and combinations of these substituents are shown in Table 1.

[0036]

[Table 1] Here, A: one group selected from a sulfonic acid group or a carboxylic acid group, an alkali metal salt, an ammonium salt, and a substituted ammonium salt thereof; B: a methyl group, an ethyl group, an n-propyl group, an iso-propyl Groups, n-butyl groups, sec-butyl groups, alkyl groups such as t-butyl groups, methoxy groups, ethoxy groups, n-
One selected from an alkoxy group such as a propoxy group, an iso-propoxy group, an n-butoxy group, a sec-butoxy group and a t-butoxy group, and a halogen group such as a hydroxy group, a nitro group, a fluoro group, a chloro group and a bromo group. H represents hydrogen.

Examples of the metal forming a salt in these monomers include lithium, sodium, potassium and the like.

The substituted ammonium includes aliphatic ammonium, cyclic saturated ammonium, cyclic unsaturated ammonium and the like.

The aliphatic ammoniums include the following general formula (10)

Embedded image (Wherein R _{23 to} R ₂₆ are groups independently selected from the group consisting of hydrogen and an alkyl group having 1 to 4 carbon atoms). For example, methyl ammonium, dimethyl ammonium, trimethyl ammonium,
Ethyl ammonium, diethyl ammonium, triethyl ammonium, methyl ethyl ammonium, diethyl methyl ammonium, dimethyl ethyl ammonium, propyl ammonium, dipropyl ammonium, isopropyl ammonium, diisopropyl ammonium, butyl ammonium, dibutyl ammonium, methyl propyl ammonium, ethyl propyl ammonium, methyl isopropyl Examples include ammonium, ethyl isopropyl ammonium, methyl butyl ammonium, ethyl butyl ammonium, tetramethyl ammonium, tetramethylol ammonium, tetraethyl ammonium, tetra n-butyl ammonium, tetra sec-butyl ammonium, tetra t-butyl ammonium, and the like. Of these, the most preferred case one is hydrogen, the other three are alkyl groups having 1 to 4 carbon atoms of R ₂₃ to R _26, and then two of hydrogen, the other two of R ₂₃ to R ₂₆
One is preferably an alkyl group having 1 to 4 carbon atoms.

Examples of the cyclic saturated ammoniums include piperidinium, pyrrolidinium, morpholinium, piperazinium, and derivatives having these skeletons.

The cyclic unsaturated ammoniums include pyridinium, α-picolinium, β-picolinium, γ-
Examples include picolinium, quinolinium, isoquinolinium, pyrrolium, and derivatives having these skeletons.

Next, the basic compound (b) used in the present invention may be any compound as long as it forms a salt with the above-mentioned acidic group-substituted anilines. Cyclic saturated amines, cyclic unsaturated amines, inorganic bases and the like are preferably used. Above all, aliphatic amines, cyclic saturated amines, cyclic unsaturated amines and the like are preferable.

As the fatty amines, the following general formula (1)
1)

Embedded image (Wherein, R _{27 to} R ₂₉ are independently selected from the group consisting of alkyl groups having 1 to 4 carbon atoms).

Or the following general formula (12)

Embedded image (Wherein, R _{30 to} R ₃₃ are each independently selected from the group consisting of hydrogen and an alkyl group having 1 to 4 carbon atoms.)
Can be mentioned.

The cyclic saturated amines include piperidine,
Pyrrolidine, morpholine, piperazine, derivatives having these skeletons, and ammonium hydroxide compounds thereof are preferably used.

As the cyclic unsaturated amines, pyridine,
α-picoline, β-picoline, γ-picoline, quinoline, isoquinoline, pyrroline, derivatives having these skeletons, and ammonium hydroxide compounds thereof are preferably used.

As the inorganic base, salts of hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide are preferably used, and the above-mentioned aliphatic amines, cyclic saturated amines, and cyclic unsaturated amines are preferably used. The resulting polymers tend to be inferior in conductivity to amines.

The concentration of the basic compound (b) is 0.1.
1 mol / liter or more, preferably 0.1 to 10.0
mol / liter, more preferably 0.2 to 8.0 mo
It is used in the range of 1 / liter. At this time, 0.1mo
When the amount is 1 / liter or less, the yield of the obtained polymer decreases. When the amount is 10.0 mol / liter or more, the conductivity tends to decrease. The basic compound (b) can be used by mixing at an arbitrary ratio.

The aniline derivative (c) is represented by the following general formula (4)

Embedded image (Wherein, R _{6 to} R ₁₀ are each composed of hydrogen, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxy group having 1 to 24 carbon atoms, a hydroxyl group, a nitro group, and a halogen group. And a group consisting of substituents).

The most typical aniline derivative (c) is aniline. In addition, methylaniline, ethylaniline, n-propylaniline, iso-
Alkyl anilines such as propyl aniline, n-butyl aniline, sec-butyl aniline, t-butyl aniline, methoxy aniline, ethoxy aniline, n-propoxy aniline, iso-propoxy aniline, n-butoxy aniline, sec-butoxy aniline, t- Examples include alkoxy aniline such as butoxy aniline, halogen aniline such as hydroxy aniline, nitro aniline, fluoro aniline, chloro aniline, and bromo aniline. The coexistence of the aniline derivative (c) has an effective action for improving the conductivity, coating properties and the like of the obtained conductive polymer.

The weight ratio of the compound (a) such as the above-mentioned acidic group-substituted aniline to the basic compound (b) is as follows:
(B) = 1: 100-100: 1, preferably 10: 9
0 to 90:10 is used. Here, if the ratio of the basic compound is low, the reactivity decreases and the conductivity also decreases. Conversely, when the ratio is high, the ratio of the salt formed between the acidic group and the basic compound in the obtained polymer increases, and the conductivity tends to decrease.

The weight ratio of the compound (a) such as the acid group-substituted aniline and the aniline derivative (c) to the basic compound (b) is (a) + (c) :( b) = 1: 1.
00 to 100: 1, preferably 10:90 to 90:10
Is used. Here, if the ratio of the basic compound is low, the reactivity decreases and the conductivity also decreases. Conversely, when the ratio is high, the ratio of the salt formed between the acidic group and the basic compound in the obtained polymer increases, and the conductivity tends to decrease.

The ratio (mol) of the compound (a) such as the above-mentioned acid-substituted aniline to the aniline derivative (c) is
(A): (c) = 100: 0 to 30:70, preferably 99.999: 0.001 to 50:50, more preferably 99.999: 0.001 to 70:30. Here, if the ratio of the aniline derivative is high (exceeding 70), the content of the sulfone group in the obtained polymer is not sufficient, and the solubility tends to decrease.

The molar ratio between the acidic group (d) and the basic compound (b) in the compound (a) such as the above-mentioned acid-substituted aniline is (d) :( b) = 1: 100 to 100: 1, preferably 1: 0.25 to 1:20, more preferably 1: 0.5 to 1:15. here,
When the ratio of the basic compound is low, the reactivity is reduced and the conductivity is also reduced. Conversely, when the ratio is high, the ratio of the salt formed between the acidic group and the basic compound in the obtained polymer increases, and the conductivity tends to decrease.

The concentration of the compound (a) such as an aniline substituted with an acidic group and the aniline derivative (c) at the time of electrolytic polymerization are 0.1% or more, preferably 0.5 to 50%, more preferably 1 to 50% based on the solvent. -30%.

The polymerization or copolymerization is carried out by electrolytic oxidation polymerization in a solution containing these basic compounds. Solvents are water, methanol, ethanol, isopropanol,
Acetonitrile, methyl isobutyl ketone, methyl ethyl ketone, dimethylformamide, dimethylacetamide and the like are preferably used.

As the electrode material at the time of electrolytic oxidation polymerization, gold,
Silver, platinum, nickel, mercury, stainless steel, copper, zinc, tin, lead, iron, aluminum, titanium, ruthenium, iridium, or a metal plate or net electrode of these oxides, or a carbon electrode such as glassy carbon; A glass electrode provided with a metal oxide such as ITO, tin-indium oxide, and tin oxide can be used. Among them, silver, platinum, titanium, glassy carbon, and ITO glass are preferable.

As the electrolysis method, any of a constant current electrolysis method, a constant potential electrolysis method and a constant voltage electrolysis method can be used. The current density during the constant current electrolytic polymerization is 5 to 200 mA /
cm ² , preferably 10 to 200 mA / cm ² , more preferably 15 to 150 mA / cm ² . The potential during the constant potential electrolytic polymerization is -0.5 V or less, preferably -1 V to -10 V, more preferably -1 with respect to the standard electrode.
It is advantageous to apply a potential of V to -7 V to the working electrode.

As the electrolyte, if necessary, Li
Salts such as BF ₄ , HBF ₄ , HClO ₄ , HCl, and H ₂ SO ₄ can be added. However, in the present method, the compound (a) itself such as an acid group-substituted aniline and the polymer itself serve as electrolytes, and thus polymerization can be performed without these electrolytes.

The reaction is preferably carried out in a temperature range of -15 to 70 ° C, more preferably -5 to 70 ° C.
A range of 60 ° C. applies. Here, when the temperature is lower than −15 ° C. or higher than 70 ° C., the conductivity tends to decrease.

The hydrogen at the sulfonic or carboxylic acid groups in the polymers produced according to the invention is hydrogen,
It is a group independently selected from the group consisting of alkali metals, ammonium and substituted ammonium, that is, these groups can be obtained not only alone but also in a mixed state.

Specifically, when polymerized in the presence of sodium hydroxide, most of the hydrogen in the sulfonic acid group or carboxylic acid group in the isolated polymer has been replaced with sodium.

Similarly, most of the hydrogen in the sulfonic acid group or carboxylic acid group in the polymer is ammonium when polymerized in the presence of ammonia, and is mostly trimethylammonium when polymerized in the presence of trimethylamine. When polymerized in the presence, it is mostly obtained with quinolinium.

When a mixture of basic compounds is used, it is obtained in a mixed state. Specifically, when the polymerization is carried out in the presence of sodium hydroxide and ammonia, the hydrogen in the sulfonic acid group or carboxylic acid group in the isolated polymer is obtained in the presence of both sodium and ammonium. Similarly, when the obtained polymer is treated with a solution in which both sodium hydroxide and ammonia are present, hydrogen in the sulfonic acid group or carboxylic acid group in the polymer is obtained in a state where both sodium and ammonium are present. Can be

The above-mentioned polymer in which a part of the acidic group forms a salt can be converted into a polymer having an acidic group which does not form a salt by treating and isolating in a acidic solution. .

Examples of the acidic solution include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, nitric acid and the like. However, it is difficult to prevent the acidic group from forming a salt at all even if the acid substitution is sufficiently performed.

The weight-average molecular weight of the thus obtained soluble conductive polymer having an acidic group containing a sulfonic acid group or a carboxylic acid group in the aromatic ring is 3,000 or more, preferably 3,000 to 1,000,000, and more preferably 3,000 to 1,000,000. Preferably it is 5,000 to 500,000. The introduction ratio of the acidic group to the aromatic ring is 50% or more, preferably 70% or more.
%, More preferably 80% or more. Here, if the introduction ratio of the acidic group is less than 50%, the solubility in water tends to decrease, and it becomes difficult to apply the compound industrially.

This conductive polymer can be used without further sulphonation operation without adding water, a base such as ammonia or alkylamine or water containing a base and a basic salt such as ammonium acetate and ammonium oxalate, hydrochloric acid and sulfuric acid. In water or a solvent such as methyl alcohol, ethyl alcohol, or isopropyl alcohol, or a mixture thereof.

To explain the solubility in detail, the soluble conductive polymer having an acidic group in the present invention is 0.1 mol / mol.
1% by weight or more dissolved in 1 liter of an aqueous alkaline solution such as aqueous ammonia, 1% by weight or more in an aqueous acidic solution such as 0.1 mol / liter aqueous sulfuric acid, and 1% by weight or more in a neutral aqueous solution such as water Dissolve and further add 1 mol / l organic solvent such as ammonia alcohol solution.
It has the property of dissolving by weight percent or more.

The polymer or copolymer synthesized by the above method is presumed to have a structure represented by the following formula (13).

Embedded image (Wherein, R _{34 to} R ₄₉ represent hydrogen, 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 hydroxyl group, a nitro group, and a halogen atom) A group selected from the group consisting of the following groups: The introduction ratio of the acidic group is at least 50% based on the aromatic ring, and the acidic group is a sulfonic acid group or a carboxylic acid group. Represents an arbitrary number of 0 to 1, and n is a number of 2 to 1500 indicating the degree of polymerization.)

[0071]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

[Measurement Method] The IR spectrum was measured using an apparatus manufactured by PerkinElmer (model 1600). GPC measurement (in terms of polyethylene oxide) using a GPC column for aqueous solution for measurement of molecular weight distribution and molecular weight
Was done. Column is for aqueous solution; TSK manufactured by Tosoh
-GEL G-5000PWKL and TSK-GEL G
Two types of -3000PWXL were connected in series and used.
Further, a 0.2 mol / l phosphate buffer solution was used as an eluent. For the conductivity, a four-terminal method was used for measuring the conductivity, and a two-terminal method was used for measuring the surface resistance.

Example 1 A 150 mol pyridine solution having a concentration of 0.05 mol / l was added to 150 ml
4.06 g of -aminoanisole-4-sulfonic acid are dissolved, glassy carbon is immersed in the solution as a working electrode, and platinum is immersed in a cathode.
Was applied for 1 hour to carry out electrolytic polymerization. Immediately after the start of electrolytic polymerization, a polymerization reaction occurred on the surface of the polymerization electrode, and after 5 minutes, the colorless and transparent reaction solution turned brown. After the completion of the polymerization reaction, there was no precipitation of the polymer on the polymerization electrode and the polymerization liquid was uniform. In addition, elution of metal components from the polymerization electrode, oligomers and the like were hardly detected. The obtained polymer solution was applied on a glass substrate by spin coating,
Dry at ℃. A film having a smooth surface resistance of 2 × 10 ⁵ Ω / □ with a thickness of 0.1 μm was obtained.

As a result of the molecular weight measurement, the number average molecular weight (Mn)
20,000, weight average molecular weight (Mw) 22,000,
Z average molecular weight 24,000, dispersity Mw / Mn = 1.
1, Mz / Mw = 1.1.

The obtained polymer solution was concentrated under reduced pressure to isolate the polymer, and the amount of the polymer dissolved was measured. The method is water, 0.1
The polymer was filtered in a small amount in a 10 mol / L aqueous sulfuric acid solution or in 10 ml of 0.1 mol / L aqueous ammonia when the polymer was no longer dissolved. The dissolved amount of the soluble conductive polymer synthesized in Example 1 was 250 mg / ml of water, 245 mg / ml of sulfuric acid, and 260 mg / ml of aqueous ammonia.

FIG. 1 shows an IR chart of the soluble conductive polymer, and FIG. 2 shows a GPC measurement chart of the polymer. The assignment of the IR spectrum is as follows. Sulfone group; 1120, around 1020 cm ^-1 Polymer backbone; absorption around 1500 cm ^-1

Example 2 150 ml of 0.05 mol / l α-picoline solution
3.7 g of 2-aminobenzenesulfonic acid was dissolved in
Glassy carbon as a working electrode and platinum as a cathode were immersed in this solution, and a constant voltage of 2.0 V was applied thereto at room temperature with stirring to carry out electrolytic polymerization for 0.5 hours. After the completion of the polymerization reaction, there was no precipitation of the polymer on the polymerization electrode and the polymerization liquid was uniform. In addition, elution of metal components from the polymerization electrode, oligomers and the like were hardly detected. The obtained polymer solution was applied on a glass substrate by spin coating,
And dried. A film having a smooth surface resistance of 5 × 10 ⁶ Ω / □ with a thickness of 0.1 μm was obtained.

Example 3 A 0.05 mol / l triethylamine solution (water /
3.6 g of 2-aminobenzenesulfonic acid and 0.1 g of aniline are dissolved in 150 ml of isopropanol (1/1), and an ITO electrode as a working electrode and platinum as a cathode are immersed in this solution, and stirred at room temperature for 2 hours. Electrolytic polymerization was performed for 0.5 hour by applying a constant voltage of 0V. After the completion of the polymerization reaction, there was no precipitation of the polymer on the polymerization electrode and the polymerization liquid was uniform. In addition, elution of metal components from the polymerization electrode, oligomers and the like were hardly detected. The obtained polymerization liquid was applied on a glass substrate by spin coating and dried at 100 ° C. A film having a smooth surface resistance of 1 × 10 ⁷ Ω / □ with a thickness of 0.1 μm was obtained.

Example 4 50 parts by weight of the polymer solution obtained in Example 1 and 100 parts by weight of an aqueous acrylic emulsion resin [Nicazole RX-301C, manufactured by Nippon Carbide Co., Ltd.] were added to 100 parts by weight of water at room temperature. Stirring was performed to prepare a conductive crude product. The solution thus obtained was applied on a PET film using a gravure coater having a depth of 40 μm, and dried at 120 ° C.
Smooth surface resistance value of surface of 0.2 μm thickness 1 × 10 ⁷ Ω /
The film of □ was obtained.

Example 5 100 parts by weight of the polymer solution obtained in Example 1 and 5 parts by weight of polyvinyl alcohol as a crosslinking agent were stirred and dissolved at room temperature to prepare a crosslinkable conductive composition. The solution obtained in this manner is converted into a P by a gravure coater having a depth of 40 μm.
It was applied on an ET film and dried at 150 ° C. A film having a smooth surface resistance of 5 × 10 ⁶ Ω / □ on a 0.8 μm-thick surface was obtained. When this conductive film was immersed in water and acetone, the film was cross-linked and no dissolution or peeling was observed.

Example 6 100 parts by weight of the polymer solution obtained in Example 1, 5 parts by weight of polyvinyl alcohol as a crosslinking agent, and 100 parts by weight of an aqueous acrylic emulsion resin [Nicazole RX-301C, manufactured by Nippon Carbide Co., Ltd.] Parts were stirred and dissolved in 100 parts by weight of water at room temperature to prepare a crosslinkable conductive composition. The solution obtained in this manner was applied to a galvanized plate (20 mm × 50
mm x 1 mm) by dip coating.
It was dried at 0 ° C. to form a 0.5 μm conductive layer. This zinc plate with a conductive layer --- NO.1-and a zinc plate coated with a chromium compound as a comparison (coating thickness 5-6 μm) --- NO.2-
And zinc plate --- NO.3-at 40 ° C with salt spray (JIS-
K-5400 method), and each was subjected to an anticorrosion test. Table 2 shows the results.

[Table 2]

Example 7 In 30 ml of a 0.5 mol / l aqueous ammonia solution, 2
-Aminoanisole-4-sulfonic acid (3.0 g) was dissolved in the solution. Platinum as a working electrode and glassy carbon as a cathode were immersed in the solution. Polymerization was performed. Immediately after the start of the application, a polymerization reaction occurred on the surface of the working electrode, and the reaction solution, which was initially colorless and transparent, turned black-green after 5 minutes. After the completion of the polymerization reaction, there was no precipitation of the polymer on the working electrode, and the polymerization solution was uniform. In addition, elution of metal components from the working electrode and almost no oligomers were detected. The obtained polymerization liquid was applied on a glass substrate by spin coating and dried at 100 ° C. A film having a smooth surface resistance of 2 × 10 ⁵ Ω / □ with a thickness of 0.1 μm was obtained.

Example 8 In 30 ml of a 0.5 mol / l aqueous ammonia solution, 2
3.0 g of -aminoanisole-4-sulfonic acid were dissolved. The solution was subjected to electrolytic polymerization by applying a constant voltage of 2.0 V at room temperature while circulating the solution through a series flow-through cell using platinum as a working electrode and glassy carbon as a cathode with a pump. A polymerization reaction occurred on the surface of the working electrode immediately after the start of the application, and the colorless and transparent reaction solution turned black-green after 5 minutes. After the completion of the polymerization reaction, there was no precipitation of the polymer on the working electrode, and the polymerization solution was uniform. In addition, elution of metal components from the working electrode and almost no oligomers were detected. The obtained polymerization solution was applied on a glass substrate by spin coating and dried at 80 ° C. Smooth surface resistance value of 0.1 μm thick surface 5 × 10 ⁶ Ω / □
Was obtained.

Example 9 20 ml of 0.5 mol / l diethylamine aqueous solution
3.0 g of 2-aminoanisole-4-sulfonic acid was dissolved in the solution, and platinum was immersed in the solution as a working electrode and glassy carbon was immersed as a cathode.
Electropolymerization was performed for 5 hours by applying a constant voltage of 5V. A polymerization reaction occurred on the surface of the working electrode immediately after the start of application, and a black-green film polymer adhered to the working electrode three hours later. After the completion of the polymerization reaction, peeling and dropping of the polymer on the working electrode did not occur. The obtained polymerization liquid was applied on a glass substrate by spin coating and dried at 100 ° C. Thickness 0.1μ
Thus, a film having a smooth surface resistance of 1 × 10 ⁷ Ω / □ was obtained.

Example 10 A solution of 0.5 mol / l ammonia solution in 30 ml
-Dissolve 2.5 g of aminobenzoic acid, immerse platinum in the solution as a working electrode and glassy carbon as a cathode,
Without stirring, a constant voltage of 3.0 V was applied at room temperature to perform electrolytic polymerization for 5 hours. A polymerization reaction occurred on the surface of the working electrode immediately after the start of application, and a black-green film polymer adhered to the working electrode three hours later. After the completion of the polymerization reaction, peeling and dropping of the polymer on the working electrode did not occur. The obtained polymer solution was applied on a glass substrate by spin coating,
Dry at ℃. A film having a smooth surface resistance of 5 × 10 ⁷ Ω / □ with a thickness of 0.1 μm was obtained.

Example 11 A solution of ozone was added to 30 ml of a 0.5 mol / l aqueous ammonia solution.
2.5 g of aminobenzoic acid were dissolved. While circulating the solution through a series flow-through cell with platinum as the working electrode and glassy carbon as the cathode, the solution was pumped,
Electrolytic polymerization was performed by applying a constant voltage of 3.0 V at room temperature. A polymerization reaction occurred on the surface of the working electrode immediately after the start of the application, and the colorless and transparent reaction solution turned black-green after 5 minutes. After the completion of the polymerization reaction, there was no precipitation of the polymer on the working electrode, and the polymerization solution was uniform. In addition, elution of metal components from the working electrode and almost no oligomers were detected. The obtained polymerization liquid was applied on a glass substrate by spin coating and dried at 100 ° C. A film having a smooth surface resistance of 7 × 10 ⁶ Ω / □ with a thickness of 0.1 μm was obtained.

Example 12 A solution of ozone was added to 30 ml of a 0.5 mol / l aqueous ammonia solution.
3.0 g of aminobenzenesulfonic acid were dissolved. The solution was subjected to electrolytic polymerization by applying a constant voltage of 2.0 V at room temperature while circulating the solution through a series flow-through cell using platinum as a working electrode and glassy carbon as a cathode with a pump. A polymerization reaction occurred on the surface of the working electrode immediately after the start of the application, and the colorless and transparent reaction solution turned black-green after 5 minutes. After the completion of the polymerization reaction, there was no precipitation of the polymer on the working electrode, and the polymerization solution was uniform. In addition, elution of metal components from the working electrode and almost no oligomers were detected. The obtained polymerization solution was applied on a glass substrate by spin coating and dried at 80 ° C. A film having a smooth surface resistance of 7 × 10 ⁶ Ω / □ with a thickness of 0.1 μm was obtained.

Example 13 1.0 g of thiophene-3-sulfonic acid was dissolved in 20 ml of a 0.5 mol / l pyridine aqueous solution, and platinum was immersed in this solution as a working electrode and glassy carbon was immersed as a cathode. At room temperature, a constant voltage of 2.0 V was applied to perform electrolytic polymerization for 5 hours. A polymerization reaction occurred on the surface of the working electrode immediately after the start of the application, and a black-green film polymer adhered to the working electrode three hours later. After the completion of the polymerization reaction, peeling and dropping of the polymer on the working electrode did not occur. The obtained polymerization liquid was applied on a glass substrate by spin coating and dried at 100 ° C. A film having a smooth surface resistance of 1 × 10 ⁵ Ω / □ with a thickness of 0.1 μm was obtained.

Example 14 1.0 g of thiophene-3-sulfonic acid was dissolved in 20 ml of a 0.5 mol / l aqueous pyridine solution. The solution was subjected to electrolytic polymerization by applying a constant voltage of 2.0 V at room temperature while circulating the solution through a series flow-through cell using platinum as a working electrode and glassy carbon as a cathode with a pump. A polymerization reaction occurred on the surface of the working electrode immediately after the start of the application, and the colorless and transparent reaction solution turned black-green after 5 minutes. After the completion of the polymerization reaction, there was no precipitation of the polymer on the working electrode, and the polymerization solution was uniform. In addition, elution of metal components from the working electrode and almost no oligomers were detected. The obtained polymerization liquid was applied on a glass substrate by spin coating and dried at 100 ° C. A film having a smooth surface resistance of 7 × 10 ⁵ Ω / □ with a thickness of 0.1 μm was obtained.

Comparative Example 1 Proceedings of the 64th Annual Meeting of the Chemical Society of Japan Autumn Meeting II, 706 (19
92) 2-Aminobenzenesulfonic acid was synthesized by electrolytic polymerization according to the method described in 92). The obtained polymerization solution was applied on a glass substrate by spin coating and dried at 80 ° C.
However, since the polymerization solution contained sulfuric acid, the coatability was poor and a film could not be obtained.

Comparative Example 2 As a soluble aniline soluble conductive polymer,
According to the method described in Example 1 of JP-A-324132, 2-aminobenzenesulfonic acid was synthesized by chemical polymerization. The obtained polymerization solution was applied on a glass substrate by spin coating and dried at 80 ° C. Its surface resistance is 1 × 1
0 ⁷ Ω / □. However, since the polymerization solution contained a large amount of sulfate, a smooth film could not be obtained. Separation was carried out by the method described, but the filtration was poor and the operation was very complicated.

[0092]

According to the present invention, a high-molecular-weight soluble conductive polymer having high conductivity and solubility that cannot be obtained by conventional chemical oxidation polymerization can be produced. Further, since the monomer and the polymer work as an electrolyte, an electrolyte which is indispensable in ordinary electrolytic oxidation polymerization is unnecessary, and an operation of separating the electrolyte and the soluble conductive polymer can be omitted. Therefore, the polymerization solution can be used as it is as a product such as a coating agent, which is industrially convenient. Furthermore, since the polymerized polymer is soluble in the reaction solution, a continuous electrolytic polymerization system can be applied, and industrial mass production has been enabled.

[Brief description of the drawings]

FIG. 1 is an IR chart of a polymer in Example 1.

FIG. 2 is a GPC chart of a polymer in Example 1.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Shinichi Maeda 10-1 Daikokucho, Tsurumi-ku, Yokohama-shi, Kanagawa Prefecture Nitto Chemical Industry Co., Ltd.

Claims (7)

[Claims] 1. An acid-substituted aniline, an acid-substituted pyrrole, an acid-substituted thiophene, an acid-substituted furan, an acid-substituted selenophene, an acid-substituted tellurophen, an acid-substituted isothianaphthene, an acid-substituted isobenzofuran, an acid-substituted Substituted isoindoline, acidic group-substituted isobenzoselenophene, acidic group-substituted isobenzotellurophen, at least one compound (a) selected from the group consisting of metal salts, ammonium salts and substituted ammonium salts thereof,
A method for producing a soluble conductive polymer having an acidic group, characterized in that electrolytic polymerization is carried out in a solution containing a basic compound (b). 2. The method for producing a soluble conductive polymer having an acidic group according to claim 1, wherein the electrolytic polymerization is performed continuously using a continuous cell connected in series, parallel, or a combination thereof. 3. The acid group-substituted aniline represented by the general formula (1): (Wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are hydrogen,
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 hydroxyl group, a substituent selected from the group consisting of a nitro group and a halogen group, At least one of them represents an acidic group.
Here, the acidic group indicates a sulfonic acid group or a carboxylic acid group. ) Represents an acid-substituted aniline, or the above-mentioned acid-substituted pyrrole, an acid-substituted thiophene, an acid-substituted furan, an acid-substituted selenophene, an acid-substituted tellurophen, an acid-substituted isothianaphthene, an acid-substituted isobenzofuran, The group-substituted isoindoline, the acid-substituted isobenzoselenophene, and the acid-substituted isobenzotellurophen are represented by the general formula (2) or the general formula (3). Embedded image (In the formula, Z is any of NH, S, O, Se, and Te, and R ′ ₁ , R ′ ₂ , R ′ _3, and R ′ ₄ are hydrogen, carbon number 1
-24 linear or branched alkyl group, 1-24 carbon atoms
Is a substituent selected from the group consisting of linear or branched alkoxy, acidic, hydroxyl, nitro and halogen groups, at least one of which is an acidic group. Here, the acidic group indicates a sulfonic acid group or a carboxylic acid group. ) Represented by an acid-substituted pyrrole, an acid-substituted thiophene, an acid-substituted furan, an acid-substituted selenophene,
The acidic group-substituted tellurophen, the acidic group-substituted isothianaphthene, the acidic group-substituted isobenzofuran, the acidic group-substituted isoindoline, the acidic group-substituted isobenzoselenophene, or the acidic group-substituted isobenzotellurophen according to claim 1 or 2. A method for producing a soluble conductive polymer having an acidic group. 4. An acid-substituted aniline, an acid-substituted pyrrole, an acid-substituted thiophene, an acid-substituted furan, an acid-substituted selenophene, an acid-substituted tellurophen, an acid-substituted isothianaphthene, an acid-substituted isobenzofuran, an acid-substituted At least one compound (a) selected from the group consisting of substituted isoindoline, acidic group-substituted isobenzoselenophene, acidic group-substituted isobenzotellurophen, a metal salt thereof, an ammonium salt and a substituted ammonium salt;
Aniline derivatives, pyrrole derivatives, thiophene derivatives,
At least one compound (c) selected from the group consisting of a furan derivative, a selenophene derivative, a tellurophen derivative, an isothianaphthene derivative, an isobenzofuran derivative, an isoindoline derivative, an isobenzoselenophene derivative and an isobenzotellurophen derivative, A method for producing a soluble conductive polymer having an acidic group, characterized by carrying out electrolytic polymerization in a solution containing an acidic compound (b). 5. The method for producing a soluble conductive polymer having an acidic group according to claim 4, wherein the electrolytic polymerization is performed continuously using a continuous cell connected in series, in parallel, or in a combination thereof. 6. The aniline derivative represented by the general formula (4): Wherein R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are hydrogen,
And a substituent selected from the group consisting of a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxy group having 1 to 24 carbon atoms, a hydroxyl group, a nitro group, and a halogen group. ), Or the pyrrole derivative, thiophene derivative, furan derivative, selenophene derivative, tellurophen derivative, isothianaphthene derivative, isobenzofuran derivative, isoindoline derivative, isobenzoselenophene derivative, isobenzotellurophen derivative, Formula (5) or Formula (6) Embedded image (In the formula, Z is any of NH, S, O, Se, and Te, and R ′ ₆ , R ′ ₇ , R ′ _8, and R ′ ₉ are hydrogen, carbon atom 1
-24 linear or branched alkyl group, 1-24 carbon atoms
And a substituent selected from the group consisting of linear or branched alkoxy, hydroxyl, nitro and halogen groups. ), A pyrrole derivative, a thiophene derivative,
The soluble conductive material having an acidic group according to claim 4 or 5, which is a furan derivative, a selenophene derivative, a tellurophen derivative, an isothianaphthene derivative, an isobenzofuran derivative, an isoindoline derivative, an isobenzoselenophene derivative, or an isobenzotellurophen derivative. Method for producing polymer. 7. The ratio (mol) of the compound (a) to the compound (c) is (a) :( c) = 100: 0-3.
The method for producing a soluble conductive polymer having an acidic group according to claim 4 or 5, wherein the ratio is in the range of 0:70.