JPH0971643A - Highly pure soluble conductive aniline polymer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new aniline having mainly a specific constituting unit and capable of producing a conductive membrane and a conductor expressing high conductivity and solubility and extremely excellent in applicability and membrane strength. SOLUTION: This polymer has mainly a constituting unit of formula I [R1 to R4 are each H, a 1-4C alkyl, an alkoxy, an acidic group (sufo group or carboxyl), (hydroxyl, nitro or a halogen, and at least one is an acidic group], a number average molecular weight of >=3000 and a content of residual monomers in the polymer of >=5%. Further, the objective polymer is preferably obtained by polymerizing at least one kind of compound selected from an acidic group-substituted aniline of formula II (R21 to R25 are the same as R1 to R4 ), its alkali metal or alkaline earth metal salt, and a (substituted) ammonium salt in a solution containing a basic compound (a 1-3C alkylamine and/or a heterocyclic amine) in the presence of an oxidant, and subsequently the obtained polymer is treated with an acid solution containing a protonic acid after polymerization.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a solvent-soluble high-purity aniline-based conductive polymer and a method for producing the same. The polymer can be used to form a conductor by a simple method such as a spray coating method, a dip coating method, a roll coating method, a gravure coating method, a reverse coating method, a roll brushing method, an air knife coating method and a curtain coating method. . Further, the composition containing the polymer as a main component,
It can be applied to various antistatics, capacitors, battery EMI shields, chemical sensors, display elements, etc. Examples of applications of the antistatic agent include packaging materials, magnetic cards, magnetic tapes, magnetic disks, photographic films, printing materials, release films, heat seal tapes / films, IC carrier tapes, cover tapes, and the like.

[0002]

2. Description of the Related Art Doped polyaniline (conductive polymer) is well known, but is insoluble in almost all solvents and has difficulty in molding and processing. Also, a method of subjecting aniline to electrolytic oxidative polymerization [JP-A-60-23585]
No. 1, J.I. Polymer Sci. Polyme
r Chem. Ed. , 26, 1531 (198
8)] can form a polyaniline film on the electrode, but it has a problem that the isolation operation becomes complicated and mass synthesis is difficult.

In recent years, alkali-soluble sulfonated polyaniline which exhibits conductivity without adding a doping agent and its synthesis method, and carboxylated polyaniline and its synthesis method 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 Laid-Open No. No. 166165), a method of synthesizing a sulfonated polyaniline by electrochemically polymerizing o-, m-, and p-aminobenzenesulfonic acid alone [Preliminary Proceedings II of the 64th Annual Meeting of the Chemical Society of Japan II 706 ( 199
2)], a method of chemically polymerizing aniline and o-, m-aminobenzenesulfonic acid to synthesize a sulfonated polyaniline (JP-A No. 01-301714), an aminobenzenesulfonic acid compound or an aminobenzenesulfonic acid. A method of chemically oxidatively polymerizing a monomer containing a siloxane-based compound and an aniline-based compound (JP-A-6-56987), and an emeraldine-type polymer (polyaniline) obtained by chemical or electrochemical polymerization Method of sulfonation with concentrated sulfuric acid (Japanese Patent Laid-Open No. 58-210902), sulfuric anhydride /
A method of sulfonation using a triethyl phosphate complex (JP-A-61-197633) and a method of sulfonation with fuming sulfuric acid [J. Am. Chem. Soc. , (199
1) 113, 2665-2671, J. Am. Che
m. Soc. , (1990) 112, 2800, WO9
1-06887], a method of chemically polymerizing diphenylamine-4-sulfonic acid (sodium salt) to synthesize an N-substituted sulfonated polyaniline [Polymer,
(1993) 34, 158 to 162].

A method of synthesizing a sulfonated polyaniline by electrochemically polymerizing aniline and m-aminobenzenesulfonic acid (Journal of the Chemical Society of Japan, 1985, 1124, Japanese Patent Application Laid-Open No. 02-166165) discloses that a product is formed on an electrode. Therefore, there are problems that the isolation operation is complicated and mass synthesis is difficult.

[0006] In the Preprints II, 706 (1992) of the 64th Annual Meeting of the Chemical Society of Japan, a method for synthesizing a soluble conductive polymer by electrolytic oxidation of aminobenzenesulfonic acid is described. It is hard to say that it is suitable for mass synthesis. Further, it is described that no product was obtained when aminobenzenesulfonic acid was subjected to chemical oxidative polymerization using ammonium peroxodisulfate as an oxidizing agent. Also, J.I. Am. Chem. Soc. , (1991) 11
According to 3,2665-2671, it was noted that the polymerization of o-, m-aminobenzenesulfonic acid was attempted chemically and electrochemically, but it was unsuccessful.

In Japanese Patent Application Laid-Open No. 6-56987,
A water-soluble conductive polymer can be obtained by chemically oxidatively polymerizing an aminobenzenesulfonic acid-based compound or a monomer containing an aminobenzenesulfonic acid-based compound and an aniline-based compound in any of acidic, neutral and alkaline solutions. However, there is no description about the physical properties of the polymer. 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 and in an aqueous solution using ammonium peroxodisulfate as an oxidizing agent, a water-soluble polymer was obtained, but a low molecular weight polymer was obtained. Therefore, a practical polymer for forming a film could not be obtained.

A method of chemically polymerizing aniline and m-aminobenzenesulfonic acid with ammonium peroxodisulfate described in JP-A-01-301714 and an aniline and m-method described in JP-A-6-56987. The present inventors have further tested a method of chemically polymerizing aminobenzenesulfonic acid with potassium permanganate. As a result, only one sulfone group is introduced into five aromatic rings, and high conductivity is obtained. As shown, it was completely insoluble in neutral and acidic water, and almost insoluble in alkaline aqueous solutions such as ammonia. Also, JP-A-61-19
In the case of sulfonation according to the method of JP 7633,
As described on the page, the solubility of polyaniline in the sulfonating solvent is not sufficient and the reaction is carried out in a dispersed state, so that only one sulfone group is introduced into five aromatic rings. The thus obtained sulfonated polyaniline having a small sulfone group introduction ratio has a problem that conductivity and solubility are not sufficient.

Also, 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 sulfone 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, the polymer synthesized by the above method and its sulfonated compound have a problem that they are soluble in an aqueous solution containing ammonia and a base such as an alkylamine but not in water alone.

Also, 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 carboxylated polyaniline, for example, a production method in which 2- or 3-carboxyaniline or a salt thereof is oxidatively polymerized and then treated with a basic substance to obtain a carboxyl group in a salt form ( JP 4
No. 268331), 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 expected that a low-molecular weight polymer having low reactivity of the monomer is produced.

[0013] Further, a synthesis method comprising polymerizing methyl anthranilate (methyl anthranilate) in an aqueous acidic medium in the presence of ammonium peroxodisulfate, and then saponifying the methyl ester with alcoholic potassium hydroxide (Japanese Patent Laid-Open No. 5-226238), but the operation is very complicated because the reaction has two steps.

Further, the present inventors have tried to polymerize 2-carboxyaniline using ammonium peroxodisulfate as an oxidizing agent in an aqueous solution containing a protic acid, but could not obtain a product. Further, the present inventors attempted polymerization in an aqueous solution containing a protonic acid using ammonium peroxodisulfate as an oxidizing agent using aniline and 2-carboxyaniline, and a copolymer was obtained. Both sexes were low. The copolymer obtained from this is expected to have a low copolymerization ratio of 2-carboxyaniline.

Therefore, in order to develop conductivity and improve solubility without adding a doping agent to the polymer, it is necessary to introduce more acidic groups such as sulfone groups or carboxyl groups into the aromatic ring of the main chain. It is thought that there is.

In consideration of formability 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, polyaniline sulfonates have solubility in alkaline water, but are insoluble in neutral to acidic aqueous solutions, and are not sufficiently soluble in organic solvents.

As a method of solving these various problems,
The present inventors copolymerized at least one compound selected from the group consisting of aniline, N-alkylaniline and phenylenediamines with aminobenzene sulfonic acid using an oxidizing agent in an acidic solvent, and further sulfonating agent. Proposal of a method for producing a sulfonated aniline-based copolymer, characterized in that it is sulfonated by
Issue). However, this method also requires an operation of sulfonating in concentrated sulfuric acid, and treatment of waste acid remains as a major problem. All the copolymers synthesized by this method are presumed to have the structure of the following formula (4).

[0018]

Embedded image (In the formula, R _26, R _27, R ₂₈ and R ₂₉ are each selected from the group consisting of hydrogen and a sulfone group, and R ′ is selected from the group consisting of hydrogen or an alkyl group having 1 to 4 carbon atoms; The ratio of the groups is 40 to 8 for the sulfone group with respect to the aromatic ring.
0% content, x represents an arbitrary number of 0 to 1,
n is a number from 2 to 1500 indicating the degree of polymerization. )

Further, the present inventors copolymerize at least one compound selected from the group consisting of aniline, N-alkylaniline and phenylenediamines with an alkoxy group-substituted aminobenzenesulfonic acid to produce a waste product. A method for producing an aniline-based copolymer, characterized in that a sulfonation operation that is generated in a large amount is omitted (Japanese Patent Application No.
No. 48540). Incidentally, it is presumed that each of the copolymers synthesized by the method has a structure represented by the following formula (5).

[0020]

Embedded image (In the formula, R _30, R _31, R _32, R _33, R _34, R _35, R ₃₆ or R ₃₇ are each selected from the group consisting of hydrogen, an alkoxy group and a sulfone group, and the proportion of the sulfone group is sulfone. The group has a content of 25 to 50% with respect to the aromatic ring, contains an alkoxy group and a sulfone group in the same aromatic ring, and R ^" is selected from the group consisting of hydrogen or an alkyl group having 1 to 4 carbon atoms. And x represents an arbitrary number from 0 to 1, and n is a number from 2 to 1500 indicating the degree of polymerization.)

Further, as the polymerization solvent in the chemical polymerization described above, water or an aqueous solution containing a protonic acid is used. For example, according to the above-mentioned JP-A-1-163263,
When ammonium peroxodisulfate is used as the oxidant, it is particularly preferable to contain a protic acid having a pKa of 3 or less, and aniline is used as a solvent in the polymerization of aniline.
It is described that a protic acid and an oxidizing agent which are dissolved and which are not oxidized by the oxidizing agent are used. Also,
In JP-A-4-268331, an aqueous solution of ammonium persulfate is added to an aqueous solution of anthranilic acid to carry out oxidative polymerization, and the pH of the polymerization solvent in this case is almost neutral.

[0022]

The object of the present invention is to:
Provided are a highly pure soluble aniline-based conductive polymer which exhibits high conductivity, has excellent solubility in water or an organic solvent having any pH, and has improved coatability and film strength, and a method for producing the same. There is a point to do.

[0023]

DISCLOSURE OF THE INVENTION The present inventors have proposed a method for producing an acidic group-substituted polyaniline having a high ratio of introduction of an acidic group such as a sulfone group and / or a carboxyl group to an aromatic ring as a polyaniline having high conductivity and solubility. As a result of diligent studies, when an acid group-substituted aniline such as a sulfo group-substituted aniline and / or a carboxyl group-substituted aniline as a monomer is polymerized in a solution containing a basic compound with an oxidizing agent, the reactivity is particularly improved, Contrary to the conventional theory that anilines having a sulfone group or a carboxyl group are difficult to undergo chemical oxidative polymerization by themselves, they have found that a high molecular weight polymer can be produced. Moreover, by subjecting the obtained polymer to an acid treatment, the conductivity and solubility are further improved, and the composition containing these polymers as the main components has good coatability and the film strength after coating is remarkably high. The inventors have found that they are excellent and have reached the present invention.

That is, the present invention provides a compound represented by the general formula (1):

[Chemical 6] (In the formula, R _1, R _2, R _3, R _4, are hydrogen, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxy group having 1 to 4 carbon atoms, an acidic group, A hydroxyl group, a nitro group and a halogen, at least one of which is an acidic group, and the acidic group is a sulfone group or a carboxyl group). The present invention relates to a high-purity soluble aniline-based conductive polymer having a weight average molecular weight of 3000 or more and a residual monomer content of 5% by weight or less.

The present invention also provides a compound represented by the general formula (3)

[Chemical 7] (In the formula, R _21, R ₂₂ , R _23, R _{24, and} R ₂₅ are hydrogen, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxy group having 1 to 4 carbon atoms, an acidic group. Group, a hydroxyl group, a nitro group, and a halogen, at least one of which represents an acidic group, and the acidic group represents a sulfone group or a carboxyl group). High purity characterized by polymerizing at least one compound (a) selected from alkali metal salts, alkaline earth metal salts, ammonium salts and substituted ammonium salts in a solution containing a basic compound (b) with an oxidizing agent The present invention relates to a method for producing a soluble aniline-based conductive polymer.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. [Production Method] The most typical compound represented by the general formula (3) is a sulfo group-substituted aniline or a carboxyl group-substituted aniline. The most representative of the sulfo 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 is preferably used.

Other sulfo group-substituted anilines include methylaminobenzenesulfonic acid, ethylaminobenzenesulfonic acid, n-propylaminobenzenesulfonic acid, iso-propylaminobenzenesulfonic acid, n.
-Butylaminobenzenesulfonic acid, sec-butylaminobenzenesulfonic acid, t-butylaminobenzenesulfonic acid and other alkyl group-substituted aminobenzenesulfonic acids, methoxyaminobenzenesulfonic acid, ethoxyaminobenzenesulfonic acid, propoxyaminobenzenesulfonic acid, etc. Alkoxy group-substituted aminobenzene sulfonic acids, hydroxy group-substituted aminobenzene sulfonic acids,
Examples thereof include nitro group-substituted aminobenzenesulfonic acid, fluoroaminobenzenesulfonic acid, chloroaminobenzenesulfonic acid, bromoaminobenzenesulfonic acid, and other halogen group-substituted aminobenzenesulfonic acid. Of these, alkyl group-substituted aminobenzene sulfonic acids, alkoxy group-substituted aminobenzene sulfonic acids and halogen group-substituted aminobenzene sulfonic acids are most preferable in practice. In addition, these sulfone group-substituted anilines may be used alone or may be mixed in an isomer at an arbitrary ratio.

The most representative ones of carboxyl group-substituted anilines are aminobenzenecarboxylic acids, specifically o-, m-, p-aminobenzenecarboxylic acids,
Aniline-2,6-dicarboxylic acid, aniline-2,5-
Dicarboxylic acid, aniline-3,5-dicarboxylic acid, aniline-2,4-dicarboxylic acid and aniline-3,4-dicarboxylic acid are preferably used.

Other carboxyl group-substituted anilines include methylaminobenzenecarboxylic acid, ethylaminobenzenecarboxylic acid, n-propylaminobenzenecarboxylic acid, iso-propylaminobenzenecarboxylic acid,
Alkyl-substituted aminobenzenecarboxylic acids such as n-butylaminobenzenecarboxylic acid, sec-butylaminobenzenecarboxylic acid, t-butylaminobenzenecarboxylic acid, methoxyaminobenzenecarboxylic acid, ethoxyaminobenzenecarboxylic acid, propoxyaminobenzenecarboxylic acid Halogen-substituted aminobenzenes such as alkoxy-substituted aminobenzenecarboxylic acids, hydroxy-substituted aminobenzenecarboxylic acids, nitro-substituted aminobenzenecarboxylic acids, fluoroaminobenzenecarboxylic acids, chloroaminobenzenecarboxylic acids, bromoaminobenzenecarboxylic acids, etc. Examples thereof include carboxylic acids. Among these, alkyl group-substituted aminobenzene carboxylic acids, alkoxy group-substituted aminobenzene carboxylic acids and halogen group-substituted aminobenzene sulfonic acids are most preferable in practical use. These carboxyl group-substituted anilines may be used alone or may be mixed in an isomer at an arbitrary ratio.

More specifically, the acidic group-substituted aniline of the general formula (3), preferably a sulfone group-substituted alkylaniline, a carboxyl group-substituted alkylaniline, a sulfone group-substituted alkoxyaniline, a carboxyl group-substituted alkoxyaniline, a sulfone group-substituted hydroxyaniline, Carboxyl group-substituted hydroxyaniline, sulfone group-substituted nitroaniline, carboxyl group-substituted nitroaniline, sulfone group-substituted fluoroaniline, carboxyl group-substituted fluoroaniline, sulfone group-substituted chloroaniline, carboxyl group-substituted chloroaniline, sulfone group-substituted bromoaniline and carboxyl group Substituted bromaniline and the like can be mentioned, and specific examples of positions and combinations of these substituents are shown in Table 1.

[0031]

[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 group, sec-butyl group, t-butyl group and other alkyl groups, methoxy group, ethoxy group, n
One group selected from alkoxy groups such as -propoxy group, iso-propoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, hydroxy group, fluoro group, chloro group, and bromo group; H: hydrogen, methyl group, ethyl group, n-propyl group, is
o-propyl group, n-butyl group, sec-butyl group,
t-butyl group, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, sec
-Represents one group selected from an alkyl group such as a butoxy group, an alkoxy group, a hydroxy group, a nitro group, a halogen group such as a fluoro group, a chloro group, and a bromo group.

Examples of alkali metals in these monomers include lithium, sodium and potassium. Examples of the substituted ammonium include aliphatic ammonium, cyclic saturated ammonium, and cyclic unsaturated ammonium.

As the above-mentioned lipophilic ammoniums, the following formula (6) is used.

Embedded image (In the formula, R _{26 to} R ₂₉ are groups independently selected from the group consisting of hydrogen, an alkyl group having 1 to 4 carbon atoms, CH ₂ OH, and CH ₂ CH ₂ OH.). 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 , Methylpropyl ammonium, ethyl propyl ammonium, methyl isopropyl ammonium, ethyl isopropyl ammonium, methyl butyl ammonium,
Ethyl butyl ammonium, tetramethyl ammonium, tetramethylol ammonium, tetraethyl ammonium, tetra n-butyl ammonium, tetrase
Examples thereof include c-butylammonium and tetra-t-butylammonium.

Examples of 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 thereof include picolinium, quinolinium, isoquinolinium, pyrrolinium, and derivatives having these skeletons.

Next, as the basic compound (b) used in the present invention, ammonia, aliphatic amines, cyclic saturated amines, cyclic unsaturated amines and the like are preferably used. Above all, aliphatic amines, cyclic saturated amines, cyclic unsaturated amines and the like are preferable.

Preferred aliphatic amines include the following general formula (7)

Embedded image (Wherein, R _{30 to} R ₃₂ are an alkyl group having 1 to 3 carbon atoms, C
It is a group independently selected from the group consisting of H ₂ OH and CH ₂ CH ₂ OH. ),

Or the general formula (8)

Embedded image (In the formula, each of R _{33 to} R ₃₆ is a group independently selected from the group consisting of hydrogen, an alkyl group having 1 to 3 carbon atoms, CH ₂ OH and CH ₂ CH ₂ OH.). A side compound may 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.

Among these basic compounds, particularly preferred are methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylmethylamine, ethyldimethylamine, diethylmethylamine, pyridine, α-picoline,
Examples thereof include β-picoline and γ-picoline. When these are used, a polymer having a particularly high purity can be obtained.

The concentration of the basic compound (b) is 0.1.
It is used in an amount of 1 mol / L or more, preferably 0.1 to 10.0 mol / L, more preferably 0.2 to 8.0 mol / L. At this time, when the amount is 0.1 mol / liter or less, the yield of the obtained polymer decreases, and
When it is 0.0 mol / liter or more, the conductivity tends to decrease. The basic compound (b) can be used by mixing at an arbitrary ratio.

The weight ratio of the compound (a) such as the above-mentioned acid-substituted aniline to the basic compound (b) is (a):
(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 molar ratio of the acidic group (d) to the basic compound (b) in the compound (b) such as the acidic group-substituted aniline is (d) :( b) = 1: 100 to 100: 1. , Preferably 1: 0.25 to 1:20, more preferably 1:
It can be used at 0.5 to 1:15. 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 aminobenzenesulfonic acid derivative tends to have higher conductivity than the aminobenzoic acid derivative, while the aminobenzoic acid derivative tends to have higher solubility than the aminobenzenesulfonic acid derivative. These derivatives can be copolymerized in any proportion depending on the purpose.

Polymerization or copolymerization is carried out by oxidative polymerization with an oxidizing agent in a solution containing the basic compound. As the solvent, water, alcohols such as methanol, ethanol and isopropanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, acetonitrile, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like are preferably used. Further, these solvents can be used alone or in combination of two or more.

The oxidizing agent has a standard electrode potential of 0.6 V
The oxidizing agent is not particularly limited as long as it is the above-mentioned oxidizing agent, but peroxodisulfates such as peroxodisulfate, ammonium peroxodisulfate, sodium peroxodisulfate and potassium peroxodisulfate, hydrogen peroxide and the like are preferably used, and 1 mol of the monomer is used. On the other hand, it is used in an amount of 0.1 to 5 mol, preferably 0.5 to 5 mol. At this time, it is also effective to add a transition metal compound such as iron or copper as a catalyst.

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

The hydrogen at the sulfone or carboxyl group in the polymer produced according to the invention may be 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 in a mixed state rather than alone.

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

Similarly, the hydrogen in the sulfone group or the carboxyl group in the polymer is mostly ammonium when polymerized in the presence of ammonia, and is mostly trimethylammonium in the case of polymerization in the presence of trimethylamine, in the presence of quinoline. When polymerized, it is mostly obtained with quinolinium.

When a mixture of basic compounds is used, it is obtained in a state of mixing these. Specifically, when polymerized in the presence of sodium hydroxide and ammonia, hydrogen at the sulfone or carboxyl groups in the isolated polymer is obtained in the presence of both sodium and ammonium. Also, when the obtained polymer is treated with a solution in which both sodium hydroxide and ammonia are present, hydrogen in the sulfone group or carboxyl group in the polymer is similarly obtained in the presence of both sodium and ammonium.

The above-described polymer in which a part of the acidic groups forms a salt can be treated with an acid-containing solution to obtain a polymer of higher purity.

Examples of the acid include mineral acids such as hydrochloric acid, nitric acid, sulfuric acid, and borofluoric acid; superacids such as trifluoromethanesulfonic acid; and alkyls such as methanesulfonic acid, dodecylbenzenesulfonic acid, toluenesulfonic acid, and camphorsulfonic acid. Examples include group-substituted sulfonic acids, and preferably, hydrochloric acid, nitric acid, sulfuric acid, p-toluenesulfonic acid and the like are used. These solvents are not particularly limited as long as they can be mixed with these protonic acids, but alcohols such as methyl alcohol, ethyl alcohol, iso-propyl alcohol, n-propyl alcohol, t-butyl alcohol, acetone, methyl ethyl ketone, etc. , Ketones such as methyl isobutyl ketone, glycols, glycol ethers, acetonitrile, N, N-dimethylformamide,
N-methylpyrrolidone, dimethylsulfoxide and the like are preferably used, and methyl alcohol, ethyl alcohol, iso-propyl alcohol, acetone and acetonitrile are particularly preferable. As the concentration of the acid used here,
It is 0.1 to 10 mol / liter, preferably 0.1 to 5 mol / liter.

The polymer is isolated by filtration from the reaction solution, but unreacted monomers are dissolved in the reaction solution.
At this time, as a separation device, vacuum filtration, pressure filtration,
Centrifugation, centrifugal filtration, etc. are used, especially centrifugation,
It is preferable to use a separation device such as centrifugal filtration. Also,
As the cleaning solvent, methyl alcohol, ethyl alcohol, iso-propyl alcohol, n-propyl alcohol,
Alcohols such as t-butyl alcohol, acetone, acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, etc. are used, and particularly methyl alcohol, ethyl alcohol, iso-propyl alcohol, acetone, acetonitrile are used. Is effective.

[Production Polymer] The soluble aniline-based polymer thus obtained has a residual monomer content of 5 wt%.
Below, 1 is the number of oligomers having an average weight molecular weight of 1100 or less.
0 wt% or less, residual salt, acid, or base is 10 wt% or less. If the amount of these impurities is further reduced, the conductivity and the solubility are improved, so that the residual monomer content is 3 wt% or less,
5 wt% or less of oligomer, 5 wt% of residual salt, acid and base
% Or less, residual monomer is 1 wt% or less, oligomer is 2 wt% or less, residual salt, acid or base is more preferably 2 wt% or less, residual monomer is 0.5 wt% or less,
1 wt% or less of oligomer, 1 wt% of residual salt, acid and base
% Or less is more preferable.

This polymer was subjected to no further sulfonation operation without addition of water such as water, ammonia and a base such as alkylamine or water containing a base such as ammonium acetate and ammonium oxalate and a basic salt, and acid such as hydrochloric acid and sulfuric acid. It can be dissolved in water or a solvent such as methyl alcohol, ethyl alcohol, isopropyl alcohol, or a mixture thereof.

This polymer can be expressed as the high-purity soluble aniline-based conductive polymer of the above-mentioned general formula (1). Further, this polymer has the following general formula (2)
It can be expressed as having a phenylenediamine structure (reduced type) and a quinodiimine structure (oxidized type) shown in.

Embedded image (In the formula, R _{5 to} R ₂₀ are an electron-withdrawing group, an acidic group, hydrogen, a linear or branched alkyl group having 1 to 4 carbon atoms, and 1 to 1 carbon atoms.
4 selected from the group consisting of a linear or branched alkoxy group, a hydroxyl group, a nitro group, and a halogen, at least one of which is an acidic group. Here, the acidic group indicates a sulfone group or a carboxyl group. Among them, at least two of the four substituents on each aromatic ring are preferably a combination of an acidic group and an alkyl group, a hydroxyl group, a halogen group or an alkoxy group, and particularly preferably a combination of an acidic group and an alkoxy group. )

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

When x is oxidized with an oxidizing agent such as benzoyl peroxide, ammonium peroxosodisulfate or hydrogen peroxide, it is small, but it is reduced with a reducing agent such as hydrazine, phenylhydrazine, sodium borohydride or sodium hydride. If you do, you get a big one.

The soluble aniline-based conductive polymer of the present invention has structural units other than those represented by the above general formula (1) or general formula (2) as long as it does not affect the solubility, conductivity and properties. A substituted or unsubstituted aniline,
It may contain at least one structural unit selected from thiophene, pyrrole, phenylene, vinylene, other divalent unsaturated groups and divalent saturated groups. As the soluble aniline-based conductive polymer of the present invention, a repeating unit of the general formula (1) or (2), that is, one having an acid group content of 70% or more with respect to an aromatic ring is used, preferably 80% or more. , And more preferably 90% or more is used. Here, it is not preferable that the content of the acidic group in the aromatic ring is 70% or less because the solubility in water is insufficient. Further, the higher the content of the acidic group to the aromatic ring, the higher the solubility,
The highest solubility is obtained when the content of acidic groups in the aromatic ring is 100%.

The weight-average molecular weight of the thus-obtained soluble aniline type conductive polymer having a sulfone group or a carboxy group in the aromatic ring is 3000 to 3,240,00.
0, preferably 5000 to 1,000,000, and more preferably 10,000 to 500,000.

[0063]

Embodiments will be described below with reference to embodiments. The IR spectrum was measured using an apparatus manufactured by Perkin Elmer (Model 1600). For the molecular weight distribution and the measurement of the molecular weight, GPC measurement (polyethylene oxide conversion) was performed using a GPC column for aqueous solution. Three types of columns for aqueous solution were connected and used. The eluent contains 0.
A 2M phosphate buffer solution was used. The analysis of acidic group-substituted aniline, residual salt, acid and base in the polymer was carried out by using high performance liquid chromatography. A partition adsorption column was used as the column, and a 0.2 mol / liter phosphate buffer solution was used as the eluent. The residual acid in the polymer was analyzed by using ion chromatography. An ion exchange column was used as the column, and a sodium acetate buffer solution was used as the eluent. Regarding the conductivity, the 4-terminal method was used for measuring the conductivity, and the 2-terminal method was used for measuring the surface resistance. The pencil test method was used for the film strength.

Example 1 100 mmol of o-aminobenzenesulfonic acid was added at 25 ° C.
Was dissolved in a 4 mol / liter trimethylamine aqueous solution with stirring, and an aqueous solution of 100 mmol of ammonium peroxodisulfate was added dropwise. After the dropwise addition was completed, the reaction product was further stirred at 25 ° C. for 12 hours, filtered by a centrifugal filter, washed with methyl alcohol and dried to obtain 12 g of a polymer powder. This had a volume resistance of 12.0 Ωcm.
In addition, o- which is a residual monomer contained in this polymer.
Aminobenzenesulfonic acid is 3%, trimethylamine sulfate as a by-product salt is 2.5%, and trimethylamine forming a salt with sulfonic acid which is an acidic group in the polymer is 6%.
Met.

10 g of the obtained polymer was suspended in a 1 mol / liter methanol solution of sulfuric acid for 30 minutes, desalted, filtered and washed with methyl alcohol to obtain 8 g of desalted polymer. . The volume resistance of this product was 3.0 Ωcm. The residual monomer, o-aminobenzenesulfonic acid, contained in the desalted polymer was 0.1%,
Trimethylamine sulfate as a by-product salt was 0.5%, and trimethylamine forming a salt with a sulfonic acid group which is an acidic group in the polymer was 1.0%. Polymer 3
By weight, 100 parts by weight of water was stirred and dissolved at room temperature to prepare a conductive composition. The solution thus obtained was applied on a glass substrate by a spin coating method, and dried at 100 ° C. Thickness 0.1 μm, smooth surface resistance 1.0
A film of × 10 ⁵ Ω / □ was obtained.

As a result of GPC measurement, the molecular weight of this product was number average molecular weight 150,000, weight average molecular weight 190,0.
00, Z average molecular weight 210,000, dispersity MW / MN
It was 1.5 and MZ / MW1.3.

The polymer was added little by little to 10 ml of water, a 0.1 mol / liter sulfuric acid aqueous solution or 0.1 mol / liter of ammonia water, and when the polymer was no longer dissolved, it was filtered and the amount of dissolution was determined. The solubility of the conductive polymer synthesized in 1. was 350 mg / ml water, 0.1 mol / liter sulfuric acid aqueous solution 295 mg / ml, 0.1 mol / liter ammonia water 400 mg / ml.

FIG. 1 shows the IR spectrum of the conductive polymer synthesized in Example 1 above, and FIG. 2 shows the ion chromatography of residual monomers and residual by-product salts in the polymer.
The high performance liquid chromatography of the residual monomer and basic compound in the polymer is shown in FIG. 3, and the GPC measurement chart of the polymer is shown in FIG.

[0069]

FIG. 1 is the assignment of IR spectra as follows. Sulfone group: Absorption near 1120,1020 cm | Polymer skeleton: Absorption near 1500 cm |

[0070]

FIG. 2

[0071]

FIG. 3

[0072]

FIG. 4

Example 2 2-Methyl-4-aminobenzenesulfonic acid 100 mm
is dissolved in a 4 mol / liter 2-methylpyridine aqueous solution with stirring at 4 ° C., and ammonium peroxodisulfate 10
0 mmol aqueous solution was added dropwise. 6 at 25 ° C after dropping
After stirring for a further hour, the reaction product was filtered off with a vacuum filter, washed with ethyl alcohol and dried to obtain 10 g of a polymer powder.

This polymer was stirred in an acetone solution of 1 mol / liter p-toluenesulfonic acid (PTS) for 1 hour, filtered off, washed with ethyl alcohol, and dried to obtain a polymer free of sulfone groups. 9 g of powder was obtained. The volume resistance value of this product was 2.5 Ωcm. In addition, the residual monomer contained in this desalted polymer is 2-methyl-4.
-Aminobenzene sulfonic acid is 0.3%, 2-methylpyridine PTS salt which is a by-product salt is 0.2%, and 2-methylpyridine which forms a salt with a sulfonic acid group which is an acidic group in the polymer is 0.7%. %Met.

1 part by weight of the above polymer was dissolved in 100 parts by weight of water with stirring at room temperature to prepare a conductive composition. The solution thus obtained was applied on a glass substrate by a casting method and dried at 100 ° C. A film having a film thickness of 0.1 μm and a smooth surface resistance value of 5.0 × 10 ⁵ Ω / □ was obtained.

Example 3 2-Carboxyaniline (anthranilic acid) 100 m
mol at 4 ° C. with stirring in a 4 mol / liter aqueous quinoline solution, and ammonium peroxodisulfate 100 mmo
l of aqueous solution was added dropwise. After the dropping was completed, the mixture was further stirred at 25 ° C. for 12 hours, the reaction product was separated by a centrifuge, washed with isopropyl alcohol, and dried to obtain 10 g of a polymer powder. The volume resistance value of this product was 45 Ωcm. The polymer was stirred in an acetonitrile solution of 1 mol / liter hydrochloric acid for 1 hour, separated by filtration, washed with isopropyl alcohol and dried to obtain 8 g of a polymer powder having a free sulfo group. The volume resistance value of this product is 12.
It was 5 Ωcm. The residual monomer, anthranilic acid, contained in the desalted polymer was 0.2%, the by-product salt, quinoline hydrochloride, was 0.4%, and the carboxylic acid group was an acidic group in the polymer. Quinoline forming the salt was 1.8%.

3 parts by weight of the above polymer was dissolved in 100 parts by weight of water with stirring at room temperature to prepare a conductive composition. The solution thus obtained was applied onto a PET film by spin coating and dried at 80 ° C. Film thickness 0.1 μm,
A film having a smooth surface resistance value of 3.0 × 10 ⁶ Ω / □ was obtained.

Example 4 100 mmol of 3-hydroxyanthranilic acid was added at 25 ° C.
Was dissolved with stirring in a 3 mol / liter 3-methylpyridine (β-picoline) aqueous solution, and an aqueous solution of 100 mmol of ammonium peroxodisulfate was added dropwise. 25 after dropping
After further stirring at ℃ for 12 hours, the reaction product was filtered off, washed with methyl alcohol and dried to obtain polymer powder 11
g was obtained. The volume resistance value of this product was 55 Ωcm. This polymer was stirred in an isopropyl alcohol solution of 0.5 mol / liter nitric acid for 10 minutes, filtered with a pressure filter, washed with ethyl alcohol, and then dried to obtain a powder of a polymer having a free sulfone group. 7.5 g was obtained. The volume resistance value of this product was 10.5 Ωcm. In addition, the residual monomer 3-hydroxyanthranilic acid contained in the desalted polymer was 0.3%, the by-product salt β-picoline nitrate was 0.8%, and the sulfone which was an acidic group in the polymer was used. Β-picoline forming a salt with an acid group was 0.8%.

3 parts by weight of the above polymer was dissolved in 100 parts by weight of water / isopropyl alcohol (7/3) with stirring at room temperature to prepare a conductive composition. The solution thus obtained is applied onto a glass substrate by spin coating, and the temperature is 120 ° C.
And dried. A film having a film thickness of 0.1 μm and a smooth surface resistance value of 5.0 × 10 ⁵ Ω / □ was obtained.

Example 5 100 mmol of 4-nitroanthranilic acid was added at 10 ° C. for 4 hours.
The solution was stirred and dissolved in a mol / liter aqueous solution of triethanolamine, and an aqueous solution of 100 mmol of ammonium peroxodisulfate was added dropwise. After completion of dropping, the mixture was further stirred for 12 hours at 25 ° C., the reaction product was filtered off, washed with isopropyl alcohol and dried to obtain 9.5 g of polymer powder. The volume resistance value of this product was 50 Ωcm. This polymer was stirred in a 1.5 mol / liter sulfuric acid N-methylpyrrolidone solution for 10 minutes and filtered with a centrifugal filter.
After washing with ethyl alcohol and drying, 7.5 g of powder of a polymer having a free carboxyl group was obtained. The volume resistance value of this product was 21.5 Ωcm. The residual monomer 4-nitroanthranilic acid contained in the desalted polymer was 0.4%, the triethanolamine sulfate as a by-product salt was 0.9%, and it was an acidic group in the polymer. Triethanolamine forming a salt with a carboxylic acid group was 0.5%.

3 parts by weight of the above polymer was added to a water-soluble polyester resin "Alaster 300" {manufactured by Arakawa Chemical Industry Co., Ltd.} 1
00 parts by weight were stirred and dissolved at room temperature in 100 parts by weight of water to prepare a conductive composition. The solution thus obtained was applied onto a PET film with a gravure coater having a depth of 35 μm and dried at 70 ° C. A film having a film thickness of 0.5 μm and a smooth surface resistance value of 7.5 × 10 ⁶ Ω / □ was obtained.

Example 6 100 mmol of m-nitroanilinesulfonic acid was added at 25 ° C.
Dissolve with stirring in a 4 mol / liter piperidine aqueous solution,
An aqueous solution of 100 mmol of ammonium peroxodisulfate was added dropwise. After the dropwise addition was completed, the reaction product was further stirred at 25 ° C. for 12 hours, filtered by a centrifugal filter, washed with acetone, and dried to obtain 6 g of a polymer powder. The volume resistance value of this product was 38 Ωcm. This polymer is 2.
7. Polymer powder free of carboxyl group after stirring in a 0, mol / liter hydrochloric acid solution of N, N-dimethylformamide for 5 minutes, filtering off with a pressure filter, washing with acetonitrile and drying. 5 g was obtained. The volume resistance value of this product was 9.5 Ωcm. Further, 4-nitroanilinesulfonic acid which is a residual monomer contained in the desalted polymer is 0.2%, and pyridine sulfate which is a by-product salt is 1.9%.
The amount of piperidine forming a salt with the sulfonic acid group, which is an acidic group in the polymer, was 0.5%.

2 parts by weight of the above polymer was dissolved in 100 parts by weight of 0.2 mol / liter ammonia water at room temperature with stirring to prepare a conductive composition. The solution thus obtained is
80 by spin coating on PET film
It was dried at ° C. A film having a film thickness of 0.1 μm and a smooth surface resistance value of 1.0 × 10 ⁶ Ω / □ was obtained.

Comparative Example 1 100 mmol of o-aminobenzenesulfonic acid was dissolved in a 4 mol / liter sodium hydroxide aqueous solution with stirring at 4 ° C., and an aqueous solution of ammonium peroxodisulfate 100 mmol was added dropwise. After the dropping was completed, the mixture was further stirred for 12 hours at 25 ° C., the reaction product was filtered off with a centrifugal filter, washed with acetone and dried to obtain 12 g of polymer powder. The volume resistance value of this product was 250 Ωcm. The residual monomer contained in this polymer is 15% for o-aminobenzenesulfonic acid and 2% for the by-product sodium sulfate.
0% and 20% of sodium forming a salt with a sulfonic acid group which is an acidic group in the polymer. This polymer was added to 10 mol of methanol in a 0.5 mol / l sulfuric acid solution in methanol.
After stirring for 1 minute and filtering, the filterability was poor and the polymer could not be isolated.

Comparative Example 2 2-Carboxylaniline (anthranilic acid) 100 m
mol at 25 ° C. with stirring in a 4 mol / liter aqueous ammonia solution, and ammonium peroxodisulfate 100 m
A mol aqueous solution was added dropwise. After completion of dropping, the mixture was further stirred for 12 hours at 25 ° C., the reaction product was filtered off, washed and dried to obtain 12 g of polymer powder. The volume resistance of this product is 15
It was 5 Ωcm. Anthranilic acid which is a residual monomer contained in this polymer is 10%, ammonium sulfate which is a by-product salt is 8.5%, and ammonia which forms a salt with a carboxylic acid group which is an acidic group in the polymer is It was 12%.

3 parts by weight of the powder was dissolved in 100 parts by weight of water with stirring at room temperature to prepare a conductive composition. The solution thus obtained was applied onto a glass substrate by spin coating, but no uniform film was obtained. The conductivity of the obtained film was 4 × 10 ⁸ Ω / □.

Comparative Example 3 100 mmol of 2-aminoanisole-4-sulfonic acid was dissolved with stirring at 25 ° C. in an aqueous 4 mol / liter ammonia solution, and an aqueous solution of 100 mmol ammonium peroxodisulfate was added dropwise. After the dropping was completed, the mixture was further stirred at 25 ° C. for 12 hours, and the reaction product was separated by filtration, washed and dried to obtain 12 g of polymer powder. The volume resistance value of this product was 55 Ωcm. 2-aminoanisole-4-sulfonic acid which is a residual monomer contained in this polymer is 7%, ammonium sulfate which is a by-product salt is 8.8%, carboxylic acid group which is an acidic group in the polymer and a salt. Ammonia formed was 10%.

3 parts by weight of the sulfonated polyaniline was mixed with 100 parts by weight of a 0.2 mol / liter sulfuric acid aqueous solution at room temperature to prepare a conductive composition. The solution thus obtained was applied onto a glass substrate by spin coating, but the coatability was poor and a uniform film could not be formed.

The solubility of the conductive polymer synthesized in Comparative Example 3 (conventional method) was as follows: water 50 mg / ml 0.1 mol / liter sulfuric acid aqueous solution 25 mg / ml 0.1 mol / liter ammonia water 76 mg / ml Met.

[0090]

[Effect] According to the present invention, a novel high-purity soluble aniline-based conductive polymer is provided, which can obtain a conductive film and a conductor exhibiting high conductivity and solubility and particularly excellent coatability and film strength. We were able to.

[Brief description of drawings]

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

FIG. 2 is an ion chromatography chart of residual monomer and residual by-product salt in the polymer in Example 1.

FIG. 3 is a chart of high performance liquid chromatography of the residual monomer and basic compound in the polymer in Example 1.

FIG. 4 is a GPC chart of a polymer in Example 1.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] October 8, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 2

[Correction method] Change

[Correction contents]

Embedded image (In the formula, R _{5 to} R ₂₀ are electron withdrawing groups, acidic groups, hydrogen,
A linear or branched alkyl group having 1 to 4 carbon atoms, 1 carbon atom
~ 4 straight or branched alkoxy groups, hydroxyl groups, nitro
Selected from the group consisting of group Contact and halogen, one at least of which represents an acidic group. The acidic group has a repeating unit represented by a sulfone group or a carboxyl group), and the high-purity soluble aniline-based conductive polymer according to claim 1.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0058

[Correction method] Change

[Correction contents]

This polymer can be expressed as the high-purity soluble aniline-based conductive polymer of the general formula (1) described above. Further, this polymer can be expressed as having a phenylenediamine structure (reduced type) and a quinodiimine structure (oxidized type) represented by the following general formula (2).

Embedded image (In the formula, R _{5 to} R ₂₀ are electron withdrawing groups, acidic groups, hydrogen,
A linear or branched alkyl group having 1 to 4 carbon atoms, 1 carbon atom
~ 4 straight or branched alkoxy groups, hydroxyl groups, nitro
Selected from the group consisting of group Contact and halogen, one at least of which represents an acidic group. Here, the acidic group indicates a sulfone group or a carboxyl group. Of these, at least two of the four substituents on each aromatic ring are preferably a combination of an acidic group and an alkyl group, a hydroxyl group, a halogen group or an alkoxy group, and particularly preferably a combination of an acidic group and an alkoxy group. )

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Yasuyuki Takayanagi 10-10 Daikokucho, Tsurumi-ku, Yokohama-shi, Kanagawa Nitto Chemical Industry Co., Ltd.

Claims (11)

[Claims] 1. A compound represented by the general formula (1): (In the formula, R _1, R _2, R _3, R _4, are hydrogen, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxy group having 1 to 4 carbon atoms, an acidic group, A hydroxyl group, a nitro group and a halogen, at least one of which represents an acidic group, and the acidic group mainly represents a structural unit represented by a sulfone group or a carboxyl group), A high-purity soluble aniline-based conductive polymer having a weight average molecular weight of 3000 or more and a residual monomer content of 5% by weight or less. 2. The structural formula of the soluble aniline-based conductive polymer is represented by the general formula (2): (In the formula, R _{5 to} R ₂₀ are an electron-withdrawing group, an acidic group, hydrogen, a linear or branched alkyl group having 1 to 4 carbon atoms, and 1 to 1 carbon atoms.
4 selected from the group consisting of a linear or branched alkoxy group, a hydroxyl group, a nitro group, and a halogen, at least one of which is an acidic group. The acidic group has a repeating unit represented by a sulfone group or a carboxyl group), and the high-purity soluble aniline-based conductive polymer according to claim 1. 3. R ₁ , R ₂ and R ₃ of the general formula (1) above.
And at least two of R ₄ are an acidic group and an alkyl group,
The high-purity soluble aniline-based conductive polymer according to claim 1, which is a combination with a hydroxyl group, a halogen group or an alkoxy group. 4. R ₁ , R ₂ , and R _{3 of the} above general formula (1).
2. The high-purity soluble aniline-based conductive polymer according to claim 1, wherein at least two of R ₄ and R ₄ are a combination of an acidic group and an alkoxy group. 5. The high-purity soluble aniline-based conductive polymer according to claim 1, wherein the soluble aniline-based conductive polymer contains 10% by weight or less of an oligomer having a molecular weight of 1000 or less. 6. The high-purity soluble aniline according to claim 1, wherein the content of the residual salt, acid and base contained in the soluble aniline-based conductive polymer is 10% by weight or less. Series conductive polymer. 7. A compound represented by the general formula (3): (In the formula, R _21, R ₂₂ , R _23, R _{24, and} R ₂₅ are hydrogen, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxy group having 1 to 4 carbon atoms, an acidic group. Group, a hydroxyl group, a nitro group, and a halogen, at least one of which represents an acidic group, and the acidic group represents a sulfone group or a carboxyl group). At least one compound (a) selected from an alkali metal salt, an alkaline earth metal salt, an ammonium salt and a substituted ammonium salt is polymerized with an oxidizing agent in a solution containing a basic compound (b). The method for producing a highly pure soluble aniline-based conductive polymer according to 1, 2, 3, 4, 5 or 6. 8. The method for producing a highly pure soluble aniline-based conductive polymer according to claim 7, wherein the basic compound (b) is an alkylamine having 1 to 3 carbon atoms and / or a heterocyclic amine. 9. The method for producing a highly pure soluble aniline-based conductive polymer according to claim 7, wherein after the polymerization, the polymer is acid-treated with a solution (c) containing a protonic acid. 10. After the polymerization, the polymer or the polymer after the acid treatment is washed with at least one solvent selected from methanol, ethanol, isopropyl alcohol, acetone, acetonitrile and N, N-dimethylformamide. 7. A method for producing a highly pure soluble aniline-based conductive polymer according to 7, 8 or 9. 11. The high-purity soluble aniline-based conductive polymer according to claim 7, 8 or 9, wherein after the polymerization, the polymer or the acid-treated polymer is isolated by using a separator utilizing centrifugal force. Production method.