JP3364416B2 - Method for producing soluble conductive polymer having acidic group - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a soluble conductive polymer which is soluble in a solvent. The solution containing the soluble conductive polymer as a main component is spray-coated, dip-coated, roll-coated, gravure-coated, reverse-coated, roll-coated, air knife-coated, curtain-coated, etc. on various substrates. The conductor can be formed by a simple method. Further, in order to improve the adhesiveness of the conductive film and the strength of the coating film, a suitable binder polymer may be mixed and used.

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

Further, a composition containing the polymer as a main component is used for various antistatic, antistatic, condenser, battery, 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 coating, cathodic protection, improving the storage capacity of batteries, etc. is there. Further, the polymer has high conductivity and does not depend on humidity, has high transparency, and can be stretched, molded, embossed, and the like, and thus has excellent suitability for various antistatic applications.

As antistatic applications, packaging materials, magnetic cards, magnetic tapes, magnetic disks, photographic films, printing substrates, release films, heat seal tapes / films,
There are IC trays, IC carrier tapes, cover tapes, etc.

[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 some aprotic polar solvents, and has problems in molding and processing. is there. In addition, a method of electrolytically oxidatively polymerizing aniline [JP-A-60-235831,
J. Polymer Sci. Polymer Ch
em. Ed. , 26, 1531 (1988)], it is possible to form a polyaniline film on the electrode, but there are problems that the isolation operation is complicated and mass synthesis is difficult.

Further, 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.

The sulfonated polyaniline can be synthesized, for example, by electrochemically polymerizing aniline and m-aminobenzenesulfonic acid to synthesize a sulfonated polyaniline (Journal of the Chemical Society of Japan, 1985, 1124, JP-A-02-). 166165 gazette), o-, m-, p-aminobenzenesulfonic acid is independently electrochemically polymerized to synthesize a sulfonated polyaniline [Chemical Society of Japan 64th Autumn Meeting, Proceedings II, 706 (199
2)], a method for chemically synthesizing aniline and o-, m-aminobenzenesulfonic acid to synthesize a sulfonated polyaniline (JP-A-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 A method of sulfonating with concentrated sulfuric acid (JP-A-58-210902), a method of sulfonating using a 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, J. Am.
Chem. Soc. , (1990) 112, 2800,
WO91-06887], a method for chemically polymerizing diphenylamine-4-sulfonic acid (sodium salt) to synthesize an N-substituted sulfonated polyaniline [Polyme]
r, (1993) 34, 158-162] and the like are known.

J. Am. Chem. Soc. , (199
1) 113, 2665-2671 describes that o-, m-aminobenzenesulfonic acid was attempted to be polymerized chemically and electrochemically but was unsuccessful.

Further, in Japanese Patent Laid-Open No. 6-56987,
Aminobenzenesulfonic acid-based compound or an aminobenzenesulfonic acid-based compound and an aniline-based compound are described as being capable of obtaining a soluble conductive polymer soluble in water by chemical oxidative polymerization in any of acidic, neutral and alkaline solutions. However, there is no description about the molecular weight of the polymer and other physical properties, and it is not clear what kind of physical property the polymer was obtained. According to the additional test by the present inventors, a polymer having a sufficient molecular weight for forming a film could not be obtained.

Further, the inventors of the present invention tried polymerization in an aqueous solution containing a protonic acid using ammonium peroxodisulfate as an oxidizing agent, and as a result, a water-soluble polymer was obtained, but a film was formed due to its low molecular weight. It was not possible to obtain a practical polymer that would form.

Further, the inventors of the present invention have disclosed in Japanese Patent Laid-Open No. 01-301.
No. 714, a method for chemically polymerizing aniline and m-aminobenzenesulfonic acid with ammonium peroxodisulfate, and aniline and m-aminobenzenesulfonic acid described in JP-A-6-56987. When we repeated the method of chemically polymerizing with potassium manganate, only about 1 sulfonic acid group was introduced into 5 aromatic rings, and it showed high conductivity, but it was perfect for neutral and acidic water. It was insoluble in, and almost insoluble in alkaline aqueous solutions such as ammonia. Also,
Even when sulfonation is carried out by the method of JP-A-61-197633, as described on page 7 of the publication, the solubility of polyaniline in a sulfonation solvent is not sufficient, and the sulfonation reaction is carried out in the dispersed state of the polymer. Since it is carried out, only about 1 sulfonic acid group is introduced into 5 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.

In addition, J. Am. Chem. Soc. ，
(1991) 113, 2665-2671, J. Am.
Chem. Soc. , (1990) 112, 2800, describes that when polyaniline is sulfonated with fuming sulfuric acid, about 1 sulfonic acid group is introduced into two aromatic rings. However, when it is attempted to sufficiently sulfonate polyaniline by this method, since the solubility of polyaniline in fuming sulfuric acid is not sufficient, fuming sulfuric acid is required in a large excess. Further, there is a problem that the polymer is easily solidified even when polyaniline is added to fuming sulfuric acid. Further, the polymer synthesized by the above method and its sulfonated product,
There is also a problem that it is soluble in an aqueous solution containing a base such as ammonia and an alkylamine, but is insoluble in water alone.

Further, Polymer (1993) 34,
According to 158-162, when diphenylamine-4-sulfonic acid (sodium salt) is polymerized, N-substituted sulfonated polyaniline in which one benzenesulfonic acid group is introduced to the aniline skeleton is obtained to give water alone. Although it also dissolves, it is described that an ultracentrifugation operation is necessary to isolate the polymer. As a result of additional tests by the present inventors, the yield of the polymerized product from the polymerization solvent is low due to its high solubility, and the polymerized product cannot be isolated unless the high-speed centrifugation operation is performed. It was In addition, since the N-position substitution type, J. Am. Chem. Soc. , (199
1) The conductivity was lower than that of the polymer synthesized by the method of 113,2665-2671.

As a method for synthesizing 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-
No. 268331 gazette) has been proposed, but the amount of the oxidizing agent used is required to be equal to or more than twice the amount of the raw material, and the conductivity is low. From this, it is considered that a low-molecular weight polymer having low reactivity of the monomer is produced.

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

Further, the present inventors tried polymerization of 2-carboxylic acid group-substituted aniline with ammonium peroxodisulfate as an oxidizing agent in an aqueous solution containing a protic acid, and as a result, a product could be obtained. There wasn't. In addition, when aniline and 2-carboxylic acid group-substituted aniline were used as an oxidizing agent with ammonium peroxodisulfate, an attempt was made to perform polymerization in an aqueous solution containing a protonic acid. As a result, a copolymer was obtained, but the solubility and conductivity were also high. Both were low. It is considered that the copolymer obtained from this has a low copolymerization ratio of 2-carboxylic acid group-substituted aniline.

Further, in consideration of moldability such as film formation by coating, in order to enable coating on both hydrophilic and hydrophobic substrates, it must be soluble in both water and organic solvent. Is desired. However, the sulfonated product of polyaniline is soluble in alkaline water but insoluble in neutral to acidic aqueous solutions, and its solubility in organic solvents is not sufficient.

As a method for solving these various problems,
The present inventors express conductivity without adding a doping agent to the polymer, and in order to improve solubility, more acidic groups such as sulfonic acid groups or carboxylic acid groups are added to the aromatic ring of the main chain. Considering that it is necessary to introduce, at least one compound selected from the group consisting of aniline, N-alkylaniline and phenylenediamines, and aminobenzenesulfonic acid are copolymerized with an oxidizing agent in an acidic solvent, Furthermore, a method for producing a sulfonated aniline-based copolymer which is sulfonated with a sulfonating agent has been proposed (JP-A-5-178989). However, in this method, since the operation of sulfonation in concentrated sulfuric acid is performed, there is a problem of waste acid treatment. All the copolymers synthesized by the above method are presumed to have the structure of the following formula (7).

[0019]

[Chemical 7] (In the formula, 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 ratio of the sulfonic acid group is 40 to 80 with respect to the aromatic ring.
% Content, x represents an arbitrary number of 0 to 1, and n
Is a number from 2 to 1500 indicating the degree of polymerization)

Furthermore, the present inventors have found that aniline and N-
Characterizing that at least one compound selected from the group consisting of alkylaniline and phenylenediamines and an alkoxy group-substituted aminobenzenesulfonic acid are copolymerized to omit a sulfonation operation for generating a large amount of waste. A method for producing an aniline-based copolymer (JP-A-6-293828) has been proposed. In addition,
All the copolymers synthesized by the above method are presumed to have the structure of the following formula (8).

[0021]

[Chemical 8] (In the formula, each of R _{15 to} R ₂₂ is a group selected from the group consisting of hydrogen, an alkoxy group and a sulfonic acid group, and the ratio of the sulfonic acid group is 25 with respect to the aromatic ring.
Content of 50%, an alkoxy group and a sulfonic acid group are contained in the same aromatic ring, R'is hydrogen or a group selected from the group consisting of alkyl groups 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, the present inventors have proposed a soluble aniline-based soluble conductive polymer in which an acidic group-substituted aniline such as a sulfonic acid group-substituted aniline or a carboxylic acid group-substituted aniline is polymerized in a solution containing a basic compound, and a method for producing the same ( JP-A-7-196791 and JP-A-7-324132) have been proposed. This method is contrary to the established theory that anilines having a sulfonic acid group or a carboxylic acid group is difficult to polymerize by itself, but a high molecular weight polymer can be produced. Moreover, the obtained soluble conductive polymer exhibits high conductivity and excellent dissolution in any acidic to alkaline aqueous solution. However, when isolating the soluble conductive polymer and the by-product salt of the oxidizing agent used in the oxidative polymerization,
Since the soluble conductive polymer itself has very good solubility, there is a problem that its operation is not easy in industrial practice. All the copolymers synthesized by the above method are presumed to have the structure of the following formula (9).

[0023]

[Chemical 9] (In the formula, A _{1 to} A ₄ are sulfonic acid groups, carboxylic acid groups,
It is one group selected from the alkali metal salt, ammonium salt and substituted ammonium salt, and B _{1 to} B ₄ are hydrogen,
A linear or branched alkyl group having 1 to 4 carbon atoms, 1 carbon atom
4 represents one group selected from the group consisting of linear or branched alkoxy group, acidic group, hydroxyl group, nitro group and 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 electrochemically polymerizing aniline and m-aminobenzenesulfonic acid to synthesize a sulfonated polyaniline (Journal of the Chemical Society of Japan, 1985, 1124,
JP-A-02-166165), a method of electrochemically polymerizing aminobenzenesulfonic acid (Chemical Society of Japan No. 6)
4 Autumn Meeting Proceedings II 706 (1992) is reported. However, in these methods, since an inorganic salt is added as an electrolyte, the procedure of isolating the soluble conductive polymer and the electrolyte after polymerization becomes complicated, and there is a problem that it is very difficult to apply to industrial mass synthesis.

[0025]

The object of the present invention is to:
It is an object of the present invention to provide a soluble conductive polymer having high conductivity and solubility and having a high molecular weight, and a method useful as an industrial production method thereof.

[0026]

DISCLOSURE OF THE INVENTION The present inventors have proposed, as polyaniline having high conductivity and solubility, sulfonated polyaniline having a large introduction ratio of sulfonic acid groups to aromatic rings and carboxylated polyaniline having a large introduction ratio of carboxylic acid groups. As a result of intensive studies on a method for producing an acidic group-substituted polyaniline having a large proportion of acidic group introduction, an acidic group-substituted aniline such as a sulfonic acid group-substituted aniline or a carboxylic acid group-substituted aniline as a monomer, or the acidic group-substituted aniline and aniline derivative It has been found that electrolytically oxidatively polymerizing the above compounds in a solution containing a basic compound gives a soluble conductive polymer having high conductivity, high solubility, and high molecular weight, which is not obtained by chemical oxidative polymerization. Moreover, since the monomer and the polymer act as an electrolyte, the electrolyte normally required for electrolytic oxidative polymerization is unnecessary, and the operation of separating the electrolyte and the soluble conductive polymer can be omitted.
Therefore, the polymerization liquid can be directly used as a product such as a coating agent, which is industrially convenient. Furthermore, since the polymerized polymer is soluble in the reaction solution, it can be applied to a continuous electrolysis system such as a flow system. The flow-through system is a method in which the reaction solution is circulated in a cell between the working electrode and the cathode by a feed pump to carry out the polymerization.By connecting the cells in series or in parallel, the polymerization can be performed under optimal conditions. It becomes possible to carry out the reaction. Further, the findings of electropolymerization with these acidic group-substituted anilines are exactly the same as those of the acidic group-substituted pyrrole, thiophene, furan, selenophene, tellurophene, isothianaphthene, isobenzofuran, isoindoline, isobenzoselenophene, and isobenzoselenophene. It has been found that it can also be applied to benzotellurophene.
The present invention has been achieved based on such knowledge.

That is, the present invention is directed to acidic group-substituted aniline, acidic group-substituted pyrrole, acidic group-substituted thiophene, acidic group-substituted furan, acidic group-substituted selenophene, acidic group-substituted tellurophene, acidic group-substituted isothianaphthene, acidic group-substituted iso At least one compound (a) selected from the group consisting of benzofuran, acidic group-substituted isoindoline, acidic group-substituted isobenzoselenophene, acidic group-substituted isobenzotellurophene, their metal salts, ammonium salts and substituted ammonium salts. , A method for producing a soluble conductive polymer having an acidic group, which comprises electrolytically polymerizing in a solution containing a basic compound (II).

Another aspect of the present invention is that acidic group-substituted aniline, acidic group-substituted pyrrole, acidic group-substituted thiophene, acidic group-substituted furan, acidic group-substituted selenophene, acidic group-substituted tellurophene, acidic group-substituted isothianaphthene, acidic At least one compound selected from the group consisting of group-substituted isobenzofuran, acidic group-substituted isoindoline, acidic group-substituted isobenzoselenophene, acidic group-substituted isobenzotellurophene, a metal salt thereof, an ammonium salt and a substituted ammonium salt ( B) and aniline derivative, pyrrole derivative, thiophene derivative, furan derivative, selenophene derivative, tellurophene derivative, isothianaphthene derivative,
Electrolytic polymerization of at least one compound (c) selected from the group consisting of an isobenzofuran derivative, an isoindoline derivative, an isobenzoselenophene derivative and an isobenzotellophene 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 The present invention will be described in detail below by taking an acidic group-substituted aniline system, which is the most preferable example, as an example. The acidic group-substituted pyrrole, thiophene, furan,
The same is true for selenophene, tellurophene, isothianaphthene, isobenzofuran, isoindoline, isobenzoselenophene and isobenzotellurophene. The acidic group-substituted aniline has the general formula (1)

[Chemical 10] (In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are hydrogen,
It is 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, an acidic group, a hydroxyl group, a nitro group and a halogen group, At least one of them represents an acidic group.
The term "acidic group" here means at least one compound selected from the group consisting of acidic group-substituted aniline represented by sulfonic acid group or carboxylic acid group), its 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 is superior in the performance such as conductivity and solubility of the obtained polymer.

The most typical acid group-substituted aniline is sulfonic acid group-substituted aniline or carboxylic acid group-substituted aniline. Sulfonic acid group-substituted aniline is preferable, and it tends to have higher conductivity than carboxylic acid group-substituted aniline.

The most representative sulfonic acid group-substituted anilines are aminobenzenesulfonic acids, specifically, o-, m-, p-aminobenzenesulfonic acid, aniline-2,6-disulfonic acid and aniline. -2,5-Disulfonic acid, aniline-3,5-disulfonic acid, aniline-2,4-disulfonic acid and aniline-3,4-disulfonic acid are preferably used.

Other sulfonic acid 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, n-propoxyaminobenzenesulfone Acid, iso-propoxyaminobenzenesulfonic acid, n-butoxyaminobenzenesulfonic acid, se
Alkoxy group-substituted aminobenzene sulfonic acids such as c-butoxyaminobenzene sulfonic acid and t-butoxyaminobenzene sulfonic acid, hydroxy group-substituted aminobenzene sulfonic acids, nitro group-substituted aminobenzene sulfonic acids, fluoroaminobenzene sulfonic acid, chloroaminobenzene Examples thereof include halogen group-substituted aminobenzenesulfonic acids such as sulfonic acid and bromoaminobenzenesulfonic acid. Of these, alkyl group-substituted aminobenzene sulfonic acids, alkoxy group-substituted aminobenzene sulfonic acids and hydroxy group-substituted aminobenzene sulfonic acids are most preferable in practical use. These sulfonic acid group-substituted anilines may be used alone, or the isomers may be mixed in an arbitrary ratio.

The most representative carboxylic acid group-substituted anilines are aminobenzenecarboxylic acids, specifically, o-, m-, p-aminobenzenecarboxylic acid, aniline-2,6-dicarboxylic acid and 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 carboxylic acid group-substituted anilines include methylaminobenzenecarboxylic acid, ethylaminobenzenecarboxylic acid, n-propylaminobenzenecarboxylic acid, iso-propylaminobenzenecarboxylic acid, n.
-Butylaminobenzenecarboxylic acid, sec-butylaminobenzenecarboxylic acid, t-butylaminobenzenecarboxylic acid and other alkyl group-substituted aminobenzenecarboxylic acids, methoxyaminobenzenecarboxylic acid, ethoxyaminobenzenecarboxylic acid, n-propoxyaminobenzenecarboxylic acid Acid, iso-propoxyaminobenzenecarboxylic acid, n-butoxyaminobenzenecarboxylic acid, se
Alkoxy group-substituted aminobenzenecarboxylic acids such as c-butoxyaminobenzenecarboxylic acid and t-butoxyaminobenzenecarboxylic acid, hydroxy group-substituted aminobenzenecarboxylic acids, nitro group-substituted aminobenzenecarboxylic acids, fluoroaminobenzenecarboxylic acid, chloroaminobenzene Examples thereof include halogen group-substituted aminobenzenecarboxylic acids such as carboxylic acid and bromoaminobenzenecarboxylic acid. Of these, alkyl group-substituted aminobenzene carboxylic acids, alkoxy group-substituted aminobenzene carboxylic acids, and hydroxy group-substituted aminobenzene carboxylic acids are most practically preferred. These carboxylic acid group-substituted anilines may be used alone, or the isomers may be mixed in an arbitrary ratio.

More specifically, specific examples of the acidic group-substituted aniline of 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 group-substituted hydroxyaniline sulfonic acid group-substituted nitroaniline carboxylic acid group-substituted nitroaniline sulfonic acid group-substituted fluoroaniline carboxylic acid group-substituted fluoroaniline sulfonic acid group-substituted chloroaniline carboxylic acid group-substituted chloroaniline sulfonic acid group-substituted bromoaniline Further, carboxylic acid group-substituted bromaniline and the like can be mentioned, and specific examples of 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 group. Group, n-butyl group, sec-butyl group, alkyl group such as t-butyl group, methoxy group, ethoxy group, n-
One selected from alkoxy groups such as propoxy group, iso-propoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, and halogen groups such as hydroxy group, nitro group, fluoro group, chloro group, and bromine group. Two groups are shown, and H: hydrogen is shown.

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

Examples of the substituted ammonium include aliphatic ammonium, cyclic saturated ammonium, cyclic unsaturated ammonium and the like.

The above-mentioned fatty ammoniums are represented by the following general formula (10)

[Chemical 11] (Wherein R _{23 to} R ₂₆ are groups independently selected from the group consisting of hydrogen and alkyl groups 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 thereof include ammonium, ethylisopropylammonium, methylbutylammonium, ethylbutylammonium, tetramethylammonium, tetramethylammonium, tetraethylammonium, tetra-n-butylammonium, tetrasec-butylammonium, and tetra-t-butylammonium. Among them, it is most preferable that one of R _{23 to} R ₂₆ is hydrogen and the other 3 are alkyl groups having 1 to 4 carbon atoms, and then two of R _{23 to} R ₂₆ are hydrogen and the other 2
It is preferable that one is an alkyl group having 1 to 4 carbon atoms.

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

The cyclic unsaturated ammonium compounds include pyridinium, α-picolinium, β-picolinium, γ-.
Examples thereof include picolinium, quinolinium, isoquinolinium, pyrrolinium and derivatives having these skeletons.

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, but ammonia, aliphatic amines, Cyclic saturated amines, cyclic unsaturated amines, inorganic bases and the like are preferably used. Especially, aliphatic amines, cyclic saturated amines, cyclic unsaturated amines and the like are preferable.

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

[Chemical 12] (In the formula, R _{27 to} R ₂₉ are groups independently selected from the group consisting of alkyl groups having 1 to 4 carbon atoms.),

Or the following general formula (12)

[Chemical 13] (In the formula, each of R _{30 to} R ₃₃ is a group independently selected from the group consisting of hydrogen and an alkyl group having 1 to 4 carbon atoms.)
Examples thereof include a hydroxide compound.

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

Examples of the cyclic unsaturated amines include pyridine,
[alpha] -picoline, [beta] -picoline, [gamma] -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. The above-mentioned aliphatic amines, cyclic saturated amines and cyclic unsaturated amines are preferably used. The conductivity of the obtained polymer tends to be inferior to that of amines.

The concentration of these basic compounds (b) is 0.
1 mol / liter or more, preferably 0.1 to 10.0
mol / liter, more preferably 0.2 to 8.0 mo
Used in the l / l range. At this time, 0.1mo
When the amount is 1 / liter or less, the yield of the obtained polymer decreases, and when it is 10.0 mol / liter or more, the conductivity tends to decrease. The basic compound (b) can be mixed and used at an arbitrary ratio.

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

[Chemical 14] (In the formula, 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 compound represented by the formula (1).

The most typical aniline derivative (c) is aniline, and other than that, methylaniline, ethylaniline, n-propylaniline, iso-
Alkylanilines such as propylaniline, n-butylaniline, sec-butylaniline, t-butylaniline, methoxyaniline, ethoxyaniline, n-propoxyaniline, iso-propoxyaniline, n-butoxyaniline, sec-butoxyaniline, t- Examples thereof include alkoxyaniline such as butoxyaaniline, and halogen group aniline such as hydroxyaniline, nitroaniline, fluoroaniline, chloroaniline and bromaniline. The coexistence of the aniline derivative (c) exhibits an effective action for improving the conductivity and coating property of the obtained conductive polymer.

The weight ratio of the compound (a) such as aniline substituted with an acidic group and the basic compound (b) is (a):
(B) = 1: 100 to 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. On the contrary, when the ratio is high, the ratio of the acidic group and the basic compound in the obtained polymer to form a salt is high and the conductivity tends to be lowered.

The weight ratio of the compound (a) such as aniline having an acidic group and the aniline derivative (c) to the basic compound (b) is (a) + (c) :( b) = 1: 1.
00-100: 1, preferably 10: 90-90: 10
Is used. Here, if the ratio of the basic compound is low, the reactivity decreases and the conductivity also decreases. On the contrary, when the ratio is high, the ratio of the acidic group and the basic compound in the obtained polymer to form a salt is high and the conductivity tends to be lowered.

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

The molar ratio of the acidic group (d) to the basic compound (b) in the compound (a) 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: 0.5 to 1:15. here,
When the proportion of the basic compound is low, the reactivity is lowered and the conductivity is also lowered. On the contrary, when the ratio is high, the ratio of the acidic group and the basic compound in the obtained polymer to form a salt is high and the conductivity tends to be lowered.

The concentration of the compound (a) such as aniline substituted with an acidic group and the aniline derivative (c) at the time of electrolytic polymerization is 0.1% or more, preferably 0.5 to 50%, more preferably 1 with respect to the solvent. Is in the range of up to 30%.

Polymerization or copolymerization is carried out by electrolytic oxidative 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 metal plates or mesh electrodes of these oxides, carbon electrodes such as glassy carbon, A glass electrode provided with a metal oxide such as ITO, tin-indium oxide, or tin oxide can be used, and among these, 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 constant current electrolytic polymerization is 5 to 200 mA /
It is in the range of cm ² , preferably 10 to 200 mA / cm ² , and more preferably 15 to 150 mA / cm ² . The potential during potentiostatic electropolymerization is -0.5 V or less, preferably -1 V to -10 V, and more preferably -1 V with respect to the standard electrode.
It is convenient to apply a potential of V to -7 V to the working electrode.

If necessary, Li is used as the electrolyte.
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) such as an acid group-substituted aniline itself and the polymer itself function as an electrolyte, and therefore polymerization can be performed without these electrolytes.

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

Hydrogen in the sulfonic acid group or carboxylic acid group in the polymer produced by the present 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 in a mixed state rather than alone.

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 is in the state of being replaced with sodium.

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

When the basic compounds are mixed and used, they are obtained in a mixed state. Specifically, when polymerized with sodium hydroxide in the presence of ammonia, hydrogen in the sulfonic acid group or carboxylic acid group 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 sulfonic acid group or carboxylic acid group in the polymer is similarly obtained in the presence of both sodium and ammonium. To be

The above-mentioned polymer in which a part of the acidic groups forms a salt can be converted into a polymer having an acidic group in which no salt is formed by treating in an acidic solution and isolating the polymer. .

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 even if the acid substitution is sufficiently performed.

The soluble conductive polymer having an acidic group containing a sulfonic acid group or a carboxylic acid group on the aromatic ring thus obtained has a weight average molecular weight of 3,000 or more, preferably 3,000 to 1,000,000, and It is preferably 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 be small, and it becomes difficult to industrially apply.

This conductive polymer can be used without further sulfonation operation by simply adding water, a base such as ammonia and alkylamine, or water containing a base such as ammonium acetate and ammonium oxalate and a basic salt, hydrochloric acid and sulfuric acid. It can be dissolved in water containing the above acid or a solvent such as methyl alcohol, ethyl alcohol, isopropyl alcohol or a mixture thereof.

Explaining 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 an alkaline aqueous solution such as 1 liter of ammonia water, 1% by weight or more dissolved in an acidic aqueous solution such as a 0.1 mol / l sulfuric acid aqueous solution, and 1% by weight or more in a neutral aqueous solution such as water. Dissolve and add 1 mol / liter to an organic solvent such as ammonia alcohol solution.
It has the property that it dissolves by weight or more.

The polymers or copolymers synthesized by the above method are all assumed to have the structure of the following formula (13).

[Chemical 15] (In the formula, R _{34 to} R ₄₉ 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 nitro group and halogen. A group selected from the group consisting of groups, the introduction ratio of the acidic group is 50% or more based on the aromatic ring, and the acidic group is a sulfonic acid group or a carboxylic acid group. Represents an arbitrary number from 0 to 1, and n is a number from 2 to 1500 indicating the degree of polymerization).

[0071]

EXAMPLES The present invention will be described in more detail 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 Perkin Elmer (Model 1600). For the measurement of the molecular weight distribution and the molecular weight, a GPC column for an aqueous solution is used to measure the GPC (polyethyleneoxide equivalent).
I went. Column for aqueous solution; Tosoh TSK
-GEL G-5000PWKL and TSK-GEL G
Two types of -3000PWXL were connected in series and used.
A 0.2 mol / l phosphate 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.

Example 1 2 to 150 ml of 0.05 mol / l pyridine solution
-Aminoanisole-4-sulfonic acid (4.06 g) was dissolved, and glassy carbon as a working electrode and platinum as a cathode were immersed in this solution and stirred at room temperature for 1.5 V.
A constant voltage was applied to carry out electrolytic polymerization for 1 hour. A polymerization reaction occurred on the surface of the polymerization electrode immediately after the initiation of electrolytic polymerization, 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 solution was uniform. In addition, the elution of metal components from the polymerization electrode and oligomers were hardly detected. The obtained polymerization solution is applied onto a glass substrate by spin coating to form 100
It was dried at ° C. A film having a smooth surface resistance value of 2 × 10 ⁵ Ω / □ having a film thickness of 0.1 μm was obtained.

As a result of the measurement of the molecular weight, 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 polymerization solution was concentrated under reduced pressure to isolate the polymer, and the dissolved amount of the polymer was measured. The method is water, 0.1
The polymer was added little by little to 10 ml of a mol / L sulfuric acid aqueous solution or 0.1 mol / L ammonia water, and when the polymer was no longer dissolved, it was determined by filtration. The soluble 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.

An IR chart of the soluble conductive polymer is shown in FIG. 1, and a GPC measurement chart of the polymer is shown in FIG. The attribution of the IR spectrum is as follows. Backbone of 1120,1020Cm ^-1 vicinity polymer; sulfone group 1500cm absorption near ^-1

Example 2 150 ml of α-picoline solution having a concentration of 0.05 mol / l
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 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 solution was uniform. In addition, the elution of metal components from the polymerization electrode and oligomers were hardly detected. The obtained polymerization solution is applied onto a glass substrate by spin coating and the temperature is 80 ° C.
Dried. A film having a smooth surface resistance value of 5 × 10 ⁶ Ω / □ having a film thickness of 0.1 μm was obtained.

Example 3 0.05 mol / l concentration of triethylamine solution (water /
In 150 ml of isopropanol = 1/1, 3.6 g of 2-aminobenzenesulfonic acid and 0.1 g of aniline were dissolved, and an ITO electrode as a working electrode and platinum as a cathode were immersed in this solution and stirred at room temperature for 2. A constant voltage of 0 V was applied 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 solution was uniform. In addition, the elution of metal components from the polymerization electrode and oligomers were hardly detected. The obtained polymerization solution was applied onto a glass substrate by spin coating and dried at 100 ° C. A film having a smooth surface resistance value of 1 × 10 ⁷ Ω / □ having a film 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 [Nikazol RX-301C, manufactured by Nippon Carbide Co., Ltd.] were added to 100 parts by weight of water at room temperature. Stir to prepare a conductive crude product. The solution thus obtained was applied onto a PET film with a gravure coater having a depth of 40 μm and dried at 120 ° C.
Smooth surface resistance value of 0.2 μm surface 1 × 10 ⁷ Ω /
A 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 dissolved by stirring at room temperature to prepare a crosslinkable conductive composition. The solution thus obtained was subjected to P using a gravure coater with a depth of 40 μm.
It was coated on an ET film and dried at 150 ° C. A film having a smooth surface resistance value of 5 × 10 ⁶ Ω / □ having a film thickness of 0.8 μm was obtained. When this conductive film was immersed in water or 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 an aqueous acrylic emulsion resin [Nikazol RX-301C, manufactured by Nippon Carbide Co., Ltd.] 100 parts by weight Parts were stirred and dissolved in 100 parts by weight of water at room temperature to prepare a crosslinkable conductive composition. The solution thus obtained was applied to a galvanized plate (20 mm × 50
(mm × 1 mm) by the dip coating method,
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 for comparison (coating thickness 5-6 μm) --- NO.2--
And zinc plate --- NO.3 --at 40 ° C with salt spray (JIS-
(According to the K-5400 method) was performed, and a corrosion protection test was performed on each. The results are shown in Table 2.

[Table 2]

Example 7 2 to 30 ml of 0.5 mol / l concentration aqueous ammonia solution
-Aminoanisole-4-sulfonic acid (3.0 g) was dissolved, platinum as a working electrode and glassy carbon as a cathode were immersed in this solution, and a constant voltage of 2.5 V was applied at room temperature with stirring to electrolyze for 12 hours. Polymerization was carried out. A polymerization reaction occurred on the surface of the working electrode immediately after the start of application, and the initially colorless and transparent reaction liquid changed to 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 liquid was uniform. In addition, elution of metal components from the working electrode and oligomers were hardly detected. The obtained polymerization solution was applied onto a glass substrate by spin coating and dried at 100 ° C. A film having a smooth surface resistance value of 2 × 10 ⁵ Ω / □ having a film thickness of 0.1 μm was obtained.

Example 8 2 to 30 ml of 0.5 mol / l concentration aqueous ammonia solution
-Aminoanisole-4-sulfonic acid 3.0 g was dissolved. Electrolytic polymerization was performed by applying a constant voltage of 2.0 V at room temperature while circulating the solution through a series flow through cell in which platinum was used as a working electrode and glassy carbon was used as a cathode in the solution. A polymerization reaction occurred on the surface of the working electrode immediately after the start of application, and the reaction liquid, which was colorless and transparent, changed to 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 liquid was uniform. In addition, elution of metal components from the working electrode and oligomers were hardly detected. The obtained polymerization solution was applied onto a glass substrate by spin coating and dried at 80 ° C. Smooth surface resistance of the surface with a film thickness of 0.1 μm 5 × 10 ⁶ Ω / □
A film of was obtained.

Example 9 20 ml of 0.5 mol / l concentration of diethylamine aqueous solution
3.0 g of 2-aminoanisole-4-sulfonic acid is dissolved in 2., platinum as a working electrode and glassy carbon as a cathode are immersed in this solution, and the mixture is stirred at room temperature without stirring.
A constant voltage of 5 V was applied to carry out 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-like polymer adhered to the working electrode after 3 hours. After the completion of the polymerization reaction, the polymer on the working electrode did not peel off or fall off. The obtained polymerization solution was applied onto a glass substrate by spin coating and dried at 100 ° C. Film thickness 0.1μ
A film having a smooth surface resistance value of 1 × 10 ⁷ Ω / □ was obtained.

Example 10 To 30 ml of an aqueous ammonia solution having a concentration of 0.5 mol / l, o
-Dissolving 2.5 g of aminobenzoic acid, immersing platinum as a working electrode and glassy carbon as a cathode in this solution,
A constant voltage of 3.0 V was applied at room temperature without stirring to carry out 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-like polymer adhered to the working electrode after 3 hours. After the completion of the polymerization reaction, the polymer on the working electrode did not peel off or fall off. The obtained polymerization solution is applied onto a glass substrate by spin coating to form 100
It was dried at ° C. A film having a smooth surface resistance value of 5 × 10 ⁷ Ω / □ having a film thickness of 0.1 μm was obtained.

Example 11 To 30 ml of an aqueous ammonia solution having a concentration of 0.5 mol / l, o
2.5 g of aminobenzoic acid were dissolved. While circulating the solution with a pump in a series flow through cell with platinum as a working electrode and glassy carbon as a cathode in this solution,
Electrolytic polymerization was carried out 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 application, and the reaction liquid, which was colorless and transparent, changed to 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 liquid was uniform. In addition, elution of metal components from the working electrode and oligomers were hardly detected. The obtained polymerization solution was applied onto a glass substrate by spin coating and dried at 100 ° C. A film having a smooth surface resistance value of 7 × 10 ⁶ Ω / □ having a film thickness of 0.1 μm was obtained.

Example 12 Into 30 ml of an aqueous ammonia solution having a concentration of 0.5 mol / l, o
-3.0 g of aminobenzenesulfonic acid was dissolved. Electrolytic polymerization was performed by applying a constant voltage of 2.0 V at room temperature while circulating the solution through a series flow through cell in which platinum was used as a working electrode and glassy carbon was used as a cathode in the solution. A polymerization reaction occurred on the surface of the working electrode immediately after the start of application, and the reaction liquid, which was colorless and transparent, changed to 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 liquid was uniform. In addition, elution of metal components from the working electrode and oligomers were hardly detected. The obtained polymerization solution was applied onto a glass substrate by spin coating and dried at 80 ° C. A film having a smooth surface resistance value of 7 × 10 ⁶ Ω / □ having a film thickness of 0.1 μm was obtained.

Example 13 1.0 g of thiophene-3-sulfonic acid was dissolved in 20 ml of an aqueous pyridine solution having a concentration of 0.5 mol / l. Platinum as a working electrode and glassy carbon as a cathode were immersed in this solution without stirring. A constant voltage of 2.0 V was applied at room temperature to carry out 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-like polymer adhered to the working electrode after 3 hours. After the completion of the polymerization reaction, the polymer on the working electrode did not peel off or fall off. The obtained polymerization solution was applied onto a glass substrate by spin coating and dried at 100 ° C. A film having a smooth surface resistance value of 1 × 10 ⁵ Ω / □ having a film 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. Electrolytic polymerization was performed by applying a constant voltage of 2.0 V at room temperature while circulating the solution through a series flow through cell in which platinum was used as a working electrode and glassy carbon was used as a cathode in the solution. A polymerization reaction occurred on the surface of the working electrode immediately after the start of application, and the reaction liquid, which was colorless and transparent, changed to 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 liquid was uniform. In addition, elution of metal components from the working electrode and oligomers were hardly detected. The obtained polymerization solution was applied onto a glass substrate by spin coating and dried at 100 ° C. A film having a smooth surface resistance value of 7 × 10 ⁵ Ω / □ having a film thickness of 0.1 μm was obtained.

Comparative Example 1 Proceedings of the 64th Annual Meeting of the Chemical Society of Japan, II, 706 (19)
92) 2-aminobenzenesulfonic acid was synthesized by electrolytic polymerization. The obtained polymerization solution was applied onto 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-based soluble conductive polymer, Japanese Patent Laid-Open No.
2-aminobenzenesulfonic acid was synthesized by chemical polymerization by the method described in Example 1 of JP-A-324132. The obtained polymerization solution was applied onto a glass substrate by spin coating and dried at 80 ° C. The surface resistance of this product is 1 x 1
It was 0 ⁷ Ω / □. However, since the polymerization solution contained a large amount of sulfate, a smooth film could not be obtained. Moreover, although the separation was carried out by the described method, the filterability was poor and the operation was very complicated.

[0092]

[Effect] According to the present invention, it is possible to produce a high-molecular-weight soluble conductive polymer having high conductivity and solubility which cannot be obtained by conventional chemical oxidative polymerization. Further, since the monomer and the polymer act as an electrolyte, the electrolyte essential for ordinary electrolytic oxidative polymerization is unnecessary, and the operation of separating the electrolyte and the soluble conductive polymer can be omitted. Therefore, the polymerization liquid can be directly used 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, enabling industrial mass production.

[Brief description of drawings]

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

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

─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-7-238150 (JP, A) JP-A-8-59830 (JP, A) Special Table 1-500835 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08G 73/00-73/26 C08G 61/00-61/12

Claims (7)

(57) [Claims] 1. An acid group-substituted aniline, acid group-substituted pyrrole, acid group-substituted thiophene, acid group-substituted furan, acid group-substituted selenophene, acid group-substituted tellurophene, acid group-substituted isothianaphthene, acid group-substituted isobenzofuran, acid group At least one compound (a) selected from the group consisting of substituted isoindoline, acidic group-substituted isobenzoselenophene, acidic group-substituted isobenzotellurophene, metal salts thereof, ammonium salt and substituted ammonium salt,
A method for producing a soluble conductive polymer having an acidic group, which comprises electrolytically polymerizing 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 electropolymerization is continuously carried out by using continuous cells connected in series, parallel, or a combination thereof. 3. The acidic group-substituted aniline has the general formula (1): (In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are hydrogen,
It is 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, an acidic group, a hydroxyl group, a nitro group and a halogen group, At least one of them represents an acidic group.
Moreover, an acidic group here shows a sulfonic acid group or a carboxylic acid group. ) Acidic group-substituted aniline, or the acidic group-substituted pyrrole, acidic group-substituted thiophene, acidic group-substituted furan, acidic group-substituted selenophene, acidic group-substituted tellurophene, acidic group-substituted isothianaphthene, acidic group-substituted isobenzofuran, acidic The group-substituted isoindoline, the acid group-substituted isobenzoselenophene, and the acid group-substituted isobenzotellurophene are represented by the general formula (2) or the general formula (3): [Chemical 3] (In the formula, Z is any one of NH, S, O, Se, and Te, and R ′ ₁ , R ′ ₂ , R ′ ₃ and R ′ ₄ are hydrogen and 1 carbon atoms.
~ 24 linear or branched alkyl group, 1 to 24 carbon atoms
Is a substituent 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, at least one of which is an acidic group. Moreover, an acidic group here shows a sulfonic acid group or a carboxylic acid group. ) Acidic group-substituted pyrrole, acidic group-substituted thiophene, acidic group-substituted furan, acidic group-substituted selenophene,
The acidic group-substituted tellurophene, the acidic group-substituted isothianaphthene, the acidic group-substituted isobenzofuran, the acidic group-substituted isoindoline, the acidic group-substituted isobenzoselenophene, and the acidic group-substituted isobenzotellurophene. A method for producing a soluble conductive polymer having an acidic group. 4. 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. At least one compound (a) selected from the group consisting of substituted isoindoline, acidic group-substituted isobenzoselenophene, acidic group-substituted isobenzotellurophene, metal salts thereof, ammonium salts and substituted ammonium salts,
Aniline derivative, pyrrole derivative, thiophene derivative,
At least one compound (c) selected from the group consisting of furan derivatives, selenophene derivatives, tellurophene derivatives, isothianaphthene derivatives, isobenzofuran derivatives, isoindoline derivatives, isobenzoselenophene derivatives and isobenzotellophene derivatives is used as a base. A method for producing a soluble conductive polymer having an acidic group, which comprises electrolytically polymerizing in a solution containing a polymerizable compound (b). 5. The method for producing a soluble conductive polymer having an acidic group according to claim 4, wherein the electropolymerization is continuously carried out by using continuous cells connected in series, parallel, or a combination thereof. 6. The aniline derivative has the general formula (4): (In the formula, R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are hydrogen,
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 is shown. ) Or an aniline derivative represented by the above, or 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, an isobenzotellophene derivative, General formula (5) or general formula (6) [Chemical 6] (In the formula, Z is any one of NH, S, O, Se, and Te, and R ′ ₆ , R ′ ₇ , R ′ ₈ and R ′ ₉ are hydrogen and C 1
~ 24 linear or branched alkyl group, 1 to 24 carbon atoms
Represents a substituent selected from the group consisting of a linear or branched alkoxy group, a hydroxyl group, a nitro group and a halogen group. ) Pyrrole derivative, thiophene derivative,
Furan derivative, selenophene derivative, tellurophene derivative, isothianaphthene derivative, isobenzofuran derivative, isoindoline derivative, isobenzoselenophene derivative, isobenzotellophene derivative, soluble conductivity having an acidic group according to claim 4 or claim 5. 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 claim 5, wherein the range is 0:70.