JPH07196791A - Soluble aniline-based electrically-conductive polymer and its production - Google Patents

Abstract

PURPOSE:To obtain the subject new polymer useful for various antistatic treatments, showing high electrical conductivity, excellent solubility in water with an arbitrary pH or an organic solvent and improved coating performances. CONSTITUTION:This soluble aniline-based electrically-conductive polymer comprises an alkoxy group-substituted aminobenzenesulfonic acid, its alkali metal salt, ammonium salt and/or substituted ammonium salt as a repeating unit, has >= about 1,900 weight-average molecular weight and is in a solid state at a normal temperature. The polymer, for example, is shown by formula I [A is H, an alkali metal or a (substituted) ammonium; R is a 1-12C alkyl; (x) is 0-1; (n) is 3-5,000 polymerization degree]. The polymer is obtained by polymerizing a sulfonic acid of formula II, its alkali metal salt or (substituted) ammonium salt with an oxidizing agent in a solution containing a basic compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solvent-soluble aniline-based conductive polymer and a method for producing the same. The solution can be applied to various antistatic applications by a simple method such as spraying or dipping.

[0002]

2. Description of the Related Art Although doped polyaniline (conductive polymer) is well known, it is insoluble in almost all solvents and has a problem in molding and processing. Also, a method of electrolytically oxidatively polymerizing aniline [JP-A-60-23583]
No. 1, gazette, J. 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.

Further, in recent years, alkali-soluble sulfonated polyaniline which exhibits conductivity without adding a doping agent and a method for synthesizing the same have been proposed. For example, as a method of synthesizing sulfonated polyaniline, a method of electrochemically polymerizing aniline and m-aminobenzenesulfonic acid to synthesize sulfonated polyaniline (Journal of the Chemical Society of Japan, 198)
5, 1124, Japanese Patent Laid-Open No. 02-166165), o
A method of synthesizing sulfonated polyaniline by electrochemically polymerizing each of-, m-, and p-aminobenzenesulfonic acid [Proceedings of the 64th Annual Meeting of the Chemical Society of Japan, II]
706 (1992)], a method for chemically synthesizing aniline and o-, m-aminobenzenesulfonic acid to synthesize a sulfonated polyaniline (Japanese Patent Laid-Open No. 01-301714), chemical or electrochemical polymerization. The method of sulfonation of the obtained emeraldine type polymer (polyaniline) with concentrated sulfuric acid (JP-A-58-21090).
2), a method of sulfonating using a sulfuric anhydride / triethyl phosphate complex (JP-A-61-197633), a method of sulfonating with fuming sulfuric acid [J. Am. Che
m. Soc. , (1991) 113, 2665-2
671, J.I. Am. Chem. Soc. , (19
90) 112, 2800, WO 91-06 887],
A method of chemically polymerizing diphenylamine-4-sulfonic acid (sodium salt) to synthesize an N-substituted sulfonated polyaniline [Polymer, (1993) 34, 1
58-162] and the like are known.

In the 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), the product is on the electrode. Therefore, there are problems that the isolation operation becomes complicated and mass synthesis is difficult.

Also, in the proceedings of the 64th Autumn Meeting of the Chemical Society of Japan II 706 (1992), a method for synthesizing a soluble conductive polymer by electrolytic oxidation of aminobenzenesulfonic acid is explained. It is hard to say that it is suitable for synthesis. Further, it is described that no product was obtained when aminobenzenesulfonic acid was chemically oxidatively polymerized using ammonium peroxodisulfate as an oxidizing agent. Also, J. Am. Chem. Soc. , (199
1) According to 113, 2665-2671, o-, m-
Attempts to chemically and electrochemically polymerize aminobenzene sulfonic acid were noted as unsuccessful.

Further, when the present inventors attempted polymerization in an aqueous solution containing a protic acid using ammonium peroxodisulfate as an oxidizing agent, the same product could not be obtained. Further, the present inventors tried polymerization in an aqueous solution using an alkoxy group-substituted aminobenzenesulfonic acid as an oxidizing agent and ammonium peroxodisulfate, but a polymer considered to be an oligomer was obtained, but the conductivity was low. It was a thing.

The inventors of the present invention additionally tried a method of chemically polymerizing aniline and m-aminobenzenesulfonic acid with ammonium peroxodisulfate, which is described in JP-A No. 01-301714. Only one sulfone group was introduced. In addition, JP-A-61
-When sulfonated by the method of 197633, the solubility of polyaniline in the sulfonation solvent is not sufficient and the reaction is carried out in a dispersed state as described on page 7 of the same publication, so that about 5 aromatic rings are used. Only one sulfone group is introduced. The thus-obtained sulfonated polyaniline having a small introduction ratio of sulfone groups has a problem that the conductivity and the solubility are not sufficient.

Further, J. Am. Chem. So
c. , (1991) 113, 2665-2671, J.
Am. Chem. Soc. , (1990) 112,
According to 2800, when polyaniline is sulfonated with fuming sulfuric acid, about one sulfone 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 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.

In addition, 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. , (19
91) The conductivity was lower than that of the polymer synthesized by the method of 113, 2665-2671.

Therefore, it is expected that more sulfone groups need to be introduced into the aromatic ring of the main chain in order to develop conductivity and improve solubility without adding a doping agent to the polymer.

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, although the sulfonated product of polyaniline has solubility in alkaline water, its solubility in organic solvents is not sufficient.

As a method for solving these various problems,
The present inventors copolymerized at least one compound (A) selected from the group consisting of aniline, N-alkylaniline and phenylenediamines with aminobenzene sulfonic acid (B), and further sulfone with a sulfonating agent. There has been proposed a method for producing a sulfonated aniline-based copolymer, which is characterized by: However, this method also requires an operation of sulfonation in concentrated sulfuric acid, and treatment of waste acid remains a big problem.

All of the copolymers synthesized by the above method are presumed to have the structure of the following formula (5).

[Chemical 5] (In the formula, R ₁ , R ₂ , R ₃ and R ₄ are each selected from the group consisting of hydrogen, an alkoxy group and a sulfone group,
R'is selected from the group consisting of hydrogen or an alkyl group having 1 to 4 carbon atoms, the proportion of the sulfone group is 40 to 80% of the content of the sulfone group with respect to the aromatic ring, and x is any 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-
By copolymerizing at least one compound (A) selected from the group consisting of alkylanilines and phenylenediamines with aminoanisolesulfonic acid (B), a sulfonation operation for generating a large amount of waste is omitted. And a method for producing an aniline-based copolymer (Japanese Patent Application No. 5-48540). However, even the copolymer obtained by this method has a problem that it is not dissolved in water alone.

All the copolymers synthesized by the above method are presumed to have the structure of the following formula (6).

[Chemical 6] (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ or R
Each of ₈ is selected from the group consisting of hydrogen, an alkoxy group and a sulfone group, and the proportion of the sulfone group is 25 to 50% of the content of the sulfone group with respect to the aromatic ring. Contains
R'is selected from the group consisting of hydrogen or an alkyl group having 1 to 4 carbon atoms, x represents an arbitrary number from 0 to 1, and n is a number from 2 to 1500 indicating the degree of polymerization. )

As the polymerization solvent in the above-mentioned chemical polymerization, water or an aqueous solution containing a protonic acid is used. According to JP-A-1-163263, when ammonium peroxodisulfate is used as an oxidant, especially pKa
It is described that the compound contains a protic acid of 3 or less, and that a solvent used in the polymerization of aniline is one in which aniline, a protic acid and an oxidizing agent are dissolved and which is not oxidized by the oxidizing agent.

[0017]

The object of the present invention is to:
It is an object of the present invention to provide a 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 a method for producing the same. .

[0018]

Means for Solving the Problems The inventors of the present invention have earnestly studied a method for producing a sulfonated polyaniline having a high introduction ratio of a sulfone group to an aromatic ring as a polyaniline having high conductivity and solubility, and as a result, alkoxy substitution as a monomer has been performed. Polymerization of aminobenzene sulfonic acid in a solution containing a basic compound using an oxidant improves the reactivity particularly, and it is believed that conventional aniline having a sulfone group cannot be chemically oxidatively polymerized by itself. On the contrary, it was found that polymerization is possible. In addition, the obtained conductive polymer was highly conductive and was soluble in an aqueous solution of any pH from acidic to alkaline, especially water alone, and was also highly soluble in organic solvents such as alcohol.

That is, the first aspect of the present invention is that an alkoxy group-substituted aminobenzenesulfonic acid, an alkali metal salt thereof,
The present invention relates to a soluble aniline-based conductive polymer, which is a polymer having an ammonium salt and / or a substituted ammonium salt as a repeating unit and has a weight average molecular weight of about 1900 or more and is solid at room temperature.

The polymer has the general formula (1)

[Chemical 7] (In the formula, A is a group independently selected from the group consisting of hydrogen, an alkali metal, an ammonium group and a substituted ammonium, R is a linear or branched alkyl group having 1 to 12 carbon atoms, and x is 0 to 1 represents an arbitrary number, n represents a degree of polymerization, and is an alkoxy group-substituted aminobenzenesulfonic acid represented by (3 to 5000), its alkali metal salt, ammonium salt and / or substituted ammonium salt is a repeating unit. The polymer can be represented as a soluble aniline-based conductive polymer characterized by being a solid at room temperature having a weight average molecular weight of about 1900 or more. This polymer has a surface resistance of 10 ⁸ Ω /
It has an excellent feature that it is less than the order of □ (measured at a film thickness of 0.1 μm) and is soluble in an acidic solution described later.

Examples of alkali metal salts include lithium, sodium and potassium.

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

As the above-mentioned fatty ammoniums, the following formula (7) is used.

[Chemical 8] (R in the formula_{twenty one}~ R_{twenty four}Is hydrogen, alkyl having 1 to 4 carbon atoms
Group, CH₃OH, CH₃CH₂Independent of the group consisting of OH
Is the group chosen. ). For example, meth
Ruammonium, dimethylammonium, trimethylammonium
Ammonium, ethylammonium, diethylammonium
, Triethylammonium, methylethylammonium
System, diethylmethylammonium, dimethylethylan
Monium, propyl ammonium, dipropyl ammonium
Um, isopropylammonium, diisopropylan
Monium, butylammonium, dibutylammonium
System, methylpropylammonium, ethylpropylan
Monium, methyl isopropyl ammonium, ethyl
Sopropylammonium, methylbutylammonium,
Ethylbutylammonium, tetramethylammonium
System, tetramethylammonium, tetraethylan
Monium, tetra n-butyl ammonium, tetra se
c-butylammonium, tetra-t-butylammonium
And the like. Among them, R_{twenty one}~ R_{twenty four}
One of them is hydrogen, and the other three are alkyl having 1 to 4 carbon atoms.
Most preferred is a group, followed by R_{twenty one}~ R_{twenty four}Two out of
Is hydrogen and the other two are alkyl groups having 1 to 4 carbon atoms
preferable.

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.

Examples of R are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl,
Examples thereof include tert-butyl, hexyl, heptyl, octyl, nanonyl, decanyl, undecanyl and the like.

Further, the above-mentioned x can be obtained in the range of 0.2 to 0.8 in the case of the one synthesized by the present method. However, an oxidant such as benzoyl peroxide, ammonium peroxodisulfate and hydrogen peroxide can be obtained. When x is oxidized, a small x is obtained, and when reduced with a reducing agent such as hydrazine, phenylhydrazine, sodium borohydride or sodium hydride, a large x is obtained. A in the present invention is a group independently selected from the group consisting of hydrogen, alkali metal, 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 A in the isolated polymer is in a sodium state, but when treated in an acid solution, A
Most of them can be hydrogen substituted polymers. However, even if the acid substitution is sufficiently carried out, it is difficult to obtain the one completely replaced with hydrogen. Similarly, when polymerized in the presence of ammonia, most of A is ammonium, when polymerized in the presence of trimethylamine, most of A is trimethylammonium, and when polymerized in the presence of quinoline, most of A is quinolinium. can get. When basic compounds are mixed and used, A is obtained in a mixed state. Specifically, when polymerized in the presence of sodium hydroxide and ammonia, A in the isolated polymer is obtained in the presence of both sodium and ammonium. Also, when the obtained polymer is treated with a solution containing both sodium hydroxide and ammonia, A in the polymer is similarly obtained in the state where both sodium and ammonium are present.

In the present invention, "alkali water-soluble" means that no insoluble matter is generated when 1% by weight of the aniline-based conductive polymer is dissolved in 0.1N ammonia water, and "acidic water-soluble" is used. When 1% by weight of aniline-based conductive polymer is dissolved in 0.1M sulfuric acid aqueous solution, no insoluble matter is generated. Neutral water-soluble means that 1% by weight of aniline-based conductive polymer is dissolved in water alone. It means that no insoluble matter is generated when the solution is dissolved, and that the organic solvent is soluble means that no insoluble matter is generated when 1% by weight of the aniline-based conductive polymer is dissolved in 0.1N ammonia alcohol solution. ing.

The second aspect of the present invention is the general formula (2)

[Chemical 9] (In the formula, R has 1 to 12 carbon atoms, preferably 1 to 12 carbon atoms.
8, more preferably an alkoxy-substituted aminobenzenesulfonic acid represented by a linear or branched alkyl group having 1 to 4 carbon atoms, its alkali metal salt, ammonium salt and / or substituted ammonium salt, and a basic compound 5. The method for producing a soluble aniline-based conductive polymer according to claim 1, 2, 3 or 4, wherein the polymerization is carried out with an oxidizing agent in a solution containing the same. In the compound of the general formula (2), a polymer in which an amino group is bonded to the o-position or the m-position with respect to a sulfone group has a conductivity of a polymer,
Excellent performance such as solubility.

The most representative examples of the alkoxy group-substituted aminobenzenesulfonic acids are aminoanisolesulfonic acids, specifically, 2-aminoanisole-3-sulfonic acid, 2-aminoanisole-4-sulfonic acid, 2-aminoanisole-5-sulfonic acid, 2-aminoanisole-6-sulfonic acid, 3-aminoanisole-2-sulfonic acid, 3-aminoanisole-4-sulfonic acid, 3-aminoanisole-5-sulfonic acid, 3-
Aminoanisole-6-sulphonic acid, 4-aminoanisole-2-sulphonic acid, 4-aminoanisole-3-sulphonic acid and the like can be mentioned, but especially 2-aminoanisole-3-sulphonic acid and 2-aminoanisole. -4-sulfonic acid, 2-aminoanisole-6-sulfonic acid, 3-aminoanisole-2-sulfonic acid, 3-aminoanisole-4-sulfonic acid, 3-aminoanisole-5-sulfonic acid are preferably used.

Other alkoxy group-substituted aminobenzenesulfonic acids include 2-amino-4-ethoxybenzenesulfonic acid, 3-amino-4-ethoxybenzenesulfonic acid, 2-amino-4-butoxybenzenesulfonic acid and 3-amino-4-ethoxybenzenesulfonic acid. Amino-5-butoxybenzenesulfonic acid, 2
-Amino-4-propoxybenzenesulfonic acid, 3-amino-6-propoxybenzenesulfonic acid, 2-amino-4-isobutoxybenzenesulfonic acid, 3-amino-
4-isobutoxybenzenesulfonic acid, 3-amino-4
-T-Butoxybenzenesulfonic acid, 2-amino-4-
t-Butoxybenzenesulfonic acid, 2-amino-4-heptoxybenzenesulfonic acid, 3-amino-5-heptoxybenzenesulfonic acid, 2-amino-4-hexoxybenzenesulfonic acid, 3-amino-5 Octoxybenzenesulfonic acid, 2-amino-4-nanoxybenzenesulfonic acid, 3-amino-5-decanooxybenzenesulfonic acid, 2-amino-4-undecanoxybenzenesulfonic acid, 3-amino-5- Dodecanoxybenzene sulfonic acid etc. can be mentioned. These alkoxy group-substituted aminobenzenesulfonic acids may be used alone or as a mixture of isomers at an arbitrary ratio.

Next, the basic compound used in the present invention may be any compound as long as it forms a salt with the above-mentioned alkoxy group-substituted aminobenzene sulfonic acids, but it may be a fatty amine or a cyclic saturated compound. Amines, cyclic unsaturated amines, inorganic bases and the like are preferably used.

The fatty amines are represented by the following formula (8)

[Chemical 10] (In the formula, each of R _{11 to} R ₁₃ is a group 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.). Compound or general formula (9)

[Chemical 11] (In the formula, each of R _{14 to} R ₁₇ is a group 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.). 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.

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

As the inorganic base, salts of hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide and aqueous ammonia are preferably used.

The concentration of these basic compounds is 0.1 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 / l or less, the yield of the obtained polymer tends to decrease, and when it is 10.0 mol / l or more, the conductivity tends to decrease. The basic compounds may be mixed and used in arbitrary proportions.

Polymerization or copolymerization is carried out by oxidative polymerization with an oxidizing agent in a solution containing these basic compounds. As the solvent, water, methanol, ethanol, isopropanol, acetonitrile, methyl isobutyl ketone, methyl ethyl ketone, dimethylformamide, dimethylacetamide and the like are preferably used.

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 -15 to 70 ° C, more preferably -5 to -5 ° C.
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 soluble aniline-based conductive polymer containing sulfone groups on all aromatic rings thus obtained has a degree of polymerization of 3 to 5000, preferably 5 to 5000,
The molecular weight is about 1900 to 3240000, preferably 32.
It is 00-3240000. This polymer is not further subjected to sulfonation operation, but is simply water, a base such as ammonia and an alkylamine or water containing a base and a basic salt such as ammonium acetate and ammonium oxalate, a water containing an acid such as hydrochloric acid and sulfuric acid, or It can be dissolved in a solvent such as methyl alcohol, ethyl alcohol, isopropyl alcohol or a mixture thereof.

The solubility characteristics of the polymer of the present invention and the conventional polymer [of the formula (4) or (5)] are summarized in Table 1.
Shown in.

[Table 1] ◯: Soluble x: Insoluble *) SO ₃ M type means a case of a sulfonate type.

[0043]

EXAMPLES Examples will be described below. The IR spectrum is model 1600 manufactured by Perkin Elmer,
The UV-visible spectrum was measured using a UV-3100 apparatus manufactured by Shimadzu Corporation. For the measurement of the molecular weight distribution and the molecular weight, GPC measurement (polystyrene conversion) was performed using a GPC column for N, N-dimethylformamide. As the column, three types of columns for N, N-dimethylformamide were connected and used. The eluent is 10 mM / l triethylamine and 100 mM / l lithium bromide N, N-.
A dimethylformamide solution was used. 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-Aminoanisole-4-sulfonic acid 100 mmol
Is dissolved in a 4 mol / liter aqueous ammonia solution with stirring at 25 ° C., and ammonium peroxodisulfate (100 mmol) is added.
Was added dropwise. After completion of the dropping, the mixture was further stirred at 25 ° C. for 12 hours, and the reaction product was separated by filtration, washed and dried to obtain 15 g of polymer powder. The volume resistance of this product is 9.0Ωc
It was m. 3 parts by weight of the above polymer was dissolved in 100 parts by weight of a 0.2 mol / liter sulfuric acid aqueous solution with stirring at room temperature to prepare a conductive composition. The solution thus obtained was applied on a glass substrate by spin coating and dried at 100 ° C. 2. A smooth surface resistance value of 0.1 μm thick film surface 3.
A film of 5 × 10 ⁶ Ω / □ was obtained. FIG. 1 is a chart in measuring the molecular weight of the conductive polymer synthesized in Example 1. To measure the molecular weight distribution and molecular weight,
GPC measurement (in terms of polystyrene) was performed using a GPC column for N, N-dimethylformamide. As the column, three types of columns for N, N-dimethylformamide were connected and used. As the eluent, 0.01 mol / liter of triethylamine and 0.1 mol / liter of lithium bromide in N, N-dimethylformamide were used.
As a result of the measurement, the number average molecular weight was 200,000, the weight average molecular weight was 330,000, the Z average molecular weight was 383,000, and the dispersity was MW / MN1.64 and MZ / MW1.16. Water, 0.1 mol / liter sulfuric acid aqueous solution or 0.1
The polymer was added little by little to 10 ml of mol / liter ammonia water, and when the polymer became insoluble, it was filtered and the dissolved amount was determined. The solubility of the conductive polymer synthesized in Example 1 was 210 mg / ml of water. It was a 1 mol / liter sulfuric acid aqueous solution 205 mg / ml and 0.1 mol / liter ammonia water 190 mg / ml.

Example 2 100 mmol of 2-aminoanisole-4-sulfonic acid
Is dissolved in a 4 mol / liter trimethylamine aqueous solution with stirring at 4 ° C., and ammonium peroxodisulfate 100 mm is added.
An aqueous solution of ol was added dropwise. After the dropwise addition was completed, the mixture was further stirred at 25 ° C. for 6 hours, and the reaction product was separated by filtration, washed and dried to obtain 12 g of polymer powder. 1 mol / l P of this polymer
The mixture was stirred for 1 hour in an acetone solution of TS, washed by filtration, and dried to obtain 10 g of a polymer powder having a free sulfo group. The volume resistance value of this product was 5.5 Ωcm. 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. Since the pH of the composition was about 3.5, it is estimated that about 80% or more of the sulfonic acid groups in the polymer are free. The solution thus obtained was applied onto a glass substrate by a casting method,
It was dried at 00 ° C. A film having a smooth surface resistance value of 6.0 × 10 ⁷ Ω / □ having a film thickness of 0.1 μm was obtained. FIG. 2 shows the conductive polymer synthesized in Example 2 at 190 nm in a 0.1 mol / liter sulfuric acid aqueous solution.
FIG. 3 is a UV-visible spectrum of 00 nm, and FIG.
4 is a UV-visible spectrum from 0 nm to 900 nm, and FIG. 4 shows 190 nm of the conductive polymer synthesized in Example 2 in a 0.2 mol / liter ammonia aqueous solution.
Is an ultraviolet-visible spectrum from 900 nm to 900 nm. Figure 5
1 shows an IR spectrum of a conductive polymer (sulfonic acid group-free type) synthesized in Example 2. Assignment of IR spectrum is as follows. Sulfone group: Absorption near 1120, 1020 cm ^-1 Ammonium salt of sulfo group: Absorption near 1400 cm ^-1 Polymer skeleton: Absorption near 1500 cm ^-1

Example 3 100 mmol of 2-aminoanisole-4-sulfonic acid
Was dissolved in a 4 mol / l quinoline aqueous solution with stirring at 4 ° C., and an aqueous solution of 100 mmol of ammonium peroxodisulfate was added dropwise. After completion of the dropping, the mixture was further stirred at 25 ° C. for 12 hours, and the reaction product was separated by filtration, washed and dried to obtain 16 g of polymer powder. The volume resistance of this product is 11.0 Ωcm
Met. 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. PH of the composition
Since it was about 6.0, it is estimated that about 20% or more of the sulfonic acid groups in the polymer form a salt. The solution thus obtained was applied onto a PET film by spin coating and dried at 80 ° C. Smooth surface resistance value of 0.1 μm surface 6.0 × 10 ⁶ Ω /
A film of □ was obtained.

Example 4 3-Amino-4-ethoxybenzenesulfonic acid 100 m
mol was dissolved with stirring at 25 ° C. in a 3 mol / liter 2-methylpyridine (α-picoline) aqueous solution, and an aqueous solution of ammonium peroxodisulfate 100 mmol was added dropwise.
After the dropwise addition 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 14 g of polymer powder. The volume resistance value of this product was 8.4 Ωcm. 3 parts by weight of the above polymer was added to water / isopropyl alcohol (7/3) 1
A conductive composition was prepared by stirring and dissolving in 100 parts by weight at room temperature. The solution thus obtained was applied onto a glass substrate by spin coating and dried at 120 ° C. Smooth surface resistance of film thickness 0.1 μm 4.5 × 10 ⁶ Ω /
A film of □ was obtained.

Example 5 100 mmol of 2-aminoanisole-4-sulfonic acid
Was dissolved in a 4 mol / liter aqueous solution of triethanolamine with stirring at 10 ° C., and ammonium peroxodisulfate 10 was added.
A 0 mmol aqueous solution was added dropwise. 1 at 25 ° C after completion of dropping
After further stirring for 2 hours, 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 12 Ωcm. A conductive composition was prepared by dissolving 3 parts by weight of the above polymer in 100 parts by weight of water-soluble polyester resin "ARASTAR 300" (manufactured by Arakawa Chemical Industry Co., Ltd.) in 100 parts by weight of water at room temperature with stirring. The solution thus obtained was PET-coated with a gravure coater having a depth of 35 μm.
It was coated on a film and dried at 70 ° C. Film thickness 0.5
A film having a smooth surface resistance value of 4.5 × 10 ⁶ Ω / □ on the μm surface was obtained. FIG. 6 shows an IR spectrum of the conductive polymer (salt type) synthesized in Example 5.

Example 6 100 mmol of 2-aminoanisole-4-sulfonic acid
Was dissolved in a 4 mol / liter piperidine aqueous solution with stirring at 25 ° C., and ammonium peroxodisulfate (100 mmol) was added.
Was added dropwise. After completion of the dropping, the mixture was further stirred at 25 ° C. for 12 hours, and the reaction product was separated by filtration, washed and dried to obtain 15 g of polymer powder. The volume resistance of this product is 18 Ωcm
Met. 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 was mixed with P
It is applied on the ET film by spin coating method at 80 ° C.
Dried. A film having a smooth surface resistance value of 4.0 × 10 ⁷ Ω / □ having a film thickness of 0.1 μm was obtained.

Example 7 3-Amino-4-ethoxybenzenesulfonic acid 100 m
mol was dissolved in a 3 mol / liter sodium hydroxide aqueous solution with stirring at 4 ° C., and ammonium peroxodisulfate 10
A 0 mmol aqueous solution was added dropwise. After the dropping, 25 ℃, 6
After further stirring for an hour, the reaction product was separated by filtration, washed and dried to obtain 15 g of a polymer powder. The volume resistance value of this product was 20 Ωcm. This polymer was stirred in an acetone solution of 1 mol / liter of PTS for 1 hour, filtered and washed,
After drying, 10 g of a polymer powder having a free sulfonic acid group was obtained. 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 viscosity of the composition is 2.
It was 75 cp (25 ° C.). This viscosity was measured using an Ubbelohsi viscometer. Since the pH of the composition was about 3.8, it is estimated that about 80% or more of the sulfonic acid groups in the polymer are free. The solution thus obtained was applied on a glass substrate by spin coating and dried at 80 ° C. A film having a smooth surface resistance value of 8.0 × 10 ⁷ Ω / □ having a film thickness of 0.1 μm was obtained.

Comparative Example 1 2-Aminoanisole-4-sulfonic acid 100 mmol
Was stirred and suspended in water at 4 ° C., and an aqueous solution of 100 mmol of ammonium peroxodisulfate was added dropwise. 2 after completion of dropping
After further stirring at 5 ° C. for 12 hours, the reaction solution was distilled off under reduced pressure, the concentrate was isolated and washed, and then dried to obtain 6 g of a polymer powder. The volume resistance value of this product was> 10 ⁶ Ωcm. 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 is
80 by spin coating on PET film
It was dried at ° C. A film having a surface resistance value of 6.0 × 10 ¹² Ω / □ or more and having a low film-forming property with a film thickness of 0.1 μm was obtained.

Comparative Example 2 100 mmol of 2-aminoanisole-4-sulfonic acid
Was stirred and suspended in a 1 mol / liter sulfuric acid aqueous solution at 25 ° C., and 100 mmol of ammonium peroxodisulfate (1 mmol) was added.
A mol / l sulfuric acid aqueous solution was added dropwise. 2 after completion of dropping
After further stirring at 5 ° C. for 12 hours, the reaction solution was distilled off under reduced pressure, and the concentrate was isolated, washed and dried to obtain 3 g of a polymer powder. The volume resistance value of this product was> 10 ⁶ Ωcm.
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 glass substrate by spin coating,
No film was formed due to the oligomer.

Comparative Example 3 Sulfonated polyaniline was used as an aniline-based conductive polymer by a known method [J. Am. Chem. Soc. ，
(1991), 113, 2665-2666]. The content of the obtained sulfone group was 52% based on the aromatic ring. 3 parts by weight of the sulfonated polyaniline was mixed at room temperature with 100 parts by weight of a 0.2 mol / liter sulfuric acid aqueous solution to prepare a conductive composition. The solution thus obtained was applied onto a glass substrate by a spin coating method, but no film was formed because the sulfonated polyaniline was insoluble in a 0.2 mol / l sulfuric acid aqueous solution. FIG. 7 is an ultraviolet-visible spectrum from 190 nm to 900 nm in a 0.2 mol / liter aqueous ammonia solution of the conductive polymer synthesized by Comparative Example 3 (conventional method). Since the polymer synthesized in Comparative Example 3 was insoluble in an aqueous solution or an acidic aqueous solution, it could not be measured in these solutions. The solubility of the conductive polymer synthesized in Comparative Example 3 (conventional method) was as follows: water 0 mg / ml 0.1 mol / liter sulfuric acid aqueous solution 0 mg / ml 0.1 mol / liter ammonia water 50 mg / ml. .

[0054]

[Effect] According to the present invention, by having sulfone groups and alkoxy groups in all of the benzene nuclei, high conductivity, alkaline, neutral (especially water), acidic aqueous solutions and alcohols having all pH are obtained. It was possible to provide a novel polyaniline-based polymer having excellent solubility in an organic solvent. According to the present invention, anilines having a sulfone group have been able to break the stereotype that was previously thought not to undergo chemical oxidative polymerization alone.

[Brief description of drawings]

FIG. 1 is a chart in measuring the molecular weight of a conductive polymer synthesized in Example 1.

FIG. 2 is a graph of 190 of the conductive polymer synthesized in Example 2 in a 0.1 mol / l sulfuric acid aqueous solution.
It is a UV-visible spectrum from nm to 900 nm.

FIG. 3 is an ultraviolet-visible spectrum from 190 nm to 900 nm in an aqueous solution of a conductive polymer synthesized in Example 2.

FIG. 4 is a UV-visible spectrum from 190 nm to 900 nm of a conductive polymer synthesized in Example 2 in a 0.2 mol / liter aqueous ammonia solution.

FIG. 5 shows an IR spectrum of a conductive polymer (sulfonic acid group-free type) synthesized in Example 2.

FIG. 6 shows an IR spectrum of a conductive polymer (salt type) synthesized in Example 5.

FIG. 7 is a UV-visible spectrum from 190 nm to 900 nm of a conductive polymer synthesized in Comparative Example 3 (conventional method) in an aqueous 0.2 mol / liter ammonia solution.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yasuyuki Takayanagi 10-1 Daikokucho, Tsurumi-ku, Yokohama-shi, Kanagawa Nitto Chemical Co., Ltd. Central Research Laboratory

Claims (6)

[Claims] 1. A polymer comprising an alkoxy group-substituted aminobenzene sulfonic acid, an alkali metal salt, an ammonium salt and / or a substituted ammonium salt thereof as a repeating unit, which is a solid at room temperature having a weight average molecular weight of about 1900 or more. A soluble aniline-based conductive polymer characterized by the above. 2. A compound represented by the general formula (1): (In the formula, A is a group independently selected from the group consisting of hydrogen, alkali metal, ammonium and substituted ammonium, R is a linear or branched alkyl group having 1 to 12 carbon atoms, and x is 0 to 1 , N is the degree of polymerization,
A number of 3 to 5000), a polymer having an alkoxy group-substituted aminobenzenesulfonic acid, an alkali metal salt, an ammonium salt and / or a substituted ammonium salt as a repeating unit, and having a molecular weight of about 1900.
A soluble aniline-based conductive polymer characterized by being a solid at room temperature as described above. 3. The surface resistance value is 10 ⁸ Ω / □ (film thickness 0.1
3. The soluble aniline-based conductive polymer according to claim 1 or 2, which is on the order of (measured in μm) or less. 4. The method according to claim 1, which is soluble in an acidic aqueous solution.
Or the soluble aniline-based conductive polymer described in 3 above. 5. A compound represented by the general formula (2): An alkoxy-substituted aminobenzenesulfonic acid represented by
4. The alkali metal salt, ammonium salt and / or substituted ammonium salt is polymerized by an oxidizing agent in a solution containing a basic compound.
Alternatively, the method for producing the soluble aniline-based conductive polymer described in 4 above. 6. A compound represented by the general formula (3): (In the formula, R represents a linear or branched alkyl group having 1 to 12 carbon atoms) or the general formula (4): (Wherein R represents a straight-chain or branched alkyl group having 1 to 12 carbon atoms), an alkoxy-substituted aminobenzenesulfonic acid, an alkali metal salt, an ammonium salt and / or a substituted ammonium salt thereof is a basic compound. The method for producing a soluble aniline-based conductive polymer according to claim 1, wherein the polymerization is carried out with an oxidizing agent in a solution containing