JP3340893B2 - Soluble aminonaphthalene-based conductive polymer and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a solvent-soluble aminonaphthalene-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 Various conductive polymers having a cyclic hydrocarbon having an amino group as a repeating unit are known. A typical example is doped polyaniline, which is unnecessary for most solvents and has problems in molding and processing. Also, a method of electrolytic oxidation polymerization of aniline [JP-A-60-235831, J. Am. Polymer S
ci. Polymer Chem. Ed. , 26,1
531 (1988)] can form a polyaniline film on an electrode, but has the problem that the isolation operation is complicated and mass synthesis is difficult.

Further, poly (aminonaphthalene), poly (aminoanthracene) [Journal of the Chemical Society of Japan, 1987, 1
1,2038-2044], poly (1-pyreneamine)
[Bull, Chem, Soc, Jpn. , 59,20
71 (1986)], but there is a problem in molding and processing like polyaniline, and the conductivity is lower than that of polyaniline, making it difficult to say that it is a practical conductive polymer.

In recent years, an alkali-soluble sulfonated polyaniline exhibiting conductivity without adding a dopant and a method for synthesizing the same have been proposed [Journal of the Chemical Society of Japan, 1985, 1124,
Japanese Patent Application Laid-Open No. 02-166165, Proceedings of the 64th Annual Meeting of the Chemical Society of Japan II, 706 (1992), J. A
m. Chem. Soc. , (1991) 113, 2
665-2671, J.C. Am. Chem. So
c. , (1990) 112,2800, WO91-06.
887, JP-A-5-178989, Japanese Patent Application No. 5-4
No. 8540] and carboxylated polyaniline and a method for synthesizing the same [JP-A-4-268331, JP-A-5-252]
26238] has been proposed.

[0005] However, the polymers proposed above have problems such as complicated synthesis methods and low conductivity and low solubility in solvents.

Accordingly, the present inventors have proposed that at least one compound (A) selected from the group consisting of an acidic group-substituted aniline, an alkali metal salt, an ammonium salt and a substituted ammonium salt thereof is prepared in a solution containing a basic compound (B). A method for producing a soluble aniline-based conductive polymer characterized by polymerization with an oxidizing agent (Japanese Patent Application No. 6-183882) has been proposed.

[0007] The polymer obtained by the above production method exhibits high conductivity and exhibits excellent solubility in water or an organic solvent having any pH.
Because of high hydrophilicity, there is a problem in coatability to a hydrophobic substrate.

Accordingly, in order to develop conductivity without adding a dopant to a polymer, to improve solubility, and to improve coating properties on a hydrophobic substrate, more sulfone groups or carboxyl groups are required. It is thought that it is necessary to introduce an acidic group such as a group and make the aromatic ring of the main chain have a naphthalene structure which is a condensed polycyclic hydrocarbon having high hydrophobicity.

[0009]

SUMMARY OF THE INVENTION The object of the present invention is to
Soluble aminonaphthalene-based conductive polymer exhibiting high conductivity, exhibiting excellent solubility in water or an organic solvent exhibiting any pH, and having improved coatability on a hydrophobic substrate, and a method for producing the same The point is to provide.

[0010]

DISCLOSURE OF THE INVENTION The present inventors have developed a poly (aminonaphthalene) having high conductivity and solubility, which has a large ratio of sulfone groups introduced into aromatic rings and a sulfonated poly (aminonaphthalene) and a carboxyl group. Carboxylated poly (aminonaphthalene) with high introduction ratio
As a result of intensive studies on the production method of acidic group-substituted poly (aminonaphthalene) such as, for example, acid-substituted aminonaphthalene such as sulfone-substituted aminonaphthalene or carboxyl-substituted aminonaphthalene was oxidized in a solution containing a basic compound. In particular, the reactivity increases when polymerized with a chemical agent, and it is possible to produce high-molecular-weight polymers, contrary to the conventional belief that conventional aminonaphthalenes having a sulfone or carboxyl group are unlikely to be chemically oxidized and polymerized by themselves. It was found that. Moreover, the obtained conductive polymer exhibited high conductivity and was soluble in aqueous solutions having any of acidic to alkaline pH, particularly in single water, and also showed excellent solubility in organic solvents such as alcohols. Further, the coating properties on a hydrophobic substrate such as a polymer compound also showed good properties.

That is, a first aspect of the present invention is a polymer having an acid group-substituted aminonaphthalene, an alkali metal salt, an ammonium salt and / or a substituted ammonium salt thereof as a repeating unit, and having a weight average molecular weight of about 1,000.
The present invention relates to a soluble aminonaphthalene-based conductive polymer characterized by being a solid at room temperature.

The polymer has the general formula (1) (Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are hydrogen,
A linear or branched alkyl group having 1 to 4 carbon atoms, 1 carbon atom
4 to 4 are selected from the group consisting of linear or branched alkoxy groups, acidic groups, hydroxyl groups, nitro groups, and halogens, at least one of which represents an acidic group. In addition, the acidic group here represents a sulfone group or a carboxyl group), a polymer having a repeating unit of an acidic group-substituted aminonaphthalene represented by the formula (I), an alkali metal salt thereof, an ammonium salt and / or a substituted ammonium salt thereof, It can also be expressed as a soluble aminonaphthalene-based conductive polymer characterized by being a solid at room temperature having a weight average molecular weight of about 1000 or more. This polymer exhibits excellent characteristics that it has a surface resistance value of not more than 10 ⁹ Ω / □ (measured at a film thickness of 0.1 μm) and is soluble in an acidic aqueous solution described later.

Examples of the alkali metal include lithium, sodium, potassium and the like.

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

The above-mentioned aliphatic ammoniums include the following formula (3) (In the formula, R _{14 to} R ₁₇ are each independently selected from the group consisting of hydrogen, an alkyl group having 1 to 4 carbon atoms, CH ₂ OH, and CH ₂ CH ₂ OH.) For example, methyl ammonium, dimethyl ammonium, trimethyl ammonium, ethyl ammonium, diethyl ammonium, triethyl ammonium, methyl ethyl ammonium, diethyl methyl ammonium, dimethyl ethyl ammonium, propyl ammonium, dipropyl ammonium, isopropyl ammonium, diisopropyl ammonium, butyl ammonium, dibutyl ammonium , Methylpropyl ammonium, ethyl propyl ammonium, methyl isopropyl ammonium, ethyl isopropyl ammonium, methyl butyl ammonium,
Ethyl butyl ammonium, tetramethyl ammonium, tetramethylol ammonium, tetraethyl ammonium, tetra n-butyl ammonium, tetrase
Examples thereof include c-butylammonium and tetra-t-butylammonium. Among them, R _{14 to} R ₁₇
Most preferably, one of them is hydrogen and the other three are alkyl groups having 1 to 4 carbon atoms. Then, when two of R _{14 to} R ₁₇ are hydrogen and the other two are alkyl groups having 1 to 4 carbon atoms. Is preferred.

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

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

A second aspect of the present invention is that at least one compound (A) selected from an acidic group-substituted aminonaphthalene, an alkali metal salt, an ammonium salt, and a substituted ammonium salt thereof.
Is polymerized with an oxidizing agent in a solution containing a basic compound (B), and a method for producing a soluble aminonaphthalene-based conductive polymer. The acidic group-substituted aminonaphthalene has a general formula (2)

Embedded image (Wherein R ₉ represents hydrogen, R ₇ , R ₈ , R ₁₀ , R ₁₁ ,
R ₁₂ and R ₁₃ are selected from the group consisting of hydrogen, a linear or branched alkyl group having 1 to 4 carbon atoms, an acidic group, a hydroxyl group, a nitro group and a halogen, at least one of which represents an acidic group.
Here, the acidic group indicates a sulfone group or a carboxyl group. ) Represented by an acidic group-substituted aminonaphthalene,
It represents at least one compound among the alkali metal salt, ammonium salt and substituted ammonium salt.

The most typical examples of the acidic group-substituted aminonaphthalene are a sulfone group-substituted aminonaphthalene and a carboxyl group-substituted aminonaphthalene. Preferably, it is a sulfone group-substituted aminonaphthalene, which has a higher conductivity than a carboxyl group-substituted aminonaphthalene.

The most typical examples of the sulfona group-substituted aminonaphthalenes are aminonaphthalenesulfonic acids, specifically, 1-aminonaphthalene-2-sulfonic acid, 1-aminonaphthalene-3-sulfonic acid, 1-amino Naphthalene-4-sulfonic acid, 1-aminonaphthalene-5-sulfonic acid, 1-aminonaphthalene-6-sulfonic acid, 1-aminonaphthalene-7-sulfonic acid, 1-aminonaphthalene-8-sulfonic acid, and the like. .

Other sulfonated aminonaphthalenes include methylaminonaphthalenesulfonic acid, ethylaminonaphthalenesulfonic acid, n-propylaminonaphthalenesulfonic acid, iso-propylaminonaphthalenesulfonic acid, n-butylaminonaphthalenesulfonic acid,
alkyl-substituted aminonaphthalenesulfonic acids such as sec-butylaminonaphthalenesulfonic acid and t-butylaminonaphthalenesulfonic acid, methoxyaminonaphthalenesulfonic acid, ethoxyaminonaphthalenesulfonic acid,
n-propoxyaminonaphthalenesulfonic acid, iso
-Alkoxy-substituted aminonaphthalene sulfonic acids such as propoxyaminonaphthalenesulfonic acid, n-butoxyaminonaphthalenesulfonic acid, sec-butoxyaminonaphthalenesulfonic acid, t-butoxyaminonaphthalenesulfonic acid, hydroxy-substituted aminonaphthalenesulfonic acids, nitro Examples include halogen-substituted aminonaphthalenesulfonic acids such as group-substituted aminonaphthalenesulfonic acids, fluoroaminonaphthalenesulfonic acid, chloroaminonaphthalenesulfonic acid, and bromoaminonaphthalenesulfonic acid. These sulfone group-substituted aminonaphthalenes may be used alone or in a mixture of isomers at an arbitrary ratio.

The most typical carboxyl-substituted aminonaphthalenes are aminonaphthalenecarboxylic acids, specifically, 1-aminonaphthalene-2-carboxylic acid, 1-aminonaphthalene-3-carboxylic acid, 1-amino Naphthalene-4-carboxylic acid, 1-aminonaphthalene-5-carboxylic acid, 1-aminonaphthalene-6-carboxylic acid, 1-aminonaphthalene-7-carboxylic acid, 1-
And aminonaphthalene-8-carboxylic acid.

Other carboxyl group-substituted aminonaphthalenes include methylaminonaphthalenecarboxylic acid, ethylaminonaphthalenecarboxylic acid, n-propylaminonaphthalenecarboxylic acid, iso-propylaminonaphthalenecarboxylic acid, n-butylaminonaphthalenecarboxylic acid, sec. -Butylaminonaphthalenecarboxylic acid, t-
Alkyl-substituted aminonaphthalenecarboxylic acids such as butylaminonaphthalenecarboxylic acid, methoxyaminonaphthalenecarboxylic acid, ethoxyaminonaphthalenecarboxylic acid, n-propoxyaminonaphthalenecarboxylic acid, i
so-propoxyaminonaphthalenecarboxylic acid, n-
Alkoxy-substituted aminonaphthalenecarboxylic acids such as butoxyaminonaphthalenecarboxylic acid, sec-butoxyaminonaphthalenecarboxylic acid, t-butoxyaminonaphthalenecarboxylic acid, hydroxy-substituted aminonaphthalenecarboxylic acids, nitro-substituted aminonaphthalenecarboxylic acids, fluoroaminonaphthalene Examples thereof include halogen-substituted aminonaphthalenecarboxylic acids such as carboxylic acid, chloroaminonaphthalenecarboxylic acid, and bromoaminonaphthalenecarboxylic acid. Each of these carboxyl group-substituted aminonaphthalenes may be used alone, or the isomers may be mixed at an arbitrary ratio.

Examples of the alkali metal in these monomers include lithium, sodium, potassium and the like.

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

As the aliphatic ammoniums, the following formula (4) (Wherein R _{18 to} R ₂₁ are each independently selected from the group consisting of hydrogen, an alkyl group having 1 to 4 carbon atoms, CH ₂ OH, and CH ₂ CH ₂ OH). For example, methyl ammonium, dimethyl ammonium, trimethyl ammonium, ethyl ammonium, diethyl ammonium, triethyl ammonium, methyl ethyl ammonium, diethyl methyl ammonium, dimethyl ethyl ammonium, propyl ammonium, dipropyl ammonium, isopropyl ammonium, diisopropyl ammonium, butyl ammonium, dibutyl ammonium , Methylpropyl ammonium, ethyl propyl ammonium, methyl isopropyl ammonium, ethyl isopropyl ammonium, methyl butyl ammonium,
Ethyl butyl ammonium, tetramethyl ammonium, tetramethylol ammonium, tetraethyl ammonium, tetra n-butyl ammonium, tetrase
Examples thereof include c-butylammonium and tetra-t-butylammonium. Above all, R ₁₈ -R ₂₁
Most preferably, one of them is hydrogen and the other three are alkyl groups having 1 to 4 carbon atoms. Then, when two of R _{18 to} R ₂₁ are hydrogen and the other two are alkyl groups having 1 to 4 carbon atoms. Is preferred.

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

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

Next, as the basic compound used in the production method of the present invention, any compound may be used as long as it forms a salt with the above-mentioned amino-substituted aminonaphthalenes. Formula saturated amines, cyclic unsaturated amines, inorganic bases and the like are preferably used.

As the fatty amines, the following formula (5) (Wherein, R _{22 to} R ₂₄ are each 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) Or the general formula (6)

Embedded image (Wherein, R _{25 to} R ₁₈ are each 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) Side compounds can be mentioned.

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

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 decreases, and when it is 10.0 mol / l or more, the conductivity tends to decrease. The above-mentioned basic compounds can be used in a mixture at any ratio.

The weight ratio between the acidic group-substituted aminonaphthalene (A) and the basic compound (B) is (A) :( B) = 1: 10.
0 to 100: 1, preferably 10:90 to 90:10 is used. Here, if the ratio of the basic compound is low, the reactivity decreases and the conductivity also decreases. Conversely, when the ratio is high, the ratio of the salt formed between the acidic group and the basic compound in the obtained polymer increases, and the conductivity tends to decrease. Also,
The molar ratio of the acidic group (C) and the basic compound (B) in the acidic group-substituted aminonaphthalene (A) is (C) :( B) = 1:
100-100: 1, preferably 1: 0.25-1: 2
0, more preferably 1: 0.5 to 1:15. Here, if the ratio of the basic compound is low, the reactivity decreases and the conductivity also decreases. Conversely, when the ratio is high, the ratio of the salt formed between the acidic group and the basic compound in the obtained polymer increases, and the conductivity tends to decrease.

[0036]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Polymerization or copolymerization is carried out by oxidative polymerization with an oxidizing agent 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.

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, but peroxodisulfuric acid, ammonium peroxodisulfate, peroxodisulfuric acids such as sodium peroxodisulfate and potassium peroxodisulfate, hydrogen peroxide, and the like are preferably used, and are preferably used in 1 mole of the monomer. 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 is preferably carried out in a temperature range of -15 to 70 ° C, more preferably -5 to 70 ° C.
A range of 60 ° C. applies. Here, when the temperature is lower than −15 ° C. or higher than 70 ° C., the conductivity tends to decrease.

Hydrogen at the sulfone or carboxyl group in the polymer produced according to the present invention may be hydrogen,
It is a group independently selected from the group consisting of alkali metals, ammonium and substituted ammonium, that is, these groups can be obtained not only alone but also in a mixed state. Specifically, when polymerized in the presence of sodium hydroxide, most of the hydrogen at the sulfone group or carboxyl group in the isolated polymer has been replaced with sodium, but in an acid solution. Upon treatment, a polymer can be obtained in which most of the sodium has been replaced by hydrogen. However, even if the acid substitution is performed sufficiently, it is difficult to obtain a product completely substituted with hydrogen. Similarly, hydrogen in the sulfone group or carboxyl group in the polymer is mostly ammonium when polymerized in the presence of ammonia, when polymerized in the presence of trimethylamine, mostly trimethylammonium, and when polymerized in the presence of quinoline , Mostly obtained with quinolinium. When a basic compound is used as a mixture, the mixture is obtained in a mixed state. Specifically, when polymerized in the presence of sodium hydroxide and ammonia, hydrogen at the sulfone or carboxyl groups in the isolated polymer is obtained in the presence of both sodium and ammonium. Similarly, when the obtained polymer is treated with a solution in which both sodium hydroxide and ammonia are present, hydrogen in the sulfone group or carboxyl group in the polymer is obtained in a state where both sodium and ammonium are present.

The molecular weight of the thus obtained soluble aminonaphthalene-based conductive polymer containing a sulfone group in every aromatic ring is about 1,000 to 3240000, preferably 3200 to 3240000. This polymer can be used without further sulphonation operation without any water, a base such as ammonia and an alkylamine or a 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 the like. It can be dissolved in a solvent such as methyl alcohol, ethyl alcohol, isopropyl alcohol or a mixture thereof.

The soluble aminonaphthalene-based conductive polymer in the present invention is dissolved in an aqueous alkali solution such as 0.1 mol / l of ammonia water in an amount of 1% by weight or more.
Dissolve 1% by weight or more in an acidic aqueous solution such as a 0.1 mol / L sulfuric acid aqueous solution, dissolve 1% by weight or more in a neutral aqueous solution such as a single water, and further dissolve a 0.1 mol / L ammonia alcohol solution or the like. 1% by weight or more in organic solvents.

[0042]

Embodiments will be described below with reference to embodiments. The IR spectrum was measured using a model 1600 manufactured by PerkinElmer. For the measurement of the molecular weight distribution and the molecular weight, GPC measurement (in terms of polystyrene) was performed using a GPC column for N, N-dimethylformamide. As the column, three kinds of columns for N, N-dimethylformamide were used in combination. The eluent was N, N-containing 10 mM / l triethylamine and 100 mM / l lithium bromide.
A dimethylformamide solution was used. For the conductivity, a four-terminal method was used for measuring the volume resistance value, and a two-terminal method was used for measuring the surface resistance value.

Example 1 1-aminonaphthalene-5-sulfonic acid 100 mmol
Is dissolved in a 4 mol / l aqueous ammonia solution at 25 ° C. with stirring to obtain 100 mmol of ammonium peroxodisulfate.
Was added dropwise. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 12 hours, and the reaction product was separated by filtration, washed and dried to obtain 16.5 g of a polymer powder. Its volume resistance is 56Ω
cm. 3 parts by weight of the above polymer was stirred and dissolved at room temperature in 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 on a glass substrate by a spin coating method, and dried at 100 ° C. A film having a smooth surface resistance of 8.5 × 10 ⁷ Ω / □ on the surface having a thickness of 0.1 μm was obtained. FIG.
1 shows an IR spectrum of a conductive polymer synthesized in Example 1. The assignment of the IR spectrum is as follows. Sulfone group: absorption around 1050, 1020 cm ^-1 Ammonium salt of sulfone group: absorption around 1400 cm ^-1 Polymer skeleton: absorption around 1500 cm ^{-1 For} measurement of molecular weight distribution and molecular weight, N, N-dimethylformamide is used. GPC measurement (in terms of polystyrene) was performed using a GPC column. As the column, three kinds of columns for N, N-dimethylformamide were used in combination. The eluent used was N, N- of 0.01 mol / L of triethylamine and 0.1 mol / L of lithium bromide.
A dimethylformamide solution was used. As a result of the measurement, the number average molecular weight was 50,000, the weight average molecular weight was 65,000,
Z average molecular weight 68,000, dispersity MW / MN 1.3,
MZ / MW was 1.0. The polymer was added little by little to 10 ml of water, 0.1 mol / l sulfuric acid aqueous solution or 0.1 mol / l ammonia water. When the polymer no longer dissolved, the mixture was filtered and the dissolved amount was determined. The solubility of the obtained conductive polymer was 160 mg / ml of water, 0.1 mol / l of sulfuric acid aqueous solution, 125 mg / ml, 0.1 mol / l of aqueous ammonia, and 190 mg / ml.

Example 2 100 mmol of 1-aminonaphthalene-6-sulfonic acid
Was stirred and dissolved in a 4 mol / L aqueous solution of trimethylamine at 4 ° C., and ammonium peroxodisulfate (100 mm) was dissolved.
ol of water was added dropwise. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 6 hours, and the reaction product was separated by filtration, washed and dried to obtain 15 g of a polymer powder. This polymer was added at 1 mol / liter P
The mixture was stirred in an acetone solution of TS for 1 hour, washed by filtration, and dried to obtain 13 g of a polymer powder free of sulfone groups. This had a volume resistivity of 48.5 Ωcm. One part by weight of the above polymer was stirred and dissolved in 100 parts by weight of water at room temperature to prepare a conductive composition. Since the pH of the composition was about 3.7, it is estimated that about 80% or more of the sulfonic acid groups in the polymer were in a free state. The solution thus obtained is applied on a glass substrate by a casting method,
Dried at 100 ° C. A film having a smooth surface resistance of 3.6 × 10 ⁷ Ω / □ on the surface having a thickness of 0.1 μm was obtained.

Comparative Example 1 1-aminonaphthalene-5-sulfonic acid 100 mmol
Was suspended in water at 4 ° C., and 100 mmol of ammonium peroxodisulfate was added dropwise. 25 after dropping
After further stirring at 12 ° C. for 12 hours, the reaction solution was distilled off under reduced pressure, and the concentrate was isolated and washed, and then dried to obtain 6 g of powder. Its volume resistivity was> 10 ⁶ Ωcm. 3 parts by weight of the above powder was stirred and dissolved in 100 parts by weight of water at room temperature to prepare a conductive composition. The solution thus obtained was applied on a PET film by spin coating, but no film was formed.

[0046]

According to the present invention, by providing all of the aromatic rings with a sulfone group or a carboxyl group, an aqueous solution having a high conductivity as well as an alkaline, neutral (particularly simple water) and acidic pH and alcohol, etc. A novel aminonaphthalene-based polymer exhibiting excellent solubility in organic solvents could be provided. According to the present invention, it has been possible to provide a novel polymerization method that breaks down the stereotype that aminonaphthalenes having an acidic group such as a sulfone group or a carboxyl group do not undergo chemical oxidative polymerization by themselves.

[Brief description of the drawings]

FIG. 1 shows an IR spectrum of a conductive polymer synthesized in Example 1.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-3-126726 (JP, A) JP-A-6-56987 (JP, A) JP-A-6-316631 (JP, A) European Patent Application Publication 662694 (EP, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 73/00-73/26 CAPLUS (STN) REGISTRY (STN)

Claims (6)

(57) [Claims] 1. A polymer comprising an acidic group-substituted aminonaphthalene, an alkali metal salt, an ammonium salt and / or a substituted ammonium salt thereof as a repeating unit, wherein the polymer is a solid at room temperature having a weight average molecular weight of 1,000 or more. Water-soluble aminonaphthalene-based conductive polymer. 2. An acidic group-substituted aminonaphthalene, its alkali metal salt, ammonium salt, or substituted ammonium salt, at least one compound (A) is polymerized with an oxidizing agent in a solution containing a basic compound (B). The general formula (1) obtained by (Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are hydrogen,
A linear or branched alkyl group having 1 to 4 carbon atoms, 1 carbon atom
4 to 4 are selected from the group consisting of linear or branched alkoxy groups, acidic groups, hydroxyl groups, nitro groups, and halogens, at least one of which represents an acidic group. Here, the acidic group indicates a sulfone group or a carboxyl group. A) a polymer having a repeating unit of an acidic group-substituted aminonaphthalene represented by the formula (I) or an alkali metal salt, an ammonium salt and / or a substituted ammonium salt thereof, wherein the polymer is a solid at room temperature having a weight average molecular weight of 1,000 or more. Water-soluble aminonaphthalene-based conductive polymer. 3. A surface resistance value of 10 ⁹ Ω / □ (film thickness of 0.1
3. The water-soluble aminonaphthalene-based conductive polymer according to claim 1, wherein the water-soluble aminonaphthalene-based conductive polymer is in the order of 1 μm or less. 4. A solution of 0.1 mol / l sulfuric acid in water
The water-soluble aminonaphthalene-based conductive polymer according to claim 1, 2 or 3, which is soluble by weight or more. 5. A compound of the general formula (2) (Wherein R ₉ represents hydrogen, R ₇ , R ₈ , R ₁₀ , R ₁₁ ,
R ₁₂ and R ₁₃ are selected from the group consisting of hydrogen, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxy group having 1 to 4 carbon atoms, an acidic group, a hydroxyl group, a nitro group, and a halogen. At least one of which represents an acidic group. Here, the acidic group represents a sulfone group or a carboxyl group), and at least one compound (A) of an acidic group-substituted aminonaphthalene represented by the following formula: 5. The method for producing a water-soluble aminonaphthalene-based conductive polymer according to claim 1, wherein the polymerization is carried out with an oxidizing agent in a solution containing the compound (B). 6. An equivalent ratio of the acidic group (C) and the basic compound (B) in the compound (A) of (C) :( B) is 1: 1.
Wherein the ratio is from 00 to 100: 1.
8. The method for producing a water-soluble aminonaphthalene-based conductive polymer according to 2, 3, 4, 5, 6, or 7.