JPH07119352B2 - Polymer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Field of Application> The present invention relates to a novel polymer composition. More specifically, the present invention relates to a novel polymer composition which is particularly excellent in processability and exhibits extremely excellent conductive properties when doped with an electron acceptor.

<Problems to be Solved by Prior Art and Invention> As a polymer used for forming a conductive polymer,
Polyacetylene, polyparaphenylene, polythiophene, polypyrrole and the like are known. These polymers can be used as a conductive polymer by doping a certain compound, but they have the drawback that they are easily denatured in the air and their electrical characteristics change. Further, these conductive polymers have problems such as extremely poor processability due to poor melting and solubility properties, which is a major obstacle to practical use. For example, as an application field of conductive polymers, application to secondary battery electrodes utilizing the reversible redox properties of conductive polymers has been proposed. Is physically or chemically unstable,
Therefore, the stable repeatability of charge and discharge (cyclability), which is the basic performance required for secondary batteries, cannot be expected. Further, since the polymer skeleton of the conductive polymer is made of a rigid π-electron conjugated system, it is insoluble and infusible, which is a major obstacle to practical use. As a method of solving these problems, US Pat. No. 4,452,725 proposes an electroactive polymer obtained by doping a polymer having a 3,6-carbazolediyl structure as a repeating unit with an electron acceptor.

However, the above-mentioned carbazole-based polymer is an oligomer having a low degree of polymerization and does not have mechanical strength and moldability that should be originally provided as a polymer compound. For example, when the polymer is used as an electrode material of a secondary battery. However, there is a problem that the soluble component elutes with repeated charge and discharge, so that cyclovirity cannot be expected. Further, in order to provide the above carbazole-based polymer with good electrochemical properties as well as mechanical strength and moldability, it is necessary to obtain a polymer having a higher degree of polymerization (high polymer). It is difficult to obtain a high molecular weight polymer even by Grignard coupling, oxidative coupling, Friedel-Crafts reaction and electrolytic oxidative polymerization, which are generally used as a synthetic method for an aromatic compound or a polyheteroaromatic compound. In addition, even if the reaction conditions are made more severe, not only can the heterogeneous bond or the cross-linking reaction be induced and the high molecular weight cannot be expected, but also one of the advantages of high molecular compounds is the loss of processability and insolubility and infusibility. There is a problem in that it becomes a chemically inactive polymer.

Further, a polymer having a repeating unit of 3,6-N-methylcarbazolylmethylene structure is soluble in an organic solvent, and by doping this polymer with an electron acceptor, the direct current conductivity is 10 ⁻³ to 10 −10. It has been reported to have a conductivity of about ^-1 S / cm (Synthetic Metals, 10, p. 281-292 (198
Five)).

However, the above-mentioned carbazolylmethylene-based polymer has reversible doping, that is, reversible redox properties because the elimination of hydrogen of methylene in the polymer main chain occurs due to the doping. There was a defect that it was not there.

In order to solve these drawbacks of the prior art, the present inventors have already been soluble in organic solvents such as N-methylpyrrolidone, nitrobenzene, and dichloroethane, and are excellent in moldability because they are thermoplastic resins. By doping with an electron-accepting compound, the electric activity is improved, the redox reaction can be performed with good repeatability, and the general formula (I) is expected to be applied to various electronic devices and batteries. (In the formula, R ¹ is H or a hydrocarbon residue having 1 to 20 carbon atoms, R ²
Is H or a hydrocarbon residue having 1 to 20 carbon atoms, or a furyl group, a pyridyl group, a methoxyphenyl group, and n and x are integers of 2 or more), and found a patent application. (Japanese Patent Application No. Sho 62-153427).

However, the above-mentioned copolymer has a problem that even if it is doped with an electron-accepting compound, sufficient conductivity cannot be obtained for use as various electronic functional materials. In particular, when the above copolymer is applied to a battery electrode, 1) the conductivity of the electrode is low, so that the resistance of the electrode itself is large and a large current cannot be obtained (the charge / discharge current is small).

2) The internal resistance becomes large and there is no voltage flatness.

3) Charge / discharge capacity is small (use efficiency of active material is poor).

There were problems such as.

In order to improve the conductivity of the battery electrode, a method of mixing carbon black or graphite into the electrode is widely known, but in this method, in order to obtain high conductivity, it is necessary to mix a large amount of carbon black or the like. As a result, the amount of the electrode active material decreases, which causes a new problem that the battery capacity is significantly reduced.

<Means for Solving the Problems> As a result of further intensive studies by the present inventors to improve these drawbacks, the copolymer represented by the general formula (I) was found to be a polypyrrole compound, a polythiophene compound or a polyaniline compound. The inventors have found that the drawbacks of the prior art can be solved by using a polymer composition obtained by mixing at least one compound selected from the following, and have reached the present invention.

That is, the present invention provides the compound represented by the general formula (I) (In the formula, R ¹ is a hydrogen atom or a hydrocarbon residue having 1 to 20 carbon atoms, R ² is hydrogen or a hydrocarbon residue having 1 to 20 carbon atoms, or a furyl group, a pyridyl group, a nitrophenyl group, a chlorophenyl group, or methoxy. A phenyl group, and n and x each represent an integer of 2 or more), the copolymer represented by the general formula (II) (Wherein R ³ , R ⁴ and R ⁵ are each a hydrogen atom or a hydrocarbon residue having 1 to 20 carbon atoms, p is an integer of 2 or more), and a general formula (III) (In the formula, R ⁶ and R ⁷ are each a hydrogen atom or a carbon number 1
To a hydrocarbon residue, q represents an integer of 2 or more), and a polythiophene compound represented by the general formula (IV) (Wherein, R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each a hydrogen atom or a hydrocarbon residue having 1 to 20 carbon atoms, and r is an integer of 2 or more). The present invention relates to a polymer composition obtained by mixing

The present invention also relates to a conductive polymer composition obtained by doping the polymer composition with an electron acceptor.

Hereinafter, the present invention will be described in detail.

(1) Copolymer Represented by General Formula (I) The copolymer represented by the general formula (I) of the present invention has a 3,6-carbazolediyl structure represented by general formula (V) as a repeating unit. It can be obtained by polycondensing a polymer and an aldehyde represented by the general formula (VI) or a polymer thereof in the presence of an acid or alkali catalyst.

R ² CHO (VI) A polymer having a 3,6-carbazolediyl structure represented by the general formula (V) as a repeating unit is synthesized by a known method. For example, Journal of Organic Synthesis, Vol. 23, No. 5
, P447 (1965), Synthesis of carbazole dimers using various oxidant / solvent systems, P. Beresford
et al., J. Chem. Soc. Perkin. I. p276 (1974), synthesis method of carbazole dimer using dehydrogenation catalyst, JP-A-61-141725 or JP-A-56- There are methods such as the oxidation coupling method or the Grignard coupling method used in 88422. In the general formula (V), R ¹ represents hydrogen or a hydrocarbon residue having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms. As the hydrocarbon residue, a methyl group,
Alkyl group or allyl group such as ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group and n-hexyl group, and various aryl groups such as phenyl group, tolyl group and ethylphenyl group , Aralkyl groups and derivatives thereof. n is 2 or more, but usually 2
50, preferably 2-30.

Examples of the aldehyde represented by the general formula (VI) include R ^{2 in the} formula.
Is hydrogen or a hydrocarbon residue having 1 to 20 carbon atoms, preferably 1 to 8, or a furyl group, a pyridyl group, a nitrophenyl group, a chlorophenyl group, a compound of a methoxyphenyl group is used, and as the hydrocarbon residue, Methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group,
An alkyl group or an allyl group such as an n-hexyl group, various aryl groups such as a phenyl group, a tolyl group and an ethylphenyl group, an aralkyl group and a derivative thereof can be used. Typical examples of these aldehydes include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, benzaldehyde, acrylaldehyde, cinnamaldehyde, anisaldehyde, nicotinaldehyde, nitrobenzaldehyde, chlorobenzaldehyde and furfural. .

Further, the aldehyde polymer means a polymer obtained by subjecting the aldehyde represented by the general formula (VI) to a concentrated solution for self-condensation or condensation in the presence of an acid catalyst. It is a compound that easily hydrolyzes to form an aldehyde monomer under the reaction conditions for synthesizing the copolymer. Typical examples include paraformaldehyde, which is a polymer of formaldehyde, and paraaldehyde, which is a trimer of acetaldehyde.

The polycondensation of the carbazole polymer and the aldehyde can be carried out in an organic solvent in which both are soluble at a temperature of 0 ° C to 200 ° C using an acid or alkali catalyst. Examples of the acid catalyst include inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid and perchloric acid, and organic acids such as formic acid, acetic acid, propionic acid, methanesulfonic acid and p-toluenesulfonic acid. Examples of preferable organic solvents include ethyl ether, tetrahydrofuran, ethers such as dioxane, chloroform,
Halogenated hydrocarbons such as dichloromethane and chlorobenzene, nitro compounds such as nitrobenzene, acetonitrile, propylene carbonate, dimethylformamide,
Examples thereof include N-methylpyrrolidone. Reaction time is 1
It can be appropriately selected within the range of minutes to 500 hours, preferably 5 minutes to 200 hours.

By the above reaction, the copolymer of the present invention which is substantially linear and has a high degree of polymerization is obtained. The copolymer of the present invention is soluble in solvents such as N-methylpyrrolidone, nitrobenzene, chloroform and sulfuric acid, but insoluble in alcohol, aliphatic hydrocarbons, acetonitrile and propylene carbonate used in organic electrolyte type batteries. Also, it is a thermoplastic resin that can be melted by heating.

As described above, the polymer composition of the present invention is obtained by mixing the copolymer with a compound selected from a polypyrrole compound, a polythiophene compound and a polyaniline compound (hereinafter referred to as a compound compound). These compounding compounds may be used alone or in combination of two or more kinds.

(2) Compounding compound The pyrrole compound in the present invention is a compound represented by the general formula (II), and two or more kinds of these compounds may be used in combination. In the general formula (II), R ³ , R ⁴ and R ⁵ are each a hydrogen atom or a carbon number of 1 to 20, preferably 1 to 10
Of the hydrocarbon residue, and examples of the hydrocarbon residue include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-
Alkyl groups such as butyl group, i-butyl group, sec-butyl group, methoxy group, ethoxy group, n-propoxy group, i
-Alkoxy groups such as propoxy group and n-butoxy group,
Examples thereof include aryl groups such as phenyl group, toluyl group and naphthyl group, allyloxy groups such as phenoxy group, methylphenoxy group and naphthoxy group, thioether groups such as methylthioether group and ethylthioether group, and derivatives thereof.

Although p is 2 or more, it is usually 2 to 10,000. Both ends of the molecule are usually nuclear-substituted hydrogens.

Specific examples thereof include polypyrrole, poly (N-methylpyrrole), poly (N-ethylpyrrole), poly (Nn-propylpyrrole), poly (3-methylpyrrole), poly (3-ethylpyrrole). , Poly (3-methyl-N-methylpyrrole), poly (3-ethyl-N-methylpyrrole), poly (3-methoxypyrrole), poly (3-ethoxypyrrole), poly (3-methoxy-N-)
Methylpyrrole), poly (3-ethoxy-N-ethylpyrrole), poly (3-phenylpyrrole), poly (3-
(Phenyl-N-methylpyrrole), poly (3-phenoxypyrrole), poly (3-naphthoxypyrrole), poly (3-methylthiopyrrole), poly (3-ethylthiopyrrole), poly (3,4- Dimethylpyrrole), poly (3,4-dimethyl-N-methylpyrrole) and the like.

The polythiophene compound in the present invention is a compound represented by the general formula (III), and two or more kinds of these compounds may be used in combination. In the general formula (III), R ⁶
And R ⁷ each represent a hydrogen atom or a hydrocarbon residue having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and as the hydrocarbon residue, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, Alkyl group such as n-butyl group, i-butyl group, sec-butyl group, methoxy group, ethoxy group, alkoxy group such as n-propoxy group, i-propoxy group, n-butoxy group, phenyl group, toluyl group, Examples thereof include aryl groups such as naphthyl groups, phenoxy groups, methylphenoxy groups, allyloxy groups such as naphthoxy groups, and derivatives thereof.

Although q is 2 or more, it is usually 2 to 10000. Both ends of the molecule are usually nuclear-substituted hydrogens.

Specific examples of these include polythiophene and poly (3-
Methylthiophene), poly (3-ethylthiophene),
Poly (3-n-propylthiophene), Poly (3-i-
Propylthiophene), poly (3-n-butylthiophene), poly (3-i-butylthiophene), poly (3-
sec butylthiophene), poly (3-methoxythiophene), poly (3-ethoxythiophene), poly (3-n)
-Propoxythiophene), poly (3-i-propoxythiophene), poly (3-n-butoxythiophene),
Poly (3-phenylthiophene), Poly (3-toluylthiophene), Poly (3-naphthylthiophene), Poly (3-phenoxythiophene), Poly (3-methylphenoxythiophene) , Poly (3-naphthoxythiophene), poly (3,4-dimethylthiophene), poly (3,4-
Diethylthiophene) and the like.

The polyaniline compound is a compound represented by the general formula (IV), and two or more kinds of these compounds may be used in combination. In the general formula (IV), R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are hydrogen atoms or have 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms.
Of the hydrocarbon residue, and examples of the hydrocarbon residue include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-
Alkyl groups such as butyl group, i-butyl group, sec-butyl group, methoxy group, ethoxy group, n-propoxy group, i
-Alkoxy groups such as propoxy group and n-butoxy group,
Examples thereof include aryl groups such as phenyl group, toluyl group and naphthyl group, allyloxy groups such as phenoxy group, methylphenoxy group, naphthoxy group and derivatives thereof.

r is 2 or more, but usually 2 to 10,000. Both ends of the molecule are usually nuclear-substituted hydrogens.

Specifically, polyaniline, poly (3-methylaniline), poly (3,5-dimethylaniline), poly (3-ethylaniline), poly (3-n-propylaniline),
Poly (3-methoxyaniline), poly (3,5-dimethoxyaniline), poly (3-ethoxyaniline), poly (3,5-diethoxyaniline), poly (3-phenylaniline), poly (3, 5-diphenylaniline), poly (3-naphthylaniline), poly (3-toluylaniline), poly (2,5-dimethylaniline), poly (3-phenoxyaniline), poly (3-naphthoxyaniline) ), Poly (N-methylaniline), poly (N-ethylaniline), poly (3-methyl-N-methylaniline), poly (3,5-dimethyl-N-ethylaniline),
Poly (3-ethyl-N-methylaniline), poly (3methoxy-N-methylaniline), poly (3,5-methoxy-N-methylaniline), poly (3-phenoxy-N-)
Methyl aniline) and the like.

(3) Mixing of Copolymer and Blending Compound The polymer composition of the present invention is obtained by uniformly dispersing and blending the blending compound in the copolymer represented by the general formula (I). At that time, the compound represented by the general formula (I) may be mixed with the compounding compound alone, or two or more compounding compounds may be used in combination, and a usual conductive auxiliary agent such as carbon black or graphite may be added. There is no problem with additional mixing.

The mixing ratio of the copolymer represented by the general formula (I) and the compounding compound is 1 to 400 parts by weight of the compounding compound, preferably 5 to 100 parts by weight, relative to 100 parts by weight of the copolymer represented by the general formula (I).
Parts by weight.

The mixing method is not particularly limited, and a known method is used. For example, by utilizing the characteristic that the copolymer represented by the general formula (I) is soluble in a solvent such as N-methylpyrrolidone, nitrobenzene, chloroform and sulfuric acid as described above, first, the copolymer is used as a solvent. After dissolution, a compounding compound is added, the mixture is uniformly dispersed, both are mixed and then dried to obtain a polymer composition, or the copolymer represented by the general formula (I) is melted by heating. After that, the compounding compound is added, and the mixture is uniformly dispersed and mixed and then cooled to obtain a polymer composition, or the copolymer represented by the general formula (I) and the compounding compound are directly mixed in the solid phase by ball milling or the like. Method etc. are mentioned.

Of course, in addition to the mixing method as described above, for example, in the presence of the copolymer represented by the general formula (I), the compounded compound is not in the form of a polymer but a monomer of a pyrrole compound, a thiophene compound or an aniline compound. In addition, in a solid phase, a liquid phase, a gas phase, preferably in a liquid phase in which the copolymer represented by the general formula (I) is dissolved, a metal salt having a strong acid residue, halogen or cyan, a peroxide or a nitrogen oxide. There is no problem even if a polymer composition is produced by polymerizing in the presence of a substance.

(4) Doping The polymer composition of the present invention shows high electric activity by being doped as an electron acceptor and a dopant, and of course, can perform a redox reaction with good repeatability.
Since it has high conductivity, it can be used for various electronic devices. For example, when used as an electrode material for secondary batteries, reversible charge / discharge is possible,
In particular, even if the number of charge / discharge cycles (cycle number) is remarkably increased, it is possible to obtain extremely stable characteristics without causing the elution phenomenon and decreasing the cyclability as seen in the case of a carbazole polymer. Not only can
A large charging / discharging current can be obtained, the voltage flatness at the time of charging / discharging is good, and moreover, the compound compound plays a role of a conductive auxiliary agent and itself performs a reversible redox reaction,
It has excellent effects such as not lowering the capacity per electrode active material.

Electron-accepting dopants include halogen compounds such as iodine, bromine, hydrogen iodide, arsenic pentafluoride, phosphorus pentachloride, phosphorus pentafluoride, antimony pentafluoride, silicon tetrafluoride, aluminum chloride, aluminum bromide. , Aluminum fluoride, metal halides such as ferric chloride, sulfuric acid, nitric acid, protic acids such as chromium sulfonic acid, sulfur trioxide, oxidizing agents such as difluorosulfonyl peroxide, such as tetracyanoquinodimethane There can be mentioned various organic substances. The electrochemical doping can _{^{dopant, PF 6 -, SbF 6 -}} , A S F 6 - , such as Va
Earth halide anions genera, BF ₄ ^- IIIa metal selected halide anions, such _{^{as, I - (I 8 -)}} , Br -, Cl - halogen anion, ClO _4, such as ^- perchloric acid such as Anions such as anions can be mentioned.

These dopings are performed by a known method. As a typical example, when the electron-accepting dopant is a gas or has a vapor pressure, a gas phase doping method in which the polymer composition is exposed to the vapor atmosphere, the electron-accepting dopant in an inert solvent is used. Wet doping method in which the polymer composition is immersed in the dissolved solution, and when the polymer composition is dissolved in the solution in which the electron accepting compound is dissolved in an inert solvent, dry film formation is performed from the solution. The method includes, for example, a method of forming a film or a coating film and performing doping at the same time, or a method of immersing the polymer composition in a solution containing a dopant and then electrochemically applying an electric field. .

The doping in the present invention may be performed on the finally obtained polymer composition, or may be performed separately before mixing the compound represented by the general formula (I) and the compounding compound.

Furthermore, when the polymer composition of the present invention is doped with an anion, the nitrogen atom in the copolymer represented by the general formula (I), which is one component constituting the composition, is in a stable state with a positive charge. Since it has the following properties, it is stable against repeated oxidation-reduction, has high conductivity, and has the excellent workability as described above. Used to construct electrodes.

That is, the copolymer represented by the general formula (I) of the present invention is dissolved in a solvent and the compounding compound is added, followed by molding.
Forming the polymer composition of the present invention by heating and melting, or press-molding the polymer composition as a main component, or forming into an arbitrary shape using a binder to form an electrode. You can Examples of the binder include, but are not limited to, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl chloride, and polyethylene.

Moreover, since the polymer composition of the present invention has a carbazole unit which is promising as a photoconductive material, it can be used as a photoconductive material.

<Effects of the Invention> Since the polymer composition of the present invention contains a linear copolymer as an essential component, it has excellent processability and can easily produce various molded products. In addition, by doping the polymer composition of the present invention with an electron acceptor, it is possible to express extremely high conductivity, and further, the doping is reversible and has extremely high cyclability. It is extremely excellent as a conductive polymer.

<Examples> Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto.

Example (Synthesis of N-ethylcarbazole dimer) N-ethylcarbazole 8.0 g, 70
% 30 ml of perchloric acid aqueous solution and 30 ml of glacial acetic acid were added to form a uniform solution, and 9.0 g of 2,3-dichloro-5,6-dicyano-p-benzoquinone dissolved in 200 ml of glacial acetic acid was stirred for 1 hour at room temperature. Dropped. After stirring at room temperature for 30 minutes, the reaction precipitate was filtered and washed with diethyl ether. The obtained black powder was dissolved in 600 ml of acetone, saturated aqueous sodium hydrosulfide solution was added dropwise under stirring to reduce the precipitate, and the precipitate was filtered and dried to give a crude yellow N-ethylcarbazole dimer 7.
3g was obtained. This was further dissolved in chloroform and passed through an alumina column to obtain 6.8 g of a pale yellowish white purified N-ethylcarbazole dimer.

As a result of infrared absorption spectrum analysis and ¹ H-NMR analysis, the obtained N-ethylcarbazole dimer was found to have 9,9′-diethyl having a structure linked at the 3-position of N-ethylcarbazole.
It was found to be 3,3'-bicarbazolyl.

(Polycondensation of N-ethylcarbazole dimer and formaldehyde) The above N-ethylcarbazole dimer was added to a 50 ml three-necked flask.
0.39 g was added and dissolved in 15 ml of 1,4-dioxane. After adding a few drops of concentrated sulfuric acid and 82 mg of a 37% aqueous formaldehyde solution, the mixture was stirred at 85 ° C. for 3 hours for reaction. After the reaction
The reaction precipitate was filtered, washed with methanol and dried to obtain 0.36 g of a blue-green polymer. The obtained copolymer is N-
Soluble in methylpyrrolidone and nitrobenzene,
It was insoluble in acetonitrile, propylene carbonate, and aliphatic hydrocarbons.

(Synthesis of Pyrrole Polymer) 50.0 g of anhydrous FeCl ₃ was placed in a 300 ml _three- necked flask, 100 ml of ethanol was added to dissolve it, and the mixture was cooled to 0 ° C. To this, 2 ml of pyrrole was added and reacted at 0 ° C. for 1 hour while stirring. After the reaction, the black-blue precipitate was filtered, washed with ethanol and ion-exchanged water, and then dried to obtain 1.5 g of a fine-particle pyrrole polymer. The pyrrole polymer was press-molded into a disk shape with a tablet molding machine, and the electrical conductivity measured by the 4-probe method was 54 S / cm at room temperature.

(Preparation of Polymer Composition by Mixing Copolymer and Pyrrole Polymer) After dissolving 0.50 g of the copolymer obtained by polycondensation of N-ethylcarbazole dimer and formaldehyde in 10 ml of chloroform, 0.20 g of the pyrrole polymer was added and stirred to prepare a copolymer solution in which the pyrrole polymer was uniformly dispersed. The copolymer solution containing this pyrrole polymer was cast on a Teflon plate and dried to obtain the thickness.
A uniform film of 20 μm was obtained. The obtained film was flexible, and the conductivity of the 4-probe method was 0.5 S / cm.

In addition, a half-cell charge / discharge test was conducted using this film as a positive electrode, a platinum sheet as a counter electrode, Ag / AgNO ₃ as a reference electrode, and an acetonitrile solution of 0.7M-Et ₄ NPF ₆ as an electrolytic solution. When the charge / discharge repetitive characteristics at a charge amount of 100 C / g and a charge / discharge current of 5 mA / cm ² were examined, it was 100 when the clone efficiency was 95% or more.
Stable cyclability was obtained more than once.

Figure 1 shows the discharge curve. In the figure, the horizontal axis represents the discharge charge amount, and the vertical axis represents the discharge potential based on Ag / AgNO ₃ . 5mA /
It has been found that even at a high current density of cm ^2, it exhibits extremely good potential stability.

[Brief description of drawings]

FIG. 1 is a diagram showing an example of a discharge curve of the polymer composition of the present invention.

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Claims (2)

[Claims] 1. A general formula (I) (In the formula, R ¹ is a hydrogen atom or a hydrocarbon residue having 1 to 20 carbon atoms, R ² is a hydrogen atom or a hydrocarbon residue having 1 to 20 carbon atoms, or a furyl group, a pyridyl group, a nitrophenyl group, a chlorophenyl group, A methoxyphenyl group, and n and x each represent an integer of 2 or more), the copolymer represented by the general formula (II) (Wherein R ³ , R ⁴ and R ⁵ are each a hydrogen atom or a hydrocarbon residue having 1 to 20 carbon atoms, p is an integer of 2 or more), and a general formula (III) (In the formula, R ⁶ and R ⁷ are each a hydrogen atom or a carbon number 1
To 10 hydrocarbon residues, q is an integer of 2 or more), and a polythiophene compound represented by the general formula (IV) (Wherein R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms, and r is an integer of 2 or more), and a compound selected from polyaniline compounds. A polymer composition obtained by mixing 2. General formula (I) (In the formula, R ¹ is a hydrogen atom or a hydrocarbon residue having 1 to 20 carbon atoms, R ² is hydrogen or a hydrocarbon residue having 1 to 20 carbon atoms, or a furyl group, a pyridyl group, a nitrophenyl group, a chlorophenyl group, or methoxy. A phenyl group, and n and x each represent an integer of 2 or more), the copolymer represented by the general formula (II) (Wherein R ³ , R ⁴ and R ⁵ are each a hydrogen atom or a hydrocarbon residue having 1 to 20 carbon atoms, p is an integer of 2 or more), and a general formula (III) (In the formula, R ⁶ and R ⁷ are each a hydrogen atom or a carbon number 1
To 10 hydrocarbon residues, q is an integer of 2 or more), and a polythiophene compound represented by the general formula (IV) (Wherein R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ represent a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms, r represents an integer of 2 or more), and a compound selected from polyaniline compounds A conductive polymer composition obtained by doping a polymer composition obtained by mixing with an electron acceptor.