JPH10308117A - Conductive composition and manufacture thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently manufacture a conductive composition, and effectively increase electric conductivity of the conductive composition and its stability, by using a thiophene derivative containing a organic acid ions and inorganic acid ions of an anionic surfactant as dopant, and a repeating unit. SOLUTION: A conductive composition is a conjugate double bonded conductive polymer composition using a thiophene derivative which contains composite dopant composed of organic acid ions and inorganic acid ions of an anionic surfactant and is expressed by the formula (A is an alkylene group which may be substituted at any time) as a repeating unit. Here, 3,4-ethylenedioxythiophene is suitably used as the thiophene drivative expressed by the formula. Besides an anion of transition metal inorganic salt used as an oxidizing agent, an organic acid anion is contained in this polymer composition as dopant, or when the concentration of the organic acid anion is high, it is dominantly contained as dopant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a conductive composition and a method for producing the same, and more particularly to a conductive composition comprising a conductive polymer having a conjugated double bond and having thiophene as a repeating unit according to the formula (2). And a method of manufacturing the same.

Embedded image

[0002]

2. Description of the Related Art In general, conjugated double bond conductive polymers represented by polyaniline, polypyrrole and polythiophene can be produced by chemical oxidation polymerization and electrolytic polymerization. In the case of using electrolytic polymerization, it is difficult to mass-produce the conductive polymer because the conductive polymer is formed in a film on the electrode, whereas in the case of using chemical oxidative polymerization, such In principle, a large amount of conductive polymer can be obtained relatively easily by the reaction between a polymerizable monomer and an appropriate oxidizing agent in principle. This can be obtained by electrolytic polymerization and chemical oxidative polymerization without exception in the case of a conjugated double bond conductive polymer having a thiophene derivative as a repeating unit shown in (Chemical Formula 2).

This thiophene derivative is, for example, 3,4
-Dihydroxythiophene-2,5-dicarboxylic acid ester is reacted with an appropriate alkylene-vic-dihalide and then hydrolyzed to give 3,4 (alkylene-vic-dioxy) thiophene-2,5-carboxylic acid. And it can be obtained by decarboxylation (Polymer, Vol. 35, No. 7, 1994)
1347 pages, Tetrahedron, 23 volumes (1
967) p. 2437 and J. Org. Am. Chem. So
c. 67 (1945), page 2217). The above-mentioned electrolytic polymerization and chemical oxidation polymerization of the thiophene derivative are disclosed in Japanese Patent Publication No. 1-313521. In the case of this thiophene derivative, a polymer conductive composition having extremely high environmental stability can be realized because an oxidation reaction does not occur at this position since the 3- and 4-positions are blocked by a substituent. It has been pointed out that the utility is high from the aspect. Regarding environmental stability, see Electrochemical Acta, Vol. 39, No. 8/9, 1345-1347.
Page (1994).

[0004]

However, since the solubility of the thiophene derivative represented by the formula (2) in water is extremely low, it has been difficult to carry out polymerization substantially in an aqueous medium. Furthermore, it is known that in the polymerization of the thiophene derivative monomer shown in (Chemical Formula 2), the presence of even a small amount of water has an effect of suppressing the polymerization reaction. It is recommended to use it for the purpose of extending the pot life later. For this reason, non-aqueous solvents such as alcohols, aromatics, ketones, acetonitrile, and propylene carbonate are used for the polymerization of the thiophene derivative monomer shown in Chemical Formula 2. Electrolytic polymerization using a flammable polymerization medium requires special precautions from the viewpoint of fire prevention, and industrial use is likely to be limited.

[0005] On the other hand, in the case of chemical oxidative polymerization, the above-mentioned problems are alleviated. However, the use of an organic solvent has a high possibility of increasing the environmental load, and many of them are harmful to the human body. There is also a problem that measures for disaster prevention are required, and the cost of the conductive composition obtained tends to be high. Furthermore, as disclosed in the above-mentioned journal, in the case of the thiophene derivative shown in (Chemical Formula 2), the polymerization rate near room temperature is low, and the electric conductivity tends to be higher when polymerized at high temperature. It is known.

The present invention solves the above-mentioned problems of the prior art, and is a highly conductive and thermally stable conductive composition containing a thiophene derivative represented by the following formula (2) as a repeating unit. Is intended to provide an efficient production method for obtaining a high yield in a short time.

[0007]

The present invention solves the above-mentioned problems of the prior art, and comprises a composite dopant comprising an anionic surfactant ion and an inorganic acid ion.
It is based on a conductive composition comprising a conjugated double bond polymer having the thiophene derivative according to (Chemical Formula 2) as a repeating unit. In order to further improve the yield and improve the thermal stability of the conductive composition, the method includes a method for producing a conductive composition which is polymerized in a system in which a phenol derivative or a nitro compound coexists. With this configuration, a conductive composition having high conductivity and high heat stability can be obtained in high yield. And this conductive composition can be obtained by a manufacturing method by chemical oxidative polymerization in a substantially aqueous medium, and an efficient manufacturing method for obtaining a high yield of the conductive composition in a short time is provided. Was done.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION
A conjugated double bond conductive polymer composition containing a composite dopant comprising an organic acid ion and an inorganic acid ion of an anionic surfactant and having a thiophene derivative represented by the following formula (2) as a repeating unit. Here, 3,4-ethylenedioxythiophene is preferably used as the thiophene derivative represented by Chemical Formula 2. Further, the substitutable alkylene group is preferably a 1,2-alkylene group such as ethene, 1-propene, 1-hexene or the like, which is obtained from alpha olefin, and furthermore, 1,2-cyclohexene , 2,3-butylene, 2,3-dimethylene 2,3-butylene and 2,3-pentylene groups. However, preferred examples include methylene,
Examples thereof include 1,2-ethylene and 1,2-propylene groups. Further, as described in claim 2, the surfactant ion may be a sulfonic acid ion or an esterified sulfate ion. Further, as described in claim 3, as the inorganic acid ion, a sulfate ion, a halogen ion, a nitrate ion, a perchlorate ion, a hexacyanoferrate ion, a phosphate ion and a phosphomolybdate ion can be used.

Further, as described in claim 4, the above conductive composition can be suitably obtained by a production method by chemical oxidative polymerization. As the polymerization oxidizing agent, a compound containing a transition metal capable of polymerizing the thiophene derivative monomer shown in (Chemical Formula 1) can be used. Specifically, as described in claim 6,
A step of preparing a thiophene derivative monomer shown in Chemical Formula 1, a step of preparing an oxidizing agent containing a transition metal capable of polymerizing the monomer, and a step of preparing a surfactant that dissociates to generate organic acid ions. And a step of chemically polymerizing the monomer and the oxidizing agent in the coexistence of the surfactant anion. Also,
The transition metal may be copper, iron, cerium, molybdenum or chromium. Further, any surfactant can be used as the surfactant that generates organic acid ions as long as it is an anionic surfactant that can be dispersed in water. Sulfonate ions or esterified sulfate ions can be used as described in. Claim 9
As mentioned, water is preferably used as the polymerization medium.
In this case, it is sufficient if the medium is substantially an aqueous medium, and may contain a trace amount of an organic medium for facilitating dispersion of the surfactant.

[0010] Further, as described in claim 10, a step of preparing a thiophene derivative represented by the formula (1), a step of preparing an anionic surfactant which dissociates to generate an organic acid ion, and A step of preparing an oxidizing agent comprising an inorganic acid containing a polymerizable transition metal, a step of preparing a phenol derivative or a nitro compound, and a method of producing a conductive composition having a step of chemically polymerizing using an oxidizing agent. The transition metal may be copper, iron, cerium, molybdenum or chromium, as described in claim 11, and the organic acid of the anionic surfactant is sulfonic acid as described in claim 12. Alternatively, it may contain esterified sulfuric acid, and the phenol derivative may be nitrophenol, cyanophenol,
The nitro compound may be hydroxybenzoic acid, hydroxyphenol or acetophenol, or a combination thereof, and the nitro compound may be an aromatic nitrocarboxylic acid, nitrobenzene, nitronaphthalene or a combination thereof, as claimed in claim 14. The polymerization medium may be substantially water, as described in claim 15.

The conductive polymer composition according to the present invention contains an organic acid anion as a dopant in addition to an anion of a transition metal inorganic salt used as an oxidizing agent.
Alternatively, when the concentration of the organic acid anion is high, it is predominantly included as a dopant. This is because, for example, per several thiophene rings, one molecule of anion can coordinate as a dopant, but in the presence of an anionic surfactant, a hydrophobic polymerizable monomer is It is considered that the surfactant anion existing in the vicinity of the produced polymer is more predominantly taken in as a dopant because the polymer is predominantly taken up therein and the polymerization predominantly proceeds therein. Since the molar concentration of the dopant per conductive polymer repeating unit is constant as described above, when the molecular weight of the surfactant anion is larger than that of the non-surfactant anion, the yield of the obtained conductive polymer is relatively low. Increase. Furthermore, when the molecular size of the dopant is large, the conductive polymer skeleton structure is not distorted, as is particularly the case with a polyvalent anion having a small molecular size, so that high electrical conductivity is realized. As shown in FIG. 1 described later, it is considered that the electric conductivity tends to be highest in a region where both organic ions and inorganic ions are doped in combination. When the organic anion is bulky, for example, having an aromatic ring, undoping due to thermal diffusion is suppressed, so that a conductive polymer having high thermal stability can be obtained. Further, even when water, which normally acts as a reaction inhibitor, is used as a medium, in the case of the structure of the present invention, the polymerization reaction proceeds rapidly because of the action of the coexisting surfactant, the thiophene derivative monomer represented by the formula (2). Is considered to be an effect of emulsification. That is, in emulsion polymerization, the phase in which the water-soluble polymerization initiator is present and the phase in which the polymerization reaction mainly proceeds (in a huge number of surfactant micelles) are different, so that the termination reaction is hard to occur and the polymerization is difficult. It is characteristic that a polymer having a high speed and a high degree of polymerization can be obtained. Since the polymerization according to the present invention is also performed in a system in which a thiophene derivative monomer emulsified with a water-soluble polymerization oxidizing agent and a surfactant is present, the polymerization reaction proceeds by a similar mechanism, resulting in a high polymerization rate and a high degree of polymerization. It is believed that a high polymer is obtained. According to the present invention, a conductive composition having high electric conductivity can be easily obtained, which can be explained by the mechanism described above.

Further, according to the method for producing a conductive composition according to the present invention, when the inorganic acid anion generated from the transition metal inorganic salt used for polymerizing the polymerizable monomer is polyvalent, a high selectivity is obtained. By utilizing the fact that the organic acid anion is easily taken in as a dopant, a conductive polymer doped with the desired organic anion can be easily synthesized in an aqueous medium. Further, by adding phenol or a derivative thereof or a nitro compound, the yield of the conductive polymer obtained from the thiophene derivative shown in Chemical formula 2 and the stability of electric conductivity are further improved. this is,
A phenolic compound or a nitro compound is not incorporated as a dopant into the conductive polymer, but is considered to be a conductive polymer having a high degree of regularity and therefore having a developed conjugate length.

(First Embodiment) First, a first embodiment of the present invention will be described. First, in the present embodiment, 10.7 g of ferric sulfate n-hydrate as an oxidizing agent containing a transition metal ion (including 0.2 mol as ferric sulfate)
Was dissolved in 100 g of water to prepare an oxidizing agent solution.
Next, 1.4 g of 3,4-ethylenedioxythiophene was added to this solution, and a sodium alkylnaphthalenesulfonate (average molecular weight: 3) was used as a substance containing organic acid ions.
28) A solution prepared by dissolving 4 g of a 40% aqueous solution in 100 g of water was added, and the mixture was polymerized with stirring at 45 ° C. and atmospheric pressure for 20 hours. Here, 3,4-ethylenedioxythiophene is commercially available from Bayer AG in Germany, but 3,4-ethylenedioxythiophene may be synthesized by a general production method. Here, as the sodium alkylnaphthalenesulfonate, one in which the number of carbon atoms of the alkyl group is mixed between 3 and 9 is used, but the number of carbon atoms is of course not particularly limited.
Next, the obtained precipitate is separated by filtration, washed with water until the filtrate exhibits neutrality, further washed with ethanol, and dried under reduced pressure at about 50 ° C. for several hours to obtain a conductive material having a conjugated double bond. A conductive composition containing poly (3,4-ethylenedioxythiophene), which is a conductive polymer, was obtained. Then, after measuring the yield of the conductive composition, a part thereof was pulverized in a mortar, and was crushed for about 30 minutes.
A disc-shaped pellet having a diameter of 13 mm was produced at a pressure of MP and used for measurement of electric conductivity. The electric conductivity was measured using a resistivity meter Loresta SP manufactured by Mitsubishi Yuka Co., Ltd.
The MCP-TP06PPSP probe was used. The obtained yield and measured values of electric conductivity are shown in the following (Table 1).

[Table 1]

Comparative Example 1 As Comparative Example 1, a poly (3,4-ethylenedioxythiophene) was prepared in the same manner as in Embodiment 1 except that a substance containing a surfactant was not added. After treatment, the yield and electrical conductivity were measured. The results are shown in the following (Table 2).

[Table 2] As is clear from the comparison between Comparative Example 1 in (Table 2) and Embodiment 1 in (Table 1), the conductive composition according to Example 1 was excellent in that yield and electric conductivity were high. It turned out that the effect was obtained. The reason is that the polymerization reaction proceeds in the micelles due to the presence of the surfactant, so that the polymerization rate is increased and that a polymer having a high degree of polymerization is obtained, so that the developed bipolaron structure is formed. It is considered an effect. Furthermore, the fact that bulky surfactant anions forming micelles are also taken in as a dopant is considered to be one of the reasons why the yield is increased and a conductive composition having high electric conductivity can be obtained.

Comparative Example 2 As Comparative Example 2, 1.4 g of 3,4-ethylenedioxythiophene and 11.4 g of iron (III) p-toluenesulfonate were added to ipropyl alcohol 15
g and n-butanol in a solution consisting of 9 g of poly (3,4-
Ethylenedioxythiophene) was prepared, and after the same treatment, the yield and the electric conductivity were measured. This method is disclosed in JP-A-2-15611,
It is a conventionally known typical polymerization method of ethylenedioxythiophene. The results are shown in the above (Table 2). In addition, since the yield obtained here is smaller than that of the first embodiment, in the first embodiment, alkylnaphthalenesulfonate ions having a large molecular weight are predominantly doped instead of divalent sulfate ions. Was determined to be.

As described above, according to the first embodiment,
By using ferric sulfate n-hydrate as an oxidizing agent and coexisting a surfactant containing an organic acid anion, sodium alkylnaphthalenesulfonate in a polymerization system, a conductive composition having high yield and high electrical conductivity is obtained. You can get things.

(Embodiment 2) Next, a second embodiment of the present invention will be described. In the present embodiment, the conductive polymer 3,4- (1,1) which similarly contains a thiophene derivative represented by the following chemical formula 2 as a repeating unit instead of 3,4-ethylenedioxyiophene in the first embodiment. 2
A conductive composition was obtained in the same manner as in Embodiment 1, except that 1.7 g of (propylene) dioxythiophene was used.
The obtained yield and measured values of the electric conductivity are shown in the above (Table 1).

Comparative Example 3 As Comparative Example 3, poly (3,4- (1,2-propylene) dioxythiophene) was prepared in the same manner as in Embodiment 2 except that a substance containing a surfactant was not added. Was prepared, and after the same treatment, the yield and the electric conductivity were measured. The results are shown in the above (Table 2).
Table 1 shows the results of this embodiment, and Table 2 shows Comparative Example 3
As is clear from the comparison with the results of the above, it was found that the conductive composition according to the present embodiment had an excellent effect in that the yield and the electric conductivity were high.

As described above, according to the second embodiment,
By using ferric sulfate n-hydrate typically as an oxidizing agent and allowing an anionic surfactant to coexist in the polymerization system, a conductive composition having high yield and high electrical conductivity can be obtained.

(Embodiment 3) Next, a third embodiment of the present invention will be described. In this embodiment, instead of the sodium alkylnaphthalenesulfonate used in the first embodiment, (A) 0.84 g of sodium dodecylbenzenesulfonate and (B) 4 g of a 40% aqueous solution of sodium alkylsulfonate (the number of alkyl groups) Are mixed in the range of 11 to 17), (C) 2.2 g of a 40% aqueous solution of sodium 2-ethylhexyl sulfate, 2.2 g,
(D) A monomer solution to which 5.7 g of a 30% aqueous solution of polyethylene oxide (the number of repeating ethylene oxide: 3) sodium alkylsulfate 30% (mixture of alkyl group having 11 to 15 carbon atoms) was used. A conductive composition containing polypyrrole was prepared in the same manner as in Embodiment 1 except for the above, and the post-treatment yield and electrical conductivity were measured in the same manner. However, it goes without saying that the number of the above alkyl groups and the number of repeating ethylene oxides are not limited. The results are shown in the above (Table 1). As is clear from a comparison between the results of each of (A) to (D) of the present example in (Table 1) and the results of Comparative Example 1 in (Table 2), the conductive composition according to the present example is: It was found that excellent effects were obtained in terms of high yield and high electrical conductivity.

As described above, according to the third embodiment,
By using ferric sulfate n-hydrate typically as an oxidizing agent and allowing various anionic surfactants to coexist in the polymerization system, a conductive composition having high yield and high electrical conductivity can be obtained.

Further, the polymerization time was set to 20 hours, 5.35 g of ferric sulfate n-hydrate was added, and the concentration of sodium alkylnaphthalenesulfonate was variously changed to obtain the obtained polypyrrole and the electric conductivity. The degree is shown in FIG. It is apparent from this figure that the yield and electric conductivity change depending on the concentration of the organic acid anion in the polymerization solution. It has been confirmed from elemental analysis that these conductive compositions contain only trace amounts of iron components. The reason for the increase in yield is that the alkylnaphthalenesulfonic acid iron salt is made of poly (3,4-ethylene It is judged that this was not due to the complexation with dioxythiophene), but because alkylnaphthalenesulfonate ions were incorporated instead of divalent sulfate ions depending on the concentration in the solution. From FIG. 1, it can be seen that the yield increases with the concentration of sodium alkylnaphthalenesulfonate, but the electrical conductivity shows a maximum in a region where sulfate ions and organic acid ions coexist as dopants.

Next, in each case of adding no surfactant and adding a surfactant, sodium alkylnaphthalenesulfonate, the yield of polypyrrole obtained is shown in FIG. 2 by varying only the polymerization time. Obviously, only when the surfactant is added, the polymerization reaction rate is increased and the conductive composition having high electric conductivity is obtained.

(Embodiment 4) Next, a fourth embodiment of the present invention will be described. In this embodiment, (A) ferric chloride hexahydrate 11.3 g and (B) ferric nitrate nonahydrate 14 are used in place of ferric sulfate used in Embodiment 1.
g, (C) ferric perchlorate g, (D) 13.2 g of potassium hexacyanoferrate (III), and 10.2 g of (E) ferric (III) diphosphate as oxidizing agents, respectively. A conductive composition was prepared in the same manner as in Embodiment 1, and the yield after treatment and the electrical conductivity were measured in the same manner. The results are shown in the above (Table 1). As is clear from the comparison between the results of each of (A) to (E) of the present embodiment (Table 1) and the results of Comparative Example 1 of (Table 2), the conductive composition according to the present embodiment. Was found to have obtained an excellent effect in that the yield and electric conductivity were high.

As described above, according to the fourth embodiment,
By using an inorganic acid salt of iron as an oxidizing agent and allowing an anionic surfactant to coexist in a polymerization system, a conductive composition having high yield and high electrical conductivity can be obtained.

(Embodiment 5) Next, a fifth embodiment of the present invention will be described. In this embodiment, instead of ferric sulfate used in Embodiment 1, (A) 10.4 g of cupric sulfate ferric chloride pentahydrate, (B) cerium (IV) sulfate water Conductivity was obtained in the same manner as in Embodiment 1, except that 16.6 g of the hydrate, (6.6 g) of (C) sodium phosphomolybdate, and (12.6 g) of (D) sodium dichromate dihydrate were used as oxidizing agents. A water-soluble composition was prepared, and the yield and electrical conductivity after the same treatment were measured. The results are shown in the above (Table 1). As is clear from the comparison between the results of each of (A) to (D) of the present embodiment in (Table 1) and the results of Comparative Example 1 in (Table 2), the conductive composition according to the present embodiment. Was found to have obtained an excellent effect in that the yield and electric conductivity were high.

As described above, according to the fifth embodiment,
By using a transition metal inorganic salt capable of polymerizing 3,4-dioxythiophene as an oxidizing agent and allowing an anionic surfactant to coexist in the polymerization system, it is possible to obtain a conductive composition having high yield and high electrical conductivity. it can.

(Embodiment 6) Next, a sixth embodiment of the present invention will be described. In the present embodiment, a conductive composition was prepared by the same operation as in Embodiment 1 except that p-nitrophenol was further added in an amount of 1.4 g as an additive. The conductivity was measured. The results are shown in the above (Table 1). As is clear from the comparison between the results of the present embodiment in (Table 1) and the results of Comparative Example 1 in (Table 2), the conductive composition according to the present embodiment has high yield and high electrical conductivity. It was found that an excellent effect was obtained in this respect.

As described above, according to the sixth embodiment,
By using p-nitrophenol as an additive and allowing a transition metal inorganic salt oxidizing agent capable of polymerizing 3,4-dioxythiophene and an anionic surfactant to coexist in the polymerization system, a conductive composition having a particularly high yield can be obtained. Obtainable.

It is presumed that polymerization may be accelerated as a result of the interaction of the polymerizable monomer and p-nitrophenol. FIG. 3 shows the change over time in the electrical conductivity of the conductive composition in air at 125 ° C. with or without the addition of p-nitrophenol. From this figure, it is clear that the conductive composition obtained in the system to which p-nitrophenol is added has higher heat resistance. This phenomenon is also considered to be an effect due to the formation of a polymer having a high degree of regularity and therefore having a small number of oxidizable defects as a result of the interaction between the monomer molecule and the p-nitrophenol molecule. In addition,
FIG. 3 shows an example of poly (3,4-ethylenedioxythiophene) obtained by a known method doped with p-toluenesulfonic acid ion as shown in Comparative Example 2. From this, it is clear that the conductive composition of the present invention is excellent in heat resistance even when obtained in a system to which p-nitrophenol is not added.

(Embodiment 7) Next, a seventh embodiment of the present invention will be described. In this embodiment, (A) 1.4 g of m-nitrophenol, (B) 1.2 g of p-cyanophenol, and (C) m-hydroxyphenol in place of p-nitrophenol of Embodiment 6. 1.
The same operation as in Embodiment 1 except that 1 g, (D) 1.6 g of p-nitrobenzoic acid, 1.2 g of (E) nitrobenzene or 0.9 g of (F) nitronaphthalene were respectively added as additives. To prepare a conductive composition, and the same post-treatment yield and electric conductivity were measured. The results are shown in the above (Table 1). As is clear from the comparison between the results of each of (A) to (F) of the present embodiment in (Table 1) and the results of Comparative Example 1 in (Table 2), the conductive composition according to the present embodiment. Was found to have obtained an excellent effect in that the yield and electric conductivity were high.

As described above, according to the seventh embodiment,
By using a phenol derivative, a nitro aromatic carboxylic acid and a nitro compound as additives, a transition metal inorganic salt oxidizing agent capable of polymerizing 3,4-dioxythiophene and an anionic surfactant are coexistent in the polymerization system, so that the yield and the yield are improved. A conductive composition having high electric conductivity can be obtained. Furthermore, the change with time of the electric conductivity was compared in the same manner as in Embodiment 5. In each case, the change with time of the electric conductivity when the additive was added tended to be smaller.
It is considered that the effect is obtained as a result of some interaction between the added phenol derivative, nitro aromatic carboxylic acid or nitro compound and the polymerizable monomer.

[0033]

According to the constitution of the present invention, the conductive composition can be obtained in a high yield, and the conductive composition can be manufactured efficiently. And the electrical conductivity of the conductive composition and its stability can also be effectively increased.

[Brief description of the drawings]

FIG. 1 is a characteristic diagram showing the relationship between the amount of sodium alkylnaphthalenesulfonate added and the electrical conductivity and yield of poly (3,4-ethylenedioxythiophene) in Embodiment 3 of the present invention.

FIG. 2 is a characteristic diagram showing the relationship between the presence or absence of addition of an organic ion of a surfactant and the polymerization rate and electric conductivity of poly (3,4-ethylenedioxythiophene) in Embodiment 3.

FIG. 3 is a characteristic diagram showing the relationship between the presence or absence of p-nitrophenol and the change over time in the electrical conductivity of the obtained poly (3,4-ethylenedioxythiophene) in Embodiment 5.

Continuation of the front page (72) Inventor Matsuya Yasu 3-10-1 Higashi-Mita, Tama-ku, Kawasaki-shi, Kanagawa Prefecture Matsushita Giken Co., Ltd.

Claims (15)

[Claims] 1. A conductive composition comprising, as a repeating unit, a thiophene derivative represented by (Chem. 1) containing an organic acid ion and an inorganic acid ion of an anionic surfactant as dopants. Embedded image 2. The conductive composition according to claim 1, wherein the anionic surfactant comprises a sulfonic acid or an esterified sulfuric acid-based surfactant. 3. The conductive composition according to claim 1, wherein the inorganic acid ion includes a sulfate ion, a halogen ion, a nitrate ion, a perchlorate ion, a hexacyanoferrate ion, a phosphate ion or a phosphomolybdate ion. . 4. A method for producing a conductive composition, comprising obtaining the conductive composition according to claim 1 by chemical oxidative polymerization. 5. A method for producing a conductive composition, wherein the conductive composition according to claim 1 is obtained by chemical oxidative polymerization using a compound containing a transition metal. 6. A step of preparing a thiophene derivative represented by the chemical formula (1), a step of preparing an anionic surfactant that dissociates to generate an organic acid ion, and an inorganic substance containing a transition metal capable of polymerizing the monomer. A method for producing a conductive composition, comprising: a step of preparing an oxidizing agent composed of an acid; and a step of performing chemical polymerization using the oxidizing agent. 7. The method for producing a conductive composition according to claim 5, wherein the transition metal includes copper, iron, cerium, molybdenum, or chromium. 8. The method for producing a conductive composition according to claim 5, wherein the organic acid of the anionic surfactant includes sulfonic acid or esterified sulfuric acid. 9. The method for producing a conductive composition according to claim 5, wherein the polymerization medium is substantially water. 10. A step of preparing a thiophene derivative represented by Chemical Formula 1, a step of preparing an anionic surfactant that dissociates to generate an organic acid ion, and an inorganic substance containing a transition metal capable of polymerizing the monomer. A method for producing a conductive composition, comprising a step of preparing an oxidizing agent composed of an acid, a step of preparing a phenol derivative or a nitro compound, and a step of chemically polymerizing using the oxidizing agent. 11. The method for producing a conductive composition according to claim 10, wherein the transition metal includes copper, iron, cerium, molybdenum or chromium. 12. The organic acid of the anionic surfactant comprises sulfonic acid or esterified sulfuric acid.
Or a method for producing a conductive composition according to item 11. 13. The method for producing a conductive composition according to claim 10, wherein the phenol derivative is nitrophenol, cyanophenol, hydroxybenzoic acid, hydroxyphenol or acetophenol, or a combination thereof. 14. The method for producing a conductive composition according to claim 10, wherein the nitro compound is an aromatic nitrocarboxylic acid, nitrobenzene, a derivative thereof, or a combination thereof. 15. The method of claim 1, wherein the polymerization medium is substantially water.
15. The method for producing a conductive composition according to any one of 0 to 14.