JP3491522B2 - Method for producing conductive composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a conductive composition, and in particular, it has a conjugated double bond using chemical polymerization, is excellent in electrical conductivity and environmental stability, and further is an anodized film of valve metal. The present invention relates to a method for producing a conductive polymer having a high repair function for

[0002]

2. Description of the Related Art Generally, a conjugated double bond conductive polymer represented by polyaniline, polypyrrole and polythiophene can be prepared by chemical oxidative polymerization and electrolytic polymerization.

When electrolytic polymerization is used, the conductive polymer is formed into a film on the electrode, which makes it difficult to mass-produce it. On the other hand, when chemical oxidation polymerization is used. Without such a restriction, a large amount of conductive polymer can be obtained relatively easily in principle by the reaction of the polymerizable monomer and a suitable oxidizing agent.

In such a conductive polymer, it is important to give high electric conductivity and high environmental stability in view of practical application, and selection of a dopant or introduction of an appropriate substituent to a polymerizable monomer. Therefore, attempts have been made to improve environmental stability.

Furthermore, in recent years, active research has been conducted on applying the conductive polymer as a solid electrolyte of an electrolytic capacitor.

At this time, it is desired to have a high repair ability for an anodized film represented by aluminum and tantalum.

At present, it is explained that the anodic oxide film repairing function is largely contributed to the decomposition and insulation of the conductive polymer by the Joule heat of the electric current concentrated in the film defect portion.

[0008]

However, it is extremely difficult to impart a sufficiently high environmental stability to the chemically polymerized polypyrrole, and its application is limited to a limited range.

Further, when a conductive polymer is used as an electrolyte of an electrolytic capacitor, for example, we have found that a phosphoric acid anion-doped one exhibits an excellent dielectric film repairing action. In that case, since de-doping is easy, there is a problem that a capacitor using this kind of conductive polymer has an improved withstand voltage but inevitably a decrease in heat resistance and moisture resistance.

Further, as represented by phosphoric acid esters, many phosphoric acid derivatives have low solubility in water, and when this is used as a dopant, it becomes difficult to use an inexpensive aqueous polymerization medium. There were also challenges.

Furthermore, since the phosphoric acid compound often forms a poorly soluble salt with a transition metal ion in many cases, the anion is doped with a highly conductive compound by chemical polymerization using the transition metal ion as an oxidant. It was difficult to obtain the molecule.

[0012]

Means for Solving the Problems The present invention is to solve the above-mentioned problems of the conductive polymer according to the prior art, and comprises a step of preparing a monomer capable of forming a conjugated double bond conductive polymer, a step of preparing an anionic surfactant, comprising the steps of providing a step of preparing the alkyl phosphoric acid esters having active hydrogen, an oxidizing agent containing a transition metal inorganic acid salt,
Alkyl having the anionic surfactant and active hydrogen
The method is basically based on a method for producing a conductive composition, which comprises a step of chemically polymerizing with a phosphoric acid ester and the above-mentioned oxidizing agent in the presence of the above-mentioned monomer.

According to this manufacturing method, it is highly conductive,
Further, a conductive composition having excellent environmental stability and having a higher valve metal dielectric film repairing function is realized.

This is because the phosphoric acid derivative having active hydrogen, which has low solubility in water, is solubilized in the aqueous medium by the action of the anionic surfactant.

It is also clear from the results of elemental analysis that the conjugated double bond conductive polymer thus obtained contains a phosphoric acid derivative having a surfactant anion and active hydrogen as a dopant. Is.

It is not clear why the conductive composition thus obtained exhibits higher environmental stability than the case where both dopants are contained alone, but it has some effect in the polymerization process. It is expected that a polymer having a dense morphology is formed and oxygen permeation is suppressed or dopant dedoping is suppressed.

The present invention also provides a method for producing a conductive composition, which comprises a step of chemically polymerizing in a system in which a phenol derivative or a nitrobenzene derivative is further coexistent in addition to the above.

It has been found that the action of these additives makes it possible to obtain a conductive composition having more excellent environmental stability.

There is no limitation on the concentration of the phosphoric acid derivative having active hydrogen to be added, as long as it is solubilized in the polymerization medium.

However, the ratio of incorporation as a dopant was lower than the molar ratio of the sulfonic acid type surfactant anion present in the medium to the phosphoric acid derivative having active hydrogen, which was about half the ratio.

Even when a small amount of a phosphoric acid derivative was added, the repair function of the anodized film was improved, but the environmental stability of the conductive composition increased with its concentration, and the molar ratio with the anionic surfactant was increased. Was found to be highest around 1: 1.

When the molar ratio of the phosphoric acid derivative to the anionic surfactant was increased, the ratio of the phosphoric acid derivative as a dopant was increased, and the environmental stability of the conductive composition was lowered.

Therefore, the molar ratio of the phosphoric acid derivative having active hydrogen and the anionic surfactant is preferably in the range of 0.1: 1 to 1: 2.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION The invention according to claim 1 of the present invention is
A step of preparing a monomer capable of forming a conjugated double bond conductive polymer, a step of preparing an anionic surfactant,
A step of preparing an alkyl phosphate having active hydrogen and a step of preparing an oxidizing agent containing a transition metal inorganic acid salt
When, Al having the anionic surface active agent and the active hydrogen
It is a method for producing a conductive composition, which comprises a step of chemically polymerizing with a phosphoric acid ester in the presence of the monomer using the oxidizing agent.

The conjugated double bond conductive polymer may be polypyrrole, polythiophene, polyaniline and their derivatives.

Further, as described in claim 3, as the anionic surfactant, one containing sulfonic acid or esterified sulfuric acid can be used.

Here, as described in claim 4, the inorganic acid is
Sulfuric acid, hydrochloric acid, nitric acid, perchloric acid or hexacyanoferric acid may be used.

Further, as described in claim 5, the transition metal inorganic salt is a phosphoric acid derivative having active hydrogen which can be used in a copper salt, an iron salt, a molybdenum salt or a chromium salt.
As described, an alkyl phosphate ester having an alkyl group having 3 to 12 carbon atoms is preferably used.

In the above manufacturing method, as described in claim 7, an additive selected from a phenol derivative or a nitrobenzene derivative can be further added and used.

Here, as described in claim 8, polypyrrole, polythiophene, polyaniline and derivatives thereof can be used as the conjugated double bond conductive polymer.

Further, as described in claim 9, sulfonic acid or esterified sulfuric acid can be used as the anionic surfactant.

As the inorganic acid, as described in claim 10,
Sulfuric acid, hydrochloric acid, nitric acid, perchloric acid or hexacyanoferric acid may be used.

As described in claim 11, the transition metal inorganic salt preferably contains a copper salt, an iron salt, a molybdenum salt or a chromium salt.

The phosphoric acid derivative having active hydrogen is claim 1.
As described in 2, an alkyl phosphate ester having an alkyl group having 3 to 12 carbon atoms can be used.

Here, as described in claim 13, nitrophenol, cyanophenol, hydroxybenzoic acid, and hydroxyphenol can be used as the phenol derivative.

Further, as described in claim 14,
As the nitrobenzene derivative, nitrobenzene, nitrobenzoic acid, nitrobenzyl alcohol can be used.

In the above production method, the addition molar ratio of the anionic surfactant to the phosphoric acid derivative may be in the range of 0.1: 1 to 2: 1.

In the above-mentioned method for producing a conductive polymer composition according to the present invention, a conductive polymer containing, as a dopant, an anion of a phosphoric acid derivative having active hydrogen in addition to a surfactant anion can be obtained.

When the molecular size of these anions is large, it is possible to obtain a conductive polymer in which diffusion is less likely to occur in high temperature or high humidity, and thus the electric conductivity is less deteriorated.

This is because the surfactant anion forms a micelle in water, in which the hydrophobic polymerizable anion,
It is considered that the phosphoric acid derivative having active hydrogen is incorporated at a high concentration, and the polymerization reaction proceeds in that.

That is, rather than the inorganic anion of the oxidant,
Since the surfactant and the phosphate derivative anion having active hydrogen exist closer to the generated conductive polymer main chain, it is considered that these are mainly incorporated.

As described below, in the present invention, the case where the surfactant is a sulfonic acid or an alkylsulfate is shown, but the conductive polymer doped with these anions alone is formed by chemical polymerization. Of course it is possible.

In this case, however, a sulfonate having a transition metal as a cation or an alkyl sulfate ester salt is used. However, when the molecular size of these cations is large, the solubility in water decreases or becomes insoluble. Water cannot be used as a solvent.

Further, the phosphoric acid derivative having active hydrogen often has low water solubility, and when it is used alone, it is easily insolubilized by combining with a transition metal ion. It is difficult to carry out chemical polymerization using a system.

In the electropolymerization, a conductive polymer doped with a phosphoric acid derivative having active hydrogen in an aqueous medium system is obtained. However, since the carbon number is limited to a small range, electroconductivity is limited. The stability of conductivity was not high.

The conductive polymer obtained by the production method of the present invention in which the sulfonic acid type anion and the phosphoric acid derivative anion having active hydrogen are compositely doped has a higher environmental stability than that in which the sulfonic acid is solely doped. Showed sex.

The reason for this is not clear yet, but it is presumed that due to some action, due to some action, a polymer having a dense structure was formed, so that diffusion of oxygen into the interior and diffusion of the dopant from the interior were suppressed. Was given.

(Embodiment 1) First, a first embodiment of the present invention will be described.

First, in this embodiment, 100 g of an aqueous oxidant solution having a concentration of 0.2 M ferric sulfate n-hydrate (mol / liter) was prepared as an oxidant containing a transition metal ion.

Next, 0.75 M of a pyrrole monomer was added to this aqueous solution, and sodium alkylnaphthalenesulfonate (average molecular weight 338) as an anionic surfactant was added.
2M and 100 g of an aqueous monomer solution having a concentration of 0.2 N (normal) of n-propyl phosphate are added, and the temperature is set to 25 ° C.
Polymerization was carried out under atmospheric pressure with stirring for 1 hour.

Here, as the sodium alkylnaphthalene sulfonate, one having an average molecular weight of 338 (a mixture of alkyl groups having 6 to 9 carbon atoms) was used, but the carbon number is not particularly limited. Of course not.

Next, the obtained precipitate is filtered off, washed with water until the filtrate becomes neutral, further washed with ethanol, and then dried under reduced pressure at about 50 ° C. for several hours to form a conjugated double bond. A conductive composition containing polypyrrole, which is a conductive polymer, was obtained.

Then, after weighing the yield of this conductive composition, a part thereof was crushed in a mortar, and a disk-shaped pellet having a diameter of 13 mm was prepared at a pressure of about 30 MP, and the disk-shaped pellet was subjected to measurement of electric conductivity.

For measuring the electric conductivity, a resistivity measuring device Loresta SP manufactured by Mitsubishi Petrochemical Co., Ltd., a 4-terminal probe,
MCP-T400 was used.

The initial electrical conductivity of the obtained polypyrrole and the electrical conductivity after holding for 500 hours in air at 125 ° C. and 85 ° C./85% RH are shown in the following (Table 1).

[0056]

[Table 1]

As a result of elemental analysis of polypyrrole immediately after polymerization, it was revealed that phosphorus was observed in addition to sulfur and that n-propyl phosphate was also incorporated as a dopant.

The doping ratio of the sulfonic acid group and the phosphoric acid ester was calculated to be about 2: 1 from the result of elemental analysis.

Further, the obtained conductive polymer is 5 mm in diameter.
The disk-shaped pellets of 1 were produced under the same conditions as those described in the first embodiment. The pellets were pressed against a smooth aluminum foil having a purity of 99.99% and having a 50 V anodic oxide film, and a voltage was applied at a boosting rate of 1 V / sec using the conductive composition as an anode under the conditions of 25 ° C. and 85% relative humidity. However, no rise of current due to dielectric breakdown was observed up to 42V.

(Comparative Example 1) As Comparative Example 1, polypyrrole was prepared by the same procedure as in Embodiment 1 except that a monomer solution containing no n-propyl phosphate was used. It was measured.

The results are shown in (Table 1). This (Table 1)
As is clear from the comparison between Comparative Example 1 and Embodiment 1, the conductive composition according to Embodiment 1 has an excellent effect in that the heat resistance and humidity resistance of the electric conductivity are high. There was found.

As described above, according to the present embodiment, ferric sulfate n-hydrate is representatively used as the oxidizing agent, and the anionic surfactant, sodium triisopropylnaphthalene sulfonate and phosphate, n By allowing propyl phosphate to coexist in the polymerization system, a conductive composition having high electrical conductivity and environmental stability can be obtained.

In addition, a disc-shaped pellet having a diameter of 5 mm manufactured in the same manner as in the first embodiment is used, and the first embodiment is used.
When a dielectric breakdown test was performed on the formed aluminum foil in the same manner as above, a sharp rise in current was observed around 35 V.

Apparently, the conductive composition of the first embodiment was found to have a high dielectric film repairing ability, which is due to the action of the phosphoric acid ester contained as the dopant. It was demonstrated that the conductive composition of No. 1 has an excellent effect.

(Second Embodiment) Next, a second embodiment of the present invention will be described.

In this embodiment, the pyrrole monomer used in the first embodiment is replaced by (A) n-methylpyrrole,
(B) A conductive composition containing polypyrrole was produced by the same operation as in Embodiment 1 except that 3,4-ethylenedioxythiophene was used, and the same post-treatment yield and electric conductivity were measured.

(Comparative Example 2) As Comparative Example 2, polypyrrole was prepared in the same manner as in Embodiment 2 except that a monomer solution containing no n-propyl phosphate was used. Was measured.

The results are shown in (Table 1). This (Table 1)
As is clear from the comparison between Comparative Example 2 and Embodiment 2, the conductive composition according to Embodiment 2 has an excellent effect in that it has high electric conductivity in heat resistance and humidity resistance. There was found.

As described above, according to the present embodiment, ferric sulfate n-hydrate is representatively used as the oxidant, and the anionic surfactant, the phosphoric acid ester and the n-propyl phosphoric acid ester are polymerized. By polymerizing the polymerizable monomer in a system coexisting with the system, a conductive composition having high environmental stability can be obtained.

(Third Embodiment) Next, a third embodiment of the present invention will be described.

In this embodiment, the sodium alkylnaphthalene sulfonate used in the first embodiment is replaced with (A) 2-ethylhexyl sulfate sodium salt (B) sodium dodecylbenzenesulfonate, which has the same concentration.
(C) Sodium alkyl sulfonate (average molecular weight 32
However, it is needless to say that the kind of the above-mentioned alkyl group is not limited to the first embodiment except that the monomer solutions added with 8) are used.

The results are shown in the above (Table 1). (Comparative Example 3) As Comparative Example 3, the third embodiment except that a monomer solution containing no n-propyl phosphate was used.
Polypyrrole was produced by the same operation as above, and the electrical conductivity was measured after the same treatment.

The results are shown in (Table 1). This (Table 1)
As is clear from the comparison between Comparative Example 3 and Embodiment 3, the conductive composition according to Embodiment 3 has an excellent effect in that it has high electric conductivity in heat resistance and humidity resistance. It has been found.

As described above, according to the present embodiment, ferric sulfate n-hydrate is representatively used as the oxidizing agent, and the anionic surfactant and the phosphoric acid ester or n-propyl phosphoric acid ester are polymerized. By coexisting in the system, a conductive composition having high environmental stability can be obtained.

(Fourth Embodiment) Next, a fourth embodiment of the present invention will be described.

In this example, (A) ferric chloride was used as an oxidizing agent in place of the ferric sulfate used in the first embodiment.
Conductivity including polypyrrole by the same operation as in Embodiment 1 except that (B) ferric nitrate, (C) ferric perchlorate, and (D) potassium hexacyanoferrate are used at the same concentration. The composition was prepared, and after the same treatment, the yield and the electric conductivity were measured.

However, it goes without saying that the acid group of the transition metal salt used for the polymerization is not limited to the above acid groups.

The results are shown in (Table 1). (Comparative Example 4) As Comparative Example 4, polypyrrole was produced by the same operation as in Embodiment 4 except that a monomer solution containing no n-propyl phosphate was used, and the electrical conductivity was measured after the same treatment. .

The results are shown in (Table 1). This (Table 1)
As is clear from the comparison between Comparative Example 4 and Embodiment 4, the conductive composition according to Embodiment 4 had an excellent effect in that the heat conductivity and humidity resistance of the electric conductivity were high. There was found.

(Fifth Embodiment) Next, a fifth embodiment of the present invention will be described.

In this example, (A) cupric sulfate (A) was used as an oxidizing agent in place of the ferric sulfate used in the first embodiment.
A conductive composition containing polypyrrole was produced by the same operation as in Embodiment 1 except that (B) sodium phosphomolybdate and (C) ammonium dichromate were used at the same concentrations, respectively, and after the same treatment, yield And the electrical conductivity was measured.

However, it goes without saying that the transition metal ion used for the polymerization is not limited to the above.

The results are shown in (Table 1). (Comparative Example 5) As Comparative Example 5, polypyrrole was produced in the same manner as in Embodiment 5 except that a monomer solution containing no n-propyl phosphate was used, and the electrical conductivity was measured after the same treatment. .

The results are shown in (Table 1). This (Table 1)
As is clear from the comparison between Comparative Example 5 and Embodiment 5, the conductive composition according to Embodiment 4 had an excellent effect in that the heat resistance and humidity resistance of the electric conductivity were high. There was found.

(Sixth Embodiment) Next, a sixth embodiment of the present invention will be described.

In this example, n− used in the first embodiment is used.
Instead of propyl phosphate, (A) isopropyl phosphate, (B) n-butyl phosphate,
A conductive composition containing polypyrrole was produced by the same operation as in Embodiment 1 except that (C) n-hexyl phosphate and (D) n-dodecyl phosphate were used at the same concentration, respectively, and after the same treatment. The yield and electrical conductivity were measured.

The results are shown in (Table 1). Further, when a dielectric breakdown test was performed on the formed aluminum foil in the same manner as in Embodiment 1, samples (A), (B), (C) and (D) were 43 V, 41 V, 42 V and 42 V, respectively.
From this, a rapid rise of current was observed.

As is clear from the comparison between Comparative Example 1 and Embodiment 6 in (Table 1), the conductive composition according to Embodiment 6 is high in heat resistance and humidity resistance of electric conductivity. It turned out that an excellent effect was obtained.

As is clear from the comparison with Comparative Example 1, the conductive composition according to the sixth embodiment is doped with the phosphoric acid derivative having active hydrogen, and therefore has a high function of repairing the conversion coating of the valve metal. It was also found that an excellent effect can be obtained in this respect.

However, it is needless to say that the kind of the alkyl group of the alkyl phosphate ester is not limited to the above.

(Seventh Embodiment) Next, a seventh embodiment of the present invention will be described.

In this example, p-nitrophenol was added to 0.05 M instead of the oxidizing agent aqueous solution of the first embodiment.
A conductive composition containing polypyrrole was produced by the same operation as in Embodiment 1 except that the added oxidizing agent aqueous solution was used, and after the same treatment, the yield and electric conductivity were measured.

The results obtained are shown in Table 1. Further, when an experiment for investigating the anodic oxide film repairing function was conducted in the same manner as in the first embodiment, a sharp increase in current was found at 43V.

(Comparative Example 6) As Comparative Example 6, polypyrrole was prepared in the same manner as in Embodiment 7 except that a monomer solution containing no n-propyl phosphate was used, and after the same treatment, the electrical conductivity was changed. It was measured.

The results are shown in (Table 1). This (Table 1)
As is clear from the comparison between Comparative Example 6 and Embodiment 7, the conductive composition according to Embodiment 7 has an excellent effect in that the heat resistance and humidity resistance of the electric conductivity are high. There was found.

As described above, according to the present embodiment, ferric sulfate n-hydrate is representatively used as the oxidizing agent, and the anionic surfactant, sodium triisopropylnaphthalenesulfonate and phosphate, n -By allowing propyl phosphate and the additive p-nitrophenol to coexist in the polymerization system, a conductive composition having high electrical conductivity and environmental stability can be obtained.

An experiment for investigating the anodic oxide film repairing function was conducted in the same manner as in the first embodiment.
A sharp rise in current was seen around V.

Apparently, the conductive composition of the seventh embodiment was found to have a high ability of repairing the dielectric film, which is based on the action of the phosphoric acid ester contained as the dopant. It was demonstrated that the conductive composition of No. 1 has excellent effects.

Further, as is clear from the comparison between Embodiment 1 and Embodiment 7 in (Table 1), the initial electrical conductivity and its environmental stability can be further improved by the addition of p-nitrophenol. I understand.

It is considered that this is because the electron-withdrawing nitro group interacts with the pyrrole ring in some way to produce polypyrrole having a skeleton structure with high structural regularity.

The effect of adding p-nitrophenol was observed in all cases, regardless of the type of polymerizable monomer, the type of transition metal used as an oxidizing agent, the type of acid, and the type of alkyl phosphate ester. .

(Embodiment 8) Next, an eighth embodiment of the invention will be described.

In this example, (A) m-nitrophenol, (B) p-cyanophenol, (C) m-hydroxybenzoic acid, (D) was used in place of the p-nitrophenol used in the seventh embodiment. A conductive composition containing polypyrrole was produced by the same operation as in Embodiment 8 except that p-nitrobenzoic acid and (E) p-nitrobenzyl alcohol were added at the same concentrations, and after the same treatment, yield and electric The conductivity was measured.

The obtained results are shown in (Table 1). Further, when an experiment for investigating the anodic oxide film repairing function was conducted in the same manner as in the first embodiment, (A), (B),
Samples according to (C), (D) and (E) are 4
A rapid increase in current was observed at 3V, 43V, 42V, 44V, 42V.

(Comparative Example 7) As Comparative Example 7, polypyrrole was prepared in the same manner as in Embodiment 8 except that a monomer solution containing no n-propyl phosphate was used. Was measured.

The results are shown in (Table 1). This (Table 1)
As is clear from the comparison between Comparative Example 7 and Embodiment 8, the conductive composition according to Embodiment 8 has an excellent effect in that the heat resistance and humidity resistance of the electric conductivity are high. There was found.

As described above, according to the present embodiment, ferric sulfate n-hydrate is representatively used as the oxidizing agent, and the anionic surfactant, sodium triisopropylnaphthalene sulfonate and phosphate, n -By allowing propyl phosphate and the additive p-nitrophenol to coexist in the polymerization system, a conductive composition having high electrical conductivity and environmental stability can be obtained.

Further, an experiment for investigating the anodic oxide film repairing function was conducted in the same manner as in the first embodiment, and m-nitrophenol, p-cyanophenol, m
-Hydroxybenzoic acid, p-nitrobenzoic acid, p-nitrobenzyl alcohol added 34V,
A sharp rise of the current was observed near 35V, 36V, 35V, and 35V.

As is clear from the comparison between Embodiment 8 and Comparative Example 7, the conductive composition of Embodiment 8 was found to have a high dielectric film repairing ability, but this was included as a dopant. It is based on the action of the phosphoric acid ester, and it was demonstrated that the conductive composition of Embodiment 8 has an excellent effect.

In the above embodiments, the conjugated double bond conductive polymer is polypyrrole or poly (N).
-Methylpyrrole) and poly (3,4-ethylenedioxythiophene) have been described, but of course the conjugated double bond conductive polymer is not limited thereto.

Further, these may be included in any combination. Further, in the above embodiments, the surfactant was described as a sulfonate, an esterified sulfate and an esterified phosphate, but an anionic surfactant generates an organic acid anion. Of course, if it is a thing, it is not limited to these things.

Further, in the above embodiments, the case where iron ions and copper ions are used as the transition metal ions in the oxidizing agent has been described as a representative, but other transition metal ions,
For example, an inorganic acid salt containing chromium ion, cerium ion, or molybdenum can be used because the conjugated double bond conductive polymer can be obtained from the polymerizable monomer.

In the above embodiments, only the case of a phosphoric acid ester containing an alkyl group as a phosphoric acid derivative having active hydrogen has been described, but a phosphoric acid derivative containing a substituent other than alkyl should be used as a matter of course. You can

Further, in the above embodiments, only the case where a phenol or benzene derivative containing only one nitro group or electron withdrawing substituent is used as an additive has been described. In addition, a derivative containing two or more electron-withdrawing groups, or a derivative having an electron-withdrawing substituent other than those mentioned in the embodiment can also be used.

[0115]

As described above, by chemically polymerizing in a system in which a phosphoric acid derivative having active hydrogen and an anionic surfactant coexist, it has high heat resistance and an excellent film metal repair function. A conductive composition can be produced.

By adding a derivative selected from a phenol derivative or a nitrobenzene derivative to the above system, a conductive composition having further excellent heat resistance can be produced.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-8-231863 (JP, A) JP-A-11-80420 (JP, A) JP-A-11-166049 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08G 81/00-85/00 C08G 61/00-61/12 C08G 73/00-73/26 CA (STN) REGISTRY (STN)

Claims (16)

(57) [Claims] 1. A step of preparing a monomer capable of forming a conjugated double bond conductive polymer, a step of preparing an anionic surfactant, and an alkyl phosphate ester having active hydrogen.
Preparing a Le, chemical with preparing a oxidizing agent, the oxidizing agent under the monomer coexist with alkyl phosphate ester having the anionic surface active agent and an active hydrogen containing a transition metal inorganic acid salt A method for producing a conductive composition, which comprises a step of polymerizing. 2. A conjugated double bond conductive polymer can be produced.
The method for producing a conductive composition according to claim 1, wherein the monomer is pyrrole, thiophene or a derivative thereof. Wherein the anionic surfactant is also sulfonic acid
The method for producing a conductive composition according to claim 1 or 2, wherein the method comprises esterified sulfuric acid. 4. The method for producing a conductive composition according to claim 1, wherein the inorganic acid contains sulfuric acid, hydrochloric acid, nitric acid, perchloric acid or hexacyanoferric acid. 5. The method for producing a conductive composition according to claim 1, wherein the transition metal inorganic salt contains a copper salt, an iron salt, a molybdenum salt or a chromium salt. 6. The method for producing a conductive conductive composition according to claim 1, wherein the phosphoric acid derivative having active hydrogen is a phosphoric acid ester containing an alkyl group having 3 to 12 carbon atoms. 7. A step of preparing a monomer capable of forming a conjugated double bond conductive polymer, a step of preparing an anionic surfactant, and an alkyl phosphate ester having active hydrogen.
Alkyl of preparing a Le, a step of preparing an oxidizing agent containing a transition metal inorganic acid salt, a step of preparing an additive selected from phenol derivatives or nitrobenzene derivative, the anionic surfactant and the active hydrogen phosphoric acid
A method for producing a conductive composition, comprising a step of chemically polymerizing an ester , an additive selected from the phenol derivative or the nitrobenzene derivative, and the oxidizing agent in the presence of the monomer. 8. A conjugated double bond conductive polymer can be produced.
The method for producing a conductive composition according to claim 7, wherein the monomer is pyrrole, thiophene, or a derivative thereof. 9. anionic surfactant, and a sulfonic acid
The method according to claim 7 or 8 conductive composition according comprising sulfuric acid which is esterified. 10. The method for producing a conductive composition according to claim 7, wherein the inorganic acid contains sulfuric acid, hydrochloric acid, nitric acid, perchloric acid or hexacyanoferric acid. 11. The method for producing a conductive composition according to claim 7, wherein the transition metal inorganic salt contains a copper salt, an iron salt, a molybdenum salt or a chromium salt. 12. An alkylphosphoric acid ester having active hydrogen
Method for producing ethers is Shirubeshirube conductive composition according to any of 5 to claim 1 is intended composed of 12 3 carbon atoms 13. Phenol derivatives, nitrophenol, cyanophenol, the manufacturing method of the hydroxybenzoic acid or hydroperoxide <br/> alkoxy phenol in which claims 7 to either serial <br/> mounting of the electrically conductive composition of 12 . 14. nitrobenzene derivative nitrobenzene process according to claim 7 to a conductive composition of any one of 12 is nitro benzoic acid or nitrobenzyl alcohol. 15. A conductive composition produced by the production method according to claim 1. 16. A conductive composition produced by the production method according to claim 7.