JPH0655840B2 - Electrically conductive organic polymer materials - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an electrically conductive organic polymer material, and more specifically, an electrically conductive organic material that is a heat-treated product of a composite molded article composed of a phenol resin and phenol fiber. It relates to a polymeric material.

(Prior Art) Polymer materials are excellent in moldability, light weight, and mass productivity. Therefore, by utilizing these characteristics of the polymer material, an organic polymer material having electrical semiconductivity is desired in many industrial fields including the electronics industry. The initial organic semiconductor was difficult to be formed into a film or a plate, and did not have the property as an n-type or p-type impurity semiconductor, so that its application was limited. In recent years, organic semiconductors having relatively excellent moldability have been obtained, and it is possible to obtain an n-type or p-type organic semiconductor by doping these semiconductors with an electron-donating dopant or an electron-accepting dopant. Became. Polyacetylene is a typical example of such an organic semiconductor. This organic semiconductor has an electric conductivity of about 10 ^-5 (Ω · cm) ^-1
I _2, AsF ₅ and the like electron-accepting dopant or Li, and can be improved by a large margin the electrical conductivity by doping an electron donating dopant such as Na, 10 ² to 10 ³
A conductivity of (Ω · cm) ^-1 is obtained. However, polyacetylene has a drawback that it is easily oxidized by oxygen. For this reason, it is difficult to handle in air, and it is not practical as an industrial material.

Further, Japanese Patent Application Laid-Open No. 58-1366 filed by the same applicant as the present application
No. 49 discloses a heat-treated product of (A) an aromatic condensation polymer composed of carbon, hydrogen and oxygen, which has a polyacene skeleton structure having an atomic ratio of hydrogen atoms / carbon atoms of 0.60 to 0.15. An electrically conductive organic polymer comprising an insoluble and infusible substrate contained therein, and (B) an electron donating doping agent or an electron accepting doping agent, and (C) an electrical conductivity higher than that of the undoped substrate. A system material is disclosed. The insoluble and infusible substrate is excellent in heat resistance and oxidation resistance, can be doped with an electron donating doping agent or an electron accepting doping agent as described above, and exhibits p-type or n-type properties. Give semiconductors. However, the above publication does not describe the specific surface area by the BET method.

In addition, Japanese Patent Application No. Sho 59, which is an earlier application filed by the same applicant as this application
No. -8152 has not been published yet, but in the prior application, it is a heat-treated product of (A) an aromatic condensation polymer composed of carbon, hydrogen and oxygen, and the atomic ratio of hydrogen atom / carbon atom is 0.60. To 0.15 and a specific surface area value by the BET method of 600 m ² / g or more containing an insoluble infusible substrate, and (B) an electron-donating or electron-accepting doping agent And (C) an electrically conductive organic polymer material characterized by having an electric conductivity higher than that of the undoped substrate.

Since this organic polymer material has a specific surface area ratio of 600 m ² / g or more, it can be smoothly doped with a dopant having a relatively large ionic radius, such as ClO ₄ ⁻ or BF ₄ ⁻ . However, also in this prior application, the electrically conductive polymer material composed of an insoluble and infusible substrate having a polyacene skeleton structure has a problem in mechanical strength, and in that respect, its practical application is still insufficient.

(Problems to be Solved by the Invention) An object of the present invention is to provide an electrically conductive organic polymer material excellent in mechanical strength.

Another object of the present invention is to provide an electrically conductive organic polymer material having excellent heat resistance and oxidation resistance.

Still another object of the present invention is to provide an electrically conductive organic polymer material doped with an electron donating dopant and / or an electron accepting dopant.

Still another object of the present invention is to provide an electrically conductive organic polymer material capable of smoothly doping an electron donating dopant and / or an electron accepting dopant having a relatively large ionic radius.

Still another object of the present invention is to provide an electrically conductive organic polymer material which is a film-shaped, plate-shaped or the like formed body.

Further objects and advantages of the present invention will be apparent from the following description.

(Means for Solving Problems) The above-mentioned object is a heat-treated product of a composite molded article composed of a phenol resin, a phenol fiber or a fiber structure, and zinc chloride, wherein the atomic ratio of hydrogen atoms / carbon atoms is 0. 0.05
0.6 and specific surface area value by BET method is 600 m ²
/ G or more is achieved by the electrically conductive organic polymer material composed of an insoluble and infusible substrate having a polyacene skeleton structure.

The composite molded article in the present invention is a moldability having an arbitrary shape such as a film shape or a plate shape made of a phenol resin, a phenol fiber or a fiber structure, and zinc chloride. Phenol resin is preferably an uncured condensate of an aromatic hydrocarbon compound having a phenolic hydroxyl group and an aldehyde, and specific examples of such an aromatic compound include phenols such as phenol, cresol, and xylenol. Other than these, for example, methylenebisphenols, hydroxybiphenyls and hydroxynaphthalenes can be applied. Of these compounds, phenols, particularly phenol, are suitable for practical use. As the aldehyde used in the present invention, acetaldehyde and other aldehydes can be used, but formaldehyde is particularly preferable. Phenol fibers include, for example, fibers obtained by melt-spinning a novolac type phenolic resin with a curing agent such as formaldehyde under an acid or basic catalyst, and a phenol fiber structure and a structure composed of such fibers, for example, a knitted fabric. , Nonwoven fabrics, and the like.

A composite molded body formed from these materials can be obtained by, for example, mixing and molding an uncured phenol resin, a phenol fiber or a fiber structure, and zinc chloride under appropriate conditions and curing. As the mixing method, the above 3
Any method such as dry mixing and wet mixing may be used as long as the components can be uniformly mixed, but for sufficiently uniform mixing, an uncured phenol resin and an uncured phenol resin can be prepared by adding an appropriate solvent such as water, methanol, or acetone. It is desirable to add the phenolic fiber or fiber structure and mix after making the zinc chloride into solution. When the phenolic fiber or the fiber structure is in the form of cloth or felt, it may be impregnated with the solution of the uncured phenolic resin and zinc chloride to form a prepreg. As a molding method, generally, the same method as in the case of producing a resin molded product can be used.
A film of the component-mixed slurry may be formed into an appropriate thickness by an applicator, and when a plate-like body is obtained, a mold may be formed and pressure-molded, as is well known. If the prepreg described above is put between flat plates of metal or the like and pressure-molded, a plate having an appropriate thickness can be obtained. As a curing method, when a resol is used as an uncured phenol resin, it is convenient to heat cure at a temperature of 50 to 200 ° C. during or after molding. Particularly, in the method of press molding using a mold or the like, it is possible to heat and cure at the same time as molding. When novolac is used as the uncured phenolic resin, a suitable curing agent, for example, a curing agent which is itself a formaldehyde generator such as hexamethylenetetramine and at the same time an organic base generator is mixed in advance and molded. It may be cured by heating.

The thus obtained composite molded article is composed of phenolic resin, phenolic fiber or fiber structure and zinc chloride, and is a molded article having an arbitrary shape such as a film shape or a plate shape and excellent in mechanical strength. It is possible to cut it into an appropriate size and process it into a shape such as a circle or a rectangle.
This composite molded body is made into an insoluble and infusible substrate containing a polyacene-based skeleton structure by the method described later.
The mechanical strength of the substrate is the phenol fiber in the composite molded body,
It is demonstrated by the fiber structure. That is, the use of the phenol fiber or the fiber structure significantly improves the strength of the electrically conductive organic polymer material composed of the insoluble and infusible substrate. The effect is recognized even if the amount of phenolic fiber or fiber structure in the composite molded product is extremely small, but preferably phenolic fiber (fiber structure)
The weight ratio of / phenol resin is 0.05 or more. 0.05
Above all, the strength of the insoluble infusible substrate containing the polyacene-based skeleton structure obtained is particularly improved, which is preferable. Further, zinc chloride has the effect of increasing the specific surface area value (BET method) of the substrate when the composite molded body is made into an insoluble and infusible substrate by the method described later, but even if the amount is small, the effect can be obtained. However, the weight ratio of zinc chloride / [phenolic resin + phenolic fiber (fiber structure)] is preferably 0.5 to 7. When it is 0.5 or more, zinc chloride exerts a sufficient effect, and the specific surface area of the insoluble and infusible substrate can be greatly increased,
It is suitable.

On the other hand, when the above-mentioned amount of zinc chloride exceeds 7, the absolute amount of the phenolic resin becomes small, making it difficult to form a film or a plate, and the curing reaction of the uncured phenolic resin becomes difficult to occur. Occurs.

Next, this composite molded body is heat treated in a non-oxidizing atmosphere,
It is possible to obtain an insoluble and infusible substrate having a polyacene-based skeleton structure with an atomic ratio of hydrogen atoms / carbon atoms of 0.05 to 0.6, preferably 0.15 to 0.60. Heat treatment temperature is usually 40
It is 0 to 800 ° C., and the preferable temperature rising condition of the heat treatment is somewhat different depending on the composition ratio of the composite molded body, the curing conditions or the shape thereof, but generally a relatively high temperature rising rate from room temperature to about 300 ° C. It is possible, for example, to use a rate of 100 ° C./hour. Thirty
When the temperature reaches 0 ° C or higher, thermal decomposition of the phenol resin and the phenol fiber (fiber structure) starts, and steam, hydrogen,
Since gas such as methane and carbon monoxide begins to be generated, it is advantageous to raise the temperature at a sufficiently slow rate. Next, the substrate having a polyacene skeleton structure thus obtained is washed with warm water at 50 to 100 ° C. to remove zinc chloride remaining in the substrate and dried. In this way, an electrically conductive organic polymer material comprising an insoluble and infusible substrate containing a polyacene skeleton structure is obtained. When the atomic ratio of hydrogen atom / carbon atom of this substrate exceeds 0.6, Since the polyacene-based skeleton structure has not yet been developed, it is considered that the conjugated system of electrons is localized, and even if the dopant is doped, the electrical conductivity does not increase and the semiconductor does not become an n-type or p-type semiconductor. When the H / C atomic ratio is less than 0.05, the polyacene skeleton structure is fully developed, the conjugated system of electrons is sufficiently delocalized, and the dopant is doped but the substrate itself before doping is Since the electric conductivity of the is very high, the contribution of the doping to the electric conductivity is small, and the electric conductivity is not so much increased as compared with the undoped substrate.

Further, the specific surface area value of the insoluble and infusible substrate containing the polyacene skeleton structure by the BET method is extremely large because it is manufactured using zinc chloride, but it is 600 m ² / g.
It is especially preferable that it is above.

The insoluble and infusible substrate having a polyacene skeleton structure of the present invention has a very large specific surface area value of 600 m ² / g or more as measured by the BET method, so that the doping rate is high and it is possible to dope a thick substrate in a short time. In addition, it is possible to smoothly dope the substrate with a dopant having a large ionic radius, such as ClO ₄ ⁻ and BF ₄ ⁻ . For example ClO ₄ ^- ion in the substrate Li / LiClO ₄ 1 mol /
When electrolytically doping with a propylene carbonate / substrate structure, it is difficult to dope with a potential difference of 4 V between electrodes when the specific surface area is less than 600 m ² / g, but with a substrate of 600 m ² / g or more according to the present invention, this potential difference. Is enough Cl
O ₄ ⁻ ions can be introduced into the substrate.

In addition, the electrically conductive organic polymer material consisting of insoluble and infusible substrate can be processed into a molded body of any shape such as film, plate or cylinder, but it is manufactured using phenol fiber or fiber structure. Therefore, it has excellent mechanical strength, and has practically sufficient strength. In particular, when the knitted fabric or the felt-like fiber aggregate is used as the phenolic fiber or the fiber structure, the thickness, size, density, etc. of the molded body composed of the substrate can be arbitrarily set, and its strength is also particularly excellent. You can get what you want.

By the way, the electric conductivity of the insoluble and infusible substrate having a polyacene skeleton structure of H / C atomic ratio of 0.60 to 0.05 of the present invention is largely different depending on the H / C atomic ratio. When H / C = 0.6, it is about 10 ^-11 Ω ^-1 cm ^-1 or less, and when H / C = 0.05, it is a semiconductor of about 10 ⁰ Ω ^-1 cm ^-1 . When the substrate is doped with an electron-donating dopant or an electron-accepting dopant as described below, the electric conductivity is greatly increased, and the substrate becomes an n-type or p-type semiconductor.

Further, since the insoluble and infusible substrate having the polyacene skeleton structure shows a very large specific surface area value of 600 m ² / g or more by the BET method, it is considered that gas such as oxygen penetrates and is easily deteriorated. However, in reality, even if left in the air for a long time, the physical properties and the like do not change. For example, even if left in the air for 1000 hours, the electrical conductivity does not change, and the oxidation stability is excellent. .

Either an electron donating dopant or an electron accepting dopant which can be doped into the insoluble and infusible substrate of the present invention can be any of the dopants generally known.

As the electron-donating dopant, a substance that easily causes electrons is used. For example, a Group 1A metal of the periodic table such as lithium, sodium, potassium, rubidium or cesium is preferably used. Further, tetraalkylammonium cations such as (C ₂ H ₅ ) ₄ N ⁺ (C ₄ H ₉ ) ₄ N ⁺ are also preferably used.

A substance that easily accepts electrons is used as the electron-accepting dopant. For example, halogens such as fluorine, chlorine, bromine and iodine, halogen compounds such as AsF ₅ , PF ₅ , BF ₃ , BCl ₃ and BBr ₃ , oxides of non-metal elements such as SO ₃ or N ₂ O ₅ or H ₂ SO 5. Anions derived from an inorganic acid such as ₄ , HNO ₃ or HClO ₄ are preferably used.

As a doping method of such a dopant, essentially the same doping method as that conventionally used for polyacetylene or polyphenylene can be used.

When the dopant is an alkali metal, it can be doped by bringing molten alkali metal or vapor of the alkali metal into contact with the insoluble and infusible substrate, and is insoluble and insoluble with the alkali metal naphthalene complex produced in tetrahydrofuran, for example. It is also possible to dope by contacting with a fusible substrate.

When the dopant is halogen, a halogen compound or an oxide of a non-metal element, the doping can be easily performed by bringing these gases into contact with the insoluble and infusible substrate.

When the dopant is an anion derived from an inorganic acid, the insoluble infusible substrate is directly coated or impregnated with the inorganic acid, or electrolysis is performed using the insoluble infusible substrate as an anode in an electrolytic solution containing these inorganic acids. Then, the doping can be performed.

The dopant is generally used so as to be present in the organic polymer material of the present invention obtained in a ratio of 10 ⁻⁵ mol or more based on the repeating unit of the aromatic condensation polymer.

The organic polymer material of the present invention obtained by doping the insoluble infusible substrate having a polyacene skeleton structure having an H / C atomic ratio of 0.60 to 0.05 thus obtained with the dopant is insoluble infusible before doping. Electrical conductivity higher than that of the substrate, preferably 1 than the insoluble infusible substrate before doping.
0 times or more or more 10 ³ to 10 ^{8 by a} suitable method
It shows high electrical conductivity, which is double or more.

The electrically conductive organic polymer material of the present invention doped with an electron donating dopant has the electrical conductivity of an n-type (electron excess type) semiconductor or conductor. The electrically conductive organic polymer material of the present invention doped with an electron-accepting dopant has the electrical conductivity of a p-type (hole excess type) semiconductor or conductor.

On the other hand, according to the present invention, an electron donating dopant and an electron accepting dopant can be used together as a dopant. When these dopants are almost uniformly mixed in the electrically conductive organic polymer material of the present invention, either one of them is p-type or n-type depending on which one is most abundant. For example, when there are many electron-donating dopants, it becomes n-type, and when there are many electron-accepting dopants, it becomes p-type. Such an electrically conductive organic polymer material containing a mixture of dopants is produced by contacting a mixture of dopants with an insoluble infusible substrate, or by contacting one dopant and then another dopant. it can.

The present invention also includes an electrically conductive organic polymer material having a so-called pn junction surface. Such a material can be doped with an electron-donating dopant from one of the insoluble and infusible substrate compacts and doped with an electron accepting dopant from the other, or with one of the dopants on the entire surface of the insoluble and infusible substrate compact. It can be made by doping and then doping the other dopant only in part of its face.

(Effect of the invention) Since the electrically conductive organic polymer material of the present invention is excellent in mechanical strength, it is possible to form a thin film into a thick plate-shaped body or a molded body of any shape such as a cylindrical shape. , These are used in various fields, for example, as electrodes for diode solar cells or batteries.

Hereinafter, the present invention will be described in more detail with reference to examples.

Example 1 Resol type phenol resin (about 65% concentration aqueous solution) /
A plain weave cloth of phenolic fiber (manufactured by Nippon Kynol Co., Ltd.) was impregnated with a solution in which water / zinc chloride was mixed at a weight ratio of 10/3/12.
Using a pressure molding machine for laminated plates heated to 0 ° C., about 10
The mixture was molded and cured under pressure for a minute to obtain a plate-shaped composite molded body having a thickness of about 500μ. In this composite molded body, the weight ratio of phenolic fiber / phenolic resin was 0.15. The weight ratio of zinc chloride / (phenolic resin + phenolic fiber) is
It was 1.6. Further, after forming a film of the above-mentioned mixed solution of resole, water and zinc chloride with an applicator, a curing reaction was carried out at a temperature of 100 ° C. for about 20 minutes to obtain a plate-shaped molded product having a thickness of 500 μm. In this plate-shaped molded body, the weight ratio of phenol fiber / phenol resin is 0, and zinc chloride /
The weight ratio of (phenolic resin + phenolic fiber) was 1.8. Next, the composite molded body and the molded body are placed in a silicon knit electric furnace and heated to about 550 ° C. in a nitrogen atmosphere for about 40 minutes.
Heat treatment was performed at a temperature rising rate of ° C / hour. Next, these heat-treated products were washed with warm water at 100 ° C. for about 5 hours to remove residual zinc chloride. After washing, it was dried under reduced pressure at a temperature of 60 ° C. for 3 hours to obtain a plate-like body of an insoluble and infusible substrate. Among these insoluble and infusible substrate plates, the plate substrate obtained from the above-mentioned composite molded article of the present invention had excellent mechanical strength and was easy to handle, but using phenol fiber The plate-shaped substrate obtained from the molded product made without
Careful handling was required. Table 1 shows the measured values of bending strength.

Next, when the insoluble and infusible substrate of the present invention obtained from the composite molded body was subjected to a fluorescent X-ray analysis, Zn was 0.01% by weight (relative to the substrate) or less, and Cl was 0.5% by weight or less. It was found that zinc chloride hardly remained in the substrate.
When X-ray diffraction of the substrate was conducted, a main peak was present at 20 to 22 ° at 2θ and a small peak was observed in the range of 41 to 46 °, confirming that the substrate had a polyacene skeleton structure. Was done.

Next, the insoluble infusible substrate obtained from the composite molded article of the present invention and the insoluble infusible substrate prepared without using the phenol fiber were subjected to electrical conductivity elemental analysis and specific surface area value by BET method. The results are summarized in Table 1.

Next, LiAsF ₆ is dissolved in sufficiently dehydrated propylene carbonate to obtain a solution of about 1.0 mol / liter, lithium metal is used as a negative electrode, insoluble and infusible substrate plate is used as a positive electrode, and the above solution is used as an electrolytic solution. Voltage of 4V is applied to AsF ₆
^- doped ions into insoluble and infusible base.

The doping amount is represented by the number of AsF ₆ ⁻ ions per carbon atom in the substrate, but in the present invention, the number of AsF ₆ ⁻ ions is obtained from the current value flowing in the circuit at the time of doping.

Thus, an electrically conductive organic polymer material composed of an insoluble and infusible substrate doped with AsF ₆ ⁻ ions was obtained. After doping, the material was taken out, washed with acetone, dried under reduced pressure at a temperature of 60 ° C. for 60 minutes, and then the electrical conductivity was measured. The results are shown in Table 1.

Example 2 Resol type phenolic resin (about 65% concentration aqueous solution) /
To a solution prepared by mixing water / zinc chloride in a weight ratio of 10/1/5, add a cut fiber (cut length of about 2 mm) of phenolic fiber (fiber diameter of about 15 μ) and mix thoroughly,
The slurry was molded and cured under pressure using a pressure molding machine heated to about 100 ° C. for about 10 minutes to obtain a film-shaped composite molded body having a thickness of about 100 μm. The weight ratio of phenolic fiber / phenolic resin in this film-form composite molded article was 0.08, and the weight ratio of zinc chloride / (phenolic resin + phenolic fiber) was 0.7. Next, this film-shaped composite molded body was heat-treated to a predetermined temperature in a silicon unit electric furnace, and then washed with warm water in the same manner as in Example 1,
After drying, film-shaped insoluble and infusible substrates having different hydrogen / carbon atomic ratios were obtained. Elemental analysis, BET
The specific surface area value and the bending strength were measured by the method. The results are summarized in Table 2.

Next, doping was performed by the same method as in Example 1. However, in this example, LiBF ₄ was used instead of LiAsF ₆ . The results are summarized in Table 2.

Example 3 Resol type phenol resin (about 65% concentration aqueous solution) /
Water / zinc chloride were mixed at a predetermined weight ratio, and the solution was impregnated into a felt of phenolic fiber (manufactured by Nippon Kynol Co., Ltd.). Then, the solution-impregnated felt was molded and cured under a predetermined pressure for about 15 minutes by a pressure molding machine heated to 100 ° C. to prepare a plate-shaped composite molded body.

The weight ratio of phenol fiber felt / phenol resin was 0.2 to 1.0, and the weight ratio of zinc chloride / (phenol fiber felt + phenol resin) was 1.5 to 4 in these composite molded bodies. Next, heat treatment, washing and drying were performed under the same conditions as in Example 1 to obtain a plate-shaped insoluble and infusible substrate. For these samples, the elemental analysis and the specific surface area and bending strength were measured by the electrical conductivity BET method. The results are shown in Table 3.

Next, the plate-like body is put into a vacuum line and the degree of vacuum is set to 10 ^-2 to
After adjusting to rr or less, iodine gas was introduced into the line at room temperature to perform doping for about 10 minutes. The electrical conductivity after doping is shown in Table 3. The iodine-doped plate was taken out of the line and subjected to EPMA (electron probe X-ray microanalysis) to examine the distribution state of iodine in the cross section of the sample. Was evenly distributed up to.

Example 4 Prepared using tetrahydrofuran, naphthalene and metallic sodium obtained by removing the substrate of the present invention of Example 1 having an H / C atomic ratio of 0.22 and a specific surface area value of 1250 m ² / g by the BET method. Sodium naphthalate solution in tetrahydrofuran was immersed in a dry box (N ₂ gas flow) to attempt sodium doping. After soaking for about 30 minutes, it was washed with dehydrated tetrahydrofuran and dried under reduced pressure at room temperature. When the electric conductivity of the sample was measured, it was found that the electric conductivity increased to a level of about 1 × 10 ⁻⁴ Ω ⁻¹ cm ^−1.
It was 0 ⁰ Ω ^-1 cm ^-1 . Also, regarding the sample, EPMA
As a result of analysis, sodium was doped into the inside of the sample.

Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location // B32B 5/00 A 7016-4F

Claims (12)

[Claims] 1. A heat-treated product of a composite molded article composed of a phenol resin, a phenol fiber or a fiber structure, and zinc chloride, wherein the atomic ratio of hydrogen atoms / carbon atoms is 0.05 to 0.5.
6 and the specific surface area value by the BET method is 600 m ² /
An electrically conductive organic polymer material comprising an insoluble and infusible substrate having a polyacene skeleton structure of g or more. 2. The electrically conductive organic polymer system according to claim 1, wherein the composite molded article contains phenolic fibers or fiber structures in a weight ratio to the phenolic resin of 0.05 or more. material. 3. The composite molded article is 0.5 to 7 relative to the total weight of the phenolic resin and the phenolic fiber or fiber structure.
The electrically conductive organic polymer material according to claim (1) or (2), wherein the material contains zinc chloride. 4. The electrically conductive organic polymer material according to any one of claims (1) to (3), wherein the phenolic fiber structure is a knitted fabric or a felt-like structure. 5. The heat-treated product of the composite molded article according to any one of claims (1) to (4), wherein the atomic ratio of hydrogen atoms / carbon atoms is 0.15 to 0.6. The electrically conductive organic polymer material described. 6. The organic polymer material according to any one of claims (1) to (5), wherein the organic polymer material is a molded product. 7. A heat-treated composite molded article comprising (A) a phenolic resin, a phenolic fiber or a fiber structure, and zinc chloride having an atomic ratio of hydrogen atoms / carbon atoms of 0.05.
~ 0.6 and specific surface area value by BET method is 600m
An insoluble infusible substrate having a polyacene skeleton structure of ² / g or more, and (B) an electron-donating dopant or an electron-accepting dopant, and (C) a larger electric conductivity than the undoped substrate. An electrically conductive organic polymer material characterized in that 8. A. 1.A wherein the electron donating dopant comprises lithium, sodium, potassium, rubidium and cesium.
The electrically conductive organic polymer material according to claim (7), which is a group metal. 9. The electrically conductive organic polymer material according to claim 7, wherein the electron donating dopant is a tetra (C ₁ -C ₅ lower alkyl) ammonium cation. 10. The electroconductive organic polymer material according to claim 7, wherein the electron-accepting dopant is fluorine, chlorine, bromine or iodine. 11. An electron-accepting dopant is AsF ₅ , PF ₅ , or B.
The electrically conductive organic polymer material according to claim (7), which is F ₃ , BCl ₃ , or BBr ₃ . 12. The electron-accepting dopant is SO ₃ or N.
An oxide derived from a non-metal element such as ₂ O ₅ or an anion derived from H ₂ SO ₄ , HNO ₃ or HClO ₄ (7)
The electrically conductive organic polymer material according to the item.