JPH07103246B2 - 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 to an electrically conductive organic material that is a heat-treated product of a composite molded article composed of a phenol resin and carbon 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 early organic semiconductors were difficult to form into a film or plate, and did not have the property as an n-type or p-type impurity semiconductor, so that they were limited in use. 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 electrical conductivity of about 10 ^-5 (Ω · cm) ^-1
By doping with an electron-accepting dopant such as I ₂ or AsF ₅ or an electron-donating dopant such as Li or Na, the electric conductivity can be significantly improved, and 10 ² to 10 ³ (Ω
・ Conductivity of cm) ^-1 is obtained. However, polyacetylene has a drawback that it is easily oxidized by oxygen. Therefore, 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
Japanese Patent Publication No. 49 discloses a heat-treated product of (A) an aromatic condensation polymer composed of carbon, hydrogen and oxygen, which contains a polyacene skeleton structure having an atomic ratio of hydrogen atoms / carbon atoms of 0.60 to 0.15. Disclosed is an electrically conductive organic polymer material comprising a fusible substrate and (B) an electron donating or electron accepting doping agent, and (C) having an electrical conductivity higher than that of the undoped substrate. Has been done. The insoluble and infusible substrate is excellent in heat resistance and oxidation resistance, and can be doped with an electron donating doping agent or an electron accepting doping agent as described above, and is p-type or n-type.
An organic semiconductor exhibiting mold properties is provided. 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, (A) a heat-treated product of an aromatic condensation polymer composed of carbon, hydrogen and oxygen, having an atomic ratio of hydrogen atoms / carbon atoms of 0.60 to 0.15. And the specific surface area by BET method is 6
An insoluble infusible substrate having a polyacene skeleton structure of 00 m ² / g or more, and (B) an electron donating or electron accepting doping agent, and (C) an undoped electric conductivity An electrically conductive organic polymer material having a size larger than that of a substrate has been proposed.

Since this organic polymer material has a specific surface area of 600 m ² / g or more, it has a relatively large ionic radius, such as Cl.
O ^- _4, BF ₄ ^- may be doped smoothly the like. 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 or plate-shaped molded 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 to remove zinc chloride from a heat-treated product of a phenol resin, a phenol-based carbon fiber or a phenol-based carbon fiber structure, and a composite molded article including zinc chloride. , The atomic ratio of hydrogen atoms / carbon atoms is 0.05 to 0.6
And an organic polymer material having an electric conductivity of 10 ^{0 to} 11 ^-11 Ω ^{-1 which} is composed of an insoluble and infusible substrate having a polyacene skeleton structure having a specific surface area value of 600 m ² / g or more by the BET method. To be achieved.

The composite molded article in the present invention is a molded article having an arbitrary shape such as a film shape or a plate shape made of phenol resin, carbon fiber or 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, methylene bisphenols, hydroxybiphenyls and hydroxynaphthalenes are also applicable. 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.

The carbon fibers are acrylic, pitch or phenolic carbon fibers, and may be short fibers or long fibers, and the fiber structure may be a felt-like material made of these carbon fibers, or a fibrous structure such as a knitted fabric. To be

A composite molded body formed from these materials is, for example, uncured phenolic resin, carbon fiber or fiber structure (hereinafter, both are abbreviated as fibrous carbon), and zinc chloride are mixed and molded under appropriate conditions and cured. It is obtained by doing. As a mixing method, any method such as dry mixing and wet mixing may be used as long as the above three components can be mixed uniformly, but a suitable solvent such as water, methanol, acetone or the like is added for sufficiently uniform mixing. Thus, it is desirable that the uncured phenol resin and zinc chloride be made into a solution, and then fibrous carbon be added and mixed. When the fibrous carbon is in the form of knitted fabric or felt, the prepreg may be made by impregnating these with the solution of the uncured phenol resin and zinc chloride. As a molding method, generally, the same method as in the case of producing a resin molded product can be used. However, for example, when a film form is desired, the above-mentioned three-component mixed slurry may be formed into a film with an appropriate thickness by an applicator. In the case of obtaining a plate-shaped body, 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 resol is used as an uncured phenolic resin, it is convenient to perform heat curing 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 composite molded body thus obtained is composed of phenolic resin, fibrous carbon and zinc chloride, has a desired shape such as a film or plate, and has excellent mechanical strength. It can be cut into pieces and processed into shapes such as circles and rectangles. This composite molded body is made into an insoluble and infusible substrate containing a polyacene-based skeleton structure by the method described later, and the mechanical strength of the substrate is exerted by the fibrous carbon in the composite molded body. That is, by using fibrous carbon, the strength of the electrically conductive organic polymer material composed of the insoluble and infusible substrate is greatly improved. Although the effect can be recognized even when the amount of fibrous carbon in the composite molded body is extremely small, the weight ratio of fibrous carbon / phenol resin is preferably 0.05 or more. When it is 0.05 or more, the strength of the obtained insoluble and infusible substrate containing a polyacene skeleton structure is particularly improved, which is preferable. Further, zinc chloride has an 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 thereof is small, the effect can be obtained. However, the weight ratio of zinc chloride / [phenolic resin + fibrous carbon] is preferably 0.5 to 7. When it is 0.5 or more, zinc chloride exhibits a sufficient effect and can greatly increase the specific surface area of the insoluble and infusible substrate, which is preferable.

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,
The atomic ratio of hydrogen atoms / carbon atoms is 0.05 to 0.6, preferably
An insoluble and infusible substrate having a polyacene skeleton structure of 0.15 to 0.60 can be obtained. Heat treatment temperature is usually 400-800 ℃
The preferable temperature rising condition of the heat treatment is slightly different depending on the composition ratio of the composite molded body, the curing condition or the shape thereof.
Generally, it is possible to set a relatively large temperature rising rate from room temperature to about 800 ° C., for example, 100 ° C./hour. At temperatures above 300 ° C, thermal decomposition of the phenolic resin begins 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 the 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-based skeleton structure is sufficiently developed, the conjugated system of electrons is sufficiently delocalized, and the dopant is doped but the electrical conductivity of the substrate itself before doping is increased. Due to the rather high conductivity, the contribution of the doping to the electrical conductivity is small and the electrical conductivity does not increase much over the undoped substrate.

Further, the specific surface area value by the BET method of the insoluble infusible substrate containing this polyacene-based skeleton structure is an extremely large value because it is manufactured using zinc chloride, but especially when it is 600 m ² / g or more. preferable.

The insoluble and infusible substrate having the polyacene-based skeleton structure of the present invention has a very large specific surface area value of 600 m ² / g or more by the BET method, so that the doping rate is high and it is possible to dope even 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, when electrolytically doping ClO ₄ ⁻ ions into a substrate with Li / LiClO ₄ 1 mol / l propylene carbonate / substrate, 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. With the substrate of 600 m ² / g or more of the present invention, this potential difference allows sufficient introduction of ClO ₄ ⁻ ions into the substrate.

Further, the electrically conductive organic polymer material composed of an insoluble and infusible substrate can be processed into a molded body of any shape such as a film shape, a plate shape or a cylindrical shape, but it is manufactured by using fibrous carbon. Therefore, the molded product is excellent in mechanical strength and has flexibility. In particular, when the knitted woven 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-based skeleton structure in which the H / C atomic ratio of the present invention is 0.60 to 0.05 is H / C.
It depends greatly on the atomic ratio of C, but for example H / C = 0.
In the case of 6, it is about 10 ^-11 Ω ^-1 cm ^-1 or less, and H / C = 0.0.
In 5, 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 shown below, the electric conductivity is greatly increased, and n
Type or p-type semiconductor.

Further, the insoluble and infusible substrate having the polyacene skeleton structure is
Since the specific surface area value by the BET method shows a very large value of 600 m ² / g or more, it is considered that gas such as oxygen invades and easily deteriorates, but in reality, even if left in the air for a long time, There is no change in physical properties and the like, and there is no change in electrical conductivity even when left in the air for 1000 hours, for example, and it has excellent oxidation stability.

As the electron-donating dopant or the electron-accepting dopant which can be doped into the insoluble and infusible substrate of the present invention, any of the doping agents generally known can be used.

As the electron donating dopant, a substance that easily releases electrons is used. For example, a Group 1A metal of the periodic table such as lithium, sodium, potassium, rubidium or cesium is preferably used.

Also tetraalkylammonium cations such as (C
₂ H ₅ ) ₄ N ⁺ , (C ₄ H ₉ ) ₄ N ^{+ and the} like 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 the 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 an insoluble infusible substrate having a polyacene skeleton structure having an H / C atomic ratio of 0.60 to 0.05 thus obtained with an organic polymer material of the present invention has an electric conductivity of the insoluble infusible substrate before doping. Higher electrical conductivity, preferably 10 times or more than the insoluble infusible substrate before doping, or 10 ³ to 10 ⁸ times or more higher by a suitable method.

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 and 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 to 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 A plain weave cloth (manufactured by Nippon Kynol Co., Ltd.) of phenolic carbon fiber was prepared by mixing a solution of a resol type phenolic resin (aqueous solution having a concentration of about 65%) / water / zinc chloride in a weight ratio of 10/3/12. Impregnate the obtained solution-impregnated cloth at 100 ° C.
Using a pressure molding machine for laminated plates heated to
Molding and curing under pressure gave a plate-shaped composite molded body with a thickness of about 500μ. In this composite molded body, the weight ratio of phenolic carbon fiber / phenolic resin was 0.12. The weight ratio of zinc chloride / (phenolic resin + phenolic carbon fiber) was 1.5. After forming a film of the mixed solution of the above-mentioned resole, water and zinc chloride with an applicator,
A curing reaction was carried out at the temperature of about 20 minutes for a plate-shaped molded body having a thickness of 500 μm. In this plate-shaped molded product, the weight ratio of phenolic carbon fiber / phenolic resin was 0, and the weight ratio of zinc chloride / (phenolic resin + phenolic carbon fiber) was 1.8. Next, these composite compacts and compacts were placed in a siliconit electric furnace and heat-treated in a nitrogen atmosphere up to 550 ° C. at a heating rate of about 40 ° C./hour. Next, these heat-treated products were washed with warm water at 100 ° C. for about 5 hours to remove the remaining 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-described composite molded article of the present invention has excellent mechanical strength and flexibility, and is easy to handle. However, the plate-like substrate obtained from the molded product made without using fibrous carbon has low strength and requires careful handling. 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.

Next, the electric conductivity, the elemental analysis, and the specific surface area value by the BET method of the insoluble infusible substrate obtained from the composite molded article of the present invention and the insoluble infusible substrate prepared without using fibrous carbon were measured. . 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. a voltage of 4V is given to, AsF ₆ ^-
Ions were doped into the insoluble and infusible substrate. 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 the 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.

However, in Table 1, the product of the present invention represents an electrically conductive organic polymer material composed of an insoluble and infusible substrate obtained from a composite molded article prepared by using carbon fibers. In addition, the comparative product represents an electrically conductive organic polymer material composed of an insoluble and infusible substrate obtained from a molded body prepared in the same manner as in the above-mentioned example except that fibrous carbon is not used.

As is clear from Table 1, the insoluble and infusible substrate using fibrous carbon has excellent mechanical strength. In Table 1, the bending strength of the product of the present invention is 50 or more because the sample is flexible and no clear breakage occurs.

Example 2 A cut fiber of acrylic carbon fiber (fiber diameter of about 15 μm) was mixed with a solution in which a resole type phenol resin (aqueous solution having a concentration of about 65%) / water / zinc chloride was mixed at a weight ratio of 10/1/5. (Cut length about 2 mm) is added and mixed well, then the slurry is molded and cured under pressure using a pressure molding machine heated to about 100 ° C for about 10 minutes to form a film-like composite with a thickness of about 100 μm. A molded body was obtained. The acrylic carbon fiber / phenol resin weight ratio in this film-form composite molded article was 0.08, and the zinc chloride / (phenol resin + phenol fiber) weight ratio was 0.8. Next, this film-shaped composite molded body is heat-treated to a predetermined temperature in a silicon knit electric furnace, then washed with hot water in the same manner as in Example 1 and dried to form a film-shaped insoluble and infusible material having a different hydrogen / carbon atomic ratio A conductive substrate was obtained. This substrate was subjected to elemental analysis, BET specific surface area value and bending strength measurement. 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 Resole type phenolic resin (about 65% concentration aqueous solution) / water / zinc chloride were mixed at a predetermined weight ratio, and the felt was impregnated with a phenolic carbon fiber felt (manufactured by Nippon Kynol Co., Ltd.). Next, 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.

In these composite molded bodies, the weight ratio of the phenolic carbon fiber felt / phenolic resin was 0.2 to 1.0, and the weight ratio of zinc chloride / (phenolic carbon fiber felt + phenolic resin) was 1.5 to 4 . Next, Example 1
Heat treatment, washing and drying were carried out under the same conditions as above to obtain a plate-shaped insoluble and infusible substrate. For these samples, elemental analysis, electrical conductivity, BET specific surface area and bending strength were measured. 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 torr.
After the following, 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 H / C atomic ratio is 0.20 and specific surface area value by BET method is 1050.
The substrate of the present invention of Example 1 having m ² / g was immersed in a tetrahydrofuran solution of sodium naphthalate prepared by using dehydrated tetrahydrofuran, naphthalene and metallic sodium in a dry box (N ₂ gas flow) to perform sodium doping. Tried. 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 to increase to about 10 ⁰ Ω ^-1 cm ^-1 , which is much larger than the undoped about 10 ^-4 Ω ^-1 cm ^-1 . When EPMA analysis was performed on the sample, sodium was doped into the inside of the sample.

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area C08K 7:00)

Claims (12)

[Claims] 1. A heat-treated product of a composite molding comprising a phenol resin, a phenol-based carbon fiber or a phenol-based carbon fiber structure and zinc chloride, from which zinc chloride has been removed, wherein the atomic ratio of hydrogen atoms / carbon atoms is An organic polymer having an electric conductivity of 10 ^{0 to} 11 ^-11 Ω ^-1 which is 0.05 to 0.6 and which is composed of an insoluble and infusible substrate having a polyacene skeleton structure having a specific surface area value of 600 m ² / g or more by the BET method. System material. 2. The electrically conductive organic material according to claim 1, wherein the composite molded article contains a phenolic carbon fiber or a phenolic carbon fiber structure in a weight ratio of 0.05 or more with respect to the phenol resin. Polymer materials. 3. The composite molded article according to claim 1, wherein the composite molded article contains 0.5 to 7 zinc chloride based on the total weight of the phenolic resin and the phenolic carbon fiber or the phenolic carbon fiber structure. The electrically conductive organic polymer material according to the item (2). 4. The electrically conductive organic polymer material according to any one of claims (1) to (3), wherein the phenolic carbon fiber structure is a knitted fabric or a felt-like one. . 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. Electrically conductive organic polymer materials. 6. The electrically conductive organic polymer material according to any one of claims (1) to (5), wherein the organic polymer material is a molded body. 7. A product obtained by removing zinc chloride from a heat-treated product of (A) a phenol resin, a phenol-based carbon fiber or a phenol-based carbon fiber structure and a zinc chloride-based composite molded article, which comprises hydrogen atoms / carbon atoms. Atomic ratio is 0.05 ~
An insoluble infusible substrate having a polyacene skeleton structure having a specific surface area value of 0.6 and a BET method of 600 m ² / g or more,
And (B) an electron-donating dopant or an electron-accepting dopant, and (C) an electrical conductivity higher than that of the undoped substrate. 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 electron-accepting dopant is fluorine, chlorine,
The electrically conductive organic polymer material according to claim (7), which is bromine or iodine. 11. An electron-accepting dopant is AsF ₅ , PF ₅ , 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.
The electrically conductive organic polymer material according to claim (7), which is 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 .