JPS6296529A - Electroconductive organic polymer material - Google Patents

Abstract

PURPOSE:To obtain the titled polymer material excellent in mechanical strength, heat resistance and oxidation resistance which is a product of heat-treatment of a composite molding comprising a phenolic resin, a carbon fiber (structure) and ZnCl2 and is specified in a H/C atomic ratio and a specific surface area value. CONSTITUTION:An uncured phenolic resin (A) is mixed with a carbon fiber (structure) (B) and ZnCl2 (C) in amounts to provide a B to A weight ratio >=0.05 and a C to (A+B) weight ratio of 0.5-7 and the mixture is pressure- molded. The product is cured by heating to 50-200 deg.C to obtain a composite molding. This composite molding is heat-treated at 400-800 deg.C in a non-oxidizing atmosphere and washed with warm water at 50-100 deg.C to remove ZnCl2. In this way, an electroconductive polymer material comprising an insoluble and infusible base of a polyacene skeletal structure having a H/C atomic ratio of 0.05-0.6 and a specific surface area value >=600m<2>/g is obtained.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to electrically conductive organic polymeric materials, and more specifically to electrically conductive materials that are heat-treated composite molded products made of phenolic resin and carbon fibers. related to organic polymeric materials.

(Prior Art) Polymer materials are excellent in moldability, light weight, and mass production. Therefore, by taking advantage of these properties of polymer materials, organic polymer materials that have electrical semiconductivity are desired in many industrial fields including the electronics industry. Early organic semiconductors were difficult to form into films or plates, and they did not have properties as n-type or p-type impurity semiconductors, so their uses were limited. In recent years, it has become possible to obtain organic semiconductors with relatively excellent formability, and it is also possible to make nu- or p-type organic semiconductors by doping these semiconductors with electron-donating dopants or electron-accepting dopants. became possible. Polyacetylene is a typical example of such an organic semiconductor. This organic semiconductor has an electrical conductivity of about 10-6
By doping with electron-donating dopants such as i and Na, the electrical conductivity can be greatly improved,
A conductivity of 102 to 108 (Ω·cm)-' was obtained.

However, polyacetylene has the disadvantage of being easily oxidized by oxygen. For this reason, it is difficult to handle in the air, and it lacks practicality as an industrial material.

In addition, Japanese Patent Application Laid-open No. 58-1 filed by the same applicant as the present application
Publication No. 86649 describes tA) A heat-treated product of an aromatic condensation polymer consisting of carbon, hydrogen and oxygen, which contains a polyacene skeleton structure with an atomic ratio of hydrogen atoms/carbon atoms of 0.60 to 0.15. (1) an electron-donating doping agent or an electron-accepting doping agent; system materials are disclosed. The above-mentioned insoluble and infusible substrate has excellent heat resistance and oxidation resistance, and can be doped with an electron-donating doping agent or an electron-accepting doping agent as described above. Give semiconductors. However, the above publication does not include any description of the specific surface area by the BET method.

Also, please refer to the earlier patent application filed in 1973 filed by the same applicant as the present application.
No. 9-8152 is still unpublished, but in the same earlier application, (Al) is a heat-treated product of an aromatic condensation polymer consisting of carbon, hydrogen and oxygen, and the atomic ratio of hydrogen atoms / carbon atoms is 0.60. ~0.15, υ, and a polyacene skeleton structure having a specific surface area value of 600 m2/i or more according to the BET method; (C1'!) An electrically conductive organic polymeric material has been proposed which is characterized by a higher air conductivity than that of the undoped substrate.

This organic polymer material has a specific surface area of 600m2/1
Since it is above u, even dopants with a relatively large ionic radius, such as Cl0-4 and BF4-, can be doped smoothly. However, even in this prior application, the electrically conductive polymeric material consisting of an insoluble and infusible substrate having a polyacene skeleton structure had a problem in mechanical strength, and in this respect, its practical application was still insufficient.

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

Another object of the present invention is to provide an electrically conductive organic polymer material with 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 polymeric material that can be smoothly doped with 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 polymeric material in the form of a film or plate.

Further objects and advantages of the present invention will become apparent from the description below.

(Means for Solving the Problems) The above-mentioned object is to provide a heat-treated composite molded product consisting of a phenol resin, carbon fiber or fibrous structure, and zinc chloride, in which the atomic ratio of hydrogen atoms/carbon atoms is 0. 05~0.
6, and the specific surface area value according to the BET method is 600 m2
This is achieved using an electrically conductive organic polymeric material consisting of an insoluble and infusible substrate having a polyacene skeleton structure of /, 9 or more.

The composite molded article in the present invention is a phenolic resin.

It is a molded article made of carbon fibers or a fibrous structure and zinc chloride and has an arbitrary shape such as a film shape or a plate shape. The 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 aromatic compounds include phenol and cresol.

Examples include phenols such as xylenol, and in addition to these, methylene bisphenols, hydroxybiphenyls, and hydroxynaphthalenes are also applicable. Among these compounds, phenols, particularly phenol, are preferred from a practical standpoint.

Among these, formaldehyde is preferred.

The carbon fibers may be acrylic, pitch, or phenolic carbon fibers, and may be short or long fibers, and the fiber structures may include felts, knitted fabrics, and other fiber structures made of these carbon fibers. Can be mentioned.

Composite molded bodies formed from these materials include, for example, uncured phenolic resin, carbon fiber, or fiber structures (
(Hereinafter, both will be abbreviated as l# fibrous element) and zinc chloride are mixed and molded under appropriate conditions and cured. As a mixing method, any method such as Izze mixing or wet mixing may be used as long as the above-mentioned eight components can be mixed uniformly, but in order to mix sufficiently and uniformly, an appropriate solvent,
For example, it is desirable to make the undiluted phenol resin and zinc chloride into a solution by adding water, methanol, acetone, etc., and then add and mix the fibrous carbon. When the fibrous carbon is in the form of a knitted fabric or felt, a prepreg may be prepared by impregnating it with the above-described solution of uncured phenol resin and zinc chloride. The molding method can be generally the same as that used for making resin molded products, but for example, if you want to obtain a film shape, you can form a film using the above-mentioned 8-component mixed slurry with an applicator to an appropriate thickness, or In order to obtain a plate-shaped body, as is generally well known, a mold may be made and pressure molded. Moreover, if the prepreg described above is placed between flat plates such as gold maple and press-formed, a plate of an appropriate thickness can be obtained.

When using resol as the uncured phenolic resin, the curing method is 50 to 200% during or after molding.
LvI stool hardens at a temperature of .degree. In particular, in a method of press molding using a mold or the like, it is possible to heat and harden at the same time as molding.

When novolak is used as the uncured phenolic resin, a suitable curing agent such as hexamethylenetetramine, which itself is a formaldehyde generator, is mixed in advance with a curing agent which is an organic base generator and molded. After that, it may be heated and cured.

The composite molded product obtained in this way is made of phenolic resin, fibrous carbon, and zinc chloride, and has an arbitrary shape such as a film shape or a plate shape and has excellent mechanical strength. It can be cut to size or processed into shapes such as circles and rectangles. This composite molded body is made into an insoluble and infusible substrate containing a polyacene skeleton structure by the method described later, but the basic binaric strength is developed by the fibrous carbon 44 in the composite molded body. It is something that That is, by using fibrous carbon, the strength of the electrically conductive organic polymeric material consisting of an insoluble and infusible base material is greatly improved. Although the effect can be observed even if the amount of fibrous carbon in the composite molded article is extremely small, it is preferable that the weight ratio of fibrous carbon/phenolic resin is 0.06 or more. 0
．． 05 or more is preferable because the strength of the resulting insoluble and infusible substrate containing a polyacene skeleton structure is particularly improved. Furthermore, 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 shown below, but the company claims that even a small amount can increase this effect. Preferably, the weight ratio of zinc chloride/[phenol resin raw fibrous carbon] is 0.5 to 7. If it is 0.5 or more, zinc chloride exhibits a sufficient effect and the specific surface area value of the insoluble and infusible substrate can be made medium high, which is preferable.

On the other hand, if the above-mentioned amount of zinc chloride exceeds 7, the absolute amount of phenolic resin will be small, making it difficult to form a film or plate, and the curing reaction of uncured phenol resin will be difficult to occur. A problem arises.

Next, this composite molded body is heat treated in a non-oxidizing atmosphere,
An insoluble and infusible substrate having a polyacene skeleton structure with a hydrogen atom/carbon atom atomic ratio of 0.05 to 0.6, preferably 0.15 to 0.60 can be obtained. The heat treatment temperature is usually 400 to SO0°C, and the preferable heating conditions for the heat treatment are based on the composition ratio of the composite molded body.

Although it varies somewhat depending on the curing conditions or its shape, it is generally possible to raise the temperature at a relatively high rate from room temperature to a temperature of about 0° C., for example, at a rate of 100° C./hour.

When the SO temperature reaches 0 DEG C. or higher, thermal decomposition of the phenolic resin begins and gases such as water vapor, hydrogen, methane, and carbon oxide begin to be generated, so it is advantageous to raise the temperature at a sufficiently slow rate. Next, the substrate having a polyacene skeleton structure obtained in this way was heated with F at 50 to 100°C.
C. to remove zinc chloride remaining in the substrate and dry. In this way, an electrically conductive organic polymer material consisting of an insoluble and infusible substrate containing a polyacene skeleton structure is obtained, but when the atomic ratio of hydrogen atoms/carbon atoms of this substrate exceeds 0.6. Because the polyacene skeleton structure has not yet developed, it is thought that the conjugated electron system is localized, and even when doped with a dopant, the electrical conductivity does not increase and it does not become a nm or p-type semiconductor. Also H/
When the atomic ratio of C is less than 0.05, the polyacene skeleton structure is sufficiently developed, the conjugated electron system is sufficiently delocalized, and although the dopant is doped, the electrical conduction of the substrate itself before doping is Since the degree of doping is quite large, the contribution of doping to the electrical conductivity is small and the electrical conductivity does not increase as much as in the undoped substrate.

In addition, an insoluble [phase] containing this polyacene skeleton structure
The specific surface area value of the base material by BET method is extremely large because it is manufactured using zinc chloride, but it is 600 m2.
It is particularly preferable that it is 2/, F or more.

The unique insoluble substrate having a polyacene skeleton structure of the present invention has a large specific surface area value of 600 m2/I or more (approximately) by the BET method, so the doping rate is high, and even thick substrates can be doped in a short time. Doping is possible,
Also, dopants with large ionic radius, such as CZO4,
It is possible to smoothly dope a dopant such as B F 4 into the substrate. For example, using Cl0a ions as a base, Li/LiC7041 mol/! ! When electrolytically doping a propylene carbonate/substrate structure, if the specific surface area is less than 600m2/71, it is difficult to perform doping with a potential difference of 4cm between the electrodes.
, 12 on the substrate, this potential difference is sufficient for CI! 04-
Ions can be introduced into the substrate.

In addition, the gas-conducting organic polymer material consisting of an insoluble and infusible substrate can be processed into molded bodies of any shape, such as film, plate, or cylindrical shapes, but it cannot be manufactured using fibrous carbon. Therefore, the molded product has excellent mechanical strength and flexibility. In particular, when producing phenolic fibers or using fine fabrics or felt-like fiber aggregates as fiber structures, the thickness and size of the molded body consisting of the base material,
Not only can density etc. be arbitrarily set, but also particularly excellent strength can be obtained.

By the way, the H/C atomic ratio of the present invention is 0.60 to 0.05.
The electrical conductivity of an insoluble and infusible substrate having a polyacene skeleton structure varies greatly depending on the H/C atomic ratio J, but for example, in the case of H/C = 0.6, it is about 10-" Q-
'cut' (hereinafter referred to as 'tear'), and when H/C=0.05, it is a semiconductor with approximately 10[Omega]-'cxt=. When the base material is doped with an electron-donating dopant or an electron-accepting dopant as described later, the electrical conductivity of the base material increases and it becomes an n-type or p-type semiconductor.

In addition, since the insoluble and infusible substrate having the polyacene skeleton structure exhibits a very large specific surface area value of 600 m2/7 or more by the BET method, it is considered that gases such as sulfur particles can enter and deteriorate easily. However, in reality, even if it is left in the air for a long time, there is no change in its physical properties, for example, even if it is left in the air for 1000 hours, there is no change in air conductivity, and its oxidation stability is deteriorated. .

Any of the generally known doping agents can be used as an electron-donating dopant or an electron-accepting dopant that can be doped into the insoluble and infusible substrate of the present invention.

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

Also, tetraalkylammonium cations such as (C2
H5)4N, (C4H9)4N+, etc. are also preferably used.

Further, as the electron-accepting dopant, a substance that easily accepts electrons is used. For example, halogens such as fluorine, chlorine, bromine, iodine, A SF 6, PF4, SF9, BCI
3% Halogen compounds such as BnrB, oxides of nonmetallic elements such as SOa or N2O5, or u2so
4. HNO3 or HC! ! Anions derived from inorganic acids such as 04 are preferably used.

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

When the dopant is an alkali metal, the dopant can be doped by contacting the molten alkali metal or the vapor of the alkali metal with an insoluble and infusible substrate; Doping can also be carried out by contacting with a fusible substrate.

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

When the dopant is an anion derived from an inorganic acid, the inorganic acid is directly coated or impregnated onto the insoluble and infusible substrate, or the insoluble and infusible substrate is electrolyzed in an electrolytic solution containing the inorganic acid as an anode. Doping can also be carried out.

The dopant is generally used so that it is present in the organic polymer material of the present invention in a ratio of 10 moles or more to the repeating unit of the aromatic condensation polymer.

The II/C atomic ratio thus obtained is 0.60 to 0.0.
The organic polymer material of the present invention, which is obtained by doping an insoluble and infusible substrate having a polyacene skeleton structure in No. 5 with a dopant, has an electrical conductivity higher than that of the insoluble and infusible substrate before doping, preferably doping. 10 times or more than the previous insoluble and infusible substrate.
It shows 108 times higher electrical conductivity 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 charge type) semiconductor or conductor. Further, 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 charge type) semiconductor or conductor.

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

The present invention also includes an electrically conductive organic polymer material having an ff1p-n junction. Such materials can be prepared by doping an electron-donating dopant from one side of the insoluble and infusible base molded body and doping an electron-accepting dopant from the other side, or doping one of the dopants over the entire surface of the insoluble and infusible base molded body. It can be produced by doping and then doping only a portion of its surface with the other dopant.

(Effects of the Invention) Since the electrically conductive organic polymer material of the present invention has excellent mechanical strength, it can be made into molded bodies of any shape, such as a thin film, a thick plate, or a cylindrical shape. These can be used, for example, for diode solar cells or batteries.
It is used as Pt, i, etc. in plants.

The present invention will be explained in more detail with reference to Examples below.

Example A solution prepared by mixing Luzole type phenolic resin (water-soluble oil with a concentration of about 65%)/water/zinc chloride in a weight ratio of 10/8/12 was applied to a plain woven phenolic carbon fiber cloth (manufactured by Nippon Kynor Co., Ltd.). The resulting solution-impregnated cloth is
Using a pressure molding machine heated to 100°C for about 10 minutes.

The mixture was molded and cured under pressure to obtain a plate-shaped composite molded product with a thickness of about 500 t1. In this composite molded article, the weight ratio of phenolic carbon fiber/phenol resin was 0.12. Further, the weight ratio of zinc chloride/(phenol resin + phenolic charcoal fiber) was 1.5.

After forming a film using the above-mentioned mixed solution of resol, water and zinc chloride using 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 article, the weight ratio of phenolic carbon fiber/phenolic resin was 0, and the weight ratio of zinc chloride/(phenolic resin + phenolic carbon fiber m) was 1.8. Next, these composite molded bodies and molded bodies were placed in a silicone electric furnace and heated to about 550°C in a nitrogen atmosphere.
Heat treatment was carried out at a temperature increase 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 8 hours to obtain a plate-like body of an insoluble ri-resistant substrate. Among these plate-shaped insoluble and infusible substrates, the plate-shaped substrate obtained from the composite molded product of the present invention described above has excellent mechanical strength and flexibility) and is easy to handle. However, the plate-like substrate obtained was weaker than the molded body made without using fibrous carbon, and required careful handling.

The measured values of the bending strength are shown in Table 1.

Next, when the insoluble insoluble substrate of the present invention obtained from the composite molded body was subjected to fluorescent X-ray analysis, it was found that Zn was 0.01% by weight (
vs. substrate) Below, CI! It was found that almost no zinc chloride remained in the substrate.

Next, the insoluble and infusible substrate obtained from the composite molded body of the present invention and the insoluble and infusible substrate made without using fine carbon were subjected to electric conductivity two-element analysis and specific surface area values by BET method. was measured. These results are summarized in Table 1.

Next, add LiAs to sufficiently dehydrated propylene carbonate.
F5 was dissolved to form a solution of about 1.0 mol/l, lithium metal was used as the negative electrode, the plate of the insoluble and infusible substrate was used as the positive electrode, and the above solution was used as the electrolyte, and a voltage of 4 V was applied between the two electrodes. , A8Fg- ions were doped into the insoluble and infusible substrate. Doping t is A per carbon atom in the substrate.
Although it is expressed by the number of 8 F 6 - ions, in the present invention, the AsF 6 - ion sand is determined based on the value of the current flowing through the circuit during doping.

In this way, an electrically conductive organic polymeric material consisting of an insoluble and infusible substrate doped with A SF 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 its electrical conductivity was measured. The results are shown in Table 1.
7-2 (hereinafter referred to as ``Reihaku'') However, in Table 1, the product of the present invention refers to a composite molded product made using carbon fibers. Represents the material. The comparative product refers to an electrically conductive organic polymeric material consisting of an insoluble and infusible substrate obtained from a molded article prepared in the same manner as in the above example except that fibrous carbon was not used.

As is clear from Table 1, the insoluble and infusible substrate using fibrous carbon has excellent mechanical strength. The reason why the bending strength of the products of the present invention is expressed as 50 or more in Table 1 is because clear breakage does not occur due to the flexibility of the sample.

Example 2 Resol type phenolic resin (aqueous solution with approximately 65% concentration)/
Cut acrylic carbon fiber (fiber diameter approx. 15μ) (cut length: 2am) was added to a solution of water/zinc chloride mixed at a weight ratio of 10/115, and after thorough mixing, the slurry was mixed. After molding and curing for about 10 minutes under pressure using a pressure molding machine heated to about 100°C, about 1
A film-like composite molded body having a thickness of 00 μm was obtained. In this film-like composite molded article, the weight ratio of acrylic carbon fiber/phenol resin was O and OS, and the weight ratio of zinc chloride/(phenol resin + phenol fiber m) was 0.8. Next, this film-like composite molded product is heat-treated to a predetermined temperature in a siliconite electric furnace, and then washed with hot water in the same manner as in Example 1, and dried to form an insoluble and infusible film-like product with different hydrogen/carbon atomic ratios. A sexual substrate was obtained. Elemental analysis, specific surface area value and bending strength measurement by BET method were performed on this substrate.

These results are summarized in Table 2.

Next, doping was performed in the same manner as in Example 1. However, in this example, LiBF4 was used in place of LiAsF6. The results are summarized in Table 2.

Example 8 Resol type phenolic resin (aqueous solution with approximately 65% concentration)/
Water/zinc chloride were mixed at a predetermined weight/n ratio, and the solution was impregnated into phenolic carbon fiber felt (manufactured by Nippon Kynor Co., Ltd.). Next, in a pressure molding machine heated to 100° C., the solution-impregnated felt was molded and cured under a predetermined pressure for about 15 minutes to produce a plate-shaped composite molded body.

In these composite molded bodies, the 1fR ratio of phenolic carbon fiber felt/phenolic resin is 0.2 to 1.0, and the weight ratio of zinc chloride/(phenolic carbon fiber felt + phenolic resin Ii@') is 0.2 to 1.0. was 1.5-4. Next, heat treatment, washing, and soot removal were performed under the same conditions as in Example 1 to obtain a plate-like body of an insoluble and infusible substrate. Elemental analysis of these samples.

Electrical conductivity, specific surface area and bending strength were measured using the BET method. The results are shown in Table 3.

Next, the plate-like body is placed in a vacuum line, and the degree of vacuum is increased to 10 to
After reducing the temperature to below rv, doping was carried out for about 10 minutes by introducing iodine gas into the line at room temperature.

The electrical conductivity after doping is shown in Table 8. In addition, the plate-like body doped with the three elements was taken out from the line and subjected to EPMA.
(Electron probe X-ray microphone, core analysis)
When we investigated the distribution of iodine in the cross section of the sample, we found that iodine was uniformly distributed from the surface to the inside of the sample in all samples.

(LL bottom margin) Example 4 Tetrahydrofuran, naphthalene, and metal obtained by dehydrating the substrate of the present invention of Example 1, which has an H/C atomic ratio of 0.20 and a specific surface area value of 1050 "n2.Ql by pBET method. Doping with sodium was attempted by immersing it in a tetrahydrofuran solution of sodium naphthalate prepared using sodium in a dry box (N2 gas flow).

After being immersed in SO for about a minute, it was washed with dehydrated tetrahydrofuran and dried under reduced pressure at room temperature. When the electrical conductivity of the sample was measured, it was found to be about 10''''4Ω-10 undoped.
-1, it increased by a wide range to about 100 (r'ci'').When EPMA analysis was performed on the sample, it was found that the inside of the sample was doped with sodium.

Applicant: Kanebo Co., Ltd. Do',,+',',','t:
, :, ゛ゝ, τ:l・

Claims (12)

[Claims] (1) A heat-treated composite molded product consisting of a phenol resin, carbon fiber or fibrous structure, and zinc chloride,
Electric conduction consisting of an insoluble and infusible substrate having a polyacene skeleton structure with a hydrogen atom/carbon atom atomic ratio of 0.05 to 0.6 and a specific surface area value of 600 m^2/g or more by the BET method. organic polymer material. (2) The weight ratio of the composite molded body to the phenolic resin is 0.
．． The electrically conductive organic polymeric material according to claim (1), which contains carbon fibers or fiber structures of 0.05 or more. (3) Claim (1) or (2) wherein the composite molded article contains 0.5 to 7 zinc chloride based on the total weight of the phenolic resin and the carbon fiber or fibrous structure.
) The electrically conductive organic polymer material described in item 1. (4) The electrically conductive organic polymer material according to any one of claims (1) to (3), wherein the carbon fiber structure is in the form of a knitted fabric or felt. (5) Any one of claims (1) to (4), wherein the heat-treated composite molded product has an atomic ratio of hydrogen atoms/carbon atoms of 0.15 to 0.6. The electrically conductive organic polymer material described above. (6) The electrically conductive organic polymer material according to any one of claims (1) to (5), wherein the organic polymer material is a molded article. (7) (A) A heat-treated composite molded product consisting of a phenol resin, carbon fiber or fibrous structure, and zinc chloride, in which the atomic ratio of hydrogen atoms/carbon atoms is 0.05 to 0.6, and It consists of an insoluble and infusible substrate having a polyacene skeleton structure with a specific surface area value of 600 m^2/g or more by the BET method, and (B) an electron-donating dopant or an electron-accepting dopant, and (C) electrical conductivity. 1. An electrically conductive organic polymeric material, wherein the conductive organic polymer material is larger than that of the undoped substrate. (8) The electron-donating dopant is lithium, sodium,
The electrically conductive organic polymeric material according to claim (7), which is a Group 1, A metal containing potassium, rubidium, and cesium. (9) The electron-donating dopant is tetra (C_1 to C_5
The electrically conductive organic polymer material according to claim (7), which is a lower alkyl) ammonium cation. (10) The electrically conductive organic polymeric material according to claim (7), wherein the electron-accepting dopant is fluorine, chlorine, bromine, or iodine. (11) The electron-accepting dopant is AsF_4, PF_
5. The electrically conductive organic polymeric material according to claim (7), which is BF_3, BCl_3, or BBr_3. (12) The electron-accepting dopant is SO_3 or N
Oxides of nonmetallic elements such as _2O_5 or H_2SO
The electrically conductive organic polymer material according to claim (7), which is an anion derived from _4, HNO_3, or HClO_4.