JPS593806A - Electroconductive organic high molecular material and method of producing same - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electrically conductive organic polymeric material and a method for producing the same. More specifically, insoluble and infusible products, which are heat-treated aromatic polymers containing electron-donating 1/IE, doping agents, electron-accepting doping agents, or both, and which have a polyacene skeleton are oxidation-resistant and The present invention relates to an electrically semiconductive or electrically conductive organic polymer material useful as an electronics material with excellent mechanical strength and a method for producing the same.

Polymer materials have excellent moldability, light gutter properties, and yield properties. Therefore, by taking advantage of these properties of polymer materials, it is possible to develop organic
The production of molecular citrus materials is desired in many industrial fields including the electronics industry. In particular, electrical conductivity does not only exist in semiconductor or conductor regions, but also has properties as n-type or p-type semiconductors, such as inorganic semiconductors such as silicon and germanium, and utilizes their p-n junctions, etc. Therefore, organic polymer semiconductors or conductors that can be applied to diodes, transistors, solar cells, etc. are desired.

Early organic polymer semiconductors or conductors were difficult to form into films or plates, and they did not have the properties of n-type or p-type impurity semiconductors, so they were difficult to use for various purposes. was also limited. In recent years, it has relatively excellent moldability and can be made into molded products, and it is also possible to greatly increase electrical conductivity by doping with an electron-donating doping agent or an electron-accepting doping agent. Organic polymer materials having properties as n-type or p-type semiconductors have been obtained. Polyacetylene and polyphenylene are known as such organic polymer materials.

For example, "Synthetic Metals" Chemistry Special Edition 87, published in 1980, 1
(pp. 5-28), directly polymerizes acetylene to form a film of polyacetylene (electrical conductivity: 0-9 to I O
-50-1,n-1, and doping it with an i-curve doping agent or an electron-accepting doping agent to obtain a p-type or n-type semiconductor with greatly increased electrical conductivity. It describes what can be done. However, polyacetylene has the disadvantage of being easily oxidized by oxygen. For example, when polyacetylene is left exposed to air, it gradually absorbs oxygen and shows an increase in weight.
At the same time, the color changes from black to brown to pale yellow. The speed of such oxidation N reaction depends on the crystallinity of polyacetylene, but for example, Ti (On C4H9)4 At (C2HR)
11 Even powdered polyacetylene with relatively good crystallinity in the system 1'l'Jt ['J=”rfAH, for example, if left in air at room temperature for 2000 hours, rcHOo, +8) x
The composition changes and the electrical conductivity also decreases significantly. Although polyacetylene has excellent electrical conductivity, it has such problems with oxidation stability that it is extremely impractical. Furthermore, JP-A-55-129443 discloses, for example, a method of pressure-molding polyphenylene-12-1-lune (which has an electrical conductivity of about 10 Ω α and is an insulator) obtained by cationic oxidation polymerization of benzene. It is described that an n-type or p-type semiconductor with significantly increased electrical conductivity can be produced by obtaining a polyphenylene molded body by doing this and doping it with an electron-donating doping agent or an electron-accepting doping agent. ing. Unlike polyacetylene, polyphenylene has the advantage of relatively excellent oxidation stability. However, since the phenylene skeleton of polyphenylene is linearly bonded with single bonds, the conjugated system between carbon atoms is small, and therefore there is a limit to the electrical conductivity that can be achieved by doping with a doping agent. It seems that there are limits to impurity control using doping agents. In fact, even when polyphenylene is doped with halogen (an electron-accepting doping agent), the rate of increase in mechanical conductivity is smaller than that of the same halogen-doped polyacetylene, making it inferior to polyacetylene. Even if polyphenylene is doped with the maximum amount of halogen that can be doped, the electrical conductivity remains 10-
70-1 sub-1 or higher cannot be obtained (see Example 5 of the same publication).

The object of the present invention is to provide a molecule that not only has the electrical conductivity of a semiconductor or a conductor and has excellent physical properties, but also has excellent oxidation stability. The aim is to provide materials based on

Another object of the present invention is to provide an electrically conductive organic material containing an electron-donating doping agent or an electron-accepting doping agent, which is made of an insoluble and infusible material having a boriacene skeleton structure in which a conjugated system between carbon atoms is developed. Our objective is to provide polymeric materials.

Still another object of the present invention is to use p-type or n-type impurity semiconductors (extrinsic semiconductors).
An object of the present invention is to provide an electrically conductive organic polymer material having the following properties.

Yet another object of the present invention is to provide electrically conductive organic polymeric materials in the form of fibers, films, plates, or composites thereof, which have excellent physical properties.

Still another object of the present invention is to provide a method for producing the electrically conductive organic polymeric material of the present invention.

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

According to the research of the present inventors, the above objects and advantages are as follows: (A) A heat-treated product of an aromatic condensation polymer consisting of carbon, hydrogen and oxygen, in which the atomic ratio of hydrogen atoms/carbon atoms is 0. an insoluble and infusible substrate containing a boriacene skeleton structure represented by .60 to 0.15, and (I) an electron-donating doping agent or an electron-accepting doping agent; It has been found that this can be achieved with an electrically conductive organic polymer-based material which has a higher f% characteristic than the undoped substrate.

According to the present invention, an electrically conductive organic polymeric material having a 75-degree bow is obtained by heat treatment by heating an aromatic condensation polymer consisting of carbon, hydrogen and oxygen at a temperature of 400 to 800°C in a non-oxidizing atmosphere. Then, the atomic ratio of hydrogen atoms/carbon atoms is 0
．． 60 to 0115 and then keto-doping it with an electron-donating doping agent, an electron-accepting doping agent, or a mixture thereof to make the electrical conductivity higher than that of the substrate. It can be manufactured by

The present invention will be explained in more detail below.

Conventionally, when a phenol-formaldehyde condensate obtained by reacting phenol with formaldehyde is heated to a temperature of about 400 to 80°C in a vacuum or non-oxidizing atmosphere and heat-treated, water vapor (H,0) is first generated, Next, decomposition gases such as hydrogen, methane, and carbon oxide are generated, and at least several benzene rings are directly bonded to the neighboring benzene ring via its two nuclear carbon atoms in the heat-treated condensate. It is known that a region with a structure c (hereinafter referred to as a polyacene structure) in which the benzene rings of P
argamon Press Ltd, 1981° “Carbon” Vol,] 9. pp, 89
-94.1981).

When a so-called phenol-formaldehyde condensate obtained by the reaction of formaldehyde with phenol such as phenol or xylenol (e.g. 35-dimethylphenol) is heated to a temperature of about 500 tons or more and heat treated, cyclic The tank Φ gradually developed, and what was initially an electrically insulating material became...
It is known that heat-treated products exhibit properties of intrinsic semiconductors ("Polymer", 1960).
Vnl, page 9.962 and Resource Technology Laboratory Report No. 7
No. 4, March 1962, p. 1()2).

According to the inventors of the present invention, it is a heat-treated product of an aromatic combination polymer consisting of carbon, hydrogen, and oxygen, in which the atomic ratio of hydrogen atoms (H)/carbon atoms (C) is 0.60 to 0.
15, particularly preferably 0.5 (1 to 0.25), the insoluble and infusible substrate containing a boriacene skeleton structure is unexpectedly doped with an electron-donating doping agent and/or an electron-accepting doping agent. It has been found that such doping can significantly increase the electrical conductivity over the undoped substrate.

As the aromatic condensation polymer composed of carbon, hydrogen and oxygen used in the production method of the present invention, a condensate of an aromatic hydrocarbon compound having a phenolic hydroxyl group and an aldehyde is suitable. Suitable examples of such aromatic compounds include so-called phenols such as phenol, cresol, and xylenol, but they are not limited thereto. For example, in the following formula, nl and nt may be the same or different, and 0
It may be a methylene-bisphenol represented by the following formula, which is an integer of 2 to 2, or it may be a hydroxy-biphenyls or a hydroxynaphthalene. Among these, phenols, particularly phenol, are preferred from a practical standpoint.

Further, as the aldehyde, not only formaldehyde but also acetaldehyde, furfural and other aldehydes can be used, but formaldehyde is preferred.

The phenol-formaldehyde condensate may be a novolac type, a resol type, or a composite thereof.

According to the present invention, as an aromatic condensation polymer consisting of carbon, hydrogen, and oxygen, a part of the aromatic hydrocarbon having a phenolic hydroxyl group is replaced with another aromatic hydrocarbon not having a phenolic hydroxyl group, for example. A modified aromatic condensation polymer prepared with xylene, toluene, etc. can also be used.

Further, according to the present invention, a condensate of an aromatic compound containing an oxygen atom as a heteroatom and an aldehyde, such as a condensate of furfuryl alcohol, which corresponds to a condensate of phthene and formaldehyde, etc. A corresponding full phase of aromatic condensation polymers may also be present.

It is advantageous to form the above-mentioned aromatic condensation polymer consisting of carbon, hydrogen and oxygen into a fiber, film, plate or composite thereof in advance and heat-treat it.

These aromatic condensation polymers usually have a hydrogen atom/carbon atom atomic ratio (hereinafter expressed as H/C) of 0 in their -it.
．． It can be said that it is 9 or more, and there are almost no cases of 0.8 or less.

According to the present invention, such an aromatic condensation polymer fan is heated at 400 to 800°C in a non-oxidizing atmosphere (including a vacuum state).
temperature, preferably 450 to 750°C, particularly suitable temperature range of 500 to 700°C, and heat treatment to obtain a H/C ratio of 0.60 to 0.15. It is particularly preferable to form a heat-treated product (substrate) of 0.50 to 1.25. Such a heat-treated product is insoluble and infusible.

The fact that the (l/C) of the condensation polymer greatly decreases in a rainbow pattern due to heat treatment is due to the development of a boriacene structure, which is a polycyclic structure of benzene, in the heat-treated product, that is, in the substrate, as disclosed in the above cited document. It is believed that this indicates that

Based on the above elemental analysis values of the substrate, it is clear that the above-mentioned heat-treated product used in this Komei, that is, the insoluble and infusible substrate, contains a considerably developed boriacene-based structure (it is believed that wrinkles are evenly contained). Not only the ratio of C, but also the atomic ratio of oxygen atoms/carbon atoms of the substrate based on the elemental analysis value c or less (shown as a ratio of 0/C) is the O/C of the condensation polymer before heat treatment.
This is further supported by the X-ray diffraction and infrared absorption spectra.

The O/C of aromatic condensation polymers is usually 0.1 or more, and it can be said that it almost never shows less than O,OS, but by heating and heat-treating it as described above, H
Similarly to /C, 0/C also decreases.

The heat-treated substrate used in the present invention has an O/C ratio of 0.
．． 06 or less, especially 0.03 or less, and the fact that the 0/C ratio is much smaller than that of the aromatic condensation polymer before heat treatment also reduces the oxygen content of such condensation polymers, such as phenolic This supports the fact that the hydroxyl group was decomposed and removed and converted to a polyacene structure.

As can be seen from the example shown in FIG. 1, the aromatic condensation polymer used in the present invention has X-ray diffraction 1 (-u Ke
x-ray), the main peak position is 20° or less, expressed as 20, and 41 to 46 expressed as 2θ.
It does not show the presence of a peak at It-11 at °.

In X-ray diffraction, the main peak that appears at 24° or less in 2θ is said to correspond to the average distance between planar boriacene molecules, and the main peak that appears at 2θ or less is 41 to 46° in 2θ.
It is said that the peak that appears in the first river corresponds to the average size of the benzene ring in molecules with a polyacene structure ("Carbon Materials Man" Carbon Materials Research Group 1. Published in 1972, 12
(See pages 21-21).

However, the insoluble and infusible substrate obtained by heat-treating the aromatic condensation polymer has a main peak position of IIJ of 20.5 to 23.5° in X-ray diffraction.
Shift to I (see Figures 2 and 3), and further 41 at 2θ
A broad diffraction peak occurs between ~46° (see Figures 2 and 3). The shift of the main peak in the front field seems to indicate that the average distance between planar polyacene molecules has shortened, and the latter broad peak indicates the development of the polycyclic structure of benzene in the polyacene system.

In fact, in the insoluble and infusible substrate used in the present invention, the main peak position in X-ray diffraction (Cu Ka ray) occurs between 20.5 and 23.5 degrees in 2θ, and the position is 41° in 2θ. Those showing a broad peak between 46° and 46° are preferable.

Furthermore, in the infrared absorption spectrum of aromatic condensation polymers, the absorption peak that appears in the range of 2900 to 2940 Kaiser (rust-') is said to correspond to the stretching motion between carbon that does not constitute a conjugated system and hydrogen bonded to it. ,
In addition, the absorption peak appearing in the range of 1560-1640 Kaiser (tM') is said to correspond to the stretching imaging between two carbons constituting the conjugated system of the benzene ring (rc
arbon,, lPergarnon Press,
L+, d, Pr1nted in GreatBri
tain, Volume 4, 5'9-66m).

According to the method of the present invention, the aromatic condensation polymer fijA
When treated, compared to the one before heat treatment, the result is as shown in Figure 4 of the attached drawing.
As can be seen from the examples shown in Figures 5.6.7.8 and 9, 2
The absorption peak occurring in the 900-294o Kaiser range is reduced. -T! In this case, the absorption peak appearing in the range of 1560 to 1640 Kaiser increases for aromatic condensed polymers having benzene rings (Figures 4.5.6.7 and 8), whereas for aromatic condensed polymers having no benzene rings, In polymers such as furan resins, a new absorption peak appears in the 156o to 164o Kaiser range (Figure 9).

This fact also indicates that the insoluble and infusible substrate used in the present invention has a developed t-benzene polycyclic structure of the boriacene type compared to that before heat treatment.

In the present invention, the insoluble and infusible substrate has an absorbance ratio (1) expressed by the following flaw determined from an infrared absorption spectrum.
), D” D 21100~2940/DI!160”
-1640, where D, ooo~, 94o is the absorbance determined from the maximum absorption peak in the range of 2900 to 2940 Kaiser in the infrared absorption spectrum, DI! 1150
〜+640 is 1560〜 in the infrared absorption spectrum
It is preferable that the absorbance calculated from the maximum absorption peak in the range of 1640 Kaiser is 0.5 or less, especially 0.3 or less (details of the calculation method of the above absorbance ratio (D) are described in Examples below. (described in Section 1).

The electrically conductive organic polymeric material of the present invention is produced by heating an aromatic condensation polymer consisting of carbon, hydrogen and oxygen to a temperature of 400 to 800°C in a non-oxidizing atmosphere, and heat-treating the hydrogen atom/carbon The ratio of atoms is 0.60 - L0.15
forming a substrate, and then doping it with an electron concentrating doping agent, a bone-accepting doping agent, or a mixture thereof, thereby making the electrical conductivity of the substrate greater than the blood conductivity. can be manufactured.

As described above, as the aromatic condensation polymer described in item 7, a condensate of an aromatic hydrocarbon compound having a phenol hydroxide group and an aldehyde is preferably used. Examples of aromatic hydrocarbon compounds include phenols such as t=t, enol, cresol, and xylenol, and methylene-
Bisphenols, hydroxybiphenyls, hydroxynaphthalenes, and especially phenol are preferably used.

Further, as the aldehyde, for example, formaldehyde, acetaldehyde, furfural, etc., and particularly formaldehyde are preferably used.

As the aromatic condensation polymer, preferably a novolac type or resol type phenol formaldehyde resin is used.

These aromatic condensation polymers can be produced by a method known per se, for example, by condensing an aromatic hydrocarbon compound having a phenol hydroxyl group and an aldehyde in the presence of an acidic or basic catalyst. .

For example, novolak-type phenol-formaldehyde resin is prepared by phenol-formaldehyde resin in the presence of an acid catalyst such as oxalic acid under conditions of excess phenol such that the molar ratio of phenol to formaldehyde is, for example, 1:0.7 to 0.9. It is produced by reacting formaldehyde with formaldehyde. The novolak type phenolic resin obtained by such a method is mainly composed of 3 to 5 JIk forms in which phenol is bonded mainly through methylene groups, contains almost no free methylol groups, and therefore has no self-crosslinking property by itself. Fibers, films or granules which do not have a thermal b] plasticity per se or are derived therefrom are particularly suitable as aromatic combination polymers of the present invention.

In addition, the resol type phenol-formaldehyde resin has a molar ratio of phenol to formaldehyde of j to 1 to 2 in the presence of a basic agent such as lithium hydroxide.
It is produced by reacting phenol and formaldehyde with fH under conditions of excess formaldehyde, such as: The resol-type phenolic resin thus obtained is mainly composed of 1-3 phenols having a relatively large amount of free methylol groups, and undergoes a crosslinking reaction simply by heating.

According to the method of the present invention, the above-mentioned aromatic condensation polymer is preferably formed into a composite of weft fibers, a film, or a board in advance, and then heated in a non-oxidizing atmosphere to undergo heat treatment. It is advantageous to do so. According to the invention, these molded bodies are advantageously subjected to a curing reaction, preferably before heating, in order to completely stabilize the molecular structure and shape.

Such molding and curing reactions can be carried out, for example, by mixing an appropriate amount of formalin into a methanol solution of a novolac type phenolic resin, forming a film on a flat substrate, and heating and curing this solution in the presence of a hydrochloric acid catalyst. I can do that.

Well, a crosslinking agent such as hexamethylenetetramine, which itself is both a formaldehyde generator and an organic base generator, is mixed into the novolac type phenol resin in advance, and after forming into a film, it is heated and cured to form a cured phenol resin film. may be created. Furthermore, even if a resol type phenolic resin is used, a cured phenolic resin film can be easily obtained in the same manner.

Alternatively, for example, a cloth made of phenolic resin fiber (for example, Kynol, manufactured by Kynol Co., Ltd., Japan) is impregnated with a methanol solution of a resol type phenol resin, and after removing the methanol by air drying or the like,
50~150su/ctn at a temperature of 0℃! Under the pressure of 3~
By curing for 60 minutes, a tithyphenol resin platelet can be obtained as a composite.

The cured body obtained by molding and curing as described above is then heated in a non-oxidizing atmosphere to form an insoluble and infusible substrate that does not melt even after heat treatment and has the shape given to the cured body. give.

According to the method of the present invention, the aromatic condensation polymer, preferably a cured product thereof, is first heated in a non-oxidizing atmosphere to a
Heat treatment is performed by heating to a temperature of 0°C. The heating temperature is preferably 450 to 750°C, particularly preferably 500°C.
~700°C.

The preferred rate of temperature increase during heat treatment varies somewhat depending on the aromatic condensation polymer used, the extent of its curing treatment, its shape, etc., but in general, a relatively high rate of temperature increase from room temperature to a temperature of about 300°C. For example, a rate of 100° C./hour is also possible. When the temperature exceeds 300°C, thermal decomposition of the aromatic condensation polymer begins and gases such as water vapor (H,0), hydrogen, methane, and carbon oxide begin to be generated, so the temperature rises at a sufficiently slow rate. It is advantageous to keep it warm.

For example, in the case of a non-porous aromatic polymer molded body, if the thickness of the molded body is hlmm), 80/h”r
It is preferable to set the column temperature rate to less than :/hour. By setting the temperature to such a rate, the H of the insoluble and infusible substrate produced is
It becomes easy to control the /C ratio to 0.60 to 0.15, and it also becomes easy to completely stabilize electrical, electrical conductivity, and other mechanical properties.

Such heating and heat treatment of the aromatic condensation polymer is performed in a non-oxidizing atmosphere. Examples of the non-oxidizing atmosphere include nitrogen, argon, -\lium, neon, carbon dioxide, etc., and nitrogen is preferably used. Such a non-oxidizing atmosphere may be stationary or flowing.

<17> By the above heating and heat treatment, the temperature is 0.60 to 0.
An insoluble and infusible substrate having an H/C ratio of 15 can be produced. If the heating and heat treatment temperature is lower than 400°C, thermal decomposition will be insufficient;
At higher temperatures, thermal decomposition becomes too rapid,
In either case, it is extremely difficult or impossible to obtain an insoluble and infusible substrate that meets the above I(/C ratio).

According to the invention, the insoluble and infusible substrate is preferably H/
The ratio of C is about 0.50 to 0.25.

Further, the ratio of 0/C is usually 0.06 or less, preferably 0.06 or less.
03 or less. According to X-ray diffraction (Cu Ka ), the position of the main peak is 20.
It exists between 5° and 23.5°, and in addition to the main peak, there is another broad peak between 41° and 46°. According to the infrared absorption spectrum, D(=D,
. . . ~,. 40/D... -164°) is usually 0.5 or less, preferably 0.3 or less.

That is, it is understood that the above-mentioned insoluble and infusible substrate is one in which the polycyclic structure of polyacene-based benzene is evenly and appropriately developed between polyacene-based molecules.

Such an insoluble, infusible substrate is then fully doped with an electron-donating dopant or an electron-accepting dopant, or both, according to the invention.

A substance that easily releases electrons is used as the electron-donating doping agent. 1A of the periodic table such as lithium, sodium, potassium, rubidium or cesium
Group metals are preferably used.

Further, as the electron-accepting doping agent, a substance that easily accepts electrons is used. For example, fluorine, fluorine, bromine,
AsF=, PF'! ! ,(
Halogen compounds such as $F1, L3CI8, BBr:
S Os or N20! Oxides of non-metallic elements such as I; or anions derived from inorganic acids such as Ti, HNO, H(, 'IQ, etc.) are preferably used.

As a doping method for such a doping agent, essentially the same doping method as conventionally used for polyacetylene or polyphenicine can be used. If we compare the doping method of the present invention with conventionally known doping methods and describe all the differences,
The insoluble and infusible substrate used in the present invention is not only extremely stable against oxygen but also has high stability against various other chemicals, so the doping method used in the present invention is different from conventionally known methods. conditions stronger than the specified method, e.g. 100°
The point is that doping can be carried out at a temperature of ~200°C. Therefore, according to the doping method of the present invention, doping can be performed more efficiently and advantageously than conventionally known methods.

When the doping agent is an alkali metal, doping can be carried out by contacting the vapor of the molten alkali metal or alkali metal group with an insoluble and infusible substrate; Doping can also be carried out by contacting an insoluble and infusible substrate.

When the doping agent is a halogen, a halogen compound, or an oxide of a non-metallic element, doping can be easily carried out by bringing the doping agent into contact with the gas-insoluble substrate.

When the doping agent is an anion derived from an inorganic acid, the insoluble and infusible substrate is directly coated or impregnated with pisoric acid, or the insoluble and infusible substrate is coated with the inorganic acid in an electrolytic solution. Doping can also be performed by applying an electric current of 1ψr to the anode.

The doping agent is generally used so that it is present in the organic polymeric material of the present invention in a proportion of 10' moles or more relative to the repeating units of the aromatic condensation polymer.

The polymer powder of the present invention obtained by scenting has a higher electrical conductivity than that of the insoluble and infusible substrate before doping, and an air conductivity that is preferably higher than that of the insoluble and infusible substrate before doping. is also 10 times or more, according to the standard method 103~1
0' 1? f father exhibits even higher electrical conductivity.

The electrically conductive organic polymer material of the present invention doped with an electron-donating doping agent has the electrical conductivity of an n-type (electron-rich) semiconductor or conductor.

However, the electrically conductive organic polymer material of the present invention doped with an electron-accepting doping agent is p-type (hole-excessive type).
It has the electrical conductivity of a semiconductor or a conductor.

On the other hand, according to the present invention, an electron-donating doping agent and an electron-accepting doping agent can be used together as a doping agent. When these doping agents are almost uniformly mixed in the electrically conductive organic polymer material of the present invention, the material becomes p-type or n 31J depending on which doping agent is present in greater amounts. For example, when there is a large amount of electron-donating doping agent, it becomes n-type, and when there is a large amount of electron-accepting doping agent, it becomes p-type. Such an electrically conductive organic polymeric material containing a mixture of doping agents can be prepared by contacting a mixture of doping agents with an insoluble and infusible substrate, or by bringing one doping agent into contact with an insoluble and infusible substrate, and then contacting the other doping agent. can be produced by contacting with a doping agent.

Further, according to the present invention, it is also possible to produce an electrically conductive organic polymer material having a so-called p-n junction surface. Such a material is released from one side of the insoluble and infusible substrate molded body.
Either dope the child-receiving doping agent from the other side and dope the child-receptive doping agent from the other side, or dope either one of the doping agents over the entire surface of the insoluble and infusible substrate molded body! It can be produced by doping only a part of the second doping agent with the other doping agent.

The box and air conductive polymeric material obtained according to the present invention preferably have a direct current conductivity of 0-40-1 sub-1 or more at room temperature.

The electrically conductive organic polymer material of the present invention has high electrical conductivity due to the electronic interaction between the polyacene skeleton structure and an electron-donating doping agent, an electron-accepting doping agent, or a mixture thereof. It is assumed that this is the case.

For example, the undoped, insoluble, infusible substrate of the present invention has an air conductivity of about 10-120-16n-1;
When doped with iodine, the electrical conductivity of the B9 polymeric material of the present invention is approximately 10 Ω, but the infrared absorption spectrum of this organic polymeric material shows that it is undoped. A peak that was not observed in the insoluble and infusible material appears. Also, when an undoped insoluble infusible substrate having an electrical conductivity of about 10-6 Ω-1,-1 is doped with iodine, the electrical conductivity of Q-1-1 becomes about 10Ω G, and in the infrared absorption spectrum. The peak +1560 to 1640 (*-'') corresponding to the stretching vibration between carbons constituting the conjugated system shifts to the higher wavelength side.

The insoluble and infusible substrate in the present invention is generally a substance with black luster, but for example, when doped with sulfur trioxide, the color changes to purple luster, and when doped with sodium father, it becomes golden luster. The color changes. Judging from these phenomena, in air-conducting organic polymer materials, there is an electronic interaction between the polyacene skeleton structure forming the skeleton and the doping agent, and therefore ′Φ.

The mechanism by which air conductivity is greatly increased is presumed to be sufficiently reliable.

Although the insoluble and infusible substrate used in this invention exhibits electrical conductivity I8 similar to that of an insulator or a semi-quartet, it has a well-developed structure in which boriacene, which constitutes a conjugated system, is not doped. The electrically conductive organic polymeric material of the present invention exhibits a large increase in electrical conductivity by doping with the agent. For example, electrical conductivity 1o Ω cm +7
) The insoluble and infusible substrate provides the organic polymeric material of the present invention with an electrical conductivity of about 10-30-] crn-1 by doping with iodine. On the other hand, JP-A-55-12944
As described in Publication No. 3, electrical conductivity] o-1
When 1Ω-1,1 polypherene is doped with halogen, the electrical conductivity increases only to 0-7Ω-1crn-1.

The insoluble and infusible substrate used in the present invention has excellent stability against oxygen, and there is almost no change in physical properties even if it is left in the air at room temperature for 5,000 hours, and electric conduction cars also
It is almost constant. In addition, the mechanical strength is high, for example, the bending strength is generally 300 kg/11''m' or more, and has sufficient physical properties for practical use.

The electrically conductive organic polymeric material of the present invention inherits the properties of the above-mentioned insoluble and infusible substrate and has similar properties.

As is already clear, the electrically conductive organic polymeric material of the present invention can be provided, for example, as a film, fiber, plate, or a composite thereof. These are for example rectifier diodes, transistors, solar cells or batteries,
Used in various fields as electrodes for ponds, etc.

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

Example 1 (1) Novolac type phenol buffing fat/methanol/
Formalin (an aqueous solution with a concentration of about 37 parts) in a weight ratio of 3 /
The solution was mixed at a ratio of 3/1 and spread on a glass plate using an applicator.
The methanol was removed by air drying for about 30 minutes (after that, the glass plate was placed in t5Nia acid and cured for 90 minutes at a temperature of 70°C. After that, it was thoroughly washed with warm water and air dried for about 1 month). A cured phenolic resin film substrate having a thickness of about 10 μm was obtained.

This resin film was placed in a siliconite electric furnace (an electric furnace using silicon carbide as a heating electrode) and heated to various predetermined temperatures shown in Table 1 in an air stream at a heating rate of 0°C/hour. A heat treatment was performed to obtain an insoluble and infusible film-like substrate. Elemental analysis, X-ray diffraction, infrared spectrum analysis, and electrical conductivity measurements were performed on each of the cured phenol resin film and the film-like substrate. The results are shown in Table 1 along with the color tone of the samples.

Further, FIG. 1, FIG. 2, and FIG. 3 of the accompanying drawings show X-ray diffraction patterns of the cured phenol resin film, the substrate sample of Flat 3, and the substrate sample of I65, respectively. In Figures 1 to 3, the horizontal axis is the diffraction angle (2θ, degrees),
The vertical axis represents strength. In addition, Figures 4 to 6 show infrared absorption spectra of the cured phenol resin film, I63 substrate sample, and A4 substrate sample, respectively (measurements were performed using the film substrate as it was).
.

Figure 5 shows the absorbance of the peak from 2900 to 2940 m-1 (D 2110Q to 104G) and the peak absorbance from 1560 to 1640 m-1.
cm-' peak absorption layer (1'1441'l~N14
The method for determining fl ) is also described. D2. . . . . . , 94o are calculated by the following formula by finding tl, 1 and tb as illustrated. Similarly, J)l! 1101-4
,1. . is calculated by determining tv)2 and tb2 and using the following formula 1 formula %.

In Table 1 above, 41
The flow peaks appearing at 2θ positions between ~46' and 46' were all located near 43°.

In addition, the electrical conductivity is measured by four parallel lead wires at equal intervals in a rectangular fillem-shaped body that is a sample. Attachment (2) The voltage and current were determined separately in a room using a crystallizer using a direct current fixed source, pressure type, and source.

From Table 1 and Figures 1 to 6 above, heat treatment? RJt
? It can be seen that by setting the temperature to 500 to 740°C, a substrate having an atomic ratio of hydrogen atoms to carbon atoms of 0.60 to 0.15 can be produced. Furthermore, it can be seen from X-ray diffraction that all of the samples A1 to A5 have a boriacene structure, and the average distance between planar boriacene molecules is considerably larger than that of graphite or the like. This average distance between molecules is a convenient distance for the doping agent described later to enter, and electron interaction occurs between the molecules and the doping agent.

(2) Next, the undoped film-like substrate is placed in a vacuum line and the degree of vacuum is increased to 10-' torr or more, and then
Iodine gas was introduced into the line at room temperature, and the doping was
It lasted 0 minutes. Doping time 5 minutes without breaking vacuum, 1
The electrical conductivity at 0 minutes, 20 minutes and 30 minutes was measured for each sample (see Table 2). Table 2 shows that the electrical conductivity of all samples increased continuously during doping. After doping for about 30 minutes, the iodine gas was removed from the line, and the vacuum was maintained for about 180 minutes to remove excess adhering iodine. When the sample was taken out into the air from the line and the electrical conductivity was compared with the conductivity in the line, there was almost no difference (see Table 2).

In addition, the infrared absorption spectrum of the film-like sample doped in this way was analyzed and compared with that of the sample before doping. In all samples, the carbon intercarbon constituting the conjugated system (G) in the vicinity of N560 to 1640 Ni-1), which corresponds to telescopic imaging, was shifted by one point toward the wavelength side. This familiar phenomenon shows that there is an interaction of electrons in the curve between iodine and the boriacene structure -Cyl. In addition, for sample I63, a new peak (around 700 cm-') that was not present in the sample before doping appeared in the spectrum. Since this absorption is not based on the doping agent iodine, this phenomenon also indicates that there is an electron interaction between iodine and the boriacene-based structure. Second
The table shows the electrical conductivity during doping, immediately after being taken out from the line into the air, and after being planted in the air for 2000 hours.

From Table 2, it was found that doping with iodine significantly increased the electrical conductivity [1]. Also, what should be noted here is the undoped material whose thickness is approximately ]θμ.

rg, :l"Itj: Doping is almost completed in a relatively short time. The obtained electrically conductive organic polymer abrasive material of the present invention has excellent stability against oxygen in the air. It was confirmed that the

Example 2 Plain weave cloth made of phenolic #fiber (Japan Kynor Co., Ltd., ltθ product name Kynor, date 2oOf/rn”)
k 401i 8% resol type phenol resin by soaking in methanol solution, squeezing with a mangle, attaching resol type phenol resin, and drying at room temperature for 24 hours to form phenolic fiber/resol type phenol resin. = 1/1 (, li: amount ratio) prepreg was made. This prepreg was heated to 150°C and was pressed into a laminate under a pressure of 150 h/cm.
A plate with a thickness of 250 μm was obtained by curing for 0 minutes.

This plate was heat-treated by heating it at a rate of 70°C/hour up to 300°C or at a rate of 10°C/hour from 300°C to 600°C in a desirable atmosphere. This undoped platelet had an atomic ratio of hydrogen atoms to carbon atoms of 0.31 and an atomic ratio of oxygen to carbon atoms of 0.01. According to X-ray diffraction, peaks were found at 2θ22.5°, and other peaks were observed around 2θ41-46°. In addition, in the infrared absorption spectrum, the absorbance ratio D (D!1100~2040/'I)
neo~1640) was 0.05.

The thus obtained plate-shaped body (one thickness approximately 200 μm) was heated to 2000 μm. 1. From the surface of the plate exposed in a gas atmosphere. Doping was carried out for about 30 minutes. When the electrical conductivity of the sample was measured after doping, it was found to be approximately 1011 times higher than before doping.

Furthermore, when EMAX (electron micro analyzer) analysis was performed to investigate the doping state of iodine inside the plate after doping, it was found that iodine had penetrated at a depth of approximately 4077 mm from the surface of the sample. Iodine was concentrated in the layered part of the outer (111i) with the interface at this point, that is, the inner FiA regenerative conductor, but the outside of this interface was a p-type semiconductor.

Example) iii Sample of flat plate 4 prepared in Example 1, that is, electrically conductive
6-, 1-] degree is about 100. film (thickness approx. 10t+)
%-Put in a vacuum chamber, deaerate and reduce vacuum to 1O-2tn.
After increasing the pressure to rr or higher, SO and gas were introduced into the line.

After introducing 803 pieces, the air conduction of the sample at 11℃ suddenly increased in force.
l, about 20 minutes after the beginning] ()]1Ω-]crn-]
The film-like sample was dug out into the air and dried in a vacuum dryer at a temperature of about 60° C. for 24 hours. When the dried sample completely disappeared and its electrical conductivity was measured, it was found to have decreased to about 10<-1>o----1. For this reason, dry it again in the vacuum dryer under the same conditions as above for about 72℃.
After drying for an hour, the electrical conductivity was measured again and it was approximately 10 Ωcrn-1.
Met. It was confirmed that this electrical conductivity no longer changes even when taken out into the air. The sample after drying was purple in color, which was different from the black color before doping.

Example 4 The A4 sample film (1Q-6-1-1) prepared in Example 1 was used as an anode, the carbon plate conductivity was about 100 and a total cathode, and about 1 mol of Li C104 was added to 1 ton of propylene carbonate. Lightning doping was performed using the dissolved solution as an electrolyte.

Immediately after the voltage was applied, the current was about 0.01 milliamps, but after 15 minutes it was about 0.2 milliamps, and after about 2 hours it increased to about 3 milliamps. At this point, the sample was immediately taken out of the electrolyte, washed several times with acetone, and dried under reduced pressure at room temperature. When the electrical conductivity of the dried sample was measured, it was about 10-3 Ω-1-1, which was about 103 times higher than the electrical conductivity before doping, which was 10-6 Ω-1-1. In addition, the dry sample showed a deep blue luster.

EXAMPLE A tetrahydrofuran solution of sodium naphthalate was prepared using dehydrated tetrahydrofuran, naphthalene and metallic sodium. Example 1 to this solution in a dry box (N, air flow).

The sample of flat plate 4 prepared in step 4 was immersed and doped at room temperature. After being crushed in V for about 10 hours, it was dehydrated in a dry box and washed with tetrahydrofuran [7]. The best part is that this sample is heated at room temperature under a reduced pressure of about 10' torr.
It was dried for about 20 hours. The dried sample had a golden color, which was different from the black color before doping. Also, the electrical conductivity of this dry sample is approximately 1O-10-1ff
It was i-1.

Example 6 The same undoped plate as used in Example 2 (thickness approximately 2
00μ) Samples were examined for temperature changes in electrical conductivity over a temperature range of about -100°C to 20°C. Similar to general semiconductors, the relationship between electrical conductivity and temperature was approximately linear, with the reciprocal of salinity plotted on the horizontal axis and the logarithm of electrical conductivity plotted on the vertical axis. That is, as the temperature rose, the electrical conductivity also increased. From this relationship, the energy gap ΔE was calculated to be about 0.55'tW sub-volt.

Next, this plate sample was heated to 200°C for 1. Doping was performed by exposing it to a gas atmosphere for about 60 minutes.

The temperature change in electrical conductivity of this doped sample was investigated. Similar to before doping, Sanki conduction No. 1 increased as the number of pumps rose. Also, if we take the reciprocal of the temperature w on the horizontal axis and the logarithm of the air conductivity on the plate axis, then it becomes straight) Hemp relationship? Showing 1-,
The energy gap ΔF was approximately 0.1'5 mV.

Example 7 Weld-shaped cresol resin (cresol formaldehyde resin, thermosetting type, PR-91 manufactured by Sumitomo Durez Co., Ltd.)
2) It was poured onto a glass plate and stretched using an applicator. After that, it was dried for about 2 days (4. Heat thinned at a temperature of 150℃ for 30 minutes, and the NK'%' was about 3 ())
A film of μ was obtained. Next, this film was placed in a siliconite blind air furnace and heat treated in a nitrogen stream at a temperature increase rate of approximately 0°C/hour from room temperature to 610°C to form an insoluble and infusible film. A film-like substrate was obtained. Regarding this film-like substrate, elemental analysis, 'XM1 diffraction (see Figure 7)
, infrared spectral analysis (see Figure 1O), and sound measurements of electrical and gas conductivity were performed. The maximum peak position (2θ) in X-ray diffraction is 22.7°, 41-46° (2θ)
The peak size of was medium. In addition, in the infrared spectrum, the absorption between 2900 and 2940>-' is so small that it is almost unrecognizable;
absorption was clearly observed. Absorbance ratio rl) 1000~
! Q46/"'110~+640) f'j: Obviously smaller than 0.3. Also, the air conductivity was 1O-3
It was 0-1ffi-1.

Next, this film-like substrate was placed in a vacuum line, and iodine doping was performed for about 30 minutes in the same manner as in Example 1, and changes in electrical conductivity were examined.

After 30 minutes of doping, the electrical conductivity of the sample had increased to 10-1 Ω-1.

The results, including the above results, are summarized in Table 3 below.

Example 8 C phenol along the welding of a polyphenol-formaldehyde resin in which a portion of the phenol was slightly mixed with xylene:
Gysilene = 1:l (molar ratio), thermally polished type, PR-144 (M) manufactured by Mitsubishi Gas Co., Ltd.) was poured onto a glass plate and stretched using an applicator. After that, the film was air-dried for about 2 hours, and then heated for about 2 hours at a temperature of 150℃ to obtain a film with a thickness of about 5011.Next, this film was placed in a siliconite city air oven, and a nitrogen gas stream was applied to the film. The material was heat-treated from room temperature to 610°C at a heating rate of about 0°C/hour to form an insoluble film-like substrate.

The X-ray diffraction diagram and infrared absorption spectrum diagram of the upper nD film-like substrate (before doping) are shown in f@8 Figure 1.
Shown on 1F21. The infrared absorption spectrum contains 290
Absorption of 0 to 2940 Rho 1 is almost not observed. There is no small crack in the f pocket, and the absorbance ratio (D!(10(
1~2041+/DI! 160 to +6401 was smaller than 0.3.

Next, this film-like substrate was placed in a vacuum line, and iodine doping was performed for about 30 minutes in the same manner as in Example 1.

The results are shown in Table 3 below.

Example 9 Furan resin (furfuryl alcohol resin, Hitafuran 3OZ manufactured by Hitachi Chemical Co., Ltd.)* was poured onto a glass plate and stretched using an applicator. After that, it was air-dried for about 2 hours, and then heated at a temperature of 100 C for about 2 hours to cure it, to obtain a film with a thickness of about 40 μm. Next, the film was placed in a silicone electric furnace and heated to zero in a nitrogen stream.
The temperature was raised at a rate of .degree. C./hour, and heat treatment was performed from room temperature to 640.degree. C. to obtain an insoluble and infusible film-like substrate. The X-ray diffraction pattern and infrared absorption spectrum of this film-like substrate are shown in FIGS. 9 and 12, respectively. From Figure 12, the absorbance ratio (D2..0~lln/DI5671~+64
11) was found to be smaller than 0.3.

Next, this film-like substrate was placed in a vacuum line, and doped with iodine in the same manner as in Example J for about 30 minutes.

The results are shown in Table 3 below.

7/ /'' Example 1O A phenolic resin film with a hardness of about 30 μm was obtained in the same manner as in Example 1, and this resin film was further heat-treated to 610 μm in the same manner as in Example 1. A film-like substrate having an air conductivity of 10-7Ω-1J-1 was obtained.

Next, this film-like substrate was placed in the full wall line 5, and the pressure was set to approximately 10-'' torr at IF, and then the chambers m and K were
TeHr.

J-doping was introduced into the gas tank line for 30 minutes.

After that, the gas was removed from the system using a pump, and the pressure inside the system was set to about 10-1 torr.
7. Introduce gas into the system and repeat doping for about 30 minutes. +X<air conductivity of the sample at this point is approximately 10-
', [l-'nn-'f shown.

Example 11 A cured phenol resin film having a thickness of 10 μm prepared in the same manner as in Example 1 was heat-treated to 590° C. to obtain a black insoluble and infusible film-like substrate.

This film-like substrate has a hydrogen atom/carbon atom ratio and an oxygen atom/carbon atom ratio of 0.36 and 0.01, respectively.
3, and the position (2θ) of the maximum X-ray peak is 21.3
The magnitude of the peak between 41° and 46° was medium.

Also, IJ2JIT11~2+140/DI! 16°~
The absorbance ratio of 164o is 0.10, and the electrical conductivity is 1
It was 0-70-1-1.

This film-like substrate was subjected to sodium doping in the same manner as in Example 5. The 2-1 sample obtained had a golden, shiny color and an electrical and electrical conductivity of 10 Ωm-1.

On the other hand, a polyacetylene film obtained by a known method (cis type, toned color, thickness about 80 μm, air conductivity] o-8Ω-)
crn-1), sodium doping was carried out in exactly the same manner as above. The resulting sample had a golden, shiny color and an electrical conductivity of 1O-2Ω-1-1.

The above results indicate that the electrically and electrically conductive organic polymer material of the present invention, which is based on an insoluble and infusible substrate containing a new polyacene skeleton structure, provides excellent electrical conductivity equivalent to that of known polyacetylene. ing.

Considering the fact that the material of the present invention exhibits excellent oxidative stability while polyacetylene has poor oxidative stability, it can be seen that the material of the present invention is excellent in practical use.

[Brief explanation of the drawing]

FIG. 1 is an X-ray diffraction diagram (measured as a powder) of the cured phenol resin used in the present invention. FIGS. 2 and 3 are both x-ray diffraction patterns of the insoluble and infusible substrate used in the present invention derived from a cured phenolic resin. FIG. 4 is an infrared absorption spectrum diagram (measured with ILM) of the cured phenol resin used in the present invention. FIG. 5 and FIG. 6 are both infrared absorption spectra of the insoluble and infusible substrate used in the present invention derived from a cured phenolic resin. FIGS. 7 and 10 are an X-ray diffraction diagram and an infrared absorption spectrum diagram, respectively, of the insoluble and infusible bulk material used in the present invention derived from a cresol tree. FIG. 8 and FIG. 11 are an X-ray diffraction diagram and an infrared absorption spectrum diagram, respectively, of an insoluble and infusible substrate derived from xylene resin and used in the present invention. FIG. 9 and FIG. 12 are an X-ray diffraction diagram and an infrared absorption spectrum diagram, respectively, of an insoluble and infusible substrate derived from a furan resin and used in the present invention. Procedural amendment February 22, 1980 Patent chief 'Jiwakasugi Oro 1, Incident display fll, +a 57 qM41㇉uul 11. e
4 5 g2, Name of the invention + 12 Air conductivity + 1 Molecular thread preparation and its manufacturing method 3 Supplementary relation to the Nagisa incident Patent applicant address 4-4 Shoku-4, 5-17 Katata, Sumida-ku, Tokyo Agent 〒107 Specification 1 Detailed explanation of the invention” Packing il + Specification i! “EMAX(
Electron Micro Analyzer)”, “Ep
Using the MA (electron probe/X-ray φ microphone four analysis) method.'' (2) Add the following between lines 9 and 10 on page 64 of the specification. Example A cured phenol resin film with a thickness of about 30μ was obtained in the same manner as in the first half of Example 1 (1), and this film was
One sheet was prepared and heat-treated in a nitrogen stream in a siliconite electric furnace to 600°C and the other to 670°C to form an insoluble and infusible film-like substrate (hereinafter, the substrate A was heat-treated to 600°C). The material that has been heat treated to 6.70"C is called Substrate B).The electrical conductivity and hydrogen/carbon ratio of Substrate A by elemental analysis are 2X10-
'Ω-1, sub-1 and 0.31. In addition, the electrical conductivity and water f/carbon ratio of the substrate B are each 3XIO
-"Ω-・inverted-1 and 0.17. These substrates were placed in a vacuum line and the degree of vacuum was increased to 10".
After increasing the pressure to over 10-' torr (less than 10-' torr), iodine gas was introduced into the vacuum line at room temperature and doping was carried out for about 8 hours. -2Ω-1・C
The film-like sample obtained by doping substrate B also shows an electrical conductivity of txto°Ω-1・o
It showed an electrical conductivity of n″″1. Elemental analysis was conducted to determine the doped iodine cap of these samples, and it was found that 6
It was found that the sample was doped with iodine corresponding to 2% by weight (sample from substrate A) and 65% by weight (sample from substrate B). Furthermore, as a result of analyzing these same doped samples using the electron probe It became clear that Example 13 Sufficiently dehydrated tetrahydrofuran, naphthalene and sodium metal were introduced into a vacuum line to prepare a tetrahydrofuran solution of sodium naphthalate in the vacuum line. Next, the electrical conductivity used in Example 12 was 2×1O-70.
A film-like substrate (substrate A) of -1".cm-" was attached to a vacuum line and immersed in the above-mentioned sodium naphthalate solution in tetrahydrofuran to start doping with sodium. Four platinum lead wires were attached to the film-like substrate, and changes in the electrical conductivity of the sample during doping were measured. At the same time as the start of doping, the electrical conductivity increases significantly, and after about 30 minutes it reaches 5X10-' Ω-1
・It became crnl. After doping for about 4 hours,
The sample doped in line was washed with tetrahydrofuran. Next, for about 2 hours, the vacuum level xo-'to
It was dried at room temperature at τr. The air conductivity of dry sample 1 was 7X10-'Ω-"l?m-'. When the sample was taken out and subjected to elemental force analysis, it was found that the undoped For the basic type set t
axis sodium was detected. When the same doped sample was analyzed by the EPMA method, it was found that sodium atoms were present in large numbers in the ridges near the film surface, but had penetrated into the interior of the film in the thickness direction. Electric conductor used in Example 12 3X10-"Ω-"f
Similar experiments were conducted on the film-like substrate f1-' (substrate B). Approximately 4 hours after the start of doping, the electrical conductivity increased to lXl0'Ω""1.crn-'. After thorough washing with tetrahydrofuran and drying, air was introduced into the vacuum line to examine stability in air. I left it for about 2 hours, but the electrical conductivity was 10°Ω-1・IM-”
The following results showed that it was quite stable in air. "that's all

Claims (1)

[Scope of Claims] 1. (A) A heat-treated product of an aromatic condensation polymer consisting of carbon, hydrogen and oxygen, which is a polyacene having an atomic ratio of hydrogen atoms/carbon atoms of 0.60 to 0.15. (B) an electron-donating doping agent or an electron-accepting doping agent; and (C) having electrical conductivity greater than that of the undoped substrate. Characteristic electrically conductive organic polymer material. 2. The organic polymer material according to item 1, wherein the aromatic condensation polymer is a condensate of an aromatic hydrocarbon compound having a phenol hydroxyl group and an aldehyde. 3. The organic polymer material according to claim 1, wherein the aromatic condensation polymer is a condensate of phenol and formaldehyde. 4. The insoluble and infusible substrate is a heat-treated product of an aromatic condensation polymer consisting of carbon, hydrogen and oxygen,
The organic polymer material according to claim 1, which contains a polyacene skeleton structure having an atomic ratio of carbon atoms of 0.50 to 0.25. 5. The insoluble and infusible substrate has an oxygen atom (0)/carbon atom (C
) contains a polyacene skeleton structure having an atomic ratio of 0.06 or less. Lj
+ The organic polymer material according to any one of items 4 to 4. 6. Claims 1 to 6, wherein the insoluble and infusible substrate contains a boriacene skeleton structure in which the atomic ratio of oxygen atom (0)/carbon □ atom (C) is 0.03 or less. The organic polymer material according to any one of Item 4. 7. The insoluble and infusible substrate has a main peak position of 20.5 in 2θ in X-ray diffraction (Cu Ka line).
7. The organic polymeric material according to any one of claims 1 to 6, which occurs in the range of 23.5 degrees. 8. Any one of claims 1 to 7, wherein the insoluble and infusible substrate exhibits the presence of a nihique in the range of 41 to 46 degrees as expressed by X-ray diffraction (f Cu Ka line) odor 20 An organic polymeric material described in Crab. 9. The absorbance ratio of the insoluble and infusible substrate is determined from the infrared absorption spectrum and is expressed by the following formula (1)), D=D20
n11-! 040 /D+! 160~l+! Of the 40 formulas,
D7. . . 4.4o is the absorbance determined from the maximum absorption peak in the range of 2900-2940 Kaiser in the infrared absorption spectrum, Dlaen ~ 1640 is the absorbance determined from the maximum absorption peak in the range of 1560-1640 Kaiser in the infrared absorption spectrum, is 0.5 or less, claims 1 to 8
The organic polymeric material according to any one of paragraphs. 10. Any one of claims 1 to iM 9 J/l, wherein the insoluble and infusible substrate has an absorbance ratio (D) as defined above determined from an infrared absorption spectrum of 0.3 or less The organic polymeric material described. 11. Is the organic polymer material v? DC conductivity at M is 1
Claim 1 which is O-40-1crn-1 or more
The organic polymer material according to any one of items 1 to 10. 12. The organic polymeric material according to any one of claims 1 to 11, wherein the electron-donating doping agent is a Group 1A metal containing lithium, sodium, potassium, rubidium, and cesium. 13. Claim 1 in which the electron-accepting doping agent is a rogene such as fluorine, chlorine, oxaline, iodine, etc.
The organic polymer material according to any one of items 1 to 11. 14. The electron-accepting doping agent is AsF'=, PF
! The organic polymer material according to any one of claims 1 to 11, which is a halide such as 11BF*, BCI s, BBr3, etc. 15. The electron-accepting doping agent is SO9 or Nt
Oxides of nonmetallic elements such as Oll or HtS0
4. The organic polymeric material according to any one of claims 1 to 11, which is an anion derived from an inorganic acid such as HNOs or HCl0. 16. The organic polymeric material is a molded article. 7. The organic polymeric material according to any one of claims 1 to 15, wherein the organic polymeric material is a film, a plate, a fiber, or a composite thereof. Organic polymeric material according to any one of claims 1 to 15. 18. Heating an aromatic condensation polymer consisting of carbon, hydrogen, and oxygen to a temperature of 400 to 800°C in a non-oxidizing atmosphere. After heat treatment, the atomic ratio of hydrogen atoms/carbon atoms becomes 0.
60 to 0.15 and then doping it with an electron-donating doping agent or an electron-accepting doping agent or a mixture thereof.
A method for producing an electrically conductive organic polymer material, characterized by making electrical conductivity greater than gas conductivity. 19. The method according to claim 18, wherein the aromatic condensation polymer is a condensate of an aromatic hydrocarbon compound having a phenolic hydroxyl group and an aldehyde. 20, a resol type in which the aromatic condensation polymer is obtained by a condensation reaction of phenol and formaldehyde;
The method according to claim 18, which is a molded article of novolac type or a mixture thereof. 21. The method according to claim 18, wherein the aromatic condensation polymer is a molded article comprising a composite of phenolic fibers and a phenol-formaldehyde condensate. 22. Doping increases electrical conductivity to 10
22. A method according to any one of claims 18 to 21, wherein the method is increased by a factor of two or more.