JPS62268004A - Conducting material - 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] <Industrial Application Field> The present invention relates to a conductive material formed by disposing a polymer of a compound having a conjugated double bond only on one side of a specific base material. .

<Prior art> Polymers having a conjugated double bond in the main chain, such as polyacetylene, polyparaphenylene, polythenylene, polypyrrole, and polyparaphenylenevinylene, are arsenic pentafluoride and antimony pentafluoride.

When treated with P-type or ＼-type doping agents such as iodine, bromine, sulfur trioxide, )-butyllidium, and naphthalene, the electrical conductivity is significantly improved, making it possible to transform it from an insulator to a semiconductor to a conductor. It is known that these conductive materials (so-called conductive polymers) are powdered 2
granular.

It can be used as it is or after being molded depending on the purpose, in block or film form, and can be used as functional devices such as antistatic materials, electromagnetic shielding stones, charge conversion elements, optical memory (bolographic memory), and various sensors. Applications to a wide range of fields such as display elements (ELEC 1 to Lochromism), switches, various hybrid materials (transparent conductive films, etc.), various terminal devices, and storage batteries are being considered.

However, this type of conductive polymer generally has poor moldability and h0 workability, and in particular, it is necessary to use a special method to prepare a film-like conductive polymer. At present, such conductivity is not possible as a polymer film.
A polyacetylene film is obtained by blowing acetylene gas onto a glass wall coated with a polymerization catalyst and then peeled off from this glass wall, or a polyacetylene film obtained by forming it on an electrolytic electrode by an electrochemical oxidation reaction (electrolytic oxidation polymerization) and then peeling it off from this glass wall. Polythenylene films and polypyrrole films that can be peeled off (q) are known.

However, the above-mentioned conventional conductive polymer films have the drawbacks that polyacetylene films are unstable in air, prone to oxidative deterioration, and have low mechanical strength.
In addition, polythenylene films produced by electrolytic oxidative polymerization (7) have disadvantages in that the size of the film is restricted by the size of the electrolytic electrode, and the manufacturing process is complicated, resulting in losses of 1 to 10%.

Therefore, the present inventors first applied for patent application No. 60-225761.
No. 1, a novel method without the above-mentioned drawbacks is produced by vapor-phase polymerizing a compound having a conjugated double bond on a substrate having a space capable of retaining the oxidizing agent in the presence of the oxidizing agent. A conductive material was proposed.

Problems to be Solved by the Invention> By the way, if it were possible to provide conductive polymer awns only on one of the base materials in this type of conductive polymer film, the field of application would further expand, for example, when the surface shape It can also be expected to be applied to heating elements, laminated photoelectric conversion function materials, TEPCO bodies, electrode materials integrated with diaphragms, electrode materials integrated with current collectors, etc.

However, in the conductive material of the above-mentioned Japanese Patent Application No. 60-225761, when it is intended to hold the oxidizing agent only on one side of the plugging material in order to form a single layer of conductive polymer on one side of the base material, the oxidizing agent is Because the oxidizing agent penetrates into the entire space of the substrate and is easily retained, the oxidizing agent also penetrates into other surfaces of the substrate, and as a result of the above-mentioned gas phase polymerization, conductive polymer is formed throughout the substrate, and as a result, the oxidizing agent penetrates into only one side of the substrate. It has been found that producing conductive polymers can be very tricky and can be extremely complex to manufacture.

In the prior art, a conductive polymer film layer is formed by coating a solution containing an oxidizing agent and a polymer binder on a suitable base material and then contacting it with pyrrole or aniline vapor to form a conductive polymer film layer on the base material. There is a composite film, but in this composite film, the presence of one layer of polymer binder between the base material and the film layer increases the thickness of the composite film, making it difficult to create a thin composite film. There is a drawback that the concentration of the conductive polymer component decreases, and when used as an electrode material for a storage battery integrated with a current collector, for example, the charging and discharging characteristics of the electrode decrease.

Means for Solving the Problems> The present inventor has developed a polymerized compound having a conjugated 2m bond on a specific base material, which does not have the above problems, is stable in air, and is easy to manufacture. In addition to this, we have conducted research to provide a conductive material that can, for example, make one side of a base material conductive in any direction, and if the following means are used, the intended purpose can be achieved. This invention was completed after learning that it was possible to achieve this.

That is, in the conductive material of the present invention, a base material having a space capable of retaining an oxidizing agent is treated with an oxidizing agent so that the oxidizing agent is retained only on one surface of the base material, and 1 q. An electrically conductive material obtained by polymerizing a compound having a double bond on the base material to form a polymer of the compound on the surface, the base material having at least one surface hydrophobic. This is the summary.

The above-mentioned oxidizing agent is a compound that has polymerization activity toward a compound having a conjugated double bond, and can be used alone or in combination.
Used in combination of more than one type. Usually, strong acid residues, halogens, metal salts containing cyanide, peroxides, etc. are used. Specifically, Fe (C/204 > 3, Fe (B
F4. >3.

Fe2 (s! F6 )3 , Cu (c! Qo4
>2゜Cu (BF4)2, cus! F6, F
eCf3.

CIJCf2, ni3 (Fe (CN)6).

RuCβ3, :'vloc2.5, WCl2゜(N
H4)2S208. 2S208°N a2 S20B
, NaBO3, H202, etc., and those having water of crystallization or those containing 1q as an aqueous solution can also be used.

Furthermore, the base material mentioned in (g) has a space capable of retaining the oxidizing agent as described above, and has at least one surface that is hydrophobic. Hydrophobicity means that the contact angle of water is 90' or more. The oxidizing agent is used as an aqueous solution so that it is easily retained on only one side of the substrate. If a solvent such as methanol, ethanol, acetylated nitrile, or tetrahydrofuran that is permeable to the H group is used as a solvent for the oxidizing agent, even if one side of the substrate is hydrophobic, the oxidizing agent will also be present on that side. It is difficult to retain the oxidizing agent only in any part of the substrate because the oxidizing agent easily penetrates the substrate. For example, when one side of the sheet 1 is hydrophobic and the other side is hydrophilic, the base material is immersed in an oxidizing agent aqueous solution, or the oxidizing agent aqueous solution is applied to the hydrophilic side. By this, the oxidizing agent can be easily retained on the hydrophilic surface of the substrate. In addition, if both sides of the sheet-like base material are hydrophobic, an oxidizing agent aqueous solution is repeatedly applied to one side, or one side is treated with a hydrophilic agent such as polyethylene oxide or polyvinyl alcohol, and then oxidized. The oxidizing agent can be retained on one surface by soaking it in an agent solution or by applying the oxidizing agent to the hydrophilic surface. Furthermore, when both sides of the C1~-shaped base material are hydrophilic, one side is made of silicone.

The oxidizing agent is retained on the hydrophilic surface by treating it with a fluorine-based lσ water agent to make it hydrophobic and then infiltrating it into an oxidizing agent aqueous solution, or by applying an oxidizing agent aqueous solution to the hydrophilic surface. Can be done.

Further, the oxidizing agent can be held in all parts on one surface of the plugging material, but it can also be held in only a predetermined part as necessary. In other words, if the oxidizing agent is held continuously in a linear manner only in a specific direction on one surface of the base material, a polymer of a compound having a conjugated double bond will be formed in a continuous linear manner only in that area. 1 d of anisotropic conductive material having conductivity only in a specific direction is provided. Furthermore, since any part on one surface of the base material can be made conductive in any direction, it can also be applied as a conductive path forming material.

The above-mentioned space that can hold the oxidizing agent only needs to have a spatial size that can hold the oxidizing agent used at least in the form of molecules or aggregates. It is undesirable if the space is too small to hold the oxidizing agent in a molecular state, or if the space is too large to hold the oxidizing agent in an aggregated state.

This space is distributed on or inside the substrate as pores or gaps of various shapes. Specifically, in the case of pores, the size thereof is such that the average pore diameter is 0.001 to 100 am, preferably 0.005 to 50 μm. It is also known that the depth of the pores is at least 0.00 μm, preferably at least 0.005 μm.

Specifically, the planar form of profiteering having such characteristics is made of porous materials (plate-shaped molded products, films, etc.).
filament), woven m, fukai iro, etc.

Further, as the base material, organic or non-organic base materials are used. Specific base materials include polyolefin, polyhalogenated vinyl, and polyfluorine.

Polyester-based, polyamide-based, polyimide-based.

Materials such as polyvinyl alcohol-based, polyacrylic-based, polycarbonate-based, rayon-based, cellulose-based, copolymer systems thereof, and mixed material systems are used.

Further, as the base material, carbonaceous materials, metal-based 8 alloys, metal oxides, metal carbides, metal nitrides, and mixtures thereof are used. Furthermore, a mixed base material of an organic base material and an inorganic base material may also be used.

Examples of such substrates include, specifically, organic substrates such as polyethylene, polypropylene, ethylene-propylene copolymer, polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, volite 1 to lafluoroethylene, and polyethylene. Terephthalate, polybutylene terephthalate-1-, polystyrene, polyamide, polyimide,
Polyamideimide, polyvinyl alcohol.

Edylene-vinyl acetate copolymer, polyacrylonitrile, polymethacrylonitrile.

Polymer methacrylate, polybutyl methacrylate, poly-1-nosdylene - acrylonitrile, polycarbonate,
Rayon, methylcellulose, nitrocellulose, carboxymethylcellulose, etc. are used. In addition, activated carbon, carbon black, graphite, and chromium are used as inorganic base materials.

Titanium, nickel, gold, platinum, tantalum, copper.

Silver, iron, stainless steel, alumina, silica, silica alumina, zirconia, beryllium oxide, potassium titanate, silicon carbide, boron carbide, titanium carbide, molybdenum carbide, tantalum carbide boron dinitride, silicon nitride, niobium nitride, etc. are used. Ru.

As the compound having a conjugated double bond used in the present invention, pyrrole-based compounds, thiophene-based compounds, etc. are used alone or in combination. Preferably, a pyrrole or thiophene compound having no substituents at the 2 or 5 positions of the ring structure of pyrrole or thiophene is used. Specific examples of the pyrrole compound include pyrrole, N-methylpyrrole, N-ethylpyrrole, and Nn-propylpyrrole.

N-n-butylpyrrole, N-phenylpyrrole, N-
i~ruylpyrrole, N-nanotylpyrrole, 3-methylpyrrole, 3,5-dimethylpyrrole, 3-ethylpyrrole, 3-n-propylpyrrole, 3~n-butylpyrrole, 3-phenylpyrrole, 3-tolylpyrrole , 3-naphthylpyrrole, 3-methoxypyrrole, 3-
5-dimethoxypyrrole, 3-ethoxypyrrole, 3-
n-propoxypyrrole, 3-phenoxypyrrole, 3
-Methylhemethylpyrrole, 3-me1-xyN-methylpyrrole, 3-chloropyrrole, 3-bromopyrrole, 3-methylthiopyrrole, 3-methylthioN-methylpyrrole, etc.

Also, what are the specific examples of thiophene compounds? , 2゛-bithiophene, 3-methyl-2,2゛-bithiophene,
3.3'-dimethyl-2.2'-bithiophene, 3,
4-Dimethyl-2,2'-bithiophene.

3,4-dimethyl-3',4°-dimethyl-2,2゛-
Bithiophene, 3-methoxy-2,2'-bithiophene, 3,3'-dimethoxy-2,2'-bithiophene.

2,2',5',2''-terthiophene, 3-methyl-2.

2',5',2'-terthiophene, 3,3'-dimethyl-2,2',5',2''-terthiophene, and the like.

The ratio of the oxidizing agent to the compound having a conjugated double bond is related to the amount of polymer produced, but is usually determined by G. OO1~10
,000 mole times, preferably 0,005 to 5,0
00 mole times.

The formation of a polymer of a compound having a conjugated double bond in Murakami is carried out in a gas phase atmosphere.

That is, the polymer formation is carried out in a gas phase atmosphere in the presence of vapor of only the compound having a conjugated double bond or with nitrogen, argon, air, other gases, or mixed gases. The entire system can be carried out under IJ11 pressure, normal pressure, or reduced pressure, but it is usually preferable to carry out the process under normal pressure from the viewpoint of process control.

The reaction temperature is not particularly defined as long as it is a temperature at which a compound having a conjugated double bond can polymerize, but it is usually -20 to
It is carried out at 150°C, preferably 0 to 100°C. In addition, the reaction time is related to the reaction temperature, the amount of oxidizing agent, the amount of compound having a conjugated double bond, etc., but is usually 0.01~
200 hours, preferably 0.02 to 100 hours.

After the polymerization reaction, a dark brown to black homogeneous polymer is produced on the portion of the base material that retains the oxidizing agent.

Once formed, an oxidizing agent is further held on top of the above-mentioned polymer, and a compound having the same or different type of conjugated double bond is brought into contact to continue the polymerization reaction, resulting in an increase in the number of polymers produced or two or more types of polymers. It is possible to form a polymer of (q).

After the polymerization reaction is completed, the compound having a conjugated double bond and the oxidizing agent remaining on the substrate are removed. Usually, it can be removed by soaking the base material in water, alcohol, or a precipitated solvent and washing it. Thereafter, the conductive material of the present invention can be obtained by drying the base material by a normal drying method.

Effect> By making at least one side of the base material hydrophobic as described above, the oxidizing agent can be easily retained only on one side of the base material.1. ′
It is possible to produce a conductive polymer only on this surface, and it is also possible to produce 1 q of conductive material that is easy to manufacture and has excellent oxidation resistance.

<Example> The present invention will be specifically described below with reference to Examples.

Examples 1 to 3 A polyethylene porous film with a pore diameter of 0.1 to 10 μm and a film thickness of 20 μm and hydrophobic on both sides (height: 10 cm, width: 20 cm)
A Fe(C!2.04)3.8H20-water saturated solution was applied three times to one side of the film to maintain the three Fe(Cff104) components uniformly on one side of the film. Then,
Pyrrole 4mN in a glass container (depth 10cm, width 25cm)
cm, height 15 cm) at the bottom, and the above treatment made it 19 cm.
The porous film was suspended from the top of a glass container, the top of the container was sealed with a glass plate, and brought into contact with pyrrole vapor.

Upon contact with pyrrole vapor, the porous film rapidly changed color from yellow to dark green to black, forming polypyrrole on one side of the porous film. After the predetermined contact time shown in Table 1, the film was removed and diluted with methanol for 3 hours.
It was immersed for 0 minutes to extract and remove unreacted virol and Fe (CJ204>3 components). After continuing this operation three times, it was air-dried to yield 1 q of flexible film with one side black.

Table 1 also shows the thickness of this film and the results of measuring the electrical conductivity in the horizontal direction on one side of the film using an electrode on one side of the film.

Table 1 Incidentally, the electrical conductivity was measured by a four-terminal method.

In addition, when we measured the electrical conductivity of the film in the vertical direction by placing electrodes on one side of the film and on the surface of the pond, we found that it was less than 10"5 cm-1 in both cases, and only one side could be made conductive. This was confirmed.

Example 4: An aqueous solution in which polyfluoroethylene propylene was dispersed was sprayed onto the top surface of a 0.5n1m thick nylon non-similar cloth (length 1Qcm, width 20CIIl) using a sprayer, and the temperature was 6.
It was dried under reduced pressure at 0'C for several hours to form a polyfluoroethylene propylene layer (hydrophobic layer) on the upper surface of the above-mentioned non-woven material. Upon contact with the pyrrole vapor, the part of the nonwoven fabric without the polyfluoroethylene propylene layer quickly changed color from yellow to dark green and then to black, and polypyrrole was formed in the same part.Pyrrole vapor After continuing contact with the nonwoven fabric for 2 hours, the nonwoven fabric was taken out and immersed in methanol for 30 minutes to extract and remove unreacted pyrrole and the remaining three components of f''e (Cβ04).

When this extraction/removal operation was continued three times (11!2) and air-dried, a black conductive layer 2 (polypyrrole layer) was formed on the bottom surface, and a hydrophobic layer 1 consisting of a polyfluoroethylene propylene layer was formed on the top surface, as shown in Figure 1. , 1q of flexible nonwoven fabric was produced. The electrical conductivity of the conductive layer 2 on the lower surface of this nonwoven fabric is 5.
2X 10”SCm, top surface electrical conductivity is 10-11
It was confirmed that only the lower surface of the nonwoven fabric could be made conductive at Sen-' or lower.

Example 5 A polypropylene porous membrane with a maximum pore diameter of 0.02 x O, 2 μm, I thickness of 25 μm, and hydrophobic on both sides (Duraguard)
2400) was used, and as a result, a glossy film having a thickness of 28 μm and black on one side was obtained. The electrical conductivity of this film in the horizontal direction was 6.5 x 10-23 cm-1, and the electrical conductivity in the vertical direction was less than 10''Scm-', making it possible to make only one side conductive.

Example 6 Film thickness 220 μm with surface treated to make it hydrophilic with surfactant
, 3 polypropylene nonwoven fabrics with a weight of 75C+/n+2
After immersing it in a 0% potassium hydroxide aqueous solution and heat-treating it at a temperature of 60'C for 1 hour, washing it thoroughly with water and drying it, the surfactant is removed and the surface of ¥1 becomes hydrophobic. Become.

Except for using this non-woven fabric 15, the same procedure as in Example 2 was carried out to hold Fe (Cβ04)3 component on one side of the non-woven fabric and contact with pyrrole vapor, resulting in a film thickness of 230 μm.
A nonwoven fabric with one side black was obtained in m. The electrical conductivity of this nonwoven fabric in the horizontal direction was 1.8×10'Scm-', and the electrical conductivity in the vertical direction was 10-10ScI11-1 or less, making it possible to make only one side of the nonwoven fabric conductive. .

Comparative Example 1 In addition to not performing the treatment with a 30% potassium hydroxide aqueous solution (also, as a result of performing the same treatment as in Example 6 above, it was impossible to retain the oxidizing agent on only one side of the nonwoven fabric, and after contact with polypyrrole vapor) Both sides of the nonwoven fabric were blackened due to the formation of boron nobilol.

The electrical conductivity of this non-woven iron in the horizontal direction is 1.5X10-
10-13C, vertical direction) 71 Air conductivity Li 4.8x
"10-23 cm-1, and it was not possible to make only one side conductive.

Comparative Example 2 Oxidizing agent solution binding TFe (Cβ204 >3 '81-
The process was carried out in the same manner as in Example 1 except that a Fe(c,co4)3.8H20-methanol saturated solution was used instead of the +20-water saturated solution, and as a result, 1q of films were obtained, both sides of which were black due to polypyrrole formation. . The electrical conductivity of this film is 2 in the horizontal direction.
．． 8×1O-18CIIl-1, vertical direction is 1.8x
10-''3 cm-1, and it was not possible to make only one side of the film conductive.

Example 7 Pore diameter o, 1 to 10 μm, film thickness 80 μm, length 10 cm
On one side of a polyethylene porous film with a diameter of 20 cm and hydrophobic on both sides, 40 straight lines with a width of 2 m and 1 Tl were drawn in the vertical direction with an aqueous saturated solution of FeCl2.6+120, and after air-drying, pyrrole vapor was added as in Example 1. It was placed in an atmosphere. As a result, a black straight line 40 with a width of 2II1 m in the vertical direction on one side.
A film with a book was sold for 1q. This film exhibited electrical conductivity of 1.3X'IO-13cm-'S- in the longitudinal direction, and insulation in the vertical direction with h'W direction E<U.

In this way, it was possible to create a conductive film that had conductivity only in the vertical direction on one side of the film.

Example 8 Using 3-methylvirol instead of pyrrole, Fe
(Cβ04)3.8H20 instead of Cu (E3 “4)
The same procedure as in Example 1 was carried out except that a 40% aqueous solution of No. 2 was used, and as a result, 1q of films having a thickness of 22 μm and black on one side were formed.

The electrical conductivity of this film in the horizontal direction is 1.8×10'5
cm-1, and the electrical conductivity in the vertical direction is 10-10-
Must be removed below 1O8C.

Examples 9 to 15 Various pyrrole compounds were polymerized by being brought into contact with various oxidizing agents shown in Table 2 on one side of various porous films in a gas phase atmosphere for 24 hours. The results are summarized in Table 2. It was shown.

Examples 16-22 Table 3 also shows end beams that were made in the same manner as in Example 1, except that various types of moldings shown in Table 3 were used.

In the case of Examples 17, 18, 20, 21, and 22, one side of each nonwoven fabric was spray-coated with a fluorine-based water repellent in advance to perform hydrophobization treatment on one side, and then soaked in a saturated aqueous solution containing an oxidizing agent. Each nonwoven fabric was impregnated to avoid retaining the oxidizing agent on the side that had not been hydrophobized.

Examples 23 to 29 The results were also shown in Table 4 in the same manner as in Example 1 except that various woven or nonwoven fabrics shown in Table 4 were used.

In addition, in these Examples, each woven fabric and nonwoven fabric 1 are as follows:
A silicone-based water repellent was spray coated on one side to make it hydrophobic, and an oxidizing agent was applied to the non-hydrophobic side to hold it.

Example 30 Table 5 shows the results of measuring changes in electrical conductivity over time of the conductive film prepared in Example 2.

I-ko.

The results shown in Table 5 and above show that the change in electrical conductivity of the conductive film subjected to IG according to the present invention is extremely small.

DAKODO 31 Foamed nickel plate with a thickness of 1.0 mm (length 1Q cm, width 20
Cm) Lafluoroethylene to Polyte 1 on the top surface? The dispersed aqueous solution was sprayed with a sprayer, dried under reduced pressure at 60'C, and then heat treated at 375°C for 30 minutes under 3 argon atmospheres to fuse the polytetrafluoroethylene.

The process was carried out in the same manner as in Example 1 except that the foamed nickel plate treated as described above was used. As a result, the electric conductivity of the black part made of polypyrrole formed on the temporary lower surface of the foamed nickel was 1. Ox 10'5 cm-1.

Nail overwhelming 32 Foamed nickel plate with a thickness of 91.0 mm (ulocm, width 20
Cm) Color was carried out in the same manner as Example 1, except that an aqueous solution of polyethylene oxide was sprayed with a sprayer on the top surface of Cm, and then dried under reduced pressure at a temperature of 60C for several hours. Black part made of polypyrrole formed on the surface 7) Electrical conductivity is 1. ixlo-1SCm-
1T” Arata.

Example 33 Pore diameter: 0.1 to 1 μm, v, thickness: 20 μm, length: 10
The same procedure as in Example 1 was used, except that an aqueous solution containing polyvinyl alcohol dispersed was applied with a roller to a polyethylene porous film measuring 20 cm wide and 20 cm wide, and dried under reduced pressure at a temperature of 60'C for several liters. As a result, the electrical conductivity of the black part made of polypyrrole formed on the bottom surface of the film was 2.5 x 10"5 cm-1 1.j?I
, Jl:'The electrical conductivity of the upper surface of the film in which low Azwo was not generated was less than 10"3 cm-1, which was 0.

A method for forming the old aqueous layer is the Doctor Plaid method (while passing the base material between the slits formed by two blades, gel-like (in this case, a gel-like aqueous dispersion of a water-repellent agent) is installed and applied), and a gel-like aqueous polytetrafluoroethylene dispersion solution is used as the coated object, and then dried after painting. As a result, the electrical conductivity of the surface where polypyrrole was formed was 2.8X 'l □
-13 cm-1. Further, the electrical conductivity in the case where polypyrrole was not generated was 10-113 Cm-1 or less.

Example 35 The same procedure as in Example 1 was carried out except that the aqueous dispersion of polyethylene was used instead of the aqueous dispersion of the old liquid medicine. As a result, the electrical conductivity of the surface where polypyrrole was formed was 2.8X 10"13 cm. The electrical conductivity of the surface on which polypyrrole was not formed was 'to-118 Cm-1 or less.

Example 36 Polypyrrole was produced in the same manner as in Example 1 except that a base material on which a former aqueous layer was formed by a plasma polymerization method using tetrafluoroethylene as a polymerization polymer was used. The degree is 2.8X 1 Q-'3cm
It was -1. The electrical conductivity of the surface on which polypyrrole was not formed was 10-118c0-1l8. Lower Tea Tsuta.

Example 37 The same procedure as in Example 3 was carried out except that 5.0 g of 2.2°-bithiophene was used instead of pyrrole and the reaction temperature was 70'C. As a result, 1 q of porous film with one side black was obtained.
It was done. The electrical conductivity of this film is 7.5 in the horizontal direction.
x 10'Scm-', vertical direction is 10-10-1O3
'It was less than.

Example 38 The same procedure as in Example 3 was carried out except that 3,3"-dimethyl-2,2°-bithiophene 5.OCl was used in place of virol and the reaction temperature was 80°C. As a result, one side had a deep blue color. The electrical conductivity of this film was 4.6 x 10' S Cm'' in the horizontal direction and less than 10-100-1 O3 in the vertical direction.

<Effects of the Invention> As described above, the conductive material of the present invention is easy to manufacture, has excellent oxidation resistance, and has extremely great practical value. Thus, the conductive material of the present invention can be used as an antistatic material, an electromagnetic wave shielding material, a photoelectric conversion element, an optical memory, various sensors, display elements, switches, various terminal devices, storage batteries, or anisotropically conductive materials.

It can be applied not only to conductive path forming materials, but also to a wide range of fields such as planar heating elements, laminated charge conversion function materials, Tokyo electric bodies, diaphragm-integrated electrode materials, and current collector-integrated electrode materials.

[Brief explanation of the drawing]

The attached drawings are fS diagrams of examples. 1... Hydrophobic layer, 2... Conductive layer.

Claims (1)

[Claims] 1. A base material having a space capable of retaining an oxidizing agent is treated with an oxidizing agent so that the oxidizing agent is retained only on one surface of the base material, and the conjugated dihydride is produced in a gaseous atmosphere. An electrically conductive material obtained by polymerizing a compound having a double bond on the base material to form a polymer of the compound on the surface, wherein the base material is characterized in that at least one surface is hydrophobic. conductive material. 2. Dip a base material with one side hydrophobic and the other side hydrophilic in an oxidizing agent aqueous solution, or apply the oxidizing agent aqueous solution to the other side to retain the oxidizing agent on the other side. The conductive material according to claim 1, wherein the conductive material is 3. The conductive material according to claim 1, characterized in that an aqueous oxidizing agent solution is applied to one surface of a base material whose both surfaces are hydrophobic to retain the oxidizing agent on the one surface. 4. The conductive material according to claim 1 or 2, which is obtained by treating one side of a base material whose both sides are hydrophobic with a hydrophilic agent. 5. The conductive material according to claim 1 or 2, which is obtained by treating one side of a hydrophilic base material with a water repellent.