JP2003123532A - Conductive composition, conductor and its forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive composition manifesting high conductivity without humidity dependency and having excellent film formability, moldability, achromatic transparency, solvent resistance, water resistance, hardness and weather resistance, and to provide a conductor and a forming method of the conductor obtained by forming a conductive film manifesting high conductivity without humidity dependency and having little dispersion of surface resistance and excellent film formability, moldability, achromatic transparency, solvent resistance, water resistance, hardness and weather resistance. SOLUTION: This conductive composition comprises an indore derivative trimer A, a solvent B and a cross-linking agent C, and further if necessary, colloidal silica E, a basic compound F, a high molecular compound G, a surfactant H and/or inorganic salt I. The conductor formed of the conductive composition, and its forming method are provided.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a conductive composition containing an indole derivative trimer, a conductor formed from the conductive composition, and a method for forming the same. The conductive composition of the present invention can be applied to various antistatic agents, capacitors, batteries, EMI shields, chemical sensors, display elements, non-linear materials, anticorrosives, adhesives by using simple methods such as coating, spraying, casting and dipping. Agent, fiber, antistatic paint, anticorrosion paint, electrodeposition paint, plating primer,
It can be applied to applications such as conductive primers for electrostatic coating, cathodic protection, and improvement of battery storage capacity. The conductor of the present invention is a semiconductor, industrial packaging materials such as electric and electronic parts, films for overhead projectors, antistatic films such as electrophotographic recording materials such as slide films, audio tapes, video tapes, computer tapes,
Antistatic for magnetic recording tapes such as floppy disks, antistatic for transparent touch panels, electroluminescent displays, liquid crystal displays and other input and display device surfaces, transparent electrodes, light-emitting materials for forming organic electroluminescent elements, buffer materials, electronic It is used as a transport material, a hole transport material and a fluorescent material.

[0002]

2. Description of the Related Art Conventionally, as a conductive component of a conductive composition, metal powder, carbon powder, an inorganic conductive agent such as ITO, an organic conductive agent such as a surfactant, and a conductive material such as polyaniline and sulfonated polyaniline. Polymers are known.

Among these, a conductive film formed from a conductive composition composed of carbon powder or metal powder and a polymer compound is excellent in the durability of the coating film, but the amount of the conductive component added is 10 to 30 parts by mass. It is necessary to some extent and lacks transparency. Further, in order to exhibit transparency, there is a drawback that sufficient conductive performance cannot be obtained if the amount of the conductive component added is reduced. On the other hand, by kneading a semi-transparent surfactant such as anionic, cationic, nonionic or amphoteric into the plastic film or coating the plastic film surface, it imparts hydrophilicity and ionicity to the film surface. A material having conductivity is known. However, since the conductive film obtained by this method is ionic conductive, its conductivity is easily affected by humidity in the atmosphere, and the surface resistance per unit area is 10 ⁹ Ω or less under low humidity conditions. However, there is a drawback in that it cannot be obtained stably.

It is known that a conductor obtained by depositing ITO (indium-tin oxide) as a conductive component is excellent in transparency and conductivity. However, since a vacuum vapor deposition apparatus is required to form the thin film, the production of the conductive film is complicated, and the apparatus is expensive. Moreover, since ITO used as a material is also expensive, there is a drawback that the obtained conductor is also expensive.

Although conductive polymers doped with polyaniline and the like are well known, they have the drawback that they are insoluble in almost all solvents and are difficult to mold and process. In addition, a method of electrolytically oxidatively polymerizing aniline [JP-A-60-2358]
31 publication, J. Polymer Sci. , Poly
mer Chem. Ed. , 26, 1531 (198
8)] is capable of forming a polyaniline film on the electrode, but has the drawback that the isolation operation becomes complicated and mass synthesis is difficult. On the other hand, a conductive composition comprising polyaniline in an undoped state obtained by chemical oxidative polymerization of aniline and an ammonium salt of a protonic acid having an acid dissociation constant pKa of 4.8 or less (JP-A-3-2
However, since polyaniline in the undoped state is soluble only in a special solvent having an extremely strong dissolving power such as N-methyl-2-pyrrolidone, it affects the coating substrate. It is difficult to say that it is suitable as a general-purpose varnish due to its drawbacks. Further, the coating film obtained from the composition has a green to blue coloration unique to the conductive polymer, which affects the color tone of the base material and the color tone of the coating material of the top coat, and thus the application is limited. There are challenges.

In order to solve the problem of the solubility of the conductive polymer, a conductive composition using a conductive polymer having an acidic group such as a sulfonic acid group (sulfonated polyaniline) in polyaniline has been proposed (Patent No. 03051).
No. 308, JP-A-8-143662). It has been reported that this composition can use water as a solvent, exhibits high conductivity without dependency on humidity, and forms a conductor having excellent film formability, moldability, and transparency. But,
Regarding the color tone of the coating film obtained from the composition, it is colored yellow by the sulfonated polyaniline, and there is a problem that the application is limited because it affects the color tone of the base material and the color tone of the coating material of the top coat. is there.

On the other hand, [Synthetic Metal
s, 80 (1996) p. 309], a method for synthesizing an unsubstituted indole trimer having conductivity by an electrolytic reaction using indole as a raw material is reported. However, in this report, there is no example in which an unsubstituted indole trimer was simply formed on the electrode and it was used as a conductive composition dissolved in a solvent.Because it is an electrode reaction, the shape and material of the base material However, it has a drawback that it is limited.

Further, a method of electrolytically oxidatively polymerizing indole-5-carbonitrile and indole-5-carboxylic acid which are indole derivatives in acetonitrile [Ph
ys. Chem. Chem. Phys. , 2,1241
-1248 (2000)], it is reported that an indole derivative trimer is formed on the electrode, but this also has a drawback that the shape and material of the base material are limited because it is an electrolytic reaction.

[0009]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art. It exhibits high conductivity without dependence on humidity, film-forming property and moldability. , Colorless and transparent, solvent resistance, water resistance, hardness, and weather resistance, and a conductive composition that exhibits high conductivity without humidity dependency and small variation in surface resistance using the composition. Another object of the present invention is to provide a conductor obtained by forming a conductive film having excellent film-forming properties, moldability, colorless transparency, solvent resistance, water resistance, hardness, and weather resistance, and a method for forming the same.

[0010]

As a result of intensive studies to solve these problems, the present inventors have found that a composition containing a trimer of an indole derivative and a crosslinking agent is suitable for this purpose. Has reached the present invention. That is, the first aspect of the present invention is to provide an indole derivative trimer (A) and a solvent (B).
And a crosslinking agent (C). This conductive composition is colloidal silica (D),
The performance can be improved by further containing the basic compound (F), the polymer compound (G), the surfactant (H), and / or the inorganic salt (I). Further, when the cross-linking agent (C) is the silane coupling agent (D), the water resistance is improved, and when the indole derivative trimer has a layered structure, high performance is exhibited.

A second aspect of the present invention is a conductor characterized by having a transparent conductive film formed from the conductive composition. By adding an acid as a dopant to this transparent conductive film, the performance can be further improved.

A third aspect of the present invention is characterized in that the conductive composition is applied to at least one surface of the base material to form a transparent conductive film, and then left standing at room temperature or subjected to heat treatment. It is a method of forming a conductor.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The conductive composition of the present invention, the conductor formed from the conductive composition, and the method for forming the same will be described in detail below.

The indole derivative trimer (A) constituting the conductive composition and conductor of the present invention is

[Chemical 7] (2) (In the above formula, R ^{1 to} R ¹² are hydrogen, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxy group having 1 to 24 carbon atoms, or 2 to 24 carbon atoms. A linear or branched acyl group, an aldehyde group, a carboxyl group, a linear or branched carboxylic acid ester group having 2 to 24 carbon atoms,
Substituents independently selected from the group consisting of sulfonic acid group, linear or branched sulfonic acid ester group having 1 to 24 carbon atoms, cyano group, hydroxyl group, nitro group, amino group, amide group and halogen group. is there. Further, X ^a- is chlorine ion, bromine ion, iodine ion, fluorine ion, nitrate ion, sulfate ion, hydrogen sulfate ion, phosphate ion,
Borofluoride ion, perchlorate ion, thiocyanate ion, acetate ion, propionate ion, methanesulfonate ion, p-toluenesulfonate ion, trifluoroacetate ion, and trifluoromethanesulfonate ion Is at least one anion selected from the group of anions, and a represents the ionic valence of X,
It is an integer of 1 to 3, m is a doping rate, and its value is 0.
~ 0.5. ) Is illustrated.

Preferably,

[Chemical 8] (3) (In the above formula, R ^{13 to} R ²⁴ are hydrogen and carbon atoms 1 to 24.
A straight chain or branched alkyl group, a straight chain or branched alkoxy group having 1 to 24 carbon atoms, a straight chain or branched acyl group having 2 to 24 carbon atoms, an aldehyde group, a carboxyl group, a straight chain group having 2 to 24 carbon atoms. Chain or branched carboxylic acid ester group, sulfonic acid group, linear or branched sulfonic acid ester group having 1 to 24 carbon atoms, cyano group, hydroxyl group, nitro group,
R ^{13 to} R ²⁴ each are independently represented by a substituent selected from the group consisting of an amino group, an amide group and a halogen group.
At least one of them is a group selected from a cyano group, a nitro group, an amide group or a halogen group. The X ^a- is,
Chlorine ion, bromine ion, iodine ion, fluorine ion, nitrate ion, sulfate ion, hydrogen sulfate ion, phosphate ion, borofluoride ion, perchlorate ion, thiocyanate ion, acetate ion, propionate ion, methanesulfonic acid Ion, a p-toluenesulfonate ion, a trifluoroacetate ion, and a trifluoromethanesulfonate ion, which is at least one anion selected from a group of 1 to 3 valent anions, and a is the ionic valence of X. It is an integer of 1 to 3, m is a doping rate, and its value is 0 to 0.5. ) Indole derivative trimer represented by

[0016]

[Chemical 9] (4) (In the above formula, R ^{25 to} R ³⁶ are hydrogen and carbon atoms of 1 to 24.
A straight chain or branched alkyl group, a straight chain or branched alkoxy group having 1 to 24 carbon atoms, a straight chain or branched acyl group having 2 to 24 carbon atoms, an aldehyde group, a carboxyl group, a straight chain group having 2 to 24 carbon atoms. Chain or branched carboxylic acid ester group, sulfonic acid group, linear or branched sulfonic acid ester group having 1 to 24 carbon atoms, cyano group, hydroxyl group, nitro group,
R ^{25 to} R ³⁶ each are independently represented by a substituent selected from the group consisting of an amino group, an amide group and a halogen group.
At least one of them is a sulfonic acid group or a carboxyl group. The X ^a- is chlorine ion, bromine ion, iodine ion, fluorine ion, nitrate ion, sulfate ion,
Hydrogen sulfate ion, phosphate ion, borofluoride ion, perchlorate ion, thiocyanate ion, acetate ion, propionate ion, methanesulfonate ion, p-toluenesulfonate ion, trifluoroacetate ion, and trifluoromethanesulfone ion At least one anion selected from a group of 1 to 3 valent anions consisting of acid ions, a represents an ionic valence of X, and is an integer of 1 to 3,
m is a doping rate, and its value is 0 to 0.5. ) Indole derivative trimer and the like.

Of these indole derivative trimers,
Carboxyl group-substituted indole trimers, sulfonic acid group-substituted indole trimers, cyano group-substituted indole trimers, nitro group-substituted indole trimers, amide group-substituted indole trimers, halogen group-substituted indoles Trimers and the like are practically preferable, and trimers having an acidic group such as carboxyl group-substituted indole trimers and sulfonic acid group-substituted indole trimers are water-soluble, and therefore water can be used as a solvent. Therefore, it can be used particularly preferably from the viewpoint of safety to human body and environment.

The indole derivative trimer (A) used in the present invention is an indole derivative trimer (A) obtained by various synthetic methods such as chemical synthesis and electrochemical synthesis.
Can be used.

In the present invention, in particular, the following general formula (5)

[Chemical 10] (5) (In the above formulas, R ^{37 to} R ⁴⁰ are hydrogen and 1 to 24 carbon atoms.
A straight chain or branched alkyl group, a straight chain or branched alkoxy group having 1 to 24 carbon atoms, a straight chain or branched acyl group having 2 to 24 carbon atoms, an aldehyde group, a carboxyl group, a straight chain group having 2 to 24 carbon atoms. Chain or branched carboxylic acid ester group, sulfonic acid group, linear or branched sulfonic acid ester group having 1 to 24 carbon atoms, cyano group, hydroxyl group, nitro group,
It is a substituent independently selected from the group consisting of an amino group, an amide group and a halogen group. The indole derivative trimer (A) obtained by reacting at least one indole derivative represented by the formula 1) in a reaction mixture containing at least one oxidizing agent and at least one solvent is preferably used.

The indole derivative represented by the general formula (4) used in the method for synthesizing the indole derivative trimer (A) is specifically 4-methylindole, 5-methylindole or 6-methylindole. , 7-methylindole, 4-ethylindole, 5-ethylindole, 6-ethylindole, 7-ethylindole, 4
-N-propyl indole, 5-n-propyl indole, 6-n-propyl indole, 7-n-propyl indole, 4-iso-propyl indole, 5-is
o-propyl indole, 6-iso-propyl indole, 7-iso-propyl indole, 4-n-butyl indole, 5-n-butyl indole, 6-n-butyl indole, 7-n-butyl indole, 4-se
c-Butylindole, 5-sec-butylindole, 6-sec-butylindole, 7-sec-butylindole, 4-t-butylindole, 5-t-butylindole, 6-t-butylindole, 7-t −
Alkyl group-substituted indoles such as butylindole,
4-methoxyindole, 5-methoxyindole, 6
-Methoxyindole, 7-Methoxyindole, 4-
Ethoxyindole, 5-ethoxyindole, 6-ethoxyindole, 7-ethoxyindole, 4-n-
Propoxyindole, 5-n-propoxyindole, 6-n-propoxyindole, 7-n-propoxyindole, 4-iso-propoxyindole, 5
-Iso-propoxyindole, 6-iso-propoxyindole, 7-iso-propoxyindole,
4-n-butoxyindole, 5-n-butoxyindole, 6-n-butoxyindole, 7-n-butoxyindole, 4-sec-butoxyindole, 5-s
ec-butoxyindole, 6-sec-butoxyindole, 7-sec-butoxyindole, 4-t-butoxyindole, 5-t-butoxyindole, 6-
Alkoxy group-substituted indoles such as t-butoxyindole and 7-t-butoxyindole, 4-acetylindole, 5-acetylindole, 6-acetylindole, acyl-group-substituted indoles such as 7-acetylindole, and indole-4- Aldehyde group-substituted indoles such as carbaldehyde, indole-5-carbaldehyde, indole-6-carbaldehyde, indole-7-carbaldehyde, indole-4-carboxylic acid, indole-5-carboxylic acid, indole-6-carvone Carboxyl group-substituted indoles such as acids and indole-7-carboxylic acids, methyl indole-4-carboxylate, methyl indole-5-carboxylate, methyl indole-6-carboxylate, methyl indole-7-carboxylate, etc. Phosphate ester group-substituted indoles, indole-4-sulfonic acid, indole-5-sulfonic acid, indole-6-sulfonic acid, indole -
Sulfonic acid group-substituted indoles such as 7-sulfonic acid,
Indole-4-methyl sulfonate, indole-5-
Sulfonic ester group-substituted indoles such as methyl sulfonate, indole-6-methyl sulfonate, indole-7-methyl sulfonate, indole-4-carbonitrile, indole-5-carbonitrile, indole-6-carbonitrile, Cyano group-substituted indoles such as indole-7-carbonitrile, 4-hydroxyindole, 5-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole and like hydroxy group-substituted indoles, 4-nitroindole, 5
-Nitro group-substituted indoles such as nitroindole, 6-nitroindole, 7-nitroindole, 4-aminoindole, 5-aminoindole, 6-aminoindole, 7-aminoindole and other amino group-substituted indoles, 4- Carbamoylindole, 5-carbamoylindole, 6-carbamoylindole, 7-
Amido group-substituted indoles such as carbamoylindole, 4-fluoroindole, 5-fluoroindole, 6-fluoroindole, 7-fluoroindole, 4-chloroindole, 5-chloroindole, 6
-Chloroindole, 7-chloroindole, 4-bromoindole, 5-bromoindole, 6-bromoindole, 7-bromoindole, 4-iodoindole, 5-iodoindole, 6-iodoindole, 7
-Halogen group-substituted indoles such as iodoindole can be mentioned.

Among these, carboxyl group-substituted indoles, sulfonic acid group-substituted indoles, cyano group-substituted indoles, nitro group-substituted indoles, amide group-substituted indoles, halogen group-substituted indoles and the like are practically preferable. Substituted indoles and sulfonic acid group-substituted indoles are particularly preferable.

The oxidizing agent used in the method for synthesizing the indole derivative trimer (A) is not particularly limited, but examples thereof include ferric chloride hexahydrate, anhydrous ferric chloride, and ferric nitrate 9-hydrate. , Ferric sulfate n-hydrate, ferric ammonium sulfate 12
Hydrate, ferric perchlorate n-hydrate, ferric tetrafluoroborate, cupric chloride, cupric nitrate, cupric sulfate, cupric tetrafluoroborate, tetrafluoroboric acid Examples thereof include nitrosonium, hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate and potassium periodate. Of these, ferric chloride hexahydrate, anhydrous ferric chloride, cupric chloride, cupric tetrafluoroborate, and ammonium persulfate are practically preferable, and among them, ferric chloride hexahydrate and anhydrous Ferric chloride is most practically preferred. These oxidizing agents may be used alone or in combination of two or more at an arbitrary ratio.

The molar ratio of the indole derivative used in the above-mentioned synthesis method of the indole derivative trimer (A) to the oxidizing agent is indole derivative: oxidizing agent = 1: 0.5 to 100,
It is preferably used in a ratio of 1: 1 to 50. Here, if the proportion of the oxidant is low, the reactivity is lowered and the raw material remains. On the contrary, if the proportion is too high, the produced trimer may be peroxidized to cause deterioration of the product.

As the solvent used in the method of synthesizing the indole derivative trimer (A), water or an organic solvent can be used. The organic solvent is not particularly limited, but methanol, ethanol,
Isopropanol, acetone, acetonitrile, propionitrile, tetrahydrofuran, 1,4-dioxane, methyl isobutyl ketone, methyl ethyl ketone, γ
-Butyl lactone, propylene carbonate, sulfolane, nitromethane, N, N-dimethylformamide, N
-Methylacetamide, dimethyl sulfoxide, dimethyl sulfone, N-methylpyrrolidone, benzene, toluene, xylene, methylene chloride, chloroform, dichloroethane and the like are used. These solvents may be used alone, or two or more kinds may be mixed and used at an arbitrary ratio. Among these solvents, acetone, acetonitrile, 1,4-dioxane, γ-butyl lactone, N, N-dimethylformamide and the like are preferable, and acetonitrile is most preferable in practical use.

The above-mentioned indole derivative trimer
In the synthesis method of (A), water and an organic solvent are allowed to coexist to react.
Is particularly preferable. With the indole derivative and water
The molar ratio of indole derivative: water = 1: 1000
~ 1000: 1, preferably 1: 100 to 100: 1
Used. However, if the oxidant has water of crystallization
Also measures the amount of water of crystallization as water. Where water is
If the content is low, the reaction will run away and the trimer will be peroxidized, resulting in structural deterioration.
At the same time, X as a dopant for the trimer ^a-
May not be doped efficiently, resulting in a decrease in conductivity.
Sometimes. On the contrary, if the ratio is too high, the oxidation reaction progresses.
Occasionally, the reaction yield may be reduced by disturbing the line.

In the above-mentioned method for synthesizing the indole derivative trimer (A), the concentration of the indole derivative at the time of reaction is 0.01% by mass or more, preferably 0.1 to 50% by mass, more preferably 0.1% by mass to the solvent. Is in the range of 1 to 30 mass%.

General formulas (2) to (4) used in the present invention
In the X ^a- indole derivatives in trimer (A) represented a dopant, an anion of a protic acid derived from the oxidation agent in the polymerization. Specifically, chlorine ion, bromine ion, iodine ion, fluorine ion, nitrate ion, sulfate ion, hydrogen sulfate ion, phosphate ion, borofluoride ion, perchlorate ion, thiocyanate ion, acetate ion, propionic acid. Ions, p-toluenesulfonate ion, trifluoroacetate ion, trifluoromethanesulfonate ion, and the like, which are 1 to 3 valent anions, and preferably chloride ion, sulfate ion, borofluoride ion, and other 1 to 2 valent anions. Ion. Most preferred are monovalent anions such as chloride. For example, when anhydrous ferric chloride is selected as the oxidant and polymerization is performed, the dopant X ^{a −} in the indole derivative trimer becomes chlorine ion, and when the polymerization is performed using cupric trifluoroacetate, , The dopant X ^a− becomes trifluoroacetate ion.

A combination of the above-mentioned indole derivative trimer (A)
The indole derivative trimer (A) obtained by the method is oxidized.
Dope unless hydrogen peroxide or ozone is used as the agent
Type indole derivative trimer (A), repeated
Dopant X for each unit ^a-Molar ratio (doping rate)
m is 0.001 to 0.5. Peroxidized water as oxidant
When elemental or ozone is used, m = 0.

The indole derivative trimer (A) may be dedoped for the purpose of further improving the solubility in the solvent (B). The dedoping treatment method is not particularly limited, but, for example, a conventionally known method is used as a dedoping step for various conductive polymers and charge transfer complexes. That is, a method of suspending the indole derivative trimer (A) in an alkaline solution such as aqueous ammonia, sodium hydroxide, potassium hydroxide or lithium hydroxide to remove the dopant ^Xa- , or a dedoping type by reduction treatment. The method for obtaining the indole derivative trimer of (i.e., the doping ratio m = 0) can be mentioned.

The dedoped indole derivative trimer is
It is possible to easily convert an arbitrary dopant into an indole derivative trimer having a desired doping ratio by treatment with an arbitrary type and an arbitrary amount of a doping agent again. For example, a doped indole derivative trimer polymerized with an oxidizing agent having a counter ion other than chloride ion is dedoped with a sodium hydroxide solution to give a dedoped indole derivative trimer, which is then treated with an aqueous hydrochloric acid solution. It is also possible to induce a chlorine-doped indole derivative trimer by re-suspending it in the solution. The conductive composition of the present invention and the like can be prepared by using the indole derivative trimer doped with any dopant thus obtained.

Since the indole derivative trimer (A) has a laminated structure, it may have better conductivity. In particular, it is preferable to have a laminated structure with a layer interval of 0.1 to 0.6 nm. The compound having such an ultrafine laminated structure has excellent physical properties such as rigidity, strength and heat resistance. However, when the layer spacing is 0.1 nm or more, the laminated structure tends to be more stable, and when the layer spacing is 0.6 nm or less, electron hopping conduction between trimers becomes easier, and conductivity tends to improve. is there.

As the solvent (B) constituting the conductive composition of the present invention, the indole derivative trimer (A), the crosslinking agent (C), the silane coupling agent (D), the colloidal silica (E), the basicity Compound (F), polymer compound (G),
There is no particular limitation as long as it can dissolve or disperse the surfactant (H) and the inorganic salt (I), and water or an organic solvent can be used. Examples of the organic solvent include alcohols such as methanol, ethanol, propanol and isopropanol, ketones such as acetone and methyl isobutyl ketone, ethers such as isopropyl ether and methyl-t-butyl ether, and cellosolves such as methyl cellosolve and ethyl cellosolve. , Propylene glycols such as methyl propylene glycol, ethyl propylene glycol,
Amides such as dimethylformamide and dimethylacetamide, and pyrrolidones such as N-methylpyrrolidone and N-ethylpyrrolidone are preferably used. In particular, water, methanol, isopropanol, acetone, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone are more preferable in terms of solubility in the indole derivative trimer. In addition, these solvents may be used alone or in a mixture at an arbitrary ratio.

The proportion of the indole derivative trimer (A) used is 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the solvent (B). When the proportion of the indole derivative trimer (A) is 20 parts by mass or less, the solubility is good and the conductivity is further improved.

The conductive composition of the present invention is imparted with the solvent resistance and water resistance of a conductor formed from the conductive composition by adding a cross-linking agent (C) which is an essential constituent.

The cross-linking agent (C) which is an essential component is not particularly limited, but the cross-linking agent itself cross-links between molecules to form a three-dimensional network structure, or the indole derivative trimer (A). , Those which react with other components such as the polymer compound (G) to form cross-links are used. In particular, those that crosslink with either or both of the indole derivative trimer (A) and the polymer compound (G) are more preferable from the viewpoint of solvent resistance and water resistance.

The cross-linking agent (C) of the present invention includes, for example, an acrylic group capable of reacting to form a cross-linking bond,
Vinyl group, epoxy group, isocyanate group, oxazoline group, silanol group, acid chloride group, carboxyl group,
A compound having two or more reactive groups such as amino groups, hydroxyl groups and mercapto groups in the molecule, or a solvent such as water is protected under normal conditions and does not react, but heating, pH
It is a compound having two or more groups in the molecule that are regenerated to the above reactive groups such as an isocyanate group by a treatment such as adjustment. Examples of such compounds include polyfunctional vinyl compounds, polyfunctional acrylic compounds, polyfunctional epoxy compounds, polyfunctional isocyanate compounds, polyfunctional oxazoline compounds, polyfunctional carboxylic acid compounds, polyfunctional amine compounds, polyfunctional hydroxy compounds, polyfunctional compounds. Examples thereof include mercapto compounds and silane coupling agents (D).

As the polyfunctional epoxy compound, bisphenol A based epoxy resin starting from bisphenol A, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether. ,
Triglycidyl tris (2-hydroxyethyl) isocyanurate, trimethylolpropane polyglycidyl ether, resorcin diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol-S-
Diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether,
Polypropylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, adipic acid glycidyl ester, o-phthalic acid glycidyl ester,
Dibromoneopentyl glycol diglycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, phenol (EO) ₅ glycidyl ether, pt-butylphenyl glycidyl ether, lauryl alcohol (E
O) ₁₅ glycidyl ether, hydroquinone diglycidyl ether, diglycidyl terephthalate, N-glycidyl phthalimide and the like.

The above-mentioned polyfunctional epoxy compound may be reacted not only with the coexisting indole derivative trimer (A) and / or the polymer compound (G) but also with a compound having other active hydrogen. It is possible. Examples of such compounds include aliphatic polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyoxypropylenepolyamine, triethyleneglycoldiamine, and tetraethyleneglycoldiamine, xylylenediamine, spiroacetaldiamine, isophoronediamine. , Bis (3-methyl-
Cyclic polyamines such as 4-aminocyclohexyl) methane, aromatic polyamines such as diaminodiphenylmethane and diaminodiphenylsulfone, polyaminoamides having a large number of active amino groups in the molecule synthesized by condensation of polyamine and dicarboxylic acid, amine adduct curing agent ,
Examples thereof include modified amines such as Mannich type curing agents.

As the polyfunctional isocyanate compound, those having two or more, preferably three or four, isocyanate groups in the molecule can be used. Specifically, 2,4-tolylene diisocyanate (2,4-TD
I), 2,6-tolylene diisocyanate (2,6-T
DI), diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, 1,5-naphthalene diisocyanate, xylylene diisocyanate (XD)
I), hydrogenated XDI, metaxylylene diisocyanate (MXDI), aromatic isocyanate compounds such as 3,3′-dimethyl-4,4′-diphenylene diisocyanate (TODI), isophorone diisocyanate (IPDI), Aliphatic isocyanate compounds such as trimethylhexamethylene diisocyanate (TMDI) and hexamethylene diisocyanate (HDI), and adducts, biurets, and isocyanurates thereof are preferably used. Generally, the molecular weight of the polyfunctional isocyanate compound is preferably about 500 to 1,000.

For example, it is available as Elastron (trade name, Daiichi Kogyo Seiyaku Co., Ltd.), which is a heat-reactive water-soluble urethane resin. This is a reactive urethane resin whose terminal isocyanate group is protected by a blocking agent so that it can be handled stably even in water. The blocking agent for elastron includes a carbamoyl sulfonate group (-N
A compound having a strong hydrophilic group such as HCOSO3-) is used. Elastron is characterized in that when it is subjected to a certain heat treatment, the blocking agent is dissociated and active isocyanate groups are regenerated. Specifically, by pre-drying at 100 ° C. or lower and heat treatment at 120-170 ° C. for a few minutes, elastron self-crosslinks with itself due to the isocyanate group regenerated by itself to form a three-dimensional network structure. Form a polyurethane film having Also, when mixed with other active hydrogen-containing compounds and subjected to heat treatment, those compounds can be modified by crosslinking.

Examples of polyfunctional vinyl compounds include polybutadiene and isoprene.

Specific examples of the polyfunctional acrylic compound include bisphenol F EO modified (4 mol) diacrylate (M-208) and bisphenol A EO modified (4 mol).
Mol) diacrylate (M-210), isocyanuric acid EO-modified diacrylate (M-215), tripropylene glycol diacrylate (M-220), polypropylene glycol diacrylate (n is about 7, PPG #).
400, M-225), pentaerythritol diacrylate monostearate (M-233), polyethylene glycol diacrylate (n is about 4, PPG # 20.
0, M-240), polyethylene glycol diacrylate (n is about 9, PPG # 400, M-245), polyethylene glycol diacrylate (n is about 13 to 1).
4, PPG # 600, M-260), polypropylene glycol diacrylate (n is about 12, M-270),
Pentaerythritol triacrylate (M-30
5), trimethylolpropane triacrylate (M-
309), trimethylolpropane PO modified (3 mol)
Triacrylate (M-310), isocyanuric acid EO
Modified triacrylate (M-315), trimethylolpropane PO modified (6 mol) triacrylate (M-3
20), trimethylolpropane EO-modified (3 mol) triacrylate (M-350), trimethylolpropane EO-modified (6 mol) triacrylate (M-36)
0), dipentaerythritol penta and hexaacrylate (M-400), ditrimethylolpropane tetraacrylate (M-408), pentaerythritol tetraacrylate (M-450), urethane acrylate (M-1100), polyester acrylate (M-). 7000 series, M-8000 series, M-
7100, M-8060).

Examples of polyfunctional oxazoline compounds include Epocros (trade name, manufactured by Nippon Shokubai Co., Ltd.) and the like.

Examples of the polyfunctional carboxylic acid compound include trimellitic anhydride, pyromellitic dianhydride, trimesic acid and the like.

Examples of polyfunctional amine compounds include polyamines or polyamidoamine compounds such as Versamine and Versamide (trade name, manufactured by Henkel Japan Ltd.), diethylenetriamine, triethylenetetramine and the like.

As the polyfunctional hydroxy compound, for example, polyvinyl alcohol, polyether polyol,
Examples thereof include polyester polyols, acrylic polyols, polycarbonate diols, trimethylolethane, trimethylolpropane, glycerin, and pentaerythritol.

Examples of polyfunctional mercapto compounds include trivinylcyclohexane-modified trimethylene diol and the like.

As the silane coupling agent (D), the silane coupling agent (D) represented by the general formula (1),

[Chemical 11] (1) (In the above formula, R ⁴⁸ , R ⁴⁹ , and R ⁵⁰ are each independently hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms,
It is a group selected from the group consisting of a linear or branched alkoxy group having 1 to 6 carbon atoms, an amino group, an acetyl group, a phenyl group, and a halogen group. X is

[Chemical 12] And n and l are numbers from 1 to 6. Y is a group selected from the group consisting of a hydroxyl group, a thiol group, an amino group, an epoxy group and an epoxycyclohexyl group. ) Is used.

As the silane coupling agent (D) which is a constituent of the present invention, one having a hydroxyl group, a thiol group, an amino group, an epoxy group or an epoxycyclohexyl group represented by the above general formula (1) is used. Specifically, those having an epoxy group include γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropylmethyldimethoxysilane, γ-glycidyloxypropyltriethoxysilane, and those having an amino group include γ.
-Aminopropyltriethoxysilane, β-aminoethyltrimethoxysilane, γ-aminopropoxypropyltrimethoxysilane, etc. As those having a thiol group, γ-mercaptopropyltrimethoxysilane, β-mercaptoethylmethyldimethoxysilane, etc., hydroxyl group Having β-hydroxyethoxyethyltriethoxysilane, γ-hydroxypropyltrimethoxysilane, etc.
Examples thereof include-(3,4-epoxycyclohexyl) ethyltrimethoxysilane.

As the cross-linking agent (C) of the present invention, any one can be used as long as it is soluble in the solvent (B) used when forming the conductive layer and is stable. Among them, polyfunctional epoxy compounds, polyfunctional isocyanate compounds, polyfunctional hydroxy compounds, and silane coupling agents (D) are preferable, and particularly water-soluble and stable water-based polyfunctional epoxy compounds, water-based polyfunctional isocyanate compounds, and water-based polyfunctional hydroxy compounds. Compounds and water-based silane coupling agents are preferred.

Further, in the above polyfunctional reactive group-containing compounds, monovinyl compounds, monoacryl compounds, monoepoxy compounds, monoisocyanate compounds, monooxazoline compounds, monocarboxylic acid compounds, monoamine compounds, monohydroxy compounds, monomercapto compounds. A compound or the like may be included.

The indole derivative trimer (A) and / or the polymer compound (G) can be self-crosslinked to further strengthen the crosslinking. For that purpose, it is necessary that these compounds (A) and (G) have a crosslinkable reactive group, and examples of such a crosslinkable reactive group include an acrylic group, a vinyl group, an epoxy group, an isocyanate group, Examples thereof include an oxazoline group, a silanol group, an acid chloride group, a carboxyl group, an amino group, a hydroxyl group and a mercapto group.

The conductor obtained from the conductive composition of the present invention may be washed with water or an organic solvent at the time of use depending on the use. The addition of the solvent property not only prevents the deterioration of the antistatic property, but also has the effect of improving the shake-off property of water and the solvent with respect to the transparent conductive film. In addition, since the transparent conductive film has a small water absorption amount of water and a solvent and does not swell due to cross-linking and curing, the drying time can be shortened. In addition, there are also effects such as less adhesion of dust and less scratches when washing with water.

However, if the cross-linking and hardening are too strong, when the conductor is stretched by processing or the like, the conductive layer cannot follow the elongation, and the antistatic property at the stretched portion is lowered, so that the surface is stretched at 150%. Make sure that the resistance does not exceed 10 times.
It is preferable to crosslink and cure.

The ratio of the component (C) to the component (B) used is 0.001 to 20 parts by mass, preferably 0.01 to 100 parts by mass of the component (B). ~
15 parts by mass. If the amount of the component (C) is less than 0.001 part by mass, the improvement in water resistance and / or solvent resistance is relatively small, while if it exceeds 20 parts by mass, the solubility, flatness, transparency, and conductivity are deteriorated. Sometimes.

The ratio of the component (D) to the component (B) used is 0.001 to 20 parts by mass, preferably 0.01 to 100 parts by mass of the component (B). ~
15 parts by mass. When the amount of the component (D) is less than 0.001 part by mass, the improvement in water resistance and / or solvent resistance is relatively small, while when it exceeds 20 parts by mass, the solubility, flatness, transparency and conductivity are deteriorated. Sometimes.

When the conductive composition of the present invention further contains colloidal silica (E), the surface hardness and weather resistance of the conductor obtained from the conductive composition are remarkably improved.

The colloidal silica (E) used in the present invention is not particularly limited, but those dispersed in water, an organic solvent or a mixed solvent of water and an organic solvent are preferably used. The organic solvent is not particularly limited, and examples thereof include alcohols such as methanol, ethanol, isopropyl alcohol, propyl alcohol, butanol, and pentanol, ketones such as acetone, methyl ethyl ketone, ethyl isobutyl ketone, and methyl isobutyl ketone, ethylene glycol, ethylene. Ethylene glycols such as glycol methyl ether and ethylene glycol mono-n-propyl ether, propylene glycols such as propylene glycol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, and propylene glycol propyl ether are preferably used.

The particle size of the colloidal silica (E) used is 1 nm to 300 nm, preferably 1 nm to 150 nm, more preferably 1 nm to 50 nm.
The range of nm is used. Here, if the particle size is too large, the hardness becomes insufficient, and the solution stability of the colloidal silica itself also deteriorates.

The ratio of the component (E) to the component (B) used is preferably 0.001 to 100 parts by mass of the component (E), and more preferably 0. It is from 01 to 50 parts by mass. When the content of the component (E) is 0.001 part by mass or more, water resistance, weather resistance and hardness are greatly improved,
On the other hand, if it exceeds 100 parts by mass, solubility, flatness, transparency, and conductivity may deteriorate.

The basic compound (F) constituting the electroconductive composition of the present invention is added to the electroconductive composition to dedope the indole derivative trimer (A), and the solvent (B).
It has the effect of further improving the solubility in water. In the case of carboxyl group-substituted indole trimers and sulfonic acid group-substituted indole trimers, the solubility in water is particularly improved by forming a salt with a sulfonic acid group and a carboxyl group. The basic compound (F) is not particularly limited, but amines, ammonium salts and the like are preferably used.

The structural formulas of amines used as the basic compound (F) are shown below.

[Chemical 13] (6) In the formula, R ^{41 to} R ⁴³ are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms (C _{1 to} C ₄ ), CH ₂ OH, and CH.
_{2 represents} CH ₂ OH, CONH ₂ or NH ₂ .

The structural formula of the ammonium salt used as the basic compound (F) of the present invention is shown below.

[Chemical 14] (7) In the formula, R ^{44 to} R ⁴⁷ are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms (C _{1 to} C ₄ ), CH ₂ OH, CH.
₂ CH ₂ OH, CONH ₂ or NH ₂ ; X ⁻ is OH ⁻ , 1/2 · SO ₄ ²⁻ , NO ₃ ⁻ , 1 / 2CO ₃
^2- , HCO ₃ ⁻ , 1/2 · (COO) ₂ ²⁻ , or R′COO ⁻ [In the formula, R ′ has ₁ to 3 carbon atoms (C ₁ to
It represents a a a] alkyl C _3).

The basic compound (F) may be used as a mixture of two or more kinds. For example, the conductivity can be further improved by using a mixture of amines and ammonium salts. _{Specifically, NH 3 / (NH 4)} 2 CO 3,
NH ₃ / (NH ₄ ) HCO ₃ , NH ₃ / CH ₃ COON
_{H 4, NH 3 / (NH} 4) 2 SO 4, N (CH 3) 3 /
CH ₃ COONH ₄ , N (CH ₃ ) ₃ / (NH ₄ ) ₂ S
O _{4 and the} like can be mentioned. The mixing ratio of these may be any ratio, but amines / ammonium salts = 1/10 to 10/0 are preferable.

The proportion of the basic compound (F) used is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the solvent (B). When the proportion of the basic compound (G) is 10 parts by mass or less, the solubility and the conductivity are both excellent, which is preferable.

The polymer compound (G) constituting the conductive composition and the conductor of the present invention is not particularly limited as long as it dissolves in the solvent (B) or forms an emulsion. . For example polyvinyl alcohol,
Polyvinyl alcohol such as polyvinyl formal and polyvinyl butyral, polyacrylic amide, poly (Nt-butyl acrylic amide), polyacrylic amide such as polyacrylic amide methylpropane sulfonic acid, polyvinylpyrrolidone, alkyd resin, melamine resin, Urea resin, phenol resin, epoxy resin, polybutadiene resin, acrylic resin, urethane resin, vinyl ester resin, urea resin, polyimide resin, maleic acid resin, polycarbonate resin, vinyl acetate resin, chlorinated polyethylene resin, chlorinated polypropylene resin, acrylic / Styrene copolymer resin, vinyl acetate /
Acrylic copolymer resin, polyester resin, styrene / maleic acid copolymer resin, fluororesin and copolymers thereof are used. Further, these polymer compounds (G) may be a mixture of two or more kinds in an arbitrary ratio.

Among these polymer compounds (G), a water-soluble polymer compound or a polymer compound which forms an emulsion in an aqueous system is preferably used, and a polymer compound having an anion group is particularly preferably used. Among them, it is preferable to use one kind or a mixture of two or more kinds of water-based acrylic resin, water-based polyester resin, water-based urethane resin and water-based chlorinated polyolefin resin.

The proportion of the polymer compound (G) used is preferably 0.1 to 400 parts by mass, and more preferably 0.5 to 300 parts by mass, relative to 100 parts by mass of the solvent (B).
When the amount is 0.1 parts by mass or more, the film formability, moldability, and strength are further improved, while when the amount is 400 parts by mass or less, the solubility of the indole derivative trimer (A) is less decreased and high conductivity is maintained. It

The conductive composition of the present invention comprises the indole derivative trimer (A), the solvent (B), a cross-linking agent (C) such as a silane coupling agent (D), colloidal silica (E) and a basic compound. Although it is possible to form a film having good performance only with the components of (F) and the polymer compound (G), the addition of the surfactant (H) further improves the flatness, coating property and conductivity. . The surfactant (H) which is a component of the conductive composition and the conductor of the present invention is an alkylsulfonic acid, an alkylbenzenesulfonic acid, an alkylcarboxylic acid, an alkylnaphthalenesulfonic acid, an α-olefinsulfonic acid,
Dialkyl sulfosuccinic acid, α-sulfonated fatty acid, N
-Methyl-N-oleyl taurine, petroleum sulfonic acid, alkyl sulfuric acid, sulfated oil and fat, polyoxyethylene alkyl ether sulfuric acid, polyoxyethylene styrenated phenyl ether sulfuric acid, alkyl phosphoric acid, polyoxyethylene alkyl ether phosphoric acid, polyoxyethylene Anionic surfactants such as alkylphenyl ether phosphoric acid, naphthalenesulfonic acid formaldehyde condensate and salts thereof, primary to tertiary fatty amines, quaternary ammonium, tetraalkylammonium, trialkylbenzylammonium alkylpyridinium, 2-alkyl -1-Alkyl-1-hydroxyethylimidazolinium, N, N
-Cationic surfactants such as dialkylmorpholinium, polyethylene polyamine fatty acid amide, polyethylene polyamine fatty acid amide urea condensate, polyethylene polyamine fatty acid amide quaternary ammonium and salts thereof, N, N-dimethyl -N-alkyl-N-carboxymethyl ammonium betaine, N,
N, N-trialkyl-N-sulfoalkylene ammonium betaine, N, N-dialkyl-N, N-bispolyoxyethylene ammonium sulfate ester betaine, 2
Betaines such as -alkyl-1-carboxymethyl-1-hydroxyethylimidazolinium betaine, N,
Amphoteric surfactants such as aminocarboxylic acids such as N-dialkylaminoalkylene carboxylates, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene-polyoxypropylene glycols, Polyoxyethylene-polyoxypropylene alkyl ether, polyhydric alcohol fatty acid partial ester, polyoxyethylene polyhydric alcohol fatty acid partial ester, polyoxyethylene fatty acid ester, polyglycerin fatty acid ester, polyoxyethylenated castor oil, fatty acid diethanolamide, poly Nonionic surfactants and surfactants such as oxyethylene alkylamine, triethanolamine fatty acid partial ester, trialkylamine oxide, etc. Oro alkyl carboxylic acids, perfluoroalkyl carboxylic acids, perfluoroalkyl benzene sulfonic acids, fluorine-based surfactants such as perfluoroalkyl polyoxyethylene ethanol is used.
Here, the alkyl group preferably has 1 to 24 carbon atoms, and more preferably 3 to 18 carbon atoms. It should be noted that two or more kinds of surfactants may be used without any problem.

The amount of the surfactant (H) used is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the solvent (B).

When the inorganic salt (I) is further added to the conductive composition of the present invention, the solubility of the indole derivative trimer (A) in the solvent (B) is improved. The inorganic salt (I) is not particularly limited, but alkali metal salts, alkaline earth metal salts and the like are preferably used. For example, lithium chloride, lithium bromide, lithium iodide, lithium hydroxide, lithium carbonate, lithium nitrate, lithium oxalate, lithium phosphate and lithium sulfate are preferably used. In addition, it does not matter even if two or more kinds of inorganic salts are used.

The ratio of the inorganic salt (I) to be used is that of the solvent (B) 1
The amount is preferably 0.1 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, based on 00 parts by weight.

Further, the conductive composition of the present invention may contain a conductive substance in order to further improve its conductivity. Examples of the conductive substance include conductive carbon black, carbon-based substances such as graphite, metal oxides such as tin oxide and zinc oxide, and metals such as silver, nickel and copper.

Further, a storage stabilizer, an adhesion aid, a dye, a pigment and the like can be added to the conductive composition used in the present invention, if necessary.

The conductive composition according to the present invention comprises an indole derivative trimer (A), a solvent (B) and a cross-linking agent (C) such as a silane coupling agent (D), and optionally colloidal silica (E) and a base. The compound (F), the polymer compound (G), the surfactant (H) and / or the inorganic salt (I) are completely dissolved or mixed at room temperature under stirring with heating. Moreover, the conductor of the present invention can be formed by applying the conductive composition prepared as described above to a substrate.

The conductor of the present invention has excellent conductivity even as it is, but after the conductive composition is applied on at least one surface of the substrate to form a transparent conductive film, the The conductivity can be further improved by performing the doping treatment by the above method and then leaving it at room temperature or performing the heating treatment.

The method of doping treatment with an acid is not particularly limited and a known method can be used. For example, the doping treatment can be carried out by immersing a conductor in an acidic solution. it can. Specific examples of the acidic solution include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid, organic acids such as p-toluenesulfonic acid, camphorsulfonic acid, benzoic acid, and derivatives having these skeletons, polystyrene sulfonic acid, and polyvinyl acid. Sulfonic acid, poly (2-acrylamido-2-methylpropane)
It is an aqueous solution containing a polymeric acid such as sulfonic acid, polyvinyl sulfuric acid and a derivative having these skeletons, or a mixed solution of water and an organic solvent. In addition, these inorganic acids, organic acids, and polymeric acids may be used alone or as a mixture of two or more kinds at an arbitrary ratio.

As the method for forming the conductor of the present invention, the conductive composition can be processed on the surface of the substrate by a method used for general paints. For example, gravure coater, roll coater, curtain flow coater, spin coater, bar coater, reverse coater, kiss coater, fan ten coater, rod coater, air doctor coater, knife coater, blade coater, cast coating, screen coating, spraying method, etc. A spraying method such as coating and a dipping method such as dipping are used.

The transparent conductive film formed from the conductive composition of the present invention can be formed to a film thickness of 0.01 to 1000 μm, but if the film thickness is large, the transparency of the transparent conductive film decreases. Therefore, the thickness is preferably as thin as possible, preferably in the range of 0.01 to 500 μm, and more preferably in the range of 0.02 to 100 μm. Further, in order to obtain a transparent conductive film having the above thickness,
The viscosity of the conductive composition is 1000 cp or less, preferably 1
To 500 cp, solid content 0.1 to 80% by weight
It is preferable to set it as the range.

The conductor having the transparent conductive film of the present invention is
Low humidity conditions (eg temperature 25 ℃, relative humidity 15%)
The surface resistance value at 10 ⁵ to 10 ¹² Ω is preferable, and the surface resistance value is more preferably 10 ⁵ to 10 ¹⁰ Ω.

The conductor having the transparent conductive film of the present invention is required to have excellent water resistance and / or solvent resistance depending on the application. For that purpose, it is necessary to impart water resistance and / or solvent resistance so that performances such as conductivity are not deteriorated by immersion in water or a solvent. For water resistance and solvent resistance, the surface resistance before immersion in temperature (SR
0), the rate of change (SR1 / SR0) of the surface resistance value (SR1) after immersion in a solvent at 40 ° C. for 1 hour is preferably 10 or less, and more preferably 5 or less. More preferable.

As the base material to which the conductive composition is applied, polymer compounds, wood, paper materials, ceramics and their films or glass plates, foams, porous materials, elastomers and the like are used. For example, as the polymer compound and film, polyethylene, polyvinyl chloride, polypropylene, polystyrene, polyester, ABS resin, AS resin, methacrylic resin, polybutadiene, polycarbonate, polyarylate, polyvinylidene fluoride, polyamide, polyimide, polyaramid, polyphenylene sulfide, Polyether ether ketone, polyphenylene ether, polyether nitrile, polyamide imide,
Examples include polyether sulfone, polysulfone, polyetherimide, polybutylene terephthalate and films thereof. These polymer films form a transparent conductive polymer film on at least one surface thereof,
The surface of the film is preferably subjected to corona surface treatment or plasma treatment for the purpose of improving the adhesion of the polymer film. In addition, after the transparent conductive film is formed on the substrate, the residual amount of the basic compound (F) is reduced by heating to improve the conductivity, and heat treatment is performed at 250 ° C or lower, preferably in the range of 40 to 200 ° C. As a result, a conductor having improved performance is formed.

[0083]

EXAMPLES The present invention will be described in more detail with reference to the following examples.

In the synthesis example of the indole derivative trimer, elemental analysis was carried out by EA11 manufactured by Thermoquest Co.
It was measured at 10. The electrical conductivity was measured with a Mitsubishi Chemical Lorester meter MCP-T350 (4 terminal method: distance between electrodes 1 mm). Furthermore, X-ray diffraction analysis (XRD) was performed by Rigaku Denki Co., Ltd. RINT-1100 (tube: CuK _α X
Line).

Synthesis Example 1 Synthesis of Indole-5-carboxylic acid trimer 10 ml of acetonitrile in a 200 ml three-necked flask.
Was added and 1.42 g of indole-5-carboxylic acid was dissolved. On the other hand, the preparation of the oxidant solution is 40 m of acetonitrile
16.2 g of anhydrous ferric chloride and 5.4 g of water were dissolved in 1 and stirred for 10 minutes. Next, after the prepared oxidizing agent solution was added dropwise to the indole-5-carboxylic acid aqueous solution over 30 minutes, the mixture was stirred at 60 ° C. for 10 hours. The reaction solution changed from pale yellow to pale green with some heat generation, and its pH was 1 or less. After completion of the reaction, the mixture was suction filtered with a Kiriyama funnel, washed with acetonitrile and then with methanol, and dried to give pale green 6,11-dihydro-5H-diindolo [2,3-a: 2 ′, 3′-c] carbazole. -2
1.12 g (yield 79%) of 9,14-tricarboxylic acid and (indole-5-carboxylic acid trimer) were obtained. The obtained trimer is pressure-molded with a tablet molding machine to obtain a diameter of 10 mm,
When it was cut into a shape having a thickness of 1 mm and the conductivity was measured by the four-terminal method, it was 0.41 S / cm. The results of elemental analysis _{(C 9 .00 H 4.90 N 1.09} O 1.98 C
l _0.11 ) ₃ . As a result of X-ray diffraction crystal analysis, the layer spacing was 0.48 nm.

Synthesis Example 2 Synthesis of Indole-5-Sulfonic Acid Trimer Polymerization was carried out in the same manner as in Synthesis Example 1 except that indole-5-sulfonic acid was used instead of indole-5-carboxylic acid in Synthesis Example 1. I went. Green 6,11-dihydro-5H-diindolo [2,3-a: 2 ', 3'-c]
Carbazole-2,9,14-trisulfonic acid, (indole-5-sulfonic acid trimer) 1.01 g (yield 71
%) Was obtained. The obtained trimer was pressure-molded with a tablet molding machine, cut into a shape with a diameter of 10 mm and a thickness of 1 mm, and the conductivity was measured by the four-terminal method, and it was 0.56 S / cm. The result of elemental analysis is (C _8.00 H _4.85 N
_{1. 06} O _3.01 S _1.06 Cl _0.11 ) ₃ .

Synthesis Example 3 Synthesis of Indole-5-carbonitrile trimer Polymerization was conducted in the same manner as in Synthesis Example 1 except that indole-5-carbonitrile was used in place of indole-5-carboxylic acid in Synthesis Example 1. I went. Green 6,11-
Dihydro-5H-diindolo [2,3-a: 2 ', 3'
-C] carbazole-2,9,14-tricarbonitrile, (indole-5-carbonitrile trimer) 1.2
2 g (yield 86%) was obtained. The obtained trimer was pressure-molded with a tablet molding machine, cut into a shape having a diameter of 10 mm and a thickness of 1 mm, and the conductivity was measured by the four-terminal method.
It was 50 S / cm. The result of elemental analysis is (C _9.00
H _{4 . 03} N _1.97 Cl _0.10 ) ₃ . As a result of X-ray diffraction crystal analysis, the layer spacing was 0.44 nm.

Synthesis Example 4 Undoped indole-5-carbonitrile trimer
Synthesis of Indole-5-carbonitrile synthesized in Synthesis Example 7
Disperse 1.00 g of trimer in 1M ammonia water,
Stir for 1 hour. After stirring, suction filtration with a Kiriyama funnel, water,
Then wash with methanol, dry, and black dedope
State indole-5-carbonitrile trimer 0.95
g was obtained. Press molding of the obtained trimer with a tablet molding machine
With a diameter of 10mm and a thickness of 1mm
Conductivity measured by the method is 0.04 S / cm or less
Met. The result of elemental analysis is (C _9.00H_4.02N
_2.02)_ThreeMet.

Synthesis Example 5 Synthesis of undoped polyaniline 100 mmol of aniline was dissolved with stirring in a 1 mol / L sulfuric acid aqueous solution at 25 ° C. to give ammonium peroxodisulfate 1
A 00 mmol aqueous solution was added dropwise. 25 ℃ after dropping
After further stirring for 12 hours, the reaction product was separated by filtration, washed and dried to obtain 8 g of polymer powder. The obtained trimer was pressure-molded with a tablet molding machine, cut into a shape with a diameter of 10 mm and a thickness of 1 mm, and the conductivity was measured by the four-terminal method.
It was 1.0 S / cm or less. This polymer at 25 ° C.
The mixture was dispersed and stirred in 1 mol / L ammonia water for a period of time, washed by filtration, and then dried to obtain 5 g of a dedoped polymer powder.

Synthesis Example 6 Synthesis of poly (2-sulfo-5-methoxy-1,4-iminophenylene) (sulfonated polyaniline) 2-aminoanisole-4-sulfonic acid 100 mmol
Was dissolved in a 4 mol / L ammonia aqueous solution with stirring at 25 ° C., and an aqueous solution of 100 mmol of ammonium peroxodisulfate was added dropwise. After the dropwise addition was completed, the mixture was further stirred at 25 ° C. for 12 hours, the reaction product was separated by filtration, washed and dried to obtain 15 g of polymer powder. The obtained trimer was pressure-molded with a tablet molding machine, cut into a shape with a diameter of 10 mm and a thickness of 1 mm, and the conductivity was measured by the four-terminal method, which was 0.11 S / cm.
It was below.

Example 1 (Conductive Composition 1) 6,11-Dihydro-5H-diindolo of Synthesis Example 1 above
[2,3-a: 2 ', 3'-c] carbazole-2,9,
14-tricarboxylic acid, (indole-5-carboxylic acid trimer) 0.2 parts by mass, 1,6-hexanediol diglycidyl ether 0.5 parts by mass were dissolved in 100 parts by mass of dimethylformamide with stirring at room temperature to conduct electricity. The composition was adjusted. The solution thus obtained was applied onto a glass substrate by spin coating and dried at 150 ° C. for 5 minutes. Smooth surface resistance of the surface with a film thickness of 0.1 μm 6.9 ×
A colorless transparent film of 10 ⁸ Ω was obtained.

Example 2 (conductive composition 2) 5 parts by mass of indole-5-carboxylic acid trimer, 0.5 part by mass of γ-glycidyloxypropyltrimethoxysilane, and 1 part by mass of ammonia were added to 100 parts by mass of water. A conductive composition was prepared by dissolving under stirring at room temperature. The solution thus obtained is applied onto a glass substrate by spin coating,
It was dried at 80 ° C. for 5 minutes. A colorless transparent film having a smooth surface resistance value of 4.8 × 10 ⁶ Ω having a film thickness of 3.5 μm was obtained.

Example 3 (Conductive composition 3) 3 parts by mass of indole-5-carboxylic acid trimer, 20 parts by mass of acrylic emulsion "Dianal MX-1708" (manufactured by Mitsubishi Rayon Co., Ltd.), γ-glycidyloxypropyl 0.5 parts by weight of trimethoxysilane, 1.0 of ammonia
A conductive composition was prepared by stirring and dissolving 100 parts by mass of water in 100 parts by mass of water at room temperature. The solution thus obtained was applied on a glass substrate by spin coating and dried at 100 ° C. for 5 minutes. A colorless transparent film having a smooth surface resistance value of 4.2 × 10 ⁷ Ω and a film thickness of 3.0 μm was obtained.

Example 4 (conductive composition 4) 5 parts by mass of indole-5-carboxylic acid trimer, 0.5 part by mass of γ-glycidyloxypropyltrimethoxysilane, 5 parts by mass of colloidal silica (particle diameter: 20 nm) Department,
1 part by mass of ammonia was stirred and dissolved in 100 parts by mass of water at room temperature to prepare a conductive composition. The solution thus obtained is applied onto a glass substrate by spin coating,
It was dried at ℃ × 5 minutes. A colorless transparent film having a smooth surface resistance value of 6.8 × 10 ⁶ Ω having a film thickness of 3.5 μm was obtained.

Example 5 (Conductive composition 5) 3 parts by mass of indole-5-carboxylic acid trimer, 20 parts by mass of acrylic emulsion "Dianal MX-1708" (manufactured by Mitsubishi Rayon Co., Ltd.), γ-glycidyloxypropyl 0.5 parts by mass of trimethoxysilane, 5 parts by mass of colloidal silica (particle size: 20 nm), and 1.0 part by mass of ammonia were stirred and dissolved in 100 parts by mass of water at room temperature to prepare a conductive composition. The solution thus obtained was applied on a glass substrate by spin coating and dried at 50 ° C. for 5 minutes. A smooth surface resistance value of 5.9 with a film thickness of 3.0 μm
A colorless transparent film of × 10 ⁷ Ω was obtained.

Example 6 (conductive composition 6) 3 parts by mass of indole-5-sulfonic acid trimer, 1 part by mass of polyvinyl alcohol, 20 parts by mass of acrylic emulsion "Dianal MX-1708" (manufactured by Mitsubishi Rayon Co., Ltd.) Then, 0.4 parts by mass of ammonia was stirred and dissolved in 100 parts by mass of water at room temperature to prepare a conductive composition. The solution thus obtained was applied onto a glass substrate by spin coating and dried at 150 ° C. for 5 minutes. A colorless transparent film having a smooth surface resistance value of 3.7 × 10 ⁷ Ω having a film thickness of 2.0 μm was obtained.

Example 7 (conductive composition 7) 1 part by mass of indole-5-carboxylic acid trimer, 2,4-
Tolylene diisocyanate 1 part by mass, ammonia 2 parts by mass, acrylic emulsion "Dianal MX-170
8 "(manufactured by Mitsubishi Rayon Co., Ltd.) and 1 part by mass of dodecylbenzenesulfonic acid were dissolved by stirring in 100 parts by mass of water at room temperature to prepare a conductive composition. The solution thus obtained was applied onto a glass substrate by spin coating, and 1
It was dried at 50 ° C. for 5 minutes. A colorless transparent film having a smooth surface resistance value of 3.9 × 10 ⁶ Ω having a film thickness of 5.0 μm was obtained.

Example 8 (Conductive composition 8) 1 part by mass of indole-5-carboxylic acid trimer, 0.5 part by mass of γ-glycidyloxypropylmethyldimethoxysilane, water-soluble polyester resin "Alastar 300".
4 parts by mass (manufactured by Arakawa Chemical Industry Co., Ltd.) and 1 part by mass of dodecylbenzenesulfonic acid were dissolved in 100 parts by mass of water with stirring at room temperature to prepare a conductive composition. The solution thus obtained was coated on a PET film by a bar code method and heated at 50 ° C.
It was dried for 5 minutes. A colorless transparent film having a smooth surface resistance value of 6.3 × 10 ⁷ Ω and a film thickness of 1.0 μm was obtained.

Example 9 (conductive composition 9) 0.5 part by mass of indole-5-carboxylic acid trimer, γ-
0.5 parts by mass of glycidyloxypropyltrimethoxysilane, 1 part by mass of ammonia, and 3 parts by mass of water-soluble polyester resin "Alaster 300" (manufactured by Arakawa Chemical Industry Co., Ltd.) were dissolved in 100 parts by mass of water with stirring at room temperature to obtain a conductive composition. Was adjusted. The solution thus obtained was applied onto a glass substrate by a spin coating method and dried at 40 ° C. for 5 minutes. Smooth surface resistance of the surface of 0.5 μm thickness 2.8 ×
A colorless transparent film of 10 ⁸ Ω was obtained.

Example 10 (conductive composition 10) 3 parts by mass of indole-5-sulfonic acid trimer, 0.5 part by mass of γ-glycidyloxypropyltrimethoxysilane, water-soluble polyester resin "Alaster 300" (Arakawa) 3 parts by mass and 0.5 parts by mass of dodecylbenzenesulfonic acid were dissolved in 100 parts by mass of water with stirring at room temperature to prepare a conductive composition. The solution thus obtained was applied onto a glass substrate by spin coating, and the temperature was 80 ° C.
It was dried in 5 minutes. A colorless transparent film having a smooth surface resistance value of 3.3 × 10 ⁷ Ω having a film thickness of 3.0 μm was obtained.

Example 11 (conductive composition 11) 1 part by mass of indole-5-carbonitrile trimer, 0.5 part by mass of polyvinyl alcohol, 0.5 part by mass of polyester resin (Toyobo Byron 290), ammonia 0.1. 7
A conductive composition was prepared by dissolving 100 parts by weight of acetone in 100 parts by weight of acetone with stirring at room temperature. The solution thus obtained was applied on a glass substrate by a dipping method and dried at 150 ° C. for 5 minutes. A colorless transparent film having a smooth surface resistance value of 3.9 × 10 ⁷ Ω having a film thickness of 1.0 μm was obtained.

Example 12 (conductive composition 12) 8 parts by mass of the undoped indole-5-carbonitrile trimer and 0.5 part by mass of polyvinyl alcohol were dissolved in 100 parts by mass of dimethylformamide with stirring at room temperature. A conductive composition was prepared. The solution thus obtained was applied on a glass substrate by spin coating and dried at 150 ° C. This glass substrate was immersed in a 1M aqueous solution of sulfuric acid for 5 minutes and then dried at 150 ° C. for 5 minutes. Smooth surface resistance value of the surface of film thickness 2.0 μm 3.1 × 10 ⁶ Ω
To obtain a colorless transparent film.

Comparative Example 1 (conductive composition 13) 5 parts by mass of indole-5-carboxylic acid trimer and 1 part by mass of ammonia were dissolved in 100 parts by mass of water with stirring at room temperature to prepare a conductive composition. The solution thus obtained was applied on a glass substrate by spin coating and dried at 80 ° C. Smooth surface resistance value of the surface with a film thickness of 3.5 μm 2.
A colorless transparent film of 2 × 10 ⁶ Ω was obtained.

Comparative Example 2 (conductive composition 14) 3 parts by mass of indole-5-carboxylic acid trimer, 20 parts by mass of acrylic emulsion "Dianal MX-1708" (manufactured by Mitsubishi Rayon Co., Ltd.), 1.0 part of ammonia Parts were stirred and dissolved in 100 parts by mass of water at room temperature to prepare a conductive composition. The solution thus obtained was applied on a glass substrate by spin coating and dried at 100 ° C. Smooth surface resistance of the surface of film thickness 3.0 μm 1.4 × 10 ⁷ Ω
To obtain a colorless transparent film.

Comparative Example 3 (Electrically Conductive Composition 15) 1 part by mass of undoped polyaniline, 20 parts by mass of acrylic emulsion "Dianal MX-1708" (manufactured by Mitsubishi Rayon Co., Ltd.), and perfluorododecylcarboxylic acid 1
A conductive composition was prepared by stirring and dissolving 100 parts by mass of N-methyl-2-pyrrolidone in 100 parts by mass at room temperature. The solution thus obtained was applied on a glass substrate by spin coating and dried at 150 ° C. This glass substrate is 1M
Immersion in an aqueous solution of sulfuric acid for 10 minutes and drying at 100 ° C., the surface having a film thickness of 1.0 μm has a smooth surface resistance value of 3.0 × 10 ⁹ Ω.
A dark blue film was obtained.

Comparative Example 4 (Conductive Composition 16) 1 part by mass of carbon black, acrylic emulsion "Dianal MX-1708" (manufactured by Mitsubishi Rayon Co., Ltd.) 20
By mass, 1 part by mass of sodium polystyrene sulfonate and 100 parts by mass of water were dissolved by stirring at room temperature to prepare a conductive composition. The solution thus obtained was applied on a glass substrate by spin coating and dried at 80 ° C. Smooth surface resistance value of the surface with a film thickness of 1.0 μm 3.0 × 10 ¹²
A black film of Ω was obtained.

Comparative Example 5 (Electrically Conductive Composition 17) 1 part by mass of sodium polystyrene sulfonate and 20 parts by mass of acrylic emulsion "Dianal MX-1708" (manufactured by Mitsubishi Rayon Co., Ltd.) were dissolved in 100 parts by mass of water with stirring at room temperature. A conductive composition was prepared. The solution thus obtained is applied onto a glass substrate by spin coating,
It was dried at 80 ° C. A film having a smooth surface resistance value of 5.0 × 10 ¹² Ω having a film thickness of 0.7 μm was obtained.

Comparative Example 6 (Conductive Composition 18) 1 part by mass of poly (2-sulfo-5-methoxy-1,4-iminophenylene) (sulfonated polyaniline), 1 part by mass of ammonia, water-soluble polyester resin "Alaster" Three
00 ”(manufactured by Arakawa Chemical Industry Co., Ltd.) 3 parts by mass, lithium chloride 1
A conductive composition was prepared by stirring and dissolving 100 parts by mass of water in 100 parts by mass of water at room temperature. The solution thus obtained was applied on a glass substrate by spin coating and dried at 80 ° C. Smooth surface resistance of the surface with a film thickness of 1.0 μm 7.5 ×
A yellow transparent film of 10 ⁷ Ω was obtained.

Evaluation Method The conductors prepared in Examples 1 to 12 and Comparative Examples 1 to 6 were evaluated for the following items. The results are shown in Table 1.・ 2 for measuring surface resistance under the condition of surface resistance of 25 ℃ and 15% RH.
The terminal method (distance between electrodes: 20 mm) was used. -Water resistance evaluation Examples 13 to 24 Surface resistance values (SR0) of the conductors obtained in Examples 1 to 12 were measured. This conductor was immersed in a solvent at 40 ° C. for 1 hour, the appearance was observed, the surface resistance value (SR1) was measured, and R1 / R0 was calculated. Comparative Examples 7 to 12 Surface resistance values (SR0) of the conductors obtained in Comparative Examples 1 to 6 were measured. This conductor was immersed in a solvent at 40 ° C. for 1 hour, the appearance was observed, the surface resistance value (SR1) was measured, and R1 / R0 was calculated. -Appearance of coating surface After dipping in a solvent for 1 hour at 40 ° C, the appearance of the coating film was visually observed to observe the state of the coating film. ◯: No change from before immersion (glossy, transparent) ×: Pencil scratch test (JIS K
5400).

[0110]

[Table 1]

[0111]

Effect of the Invention The electroconductive composition according to the present invention exhibits high electroconductivity without being dependent on humidity only by coating, spraying, casting, dipping and heat-treating the composition on a suitable substrate to form a film, formability, and colorless and transparent. Resistance, solvent resistance, water resistance,
A conductive thin film having excellent hardness and weather resistance can be obtained. 2. In the present invention, the indole derivative trimer is coated on a suitable substrate with a transparent conductive polymer film having excellent film formability, moldability, colorless transparency, solvent resistance, water resistance, hardness, and weather resistance. After being formed by processing such as spraying, casting, dipping, etc., it can be left at room temperature or only by heat treatment to exhibit high conductivity without humidity dependency, and a conductor with a small variation in surface resistance can be obtained.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 201/00 C09D 201/00 5G307 C09J 9/02 C09J 9/02 5G323 201/00 201/00 H01B 1 / 20 H01B 1/20 A 5/14 5/14 A 13/00 503 13/00 503B // C08L 101: 00 C08L 101: 00 F term (reference) 4D075 BB26Z BB93Z CA02 CA22 CA32 CA38 DC18 DC21 DC24 DC27 EB42 EC03 4F006 AA11 AA31 AB38 BA07 CA08 DA04 4J038 DL05 DL06 HA446 JA15 JB27 JC30 KA03 KA08 KA09 KA12 NA01 NA03 NA04 NA11 NA20 PB08 PB09 4J040 EK05 EK07 HB06 HC21 HD30 JB10 DA02 LA01 5A02 LA02 LA01 5A02 NA02 LA01 LA02 LA07 NA09 LA02 NA02 LA07 LA09 LA02 LA07 LA09 NA02 LA02 LA01 LA02 LA01 FC04 FC09 5G323 BA05 BB01

Claims (20)

[Claims] 1. A conductive composition comprising an indole derivative trimer (A), a solvent (B) and a crosslinking agent (C). 2. A silane coupling agent (D) represented by the general formula (1), wherein the crosslinking agent (C) is: (1) (In the above formula, R ⁴⁸ , R ⁴⁹ , and R ⁵⁰ are each independently hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms. , Amino group,
It is a group selected from the group consisting of an acetyl group, a phenyl group and a halogen group. X is [Chemical 2] And n and l are numbers from 1 to 6. Y is a group selected from the group consisting of a hydroxyl group, a thiol group, an amino group, an epoxy group and an epoxycyclohexyl group. ) Is a conductive composition according to claim 1. 3. The conductive composition is colloidal silica (E).
The electrically conductive composition according to claim 1, which comprises: 4. The particle diameter of colloidal silica (E) is 1 n.
The conductive composition according to any one of claims 1 to 3, which has a m-300 nm. 5. The conductive composition according to any one of claims 1 to 4, wherein the conductive composition contains a basic compound (F). 6. The conductive composition according to any one of claims 1 to 5, wherein the conductive composition contains a polymer compound (G). 7. The conductive composition according to claim 1, wherein the conductive composition contains a surfactant (H). 8. The conductive composition according to claim 1, wherein the conductive composition contains an inorganic salt (I). 9. The indole derivative trimer (A) is represented by the following formula: (2) (In the above formula, R ^{1 to} R ¹² are hydrogen, a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkoxy group having 1 to 24 carbon atoms, or 2 to 24 carbon atoms. Linear or branched acyl group, aldehyde group, carboxylic acid group, linear or branched carboxylic acid ester group having 2 to 24 carbon atoms, sulfonic acid group, linear or branched sulfonic acid ester having 1 to 24 carbon atoms group, a cyano group, a hydroxyl group, a nitro group, an amino group, a substituent selected independently from the group consisting of amide group and a halogen group. Further, X ^a- is chlorine ion, bromine ion, iodine ion, fluorine Ion, nitrate ion, sulfate ion, hydrogen sulfate ion, phosphate ion, borofluoride ion, perchlorate ion, thiocyanate ion, acetate ion, propionate ion, methanesulfonate ion, p -At least one anion selected from a group of 1 to 3 valent anions consisting of a toluene sulfonate ion, a trifluoroacetate ion, and a trifluoromethane sulfonate ion, and a represents an ionic valence of X,
It is an integer of 1 to 3, m is a doping rate, and its value is 0.
~ 0.5. ) Is a conductive composition according to any one of claims 1 to 8. 10. The indole derivative trimer (A) is represented by the following formula: (3) In the above formula, R ^{13 to} R ²⁴ are each hydrogen, a straight-chain or branched alkyl group having 1 to 24 carbon atoms, a straight-chain or branched alkoxy group having 1 to 24 carbon atoms, and a carbon number of 2 to 24. A linear or branched acyl group, an aldehyde group, a carboxyl group, a linear or branched carboxylic acid ester group having 2 to 24 carbon atoms,
Substituents independently selected from the group consisting of sulfonic acid group, linear or branched sulfonic acid ester group having 1 to 24 carbon atoms, cyano group, hydroxyl group, nitro group, amino group, amide group and halogen group. At least one of R ^{13 to} R ²⁴ is a group selected from a cyano group, a nitro group, an amide group or a halogen group. The X ^a- is chlorine ion, bromine ion, iodine ion, fluorine ion, nitrate ion, sulfate ion, hydrogen sulfate ion, phosphate ion, fluoroborate ion, perchlorate ion, thiocyanate ion, acetate ion, propionate At least one anion selected from a group of 1 to 3 valent anions consisting of acid ion, methanesulfonate ion, p-toluenesulfonate ion, trifluoroacetate ion, and trifluoromethanesulfonate ion, and a is It represents the ionic valence of X, is an integer of 1 to 3, m is a doping rate, and its value is 0 to 0.5. ) Is any one of claims 1 to 9.
The conductive composition according to item 1. 11. The indole derivative trimer (A) is represented by the following formula: (4) (In the above formula, R ^{25 to} R ³⁶ are hydrogen and carbon atoms of 1 to 24.
A straight chain or branched alkyl group, a straight chain or branched alkoxy group having 1 to 24 carbon atoms, a straight chain or branched acyl group having 2 to 24 carbon atoms, an aldehyde group, a carboxyl group, a straight chain group having 2 to 24 carbon atoms. Chain or branched carboxylic acid ester group, sulfonic acid group, linear or branched sulfonic acid ester group having 1 to 24 carbon atoms, cyano group, hydroxyl group, nitro group,
R ^{25 to} R ³⁶ each are independently represented by a substituent selected from the group consisting of an amino group, an amide group and a halogen group.
At least one of them is a sulfonic acid group or a carboxyl group. The X ^a- is chlorine ion, bromine ion, iodine ion, fluorine ion, nitrate ion, sulfate ion,
Hydrogen sulfate ion, phosphate ion, borofluoride ion, perchlorate ion, thiocyanate ion, acetate ion, propionate ion, methanesulfonate ion, p-toluenesulfonate ion, trifluoroacetate ion, and trifluoromethanesulfone ion At least one anion selected from a group of 1 to 3 valent anions consisting of acid ions, a represents an ionic valence of X, and is an integer of 1 to 3,
m is a doping rate, and its value is 0 to 0.5. ) Is a conductive composition according to any one of claims 1 to 10. 12. The indole derivative trimer (A) is represented by: (5) (In the above formulas, R ^{37 to} R ⁴⁰ are hydrogen and 1 to 24 carbon atoms.
A straight chain or branched alkyl group, a straight chain or branched alkoxy group having 1 to 24 carbon atoms, a straight chain or branched acyl group having 2 to 24 carbon atoms, an aldehyde group, a carboxyl group, a straight chain group having 2 to 24 carbon atoms. Chain or branched carboxylic acid ester group, sulfonic acid group, linear or branched sulfonic acid ester group having 1 to 24 carbon atoms, cyano group, hydroxyl group, nitro group,
It is a substituent independently selected from the group consisting of an amino group, an amide group and a halogen group. 1.) An indole derivative trimer obtained by reacting at least one indole derivative represented by the formula 1) in a reaction mixture containing at least one oxidizing agent and at least one solvent. Any one of 11
The electrically conductive composition according to item. 13. The conductive composition according to claim 1, wherein the indole derivative trimer (A) has a laminated structure. 14. A conductor comprising a transparent conductive film formed from the conductive composition according to claim 1. 15. The conductor according to claim 14, wherein an acid is added as a dopant to the transparent conductive film. 16. The conductor according to claim 14, wherein the transparent conductive film has a surface resistance value of 10 ⁵ to 10 ¹² Ω at a temperature of 25 ° C. and a relative humidity of 15%. 17. The rate of change in surface resistance (SR1) of the transparent conductive film after being immersed in a solvent at a temperature of 40 ° C. for 1 hour.
(Surface resistance value after immersion in a solvent at 40 ° C. for 1 hour) /
SR0 (surface resistance value before immersion) is 10 or less, The conductor of any one of Claims 14-16 characterized by the above-mentioned. 18. A transparent conductive film is formed by applying the conductive composition according to any one of claims 1 to 13 on at least one surface of a substrate and then left at room temperature or heat treated. A method for forming a conductor, which comprises: 19. The method for forming a conductor according to claim 18, wherein after the transparent conductive film is formed, a doping treatment with an acid is carried out, and then a standing treatment or a heat treatment is carried out at room temperature. 20. The method for forming a conductor according to claim 18, wherein the heat treatment is performed in a temperature range of room temperature to 250 ° C.