JP2001270999A - Crosslinkable electric conductive composition, water resistant electric conductor and process for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a crosslinkable electric conductive composition which shows no moisture dependence, exerts a high electric conductivity and has an excellent film forming property, moldability, transparency, adhesive property, hardness and water resistance, an electric conductor containing an electric conductive polymer film formed from this composition which shows no moisture dependence, exerts a high electrical conductivity and has an excellent film forming property, moldability, transparency, adhesive property, hardness and water resistance and a process for forming the same. SOLUTION: The crosslinkable electric conductive composition contains a water-soluble electric conductive polymer having a sulfonate group and/or a carboxyl group, a solvent, a silane coupling agent and a colloidal silica. The electric conductor is coated with the same.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cross-linkable conductive composition, a conductor formed from the cross-linkable conductive composition and having excellent water resistance, adhesiveness and friction resistance, and the formation thereof. It is about the method. Conductors obtained from the crosslinkable conductive composition of the present invention include various antistatic agents, batteries, capacitors, EMI shields, chemical sensors, display elements, non-linear materials, anticorrosives, adhesives, fibers, antistatic paints, anticorrosion It can be applied to paints, electrodeposition paints, plating primers, hard coat agents for antistatic, anti-corrosion, and improvement of battery storage capacity. Specific applications of antistatic agents include packaging materials, magnetic cards, magnetic tapes, magnetic disks, photographic films, printing materials, release films, heat seal tapes / films, IC trays, IC carrier tapes, cover tapes, and the like. Can be

[0002]

2. Description of the Related Art Water-soluble conductive polymers having acidic groups such as sulfonic acid groups and carboxyl groups exhibit excellent solubility in water and organic solvents due to the hydrophilic action of the acidic groups. Have been studied, and a method of forming a conductor mainly composed of these conductive polymers has been reported. (JP-A-7-196791, JP-A-7-324132, JP-A-8-41320, etc.). However, since these water-soluble conductive polymers having a sulfonic acid group or a carboxyl group are soluble in water, a conductive polymer film formed from a conductive composition composed of these polymers is not coated. There is a problem that the water resistance after the film is insufficient and cannot be applied to applications requiring water resistance. Attempts have been made to blend a polymer compound to impart water resistance, but it has not been possible to impart sufficient water resistance yet.

Further, the water-soluble conductive polymer having a sulfonic acid group or a carboxyl group has a rigid structure, and when formed into a coating film, has a low hardness and a brittle coating film.
There is a problem that the usage is limited. Attempts have been made to blend a polymer compound to solve this problem, but by mixing the polymer compound with a water-soluble conductive polymer, the coating film of the polymer compound itself becomes brittle, and a sufficient coating film is formed. Cannot be given.

[0004] As a method of solving these problems relating to imparting water resistance, the present inventors have proposed a water-soluble conductive polymer having a sulfonic acid group and / or a carboxylic acid group and a sulfonic acid group and / or a carboxylic acid group of the polymer. Composition (WO97 / 071) containing a compound (crosslinkable compound) having at least two functional groups capable of reacting with an acid group
No. 67). However, in the case of coating on a film or a resin substrate, the crosslinking temperature is preferably from room temperature to 100 ° C. or less in consideration of the influence on the substrate, but in these compositions, the crosslinking start temperature of the crosslinkable compound is 110 ° C
Since a temperature of about 200 ° C. is required, there is a problem that the types of substrates that can be applied are limited, and the applicable range is limited.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned various problems, and does not impair the properties of the water-soluble conductive polymer having a sulfonic acid group or a carboxyl group, and has a high humidity. A conductive composition that exhibits high conductivity without dependence and is excellent in film formability, moldability, transparency, adhesion, water resistance and hardness, and high conductivity without humidity dependence by using the composition. Conductor obtained by forming a conductive polymer film which exhibits excellent properties, has small variation in surface resistance value, and is excellent in film formability, moldability, transparency, adhesion, water resistance and hardness, and a method for forming the same Is to provide.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that a water-soluble conductive polymer having a sulfonic acid group and / or a carboxyl group, a solvent and a silane coupling agent. A cross-linkable conductive composition containing is suitable for this purpose, and by using this, a water-resistant conductor including a conductive polymer film excellent in water resistance, film formability, transparency, conductivity and the like can be formed. Further, the present inventors have found that an extremely excellent conductive composition having improved hardness in addition to water resistance by including colloidal silica therein and a water-resistant conductor using the same can be obtained, and the present invention has been achieved. It is.

That is, a first aspect of the present invention is to provide a water-soluble conductive polymer (a) having a sulfonic acid group and / or a carboxyl group, a solvent (b), and a silane coupling agent represented by the general formula (1) ( c),

Embedded image (In the above formula, R ₄₃ , R ₄₄ , and R ₄₅ 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, or an amino group. ,
It is a group selected from the group consisting of an acetyl group, a phenyl group, and a halogen group. X is

Embedded image And n and m are numbers from 0 to 6. Y is a group selected from the group consisting of a hydroxyl group, a thiol group, an amino group, and an epoxy group. ) Is a crosslinkable conductive composition. The performance of the crosslinkable conductive composition is improved by further containing colloidal silica and / or a polymer compound.

A second aspect of the present invention is a water-resistant conductor comprising a transparent conductive polymer film formed from the crosslinkable conductive composition, and a third aspect of the present invention.
After applying the cross-linkable conductive composition on at least one surface of the substrate to form a transparent conductive polymer film, a water-resistant conductor characterized by being subjected to standing or heating at room temperature It is a forming method.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the crosslinkable conductive composition of the present invention, a water-resistant conductor formed from the composition, and a method for forming the same will be described in detail.

The water-soluble conductive polymer (a) used in the present invention is not particularly limited as long as it is a water-soluble conductive polymer having a sulfonic acid and / or a carboxyl group. For example, Japanese Unexamined Patent Publication No. 61-197633. JP-A-63-39916, JP-A-01-301714, JP-A-05-504153, JP-A-05-50413.
No. 503953, JP-A-04-32848,
JP-A-04-328181, JP-A-06-145
386, JP-A-06-56987, JP-A-05-226238, JP-A-05-17889.
JP, JP-A-06-293828, JP-A-07
JP-A-118524, JP-A-06-32845, JP-A-06-87949, JP-A-06-25
No. 6516, JP-A-07-41756, JP-A-07-48436, JP-A-04-268331
The water-soluble conductive polymer disclosed in the publication is preferably used.

More specifically, at least one selected from the group consisting of unsubstituted and substituted phenylenevinylene, vinylene, thienylene, pyrrolylene, phenylene, iminophenylene, isothianaphthene, furylene and carbazolylen is contained as a repeating unit. A sulfonic acid group and / or a carboxyl group, or an alkyl group substituted with a sulfonic acid group and / or a carboxyl group or an alkyl group containing an ether bond is provided on the skeleton of the π-conjugated polymer or on a nitrogen atom in the polymer. And a water-soluble conductive polymer. Among them, thienylene,
Pyrrolylene, iminophenylene, phenylenevinylene,
A water-soluble conductive polymer having a skeleton containing carbazolylene and isothianaphthene is preferably used.

Preferred water-soluble conductive polymers are:

Embedded image (In the above formula, R ₁ and R ₂ are each independently H, -S
^{_{O 3 -, -SO 3 H,}} -R 35 SO 3 -, -R 35 SO
_{3 H, -OCH 3, -CH 3} , -C 2 H 5, -F, -C
_{l, -Br, -I, -N (} R 35) 2, -NHCOR
^{_{35, -OH, -O -, -SR}} 35, -OR 35, -O
_{COR 35, -NO 2, -COOH,} -R 35 COO
_{H, -COOR 35, -COR 35,} -CHO and -C
Selected from the group consisting of N, _{wherein, R 35} is 1 to carbon atoms
24 alkyl, aryl or aralkyl groups or alkylene, arylene or aralkylene groups,
And at least one of R ₁ and R ₂ is -SO ₃ ^- ,-
^{_{SO 3 H, -R 35 SO 3}} -, -R 35 SO 3 H, -C
It is OOH and _-R 35 group selected from the group consisting of COOH. )

[0013]

Embedded image (In the above formula, R ₃ and R ₄ are each independently H, -S
^{_{O 3 -, -SO 3 H,}} -R 35 SO 3 -, -R 35 SO
_{3 H, -OCH 3, -CH 3} , -C 2 H 5, -F, -C
_{l, -Br, -I, -N (} R 35) 2, -NHCOR
^{_{35, -OH, -O -, -SR}} 35, -OR 35, -O
_{COR 35, -NO 2, -COOH,} -R 35 COO
_{H, -COOR 35, -COR 35,} -CHO and -C
Selected from the group consisting of N, _{wherein, R 35} is 1 to carbon atoms
24 alkyl, aryl or aralkyl groups or alkylene, arylene or aralkylene groups,
And at least one of R ₃ and R ₄ is -SO ₃ ^- ,-
^{_{SO 3 H, -R 35 SO 3}} -, -R 35 SO 3 H, -C
It is OOH and _-R 35 group selected from the group consisting of COOH. )

[0014]

Embedded image (In the above formula, R _{5 to} R ₈ are each independently H, -S
^{_{O 3 -, -SO 3 H,}} -R 35 SO 3 -, -R 35 SO
_{3 H, -OCH 3, -CH 3} , -C 2 H 5, -F, -C
_{l, -Br, -I, -N (} R 35) 2, -NHCOR
^{_{35, -OH, -O -, -SR}} 35, -OR 35, -O
_{COR 35, -NO 2, -COOH,} -R 35 COO
_{H, -COOR 35, -COR 35,} -CHO and -C
Selected from the group consisting of N, _{wherein, R 35} is 1 to carbon atoms
24 alkyl, aryl or aralkyl groups or alkylene, arylene or aralkylene groups,
And at least one of R _{5 to} R ₈ is —SO ₃ ⁻ ,
^{_{SO 3 H, -R 35 SO 3}} -, -R 35 SO 3 H, -C
It is OOH and _-R 35 group selected from the group consisting of COOH. )

[0015]

Embedded image(In the above formula, R₉~ R₁₃Are each independently H, -SO₃
⁻, -SO₃H, -R_{3 5}SO₃ ⁻, -R₃₅SO
₃H, -OCH₃, -CH₃, -C₂H₅, -F, -C
1, -Br, -I, -N (R₃₅)₂, -NHCOR
₃₅, -OH, -O⁻, -SR₃₅, -OR₃₅, -O
COR₃₅, -NO₂, -COOH, -R₃₅COO
H, -COOR₃₅, -COR₃₅, -CHO and -C
N from the group consisting of₃₅Has 1 to 1 carbon atoms
24 alkyl, aryl or aralkyl groups or
Alkylene, arylene or aralkylene group,
And R₉~ R ₁₃At least one of which is -SO₃ ⁻,
-SO₃H, -R₃₅SO₃ ⁻, -R ₃₅SO₃H,-
COOH and -R₃₅Selected from the group consisting of COOH
Group. )

[0016]

Embedded image(In the above formula, R₁₄Is -SO₃ ⁻, -SO₃H, -R
₄₂SO₃ ⁻, -R₄₂SO₃H, -COOH and -R
₄₂Selected from the group consisting of COOH, where R ₄₂
Is an alkylene, arylene or aralkyl having 1 to 24 carbon atoms
It is a alkylene group. ) Selected from the group consisting of
Even one or more repeating units, repeating the whole polymer
Water-soluble conductive polymer containing 20 to 100% of the total number of units
It is a limer

Among these water-soluble conductive polymers, a water-soluble conductive polymer represented by the following general formula (7) is more preferably used.

Embedded image(In the above formula, y represents an arbitrary number of 0 <y <1;_Fifteen
~ R₃₂Are each independently H, -SO₃ ⁻, -SO₃H,
-R₃₅SO₃ ⁻, -R₃₅SO₃H, -OCH ₃, −
CH₃, -C₂H₅, -F, -Cl, -Br, -I,-
N (R₃₅)₂, -NHCOR₃₅, -OH, -O⁻,
-SR₃₅, -OR₃₅, -OCOR₃₅, -NO₂,
-COOH, -R₃₅COOH, -COOR₃₅, -C
OR₃₅, Selected from the group consisting of -CHO and -CN;
Where R₃₅Is an alkyl or aryl having 1 to 24 carbon atoms
Or aralkyl groups or alkylene, arylene or
Or an aralkylene group;_Fifteen~ R₃₂Few of
At least one is -SO₃ ⁻, -SO₃H, -R₃₅SO₃
⁻, -R₃₅SO₃H, -COOH and -R₃₅COO
H is a group selected from the group consisting of Repetition represented by)
Repeat units are included in the total number of repeating units in the entire polymer.
It is a water-soluble conductive polymer containing 0 to 100%. This
Where the sulfonic acid relative to the total number of repeating units in the polymer
Group and / or a carboxyl group-containing repeating unit
Soluble conductive polymer containing 50% or more is soluble
Is very good, so it is preferably used, and more preferably
Is at least 70%, more preferably at least 90%, particularly preferably
Alternatively, 100% of the polymer is used.

The substituent added to the aromatic ring is preferably an electron-donating group from the viewpoints of conductivity and solubility, and specifically, is preferably an alkyl group, an alkoxy group, a halogen group, etc., and particularly has an alkoxy group. Water-soluble conductive polymers are most preferred. The general formula (8) of the most preferred water-soluble conductive polymer among these combinations is shown below.

Embedded image (In the above formula, R ₃₃ is one group selected from the group consisting of a sulfonic acid group, a carboxyl group, and alkali metal salts, ammonium salts and substituted ammonium salts thereof, and R ₃₄ is a methyl group, an ethyl group , N-propyl group,
iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, dodecyl, tetracosyl, methoxy, ethoxy, n-propoxy, iso-butoxy, sec-butoxy Group, tert-butoxy group, heptoxy group, hexoxy group, octoxy group, dodecoxy group, tetracosoxy group, fluoro group, chloro group and bromo group, X represents 0 <X <1 And n represents the degree of polymerization and is 3 or more and 5000 or less. Here, at least a part of R ₃₃ is preferably a free sulfonic acid group and / or a carboxyl group from the viewpoint of improving conductivity.

As the water-soluble conductive polymer used in the present invention, polymers obtained by various synthetic methods such as chemical polymerization or electrolytic polymerization can be used. For example, JP-A-7-196791 proposed by the present inventors, JP-A-7-
The synthesis method described in JP-A-324132 is applied. That is, the following general formula (8):

Embedded image(In the above formula, R₃₆~ R₄₁Are each independently H, -SO
₃ ⁻, -SO₃H, -R ₃₅SO₃ ⁻, -R₃₅SO₃
H, -OCH₃, -CH₃, -C₂H₅, -F, -C
1, -Br, -I, -N (R₃₅)₂, -NHCOR
₃₅, -OH, -O⁻, -SR₃₅, -OR₃₅, -O
COR₃₅, -NO₂, -COOH, -R₃₅COO
H, -COOR₃₅, -COR₃₅, -CHO and -C
N from the group consisting of₃₅Has 1 to 1 carbon atoms
24 alkyl, aryl or aralkyl groups or
Alkylene, arylene or aralkylene group,
R_Fifteen~ R ₃₂At least one of which is -SO₃ ⁻, −
SO₃H, -R₃₅SO₃ ⁻, -R ₃₅SO₃H, -C
OOH and -R₃₅Group selected from the group consisting of COOH
It is. ) An acid-substituted aniline represented by
Limetal salts, ammonium salts and / or substituted ammonium
Polymer salt is polymerized by an oxidizing agent in a solution containing a basic compound.
Water-soluble conductive polymer obtained by
It is.

A particularly preferred water-soluble conductive polymer is obtained by polymerizing an alkoxy-substituted aminobenzenesulfonic acid, an alkali metal salt, an ammonium salt and / or a substituted ammonium salt thereof with an oxidizing agent in a solution containing a basic compound. The obtained water-soluble conductive polymer is used.

It is desirable that at least a part of the acidic group contained in the water-soluble conductive polymer used in the present invention is a free acid type from the viewpoint of improving conductivity. The water-soluble conductive polymer used in the present invention has a weight average molecular weight of G
2000 or more in terms of PC polyethylene glycol,
Those having a molecular weight of 3,000,000 or less are preferably used because they are excellent in conductivity, film formability and film strength, and those having a weight average molecular weight of 3,000 or more and 1,000,000 or less are more preferable, and those having a 5,000 or more and 500,000 or less are most preferable.

As the silane coupling agent (c) which is an essential component of the present invention, those having a hydroxyl group, a thiol group, an amino group or an epoxy group represented by the general formula (1) are used. Specifically, those having an epoxy group include γ-glycidyloxypropyltrimethoxysilane,
Those having an amino group, such as γ-glycidyloxypropylmethyldimethoxysilane and γ-glycidyloxypropyltriethoxysilane, are γ-aminopropyltriethoxysilane, β-aminoethyltrimethoxysilane, γ-aminopropoxypropyltrimethoxysilane As those having a thiol group, γ-mercaptopropyltrimethoxysilane, β-mercaptoethylmethyldimethoxysilane, etc., and those having a hydroxyl group include β-hydroxyethoxyethyltriethoxysilane, γ-hydroxypropyltrimethoxysilane, etc. No.

The solvent (b), which is another essential component of the present invention, is not particularly limited as long as it dissolves or disperses the water-soluble conductive polymer (a) and the silane coupling agent (c). Are water, alcohols such as methanol, ethanol, isopropyl alcohol, propyl alcohol and butanol, ketones such as acetone, methyl ethyl ketone, ethyl isobutyl ketone and methyl isobutyl ketone, ethylene glycol, ethylene glycol methyl ether and ethylene glycol mono-n- Propylene such as ethylene glycols such as propyl ether, propylene glycol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, and propylene glycol propyl ether Amides such as glycols, dimethylformamide and dimethylacetamide, pyrrolidones such as N-methylpyrrolidone and N-ethylpyrrolidone, and hydroxyesters such as methyl lactate, ethyl lactate, methyl β-methoxyisobutyrate and methyl α-hydroxyisobutyrate And the like are preferably used.

In the present invention, a cross-linkable conductive composition containing essential components of a water-soluble conductive polymer (a) having a sulfonic acid group and / or a carboxyl group, a solvent (b) and a silane coupling agent (c) is provided. Furthermore, colloidal silica (d)
Can be used in combination. The surface hardness of the water-resistant conductor obtained from the crosslinkable conductive composition using colloidal silica (d) is remarkably improved. The colloidal silica (d) 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. Examples of the organic solvent include, but are not particularly limited to, 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; and ethylene. Glycol methyl ether, ethylene glycol mono-n-
Ethylene glycols such as propyl ether, propylene glycol, propylene glycol methyl ether,
Propylene glycols such as propylene glycol ethyl ether, propylene glycol butyl ether and propylene glycol propyl ether are preferably used.

The colloidal silica has a particle diameter of 1 nm to 300 nm, preferably 1 nm to 150 nm, more preferably 1 nm to 50 nm.
Are used. Here, if the particle size is too large, the hardness becomes insufficient, and the solution stability of the colloidal silica itself also decreases.

The ratio of the component (a) to the solvent (b) is such that the component (a) is used in an amount of 0.
It is 1 to 20 parts by mass, preferably 0.5 to 15 parts by mass. If the amount of the component (a) is less than 0.1 part by mass, the conductivity may be poor. On the other hand, if the amount exceeds 20 parts by mass, the conductivity reaches a peak and does not increase significantly.

The component (c) and the component (b) are used in an amount of 0.001 to 20 parts by mass, preferably 0.01 part by mass, per 100 parts by mass of the component (b). ~
15 parts by mass. If the amount of component (a) is less than 0.001 part by mass, the improvement in water resistance is relatively small, while if it exceeds 20 parts by mass, the solubility, flatness, transparency, and conductivity may deteriorate.

The component (d) and the component (b) are used in an amount of 0.001 to 100 parts by weight, preferably 0.01 to 100 parts by weight of the component (b).
５０50 parts by mass. If the amount of the component (a) is less than 0.001 part by mass, the range of improvement in water resistance may be small.
If the amount is more than the above, the solubility, flatness, transparency, and conductivity may be deteriorated.

In the present invention, a water-soluble conductive polymer (a) having a sulfonic acid group and / or a carboxyl group, a solvent (b), and a silane coupling agent (c) are used.
Essential component, and if necessary, colloidal silica (d)
The polymer compound (e) can be further used in combination with the crosslinkable conductive composition containing The water resistance of the water-resistant conductor obtained from the crosslinkable conductive composition using the polymer compound (e) in combination is further improved. The polymer compound (e) used in the present invention is not particularly limited as long as it can be dissolved or dispersed in the solvent (b) used in the present invention. A polymer compound that forms an emulsion is used.

Specific examples of the water-soluble polymer compound include polyvinyl alcohols such as polyvinyl alcohol and polyvinyl formal, polyacrylamides such as polyacrylamide and polyacrylamide methylpropanesulfonic acid, polyvinylpyrrolidones, water-soluble alkyd resins, and water-soluble alkyd resins. Water soluble urea resin, water soluble phenol resin, water soluble epoxy resin, water soluble polybutadiene resin, water soluble acrylic resin, water soluble urethane resin, water soluble acrylic / styrene resin, water soluble vinyl acetate / acrylic copolymer resin , A water-soluble polyester resin, a water-soluble styrene / maleic acid copolymer resin, a water-soluble fluororesin, and a copolymer thereof.

Specific examples of the polymer compound that forms an emulsion in an aqueous system include an aqueous alkyd resin, an aqueous melamine resin, an aqueous urea resin, an aqueous phenol resin, an aqueous epoxy resin, an aqueous polybutadiene resin, an aqueous acrylic resin, an aqueous urethane resin, Water-based acrylic / styrene resin,
Examples include aqueous vinyl acetate / acrylic copolymer resins, aqueous polyester resins, aqueous styrene / maleic acid copolymer resins, aqueous fluororesins, and copolymers thereof.

The proportion of the polymer compound (e) used in the crosslinkable conductive composition is 0.1 to 400 parts by mass, preferably 0.5 to 30 parts by mass, per 100 parts by mass of the solvent (b).
0 parts by mass. If it is less than 0.1, the film formability, formation and strength may be poor, while if it exceeds 400 parts by mass, the solubility and conductivity of the water-soluble conductive polymer (a) may be reduced.

In the present invention, a polymer compound, wood, paper, ceramics, a film thereof, a glass plate, or the like is used as a substrate to which the crosslinkable conductive composition is applied to form a water-resistant conductor. For example, as the polymer compound and the film, polyethylene, polyvinyl chloride, polypropylene, polystyrene, ABS resin, AS resin, methacrylic resin, polybutadiene, polycarbonate, polyarylate, polyvinylidene fluoride, polyester, polyamide, polyimide, polyaramid, polyphenylene sulfide, Examples include polyetheretherketone, polyphenyleneether, polyethernitrile, polyamideimide, polyethersulfone, polysulfone, polyetherimide, polybutyleneterephthalate, polyurethane, films, foams, and elastomers. For these polymer films, in order to form a transparent conductive polymer film on at least one surface thereof, the film surface may be subjected to corona surface treatment or plasma treatment for the purpose of improving the adhesion of the polymer film. preferable.

The crosslinkable conductive composition used to form the conductor of the present invention is processed on the surface of a substrate by a method used for general coating to form a transparent conductive polymer film. For example, gravure coater, roll coater, curtain flow coater, spin coater, bar coater, reverse coater, kiss coater, fountain coater, rod coater, air doctor coater, knife coater, blade coater, coating method of cast coater, screen coater, etc., spraying Spraying methods such as coating and dipping methods such as dip are used.

The treatment after the application of the cross-linkable conductive composition to form the transparent conductive polymer film can be carried out at room temperature or by heating. The heat treatment further promotes the cross-linking reaction between component (c), component (d) and component (a), can provide water resistance in a shorter time, and further reduces the amount of remaining component (b). This is preferable because conductivity can be further improved. Heat treatment temperature is 250 ° C
Hereinafter, heating at 40 ° C to 200 ° C is preferable.
If the temperature is higher than 250 ° C., the water-soluble conductive polymer (a) itself is decomposed, and the conductivity is significantly reduced.

[0036]

EXAMPLES The present invention will be described in more detail with reference to examples, but the following examples do not limit the scope of the present invention.

(Production Example 1, conductive polymer (A-1)) Synthesis of poly (2-sulfo-5-methoxy-1,4-iminophenylene) 100 mmol of 2-aminoanisole-4-sulfonic acid
Was dissolved in a 4 mol / L aqueous ammonia solution at 25 ° C. with stirring, and an aqueous solution of 100 mmol of ammonium peroxodisulfate was added dropwise. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 12 hours, and the reaction product was separated by filtration, washed, and dried to obtain 15 g of a polymer powder. The volume resistivity of this polymer is 9.0Ω · c.
m.

(Production Example 2, conductive polymer (A-2)) Synthesis of poly (2-sulfo-1,4-iminophenylene) 100 mmol of m-aminobenzenesulfonic acid was added at 25 ° C.
And dissolved in a 4 mol / liter aqueous solution of trimethylamine with stirring, and an aqueous solution of 100 mmol of ammonium peroxodisulfate was added dropwise. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 12 hours, and then the reaction product was separated by filtration, washed, and dried to obtain 10 g of a polymer powder. Its volume resistance is 12.0Ω
cm.

(Production Example 3, Conductive polymer (A-3)) Synthesis of sulfonated polyaniline Poly (2-sulfo-1,4-iminophenylene) was synthesized by a known method "J. Am. Chem. Soc., (199
1), 113, 2665-2666 ". The sulfonic acid content of the obtained polymer was 52% with respect to the aromatic ring. In addition, the volume resistance value of this is 5
It was 0 Ω · cm.

(Production Example 4, conductive polymer (A-4)) Synthesis of poly (anilinepropanesulfonic acid) Poly (anilinepropanesulfonic acid) was synthesized by a known method "J. Chem. Soc., Chem. Commu."
n. , (1990), 180 ".

(Production Example 5, conductive polymer (A-5)) Synthesis of poly (3-thiophene-β-ethanesulfonic acid) Poly (3-thiophene-β-ethanesulfonic acid) was synthesized by a known method, Proceedings of the 39th Society of Polymer Science, 1990, 56
No. 1).

(Production Example 6, Conductive polymer (A-6)) Synthesis of polyaniline 100 mmol of aniline was dissolved by stirring in a 1 mol / L aqueous sulfuric acid solution at 25 ° C., and ammonium peroxodisulfate 1 was dissolved.
A 00 mmol aqueous solution was added dropwise. After dropping, 25 ° C
After further stirring for 12 hours, the reaction product was separated by filtration, washed, and dried to obtain 8 g of a polymer powder. The volume resistance value of this polymer was 1.0 Ω · cm. The polymer was dispersed and stirred in 1 mol / L aqueous ammonia at 25 ° C. for 1 hour, filtered, washed and dried to obtain 5 g of a undoped polymer powder.

(Production Example 7, Conductive polymer (A-7)) Synthesis of polypyrrole 370 mg of pyrrole was dissolved in an aqueous solution with stirring at 25 ° C., and added dropwise to a ferric chloride solution (27 g in 800 cm ³ ) with stirring. . After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 12 hours, and then the reaction product was separated by filtration, washed, and dried, and polymer powder 300
mg was obtained. The volume resistivity of this polymer is 0.1Ω · cm
Met. 1 mol / L of this polymer at 25 ° C for 1 hour
After dispersion and stirring in aqueous ammonia, the mixture is filtered, washed, and dried.
250 mg of undoped polymer powder was obtained.

Preparation of Conductive Composition Conductive Composition 1 5 parts by mass of the conductive polymer (A-1) of Production Example 1 above, γ-
1 part by mass of glycidyloxypropyltrimethoxysilane was dissolved in 100 parts by mass of water at room temperature to prepare a crosslinkable conductive composition.

Conductive Composition 2 5 parts by mass of the conductive polymer (A-2) of Production Example 2 was added to 100 parts by mass of water and 0.5 parts by mass of γ-glycidyloxypropylmethyldimethoxysilane at room temperature. By dissolving, a crosslinkable conductive composition was prepared.

Conductive composition 3 2 parts by mass of the conductive polymer (A-1) of Production Example 1, γ-
Glycidyloxypropylmethyldiethoxysilane 0.
A crosslinkable conductive composition was prepared by dissolving 5 parts by mass of 20 parts by mass of an acrylic / styrene resin “Nicazol RX-832A” (manufactured by Nippon Carbide Industry Co., Ltd.) as an aqueous emulsion in 100 parts by mass of water at room temperature.

Conductive Composition 4 5 parts by mass of the conductive polymer (A-1) of Production Example 1 was added to water 1
00 parts by mass and 0.5 parts by mass of γ-aminopropyltriethoxysilane were dissolved at room temperature to prepare a crosslinkable conductive composition.

Conductive Composition 5 5 parts by mass of the conductive polymer (A-1) of Production Example 1, γ-
1 part by mass of glycidoxypropyltrimethoxysilane and 8 parts by mass of colloidal silica (particle size: 10 to 20 nm) were dissolved in 100 parts by mass of water at room temperature to prepare a crosslinkable conductive composition.

Conductive composition 6 5 parts by mass of the conductive polymer (A-1) of Production Example 1, γ-
1 part by mass of glycidoxypropyltrimethoxysilane and 8 parts by mass of colloidal silica (particle size: 70 to 100 nm) were dissolved in 100 parts by mass of water at room temperature to prepare a crosslinkable conductive composition.

Conductive composition 7 5 parts by mass of the conductive polymer (A-1) of Production Example 1, γ-
1 part by mass of glycidoxypropyltrimethoxysilane, 5 parts by mass of colloidal silica (particle size: 10 to 20 nm),
Acrylic / styrene resin "Nicazole RX-832A" which is an aqueous emulsion (Nippon Carbide Industry Co., Ltd.)
20 parts by mass) were dissolved in 100 parts by mass of water at room temperature to prepare a crosslinkable conductive composition.

Conductive Composition 8 2 parts by mass of the conductive polymer (A-3) of Production Example 3, γ-
1 part by mass of glycidoxypropyltrimethoxysilane and 3 parts by mass of colloidal silica (particle diameter: 10 to 20 nm) are dissolved in 100 parts by mass of a water / methanol mixed solvent (mass ratio 9/1) at room temperature to be crosslinkable. A conductive composition was prepared.

Conductive composition 9 5 parts by mass of the conductive polymer (A-4) of Production Example 4, γ-
0.5 parts by mass of aminopropyltriethoxysilane, 10 parts by mass of colloidal silica (particle size: 10 to 20 nm),
Was dissolved in 100 parts by mass of water at room temperature to prepare a crosslinkable conductive composition.

Conductive composition 10 5 parts by mass of the conductive polymer (A-5) of Production Example 5, γ-
0.5 parts by mass of glycidoxypropyltrimethoxysilane, 5 parts by mass of colloidal silica (particle size: 10 to 20 nm), acrylic / styrene resin "Nicazole RX-832A" which is an aqueous emulsion (manufactured by Nippon Carbide Industry Co., Ltd.) 20 parts by mass were dissolved in 100 parts by mass of water at room temperature to prepare a crosslinkable conductive composition.

Conductive composition 11 5 parts by mass of the conductive polymer (A-1) of Production Example 1 was added to water 1
The conductive composition was dissolved in 00 parts by mass at room temperature.

Conductive composition 12 5 parts by mass of the conductive polymer (A-2) of Production Example 2 was added to water 1
The conductive composition was prepared by dissolving 00 parts by mass at room temperature.

Conductive Composition 13 5 parts by mass of the conductive polymer (A-1) of Production Example 1 and an acrylic / styrene resin “Nicazol RX-832A” as an aqueous emulsion (manufactured by Nippon Carbide Industry Co., Ltd.) 2
0 parts by mass was dissolved in 100 parts by mass of water at room temperature to prepare a conductive composition.

Conductive Composition 14 5 parts by weight of the conductive polymer (A-1) of Preparation Example 1 and 0.5 part by weight of polyvinyl alcohol were dissolved in 100 parts by weight of water at room temperature to prepare a conductive composition. Prepared.

Conductive composition 15 5 parts by mass of the conductive polymer (A-2) of Production Example 2,
One part by mass of 4-cyclohexanediol was dissolved in 100 parts by mass of water at room temperature to prepare a conductive composition.

Conductive composition 16 5 parts by mass of the conductive polymer (A-6) of Production Example 6, γ-
1 part by mass of glycidoxypropyltrimethoxysilane and 8 parts by mass of colloidal silica (particle size: 10 to 20 nm) are mixed with 100 parts by mass of N-methylpyrrolidone at room temperature, and then insolubles are filtered off to form a crosslinkable conductive material. A composition was prepared.

Conductive Composition 17 3 parts by mass of the conductive polymer (A-7) of Production Example 7, γ-
0.5 parts by mass of glycidoxypropyltrimethoxysilane, 5 parts by mass of colloidal silica (particle size: 10 to 20 nm), acrylic / styrene resin "Nicazole RX-832A" which is an aqueous emulsion (manufactured by Nippon Carbide Industry Co., Ltd.) 20 parts by mass were mixed with 100 parts by mass of water at room temperature, but the polymer of A-6 was completely insoluble in water.

Evaluation method (water resistance) The above conductive composition was spin-coated on a glass substrate
(500 rpm × 5 sec + 2000 rpm × 60 sec) to form a transparent conductive polymer film, followed by heat treatment on a hot plate. Was immersed in water, and the degree of dissolution (elution) of the transparent conductive polymer film was observed. The water resistance evaluation was based on the following criteria. ：: The glass substrate on which the transparent conductive polymer film was formed was immersed in water in a beaker, and after 3 hours, the transparent conductive polymer film was completely left by visual observation, and elution (coloring) derived from the film in water was observed. unacceptable. Δ: The glass substrate on which the transparent conductive polymer film was formed was immersed in water in a beaker, and after 3 hours, the transparent conductive polymer film was completely left by visual observation, but was eluted (colored) derived from the film in water.
Is slightly observed. X: Immediately after the glass substrate on which the transparent conductive polymer film was formed was immersed in water in a beaker, complete dissolution of the transparent conductive polymer film was observed by visual observation. The surface resistance was measured by a two-terminal method (distance between electrodes: 20 mm).

Evaluation method (hardness) The evaluation was carried out according to JIS K5400 pencil scratch test.

Examples 1 to 10 Each of the conductive compositions 1 to 4 was placed on a glass substrate (5 cm × 5
cm) on the spin coat method (500rpm × 5sec + 2000rpm × 60s)
ec) and treated under the heating conditions shown in Table 1 below to form a transparent conductive polymer film having a smooth surface, and the surface resistance was measured. Further, this glass substrate was immersed in 200 ml of water in a beaker, and the state of the transparent conductive polymer film was visually observed. The results are as shown in Table 1, and it was confirmed that the water resistance was imparted while maintaining the conductivity.

Comparative Examples 1 to 7 Each of the conductive compositions 11 to 15 was placed on a glass substrate (5 cm).
× 5cm) on the spin coat method (500rpm × 5sec + 2000rpm)
× 60 sec) and treated under the heating conditions shown in Table 1 below to form a transparent conductive polymer film having a smooth surface.
The surface resistance was measured. Further, this glass substrate was immersed in 200 ml of water in a beaker, and the state of the transparent conductive polymer film was visually observed. The results are as shown in Table 1.

Examples 11 to 18 and Reference Examples 1 and 2 (Evaluation of water resistance) The conductive compositions 5 to 10 and 1 were each placed on a glass substrate (5
cm × 5cm) and spin coating (500rpm × 5sec + 2000)
The coating was performed under the heating conditions shown in Table 2 below to form a transparent conductive polymer film having a smooth surface, and the surface resistance was measured. Further, this glass substrate was immersed in 200 ml of water in a beaker, and the state of the transparent conductive polymer film was visually observed. The results are as shown in Table 2, and it was confirmed that the water resistance was imparted while maintaining the conductivity.

Examples 11 to 18 and Reference Examples 1 and 2 (Evaluation of Hardness) Each of the conductive compositions 5 to 10 and 1 was treated with a steel plate (150 ×
70 × 0.8 mm) by a bar coating method (No. 5), and treated under the heating conditions shown in Table 2 below to form a transparent conductive polymer film having a smooth surface, and pencil scratching. A test (based on JIS K5400) was performed. The results are as shown in Table 2.

Comparative Examples 8 to 10 (Evaluation of Water Resistance) Each of the conductive compositions 13, 16 and 17 was spin-coated (500 rpm × 5 sec +) on a glass substrate (5 cm × 5 cm).
The coating was performed under the heating conditions shown in Table 2 below to form a transparent conductive polymer film having a smooth surface, and the surface resistance was measured. Further, this glass substrate was immersed in 200 ml of water in a beaker, and the state of the transparent conductive polymer film was visually observed. The results are as shown in Table 2.

Comparative Examples 8 to 10 (Evaluation of Hardness) The conductive compositions 13, 16 and 17 were each treated with a steel plate (150
× 70 × 0.8 mm) by a bar coating method (No. 5), and treated under heating conditions shown in Table 2 below to form a transparent conductive polymer film having a smooth surface, and a pencil. A scratch test (based on JIS K5400) was performed. The results are as shown in Table 2.

[0069]

[Table 1]

[0070]

[Table 2]

[0071]

1) The crosslinkable conductive composition of the present invention does not impair the properties of the water-soluble conductive polymer itself having a sulfonic acid group or a carboxyl group and exhibits high conductivity without humidity dependency. A water-resistant conductive thin film with excellent film properties, moldability, transparency, adhesion, and water resistance can be obtained, and a water-resistant conductive thin film with excellent surface hardness can be obtained by further using colloidal silica. be able to. 2) The crosslinkable conductive composition of the present invention is applied to a substrate by a process such as coating, spraying, casting, or dipping to form a water-resistant conductive thin film. Thus, it is possible to easily obtain a conductor exhibiting high conductivity and having excellent water resistance and surface hardness.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C08K 5/541 C08K 5/541 5G323 5/5419 5/5419 5/5435 5/5435 5/5445 5/5445 5/548 5/548 C08L 65/00 C08L 65/00 79/00 79/00 A 101/00 101/00 H01B 1/20 H01B 1/20 A 5/14 5/14 A 13/00 503 13/00 503B F-term (Reference) 4J002 AC11X BC04X BD12X BE02X BE06X BF02X BG00X BG13X BJ00X BQ00X CC03X CC16X CC18X CE00W CE001 CF00X CF01X CF28X CK02X CM01W CM011 DJ017 EX046 EX066 EX076 EX086 FD11W03BA03BA02BA02BA02BA CB01 CB03 CC01 CG01 4J043 PA02 PA04 PA08 QB02 QB03 RA08 RA12 SA03 SA05 SA06 SA07 SA08 SA09 SA14 SA15 SA16 SA42 SA43 SA44 SA51 SA52 SA53 SA54 SA61 SA62 SA63 SA71 SA72 SA75 SA81 SA82 UA121 UA131 XA21 XA28 ZA04 ZB ZB ZB ZB ZB ZB ZB ZB ZB ZB ZB ZB ZB ZB ZB ZB ZB ZB ZB ZB ZB ZB ZA DA23 DA28 DA42 DD01 DD02 5G307 FA01 FA02 FB03 FC03 FC04 FC05 5G323 BA05 BB01

Claims (12)

[Claims] 1. A water-soluble conductive polymer having a sulfonic acid group and / or a carboxyl group (a), a solvent (b), and a silane coupling agent (c) represented by the general formula (1): (In the above formula, R ₄₃ , R ₄₄ , and R ₄₅ 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, or an amino group. ,
It is a group selected from the group consisting of an acetyl group, a phenyl group, and a halogen group. X is And n and m are numbers from 0 to 6. Y is a group selected from the group consisting of a hydroxyl group, a thiol group, an amino group, and an epoxy group. A) a cross-linkable conductive composition comprising: 2. The crosslinkable conductive composition according to claim 1, wherein the crosslinkable conductive composition contains colloidal silica (d). 3. The cross-linkable conductive composition contains at least one polymer compound (e) selected from a water-soluble polymer compound and a polymer compound that forms an emulsion in an aqueous system. Or the crosslinkable conductive composition according to 2. 4. Sulfonic acid groups and / or carboxyls
The water-soluble conductive polymer (a) having a group is represented by the following formula:(In the above formula, R₁, R₂Are each independently H, -S
O₃ ⁻, -SO₃H, -R₃₅SO₃ ⁻, -R₃₅SO
₃H, -OCH₃, -CH₃, -C₂H₅, -F, -C
1, -Br, -I, -N (R₃₅)₂, -NHCOR
₃₅, -OH, -O⁻, -SR₃₅, -OR₃₅, -O
COR₃₅, -NO₂, -COOH, -R₃₅COO
H, -COOR₃₅, -COR₃₅, -CHO and -C
N from the group consisting of₃₅Has 1 to 1 carbon atoms
24 alkyl, aryl or aralkyl groups or
Alkylene, arylene or aralkylene group,
And R₁, R₂At least one of which is -SO₃ ⁻, −
SO₃H, -R₃₅SO₃ ⁻, -R₃₅SO₃H, -C
OOH and -R₃₅Group selected from the group consisting of COOH
It is. )(In the above formula, R₃, R₄Are each independently H, -S
O₃ ⁻, -SO₃H, -R₃₅SO₃ ⁻, -R₃₅SO
₃H, -OCH₃, -CH₃, -C₂H₅, -F, -C
1, -Br, -I, -N (R₃₅)₂, -NHCOR
₃₅, -OH, -O⁻, -SR₃₅, -OR₃₅, -O
COR₃₅, -NO₂, -COOH, -R₃₅COO
H, -COOR₃₅, -COR₃₅, -CHO and -C
N from the group consisting of₃₅Has 1 to 1 carbon atoms
24 alkyl, aryl or aralkyl groups or
Alkylene, arylene or aralkylene group,
And R₃, R₄At least one of which is -SO₃ ⁻, −
SO₃H, -R₃₅SO₃ ⁻, -R₃₅SO₃H, -C
OOH and -R₃₅Group selected from the group consisting of COOH
It is. )(In the above formula, R₅~ R₈Are each independently H, -S
O₃ ⁻, -SO₃H, -R₃₅SO₃ ⁻, -R₃₅SO
₃H, -OCH₃, -CH₃, -C₂H₅, -F, -C
1, -Br, -I, -N (R₃₅)₂, -NHCOR
₃₅, -OH, -O⁻, -SR₃₅, -OR₃₅, -O
COR₃₅, -NO₂, -COOH, -R₃₅COO
H, -COOR₃₅, -COR₃₅, -CHO and -C
N from the group consisting of₃₅Has 1 to 1 carbon atoms
24 alkyl, aryl or aralkyl groups or
Alkylene, arylene or aralkylene group,
And R₅~ R₈At least one of which is -SO₃ ⁻, −
SO₃H, -R₃₅SO₃ ⁻, -R₃₅SO₃H, -C
OOH and -R₃₅Group selected from the group consisting of COOH
It is. )(In the above formula, R₉~ R₁₃Are each independently H, -SO₃
⁻, -SO₃H, -R_{3 5}SO₃ ⁻, -R₃₅SO
₃H, -OCH₃, -CH₃, -C₂H₅, -F, -C
1, -Br, -I, -N (R₃₅)₂, -NHCOR
₃₅, -OH, -O⁻, -SR₃₅, -OR₃₅, -O
COR₃₅, -NO₂, -COOH, -R₃₅COO
H, -COOR₃₅, -COR₃₅, -CHO and -C
N from the group consisting of₃₅Has 1 to 1 carbon atoms
24 alkyl, aryl or aralkyl groups or
Alkylene, arylene or aralkylene group,
And R₉~ R ₁₃At least one of which is -SO₃ ⁻,
-SO₃H, -R₃₅SO₃ ⁻, -R ₃₅SO₃H,-
COOH and -R₃₅Selected from the group consisting of COOH
Group. )(In the above formula, R₁₄Is -SO₃ ⁻, -SO₃H, -R
₄₂SO₃ ⁻, -R₄₂SO₃H, -COOH and -R
₄₂Selected from the group consisting of COOH, where R ₄₂
Is an alkylene, arylene or aralkyl having 1 to 24 carbon atoms
It is a alkylene group. ) Selected from the group consisting of
Even one or more repeating units, repeating the whole polymer
Water-soluble conductive polymer containing 20 to 100% of the total number of units
A rimmer according to any one of claims 1 to 3,
Item 10. The crosslinkable conductive composition according to item 8. 5. A sulfonic acid group and / or a carboxyl
The water-soluble conductive polymer (a) having a group is represented by the following formula:(In the above formula, y represents an arbitrary number of 0 <y <1;_Fifteen
~ R₃₂Are each independently H, -SO₃ ⁻, -SO₃H,
-R₃₅SO₃ ⁻, -R₃₅SO₃H, -OCH ₃, −
CH₃, -C₂H₅, -F, -Cl, -Br, -I,-
N (R₃₅)₂, -NHCOR₃₅, -OH, -O⁻,
-SR₃₅, -OR₃₅, -OCOR₃₅, -NO₂,
-COOH, -R₃₅COOH, -COOR₃₅, -C
OR₃₅, Selected from the group consisting of -CHO and -CN;
Where R₃₅Is an alkyl or aryl having 1 to 24 carbon atoms
Or aralkyl groups or alkylene, arylene or
Or an aralkylene group;_Fifteen~ R₃₂Few of
At least one is -SO₃ ⁻, -SO₃H, -R₃₅SO₃
⁻, -R₃₅SO₃H, -COOH and -R₃₅COO
H is a group selected from the group consisting of Repetition represented by)
Repeat units are included in the total number of repeating units in the entire polymer.
4. The method according to claim 1, wherein the content is 0 to 100%.
The crosslinkable conductive composition according to claim 1. 6. The water-soluble conductive polymer (a) having a sulfonic acid group and / or a carboxyl group is represented by the following formula: (In the above formula, R ₃₃ is one group selected from the group consisting of a sulfonic acid group, a carboxyl group, and alkali metal salts, ammonium salts and substituted ammonium salts thereof, and R ₃₄ is a methyl group, an ethyl group , N-propyl group,
iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, dodecyl, tetracosyl, methoxy, ethoxy, n-propoxy, iso-butoxy, sec-butoxy Group, tert-butoxy group, heptoxy group, hexoxy group, octoxy group, dodecoxy group, tetracosoxy group, fluoro group, chloro group and bromo group, X represents 0 <X <1 And n represents the degree of polymerization and is 3 or more. The crosslinkable conductive composition according to any one of claims 1 to 3, wherein 7. Sulfonic acid groups and / or carboxyls
The water-soluble conductive polymer (a) having a group is represented by the following formula:(In the above formula, R₃₆~ R₄₁Are each independently H, -SO
₃ ⁻, -SO₃H, -R ₃₅SO₃ ⁻, -R₃₅SO₃
H, -OCH₃, -CH₃, -C₂H₅, -F, -C
1, -Br, -I, -N (R₃₅)₂, -NHCOR
₃₅, -OH, -O⁻, -SR₃₅, -OR₃₅, -O
COR₃₅, -NO₂, -COOH, -R₃₅COO
H, -COOR₃₅, -COR₃₅, -CHO and -C
N from the group consisting of₃₅Has 1 to 1 carbon atoms
24 alkyl, aryl or aralkyl groups or
Alkylene, arylene or aralkylene group,
R_Fifteen~ R ₃₂At least one of which is -SO₃ ⁻, −
SO₃H, -R₃₅SO₃ ⁻, -R ₃₅SO₃H, -C
OOH and -R₃₅Group selected from the group consisting of COOH
It is. ) An acid-substituted aniline represented by
Limetal salts, ammonium salts and / or substituted ammonium
Polymer salt is polymerized by an oxidizing agent in a solution containing a basic compound.
Water-soluble conductive polymer obtained by
The crosslink according to any one of claims 1 to 3, wherein
Conductive composition. 8. The water-soluble conductive polymer (a) having a sulfonic acid group and / or a carboxyl group is obtained by converting an alkoxy-substituted aminobenzenesulfonic acid, an alkali metal salt, an ammonium salt and / or a substituted ammonium salt thereof to a basic compound. The crosslinkable conductive composition according to any one of claims 1 to 3, wherein the crosslinkable conductive composition is a water-soluble conductive polymer obtained by polymerizing with a oxidizing agent in a solution containing: 9. The colloidal silica (d) having a particle size of 1 n
The crosslinkable conductive composition according to any one of claims 2 to 8, wherein the thickness is from m to 300 nm. 10. A water-resistant conductor having a transparent conductive polymer film formed from the crosslinkable conductive composition according to claim 1. Description: 11. A transparent conductive polymer film is formed on at least one surface of a substrate by applying the crosslinkable conductive composition according to claim 1 and forming the transparent conductive polymer film at room temperature. A method for forming a water-resistant conductor, wherein the method comprises leaving or heating. 12. The method for forming a water-resistant conductor according to claim 11, wherein the heat treatment is performed at a temperature in the range of room temperature to 250 ° C.