JP2002140930A - Conductive composition and flexible conductive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive composition having satisfactory flexibility, excellent stability when blending and storing, and satisfactory transparency, smoothness, and electric conductivity and provide a flexible conductive material preventing the reduction of electric conductivity due to a crack even if a soft basic material is expanded, shrunk, and deformed. SOLUTION: The conductive composition containing water soluble conductive polymer having a sulfonic acid group and/or carboxyl group, vinyl polymer emulsion B having a glass-transition temperature of 40 deg.C or less, and solvent and the flexible conductive material on which the conductive composition is applied are provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a conductive composition and a conductor formed from the conductive composition. More specifically, it can be applied well to a flexible and porous substrate, and the obtained conductor has high flexibility to maintain conductivity without being destroyed by expansion and contraction of the base material. TECHNICAL FIELD The present invention relates to a conductive composition which is excellent in stability at the time and can form a conductor having good transparency, smoothness, conductivity and the like, and a flexible conductor using the same.

[0002] The conductive composition of the present invention comprises various antistatic agents, capacitors, batteries, EMI shields, chemical sensors, display elements, non-linear materials, anticorrosives, adhesives, fibers, antistatic paints, anticorrosive paints, and electrodeposition. Paint, plating primer,
The present invention can be applied to, for example, cathodic protection, improvement of battery storage capacity, and the like.
In particular, since the conductor obtained from the conductive composition of the present invention has low conductivity dependence on humidity and high flexibility, the application of a flexible substrate to an antistatic agent is excellent. Specific uses as an antistatic agent include packaging materials, magnetic cards, magnetic tapes, magnetic disks, photographic films, printing materials, conductive rolls, release films, heat seal tape films, IC trays, IC carrier tapes and the like. And cover tape.

[0003]

2. Description of the Related Art As a means for eliminating static electricity damage to plastics, a method of imparting conductivity to plastics using a conductive primer, an antistatic agent or the like is generally used. Conventional conductive components include 7,7,
8,8-tetracyanoquinodimethane (TCNQ) complex salt,
Known are conductive polymers such as polyaniline, metallic powders and carbon powders, those using surfactants, and those combining these components with high molecular compounds.
Further, as a conductor, a conductor in which a conductive film is formed on a base material using a conductive paint made of the above composition is known. For example, in a conductive primer, a conductive filler or a conductive additive is added to the primer in order to make the non-conductive surface conductive.

[0004] As the conductive filler, specifically, a conductive primer composition for plastics using conductive carbon, silver, nickel, aluminum, etc. (JP-A-58-1983)
76266, JP-A-61-218639,
JP-A-2-120373, JP-A-2-19407
No. 1) has been proposed, but since these conductive primer compositions for plastics have a conductive filler dispersed therein, the conductive filler and the resin component may be separated and aggregated during storage and may be stored. There was a drawback that stability was poor. In addition, conductive primers using these conductive fillers are generally expensive, and furthermore, it is necessary to increase the film thickness in order to obtain practically necessary conductivity. Having.

Although a method using an inexpensive surfactant as an additive for imparting conductivity has been proposed (Japanese Patent Laid-Open No. 3-4970), the conductivity varies depending on the environment, and particularly in an environment with low humidity. There is a problem that the conductivity is significantly reduced. In addition, many of the conductive primers and antistatic agents currently used are organic solvent-based, and replacement with water-based ones is demanded due to problems such as environment and safety.

In order to solve these problems, the present inventors have developed a resin composition for conductive coating (JP-A-11-18552).
No. 3) was devised. The composition is an aqueous conductive composition composed of a water-soluble conductive polymer, and a conductive composition having good blending stability, conductivity, and transparency can be obtained by using a specific nonionic surfactant. . However, even when the composition is applied to a porous and flexible base material such as a resin foam, cracks occur in the conductive film formed by expansion and contraction of the base material, the conductive paths are cut, and the conductivity is reduced. There is a need for a conductive composition that can be applied to a flexible base material and has good adhesiveness and can form a flexible conductive material because it may disappear.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to form a conductor having good flexibility, excellent stability during blending and storage, and excellent transparency, smoothness and conductivity. In particular, it is an object of the present invention to provide a conductive composition which does not cause a decrease in conductivity due to cracks even if the base material is expanded and contracted after forming a conductor on a flexible base material such as an elastomer.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on conductive compositions in order to solve the problems of the prior art, and as a result, have found that a water-soluble conductive polymer having a specific structure and a specific physical property have been obtained. The present inventors have found that a conductive composition suitable for a flexible substrate can be obtained by the combination of the vinyl polymers described above.

That is, a first aspect of the present invention is that a water-soluble conductive polymer having a sulfonic acid group and / or a carboxyl group (A), a vinyl polymer emulsion having a glass transition temperature of 40 ° C. or lower (B), a solvent ( C) A conductive composition comprising: A second aspect of the present invention is a water-soluble conductive polymer (A) having a sulfonic acid group and / or a carboxyl group, a vinyl polymer emulsion (B) having a glass transition temperature of 40 ° C. or lower, and a solvent (C). A flexible conductor having a transparent conductive polymer film formed by applying a conductive composition containing

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the conductive composition and the flexible conductor of the present invention 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.
97633, JP-A-63-39916, JP-A-1-301714, JP-A-4-268331
JP, JP-A-4-32848, JP-A-4-32
No. 8181, JP-A-6-145386, JP-A-5-504153, JP-A-5-503953, JP-A-6-56987, JP-A-5-226
238, JP-A-5-178889, JP-A-6-293828, JP-A-7-118524, JP-A-6-32845, JP-A-6-8794
9, JP-A-6-256516, JP-A-7-256
Water-soluble conductive polymers described in JP-A-41756 and JP-A-7-48436 are preferably used.

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

Preferred water-soluble conductive polymers (A) include:

Embedded image(R in the above formula₁~ R₂Are each independently H, -SO₃ ⁻,
-SO₃H, -R₃₅SO₃ ⁻, -R₃₅SO₃H,-
OCH₃, -CH₃, -C₂H₅, -F, -Cl, -B
r, -I, -N (R₃₅)₂, -NHCOR₃₅, -O
H, -O⁻, -SR₃₅, -OR₃₅, -OCO
R₃₅, -NO₂, -COO⁻, -R₃₅COO ⁻, −
COOH, -R₃₅COOH, -COOR₃₅, -CO
R₃₅, -CHO and -CN.
Where R₃₅Is the carbon number C₁~ C₂₄The alkyl, ally
Or aralkyl group or alkylene or arylene
Or an aralkylene group, and R₁, R₂Within
At least one is -SO₃ ⁻, -SO₃H, -R₃₅S
O₃ ⁻, -R₃₅SO₃H, -COOH, -COO⁻,
-R ₃₅COO⁻And -R₃₅From the group consisting of COOH
The group of choice. )

[0013]

Embedded image(R in the above formula₃, R₄Are each independently H, -SO₃ ⁻,
-SO₃H, -R₃₅SO₃ ⁻, -R₃₅SO₃H,-
OCH₃, -CH₃, -C₂H₅, -F, -Cl, -B
r, -I, -N (R₃₅)₂, -NHCOR₃₅, -O
H, -O⁻, -SR₃₅, -OR₃₅, -OCO
R₃₅, -NO₂, -COO⁻, -R₃₅COO ⁻, −
COOH, -R₃₅COOH, -COOR₃₅, -CO
R₃₅, -CHO and -CN.
Where R₃₅Is the carbon number C₁~ C₂₄The alkyl, ally
Or aralkyl group or alkylene or arylene
Or an aralkylene group, and R₃, R₄Out of
At least one is -SO₃ ⁻, -SO₃H, -R₃₅S
O₃ ⁻, -R₃₅SO₃H, -COOH, -COO⁻,
-R ₃₅COO⁻And -R₃₅From the group consisting of COOH
The group of choice. )

[0014]

Embedded image(R in the above formula₅~ R₈Are each independently H, -SO₃ ⁻,
-SO₃H, -R₃₅SO₃ ⁻, -R₃₅SO₃H,-
OCH₃, -CH₃, -C₂H₅, -F, -Cl, -B
r, -I, -N (R₃₅)₂, -NHCOR₃₅, -O
H, -O⁻, -SR₃₅, -OR₃₅, -OCO
R₃₅, -NO₂, -COO⁻, -R₃₅COO ⁻, −
COOH, -R₃₅COOH, -COOR₃₅, -CO
R₃₅, -CHO and -CN.
Where R₃₅Is the carbon number C₁~ C₂₄The alkyl, ally
Or aralkyl group or alkylene or arylene
Or an aralkylene group, and R₅~ R₈Out of
At least one is -SO₃ ⁻, -SO₃H, -R₃₅S
O₃ ⁻, -R₃₅SO₃H, -COOH, -COO⁻,
-R ₃₅COO⁻And -R₃₅From the group consisting of COOH
The group of choice. )

[0015]

Embedded image (In the above formula, R _{9 to} R ₁₃ 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 , —COO ⁻ , and —R ₃₅ CO
O ⁻ , —COOH, —R ₃₅ COOH, —COO
R ₃₅ , —COR ₃₅ , —CHO and —CN, wherein R ₃₅ is an alkyl, aryl or aralkyl group having ₁ to ₂₄ carbon atoms or an alkylene, arylene or aralkylene group, and , R
₉ at least one of to R ₁₃ is _-SO ³ -, -SO
^{_{3 H, -R 35 SO 3 -}} , -R 35 SO 3 H, -COO
_{^{H, -COO -, -R 35 COO}} - and _-R 35 COO
H is a group selected from the group consisting of )

[0016]

Embedded image(R in the above formula₁₄Is -SO₃ ⁻, -SO₃H, -R₃₆
SO₃ ⁻, -R₃₆SO ₃H, -COOH, -CO
O⁻, -R₃₅COO⁻And -R₃₆COOH
Selected from the group₃₆Is the carbon number C₁~ C₂₄
Alkylene, arylene or aralkylene group
You. At least one group selected from the group consisting of
The repeating unit is 20 to 1 in the repeating unit of the whole polymer.
Contains 00% and has a molecular weight of 2000 to 1,000,000
The guide according to any one of claims 1 to 4, characterized in that:
Electrically conductive composition.

Of the above conductive polymers, the following general formula (6):

Embedded image(In the above formula, y represents any 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,
-COO⁻, -R₃₅COO⁻, -COOH, -R₃₅
COOH, -COOR₃₅, -COR₃₅, -CHO and
And -CN, where R₃₅Is carbon
Number C₁~ C₂₄Alkyl, aryl or aralkyl of
Group or alkylene, arylene or aralkylene
And R_Fifteen~ R ₃₂At least one of
Is -SO₃ ⁻, -SO₃H, -R₃₅SO₃ ⁻, -R
₃₅SO₃H, -COOH, -COO⁻, -R₃₅CO
O⁻And -R₃₅A group selected from the group consisting of COOH
is there. ) Is the repeating unit of the entire polymer
Water-soluble conductive resin containing 20 to 100% of the total number of repeating units
Limers are more preferably used.

Here, a water-soluble conductive polymer having a sulfonic acid group and carboxyl group content of 50% or more based on the total number of aromatic rings is preferably used because it has very good solubility, more preferably 70% or more. More preferably 9
0% or more, particularly preferably 100%, of the polymer is used.

The substituent attached to the aromatic ring is preferably an electron donating group from the viewpoints of conductivity and solubility, specifically, an alkyl group, an alkoxy group, a halogen group and the like, and particularly preferably a soluble conductive group having an alkoxy group. Water-soluble polymers are most preferred.

Among these combinations, the following general formula (7):

Embedded image (In the above formula, R ₃₃ represents a sulfonic acid group, a carboxyl group,
Showing one group selected from the group consisting of alkali metal salts, ammonium salts and substituted ammonium salts thereof,
R ₃₄ represents a methyl group, an ethyl group, an n-propyl group,
-Propyl group, n-butyl group, iso-butyl group, se
c-butyl group, tert-butyl group, dodecyl group, tetracosyl group, methoxy group, ethoxy group, n-propoxy group, iso-butoxy group, sec-butoxy group, ter
a single group selected from the group consisting of a t-butoxy group, a heptoxy group, a hexoxy group, an octoxy group, a dodecoxy group, a tetracosoxy group, a fluoro group, a chloro group, and a bromo group, wherein X is 0 <X <1 Indicating the number, n indicates the degree of polymerization and is 3 or more. ) Is most preferably used.

The method for producing the water-soluble conductive polymer (A) may be a known method, and is not particularly limited. Examples thereof include a heterocyclic compound having a skeleton such as thienylene, pyrrolylene and iminophenylene, and an aniline compound. A polymer obtained by polymerizing the polymerizable monomer of the above by various synthetic methods such as a chemical oxidation method and an electrolytic oxidation method can be used. For example, Japanese Patent Laid-Open No. 7-1967 proposed by the present inventors.
No. 91, and the synthesis method described in JP-A-7-324132 are applied.

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
In terms of polyethylene glycol of PC, those having 2,000 or more are preferably used because they have excellent conductivity, film formability and film strength, and those having a mass average molecular weight of 3,000 or more and 1,000,000 or less are more preferable, and 5,000 or more and 500,000 or less. Are more preferred. Here, the mass average molecular weight is 2000
The following polymers are excellent in solubility, but may be insufficient in conductivity and film forming property, and have a weight average molecular weight of 100
If it is 10,000 or more, the conductivity is excellent, but the solubility may be insufficient.

The vinyl polymer emulsion (B) used in the present invention is not particularly limited as long as the glass transition temperature of the polymer is 40 ° C. or lower. Examples thereof include methyl methacrylate, ethyl methacrylate, and n-methacrylic acid. Butyl,
Alkyl methacrylate such as i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, n-lauryl methacrylate, n-stearyl methacrylate, cyclohexyl methacrylate, methyl acrylate, ethyl acrylate, acrylic acid alkyl acrylates such as n-butyl, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, n-lauryl acrylate, n-stearyl acrylate, cyclohexyl acrylate, and methacrylic acid 2
Hydroxyalkyl methacrylates such as -hydroxyethyl, 4-hydroxybutyl methacrylate and 6-hydroxyhexyl methacrylate; hydroxy acrylates such as 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate and 6-hydroxyhexyl acrylate Glycidyl group-containing vinyl polymerizable monomers such as alkyl esters, glycidyl methacrylate, and glycidyl acrylate; aromatic vinyl polymerizable monomers such as styrene and α-methylstyrene; amides such as methacrylamide, acrylamide, and diacetone acrylamide Group-containing vinyl monomers,
Methacrylic acid, acrylic acid, itaconic acid, crotonic acid,
At least one monomer selected from carboxyl group-containing vinyl polymerizable monomers such as fumaric acid, maleic acid and sorbic acid, and nitrile group-containing vinyl polymerizable monomers such as acrylonitrile (hereinafter referred to as vinyl polymerizable monomers); It is called monomer (G).)
Having a glass transition temperature of 40 ° C. in a polymer or copolymer containing
The following are used:

As the glass transition temperature in the present invention, an actually measured value or a value calculated by an estimation formula such as the Fox formula can be used. In the present invention, the polymer glass transition temperature of the vinyl polymer emulsion is 40 ° C. or lower, preferably 15 ° C. or lower. Here, when the glass transition temperature exceeds 40 ° C., the flexibility of the obtained conductor is significantly reduced, and when the conductor is formed on a flexible and porous base material such as a foam or an elastomer, Since the conductor is broken by the expansion and contraction of the conductor and the conductive path is cut, the conductivity is lost. Further, the lower limit of the glass transition temperature of the polymer is preferably -10 ° C or higher in practical use.

The method for producing the vinyl polymer emulsion (B) used in the present invention is not particularly limited. For example, a method in which a vinyl polymer synthesized by solution polymerization or the like is emulsified and dispersed in a solvent, The method includes emulsion polymerization of the water-soluble monomer (G). Among them, in view of the productivity of the conductive composition, it is preferable that the monomer is produced by an emulsion polymerization method. Further, as the emulsion polymerization method, a vinyl polymerizable monomer (F) is prepared by dissolving or dispersing an acidic group-containing vinyl polymer (F) obtained by a suspension polymerization method using a basic compound. The method of emulsion polymerization of G) is more preferred.

The solvent for the above emulsion polymerization is not particularly limited, but water or water and alcohols such as methanol, ethanol, isopropyl alcohol, propyl alcohol and butanol; ketones such as acetone and ethyl isobutyl ketone; Glycols, ethylene glycols such as ethylene glycol methyl ether,
Propylene glycol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, propylene glycols such as propylene glycol propyl ether, dimethylformamide, amides such as dimethylacetamide,
Alternatively, a mixed system with pyrrolidones such as N-methylpyrrolidone and N-ethylpyrrolidone is preferably used. When used in a mixed system with water, water / organic solvent = 1/1
It is preferably from 100 to 100/1 (mass ratio).

The acidic group-containing vinyl polymer (F) is selected from acidic group-containing vinyl polymerizable monomers such as methacrylic acid, acrylic acid, crotonic acid and itaconic acid, and vinyl polymerizable monomers (G). It is composed of a monomer containing at least one of the above. The acid value of the solid content of the acidic group-containing vinyl polymer (F) is as follows:
It is preferably from 50 to 200 mgKOH / g, more preferably from 70 to 150 mgKOH / g, and within this range, the balance between solubility, water resistance and moisture resistance is particularly good. If the acid value of the solid content is less than 50 mgKOH / g, the acidic group-containing vinyl polymer (I) may be difficult to dissolve or disperse in the solvent (C) using a basic compound. The dispersion stability at the time of turbid polymerization may decrease, and the water resistance, moisture resistance, and substrate adhesion of the obtained conductor may decrease.

The weight-average molecular weight of the acidic group-containing vinyl polymer (F) is preferably in the range of 5,000 to 50,000, more preferably 8,000 to 40,000. When the weight average molecular weight is 5,000 or less, the dispersion stability during suspension polymerization may decrease, and the flexibility of the obtained conductor may decrease. When it exceeds 50,000, the acidic group-containing vinyl polymer (F ) May be difficult to disperse or dissolve in a solvent using a basic compound.

Solution polymerization or emulsion polymerization for producing the vinyl polymer emulsion (B) can be carried out under known polymerization conditions using a known radical polymerization initiator.
Specific examples of the radical polymerization initiator include azo compounds such as azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile), ammonium persulfate,
Inorganic peroxides such as potassium persulfate and sodium persulfate,
Benzoyl peroxide, t-butyl hydroperoxide,
Organic peroxides such as di-t-butyl peroxide and cumene hydroperoxide; combinations of potassium peroxide or ammonium peroxide with sodium bisulfite or Rongalite; and organic peroxides such as t-butyl hydroperoxide and cumene hydroperoxide. Redox catalysts and the like represented by a combination of an oxide and sodium hydrogen sulfate or Rongalite are exemplified.

The amount of the radical polymerization initiator to be added is usually 0.01 to the total amount of the vinyl polymerizable monomer (G).
Although it is in the range of 10 to 10% by mass, the range of 0.1 to 5% by mass is preferable in consideration of progress of polymerization and control of the reaction. Further, a compound containing a divalent iron ion such as iron sulfate and a chelating agent such as disodium ethylenediaminetetraacetate can be used to impart the activity of the polymerization initiator.

In the emulsion polymerization, known surfactants and chain transfer agents can be used if necessary.
Examples of the surfactant include anionic surfactants such as sodium dodecylbenzenesulfonate, sodium lauryl sulfonate, and sodium lauryl sulfate, anionic surfactants containing a polyoxyethylene group, polyoxyethylene nonyl phenyl ether, and polyoxyethylene nonyl phenyl ether. Examples include nonionic surfactants such as oxyethylene lauryl ether, and reactive surfactants having a vinyl polymerizable double bond in the molecule. Examples of the chain transfer agent include mercaptans such as n-dodecyl mercaptan, n-octyl mercaptan, n-tetradecyl mercaptan, n-hexyl mercaptan, and halogen compounds such as carbon tetrachloride and ethylene bromide.

The method of charging the vinyl polymerizable monomer (G) in the emulsion polymerization is not particularly limited, and any method such as batch charging, dripping, or a method in which a part is charged in a reaction vessel in advance and the rest is dropped is used. May be. When the solution is dropped, the solution may be directly dropped into the aqueous solution of the surfactant in the reaction vessel, or the surfactant may be added to the solution to be preliminarily emulsified and then dropped into the reaction vessel. When an acid component such as acrylic acid is used, the storage stability of the emulsion can be enhanced by neutralizing the emulsion after the completion of the emulsion polymerization.

The acidic group-containing vinyl polymer (F) is produced under known polymerization conditions using known initiators, dispersants and chain transfer agents. For example, specific examples of the initiator include azobisisobutyronitrile, 2,2′-azobis (2,4
-Dimethylvaleronitrile) and organic peroxides such as benzoyl peroxide. Specific examples of the chain transfer agent include n-dodecyl mercaptan, n
And mercaptans such as octylmercaptan, n-tetradecylmercaptan and n-hexylmercaptan.

The basic compound for dissolving or dispersing the acidic group-containing vinyl polymer (F) in a solvent is not particularly limited, but for example, ammonia, triethylamine, tripropylamine and the like are preferably used.
The amount of the basic compound used is preferably in the range of 0.5 to 1 equivalent to the acidic group in the acidic group-containing vinyl polymer (F). When the amount is less than 0.5 equivalent, the vinyl polymer (F) hardly dissolves or disperses in a solvent, and when the amount exceeds 1 equivalent, the emulsion polymerization stability of the vinyl polymerizable monomer (G) becomes poor. It may be defective.

The amount of the vinyl polymerizable monomer (G) to be used with respect to the acidic group-containing vinyl polymer (F) is 50 to 30 based on 100 parts by mass of the acidic group-containing vinyl polymer (F).
It is preferably in the range of 0 parts by mass. When the amount is less than 50 parts by mass, the conductivity of the conductor obtained from the conductive composition of the present invention is easily damaged. If the amount exceeds 300 parts by mass, the emulsion polymerization stability of the vinyl polymerizable monomer (G) may be poor.

The solvent (C) used in the present invention includes:
Water or water and alcohols such as methanol, ethanol, isopropyl alcohol, propyl alcohol and butanol; ketones such as acetone and ethyl isobutyl ketone; ethylene glycols such as ethylene glycol and ethylene glycol methyl ether; propylene glycol; propylene glycol methyl Ethers, propylene glycol ethyl ether, propylene glycol butyl ether, propylene glycols such as propylene glycol propyl ether, dimethylformamide,
A mixed system with an amide such as dimethylacetamide or a pyrrolidone such as N-methylpyrrolidone or N-ethylpyrrolidone is preferably used. When used in a mixed system with water, water / organic solvent = 1/100 to 100 /
1 (mass ratio) is preferred.

As the surfactant (D) used in the present invention, surfactants such as anionic surfactants, nonionic surfactants, and cationic surfactants are used. Nonionic surfactants include It is preferably used, and furthermore, H
A nonionic surfactant having an LB of 16 or more is more preferably used because it improves the stability of the conductive composition during compounding and storage and improves the appearance of the obtained conductor. Further, from a practical standpoint, the upper limit of the HLB is preferably 30 or less. Note that HLB is Hydrophile-Li
This is an abbreviation of popile balance and is an index indicating hydrophilicity of a surfactant or the like.

Specific examples of the nonionic surfactant having an HLB of 16 or more include polyoxyethylene alkylphenyl ethers having an HLB value of 16 or more, and polyoxyethylene alkyl ethers having an HLB value of 16 or more. No. Among them, a polyoxyethylene alkylphenyl ether having an HLB of 16 or more is particularly preferable because the effect of improving the stability during blending and storage and the appearance of the conductor can be obtained with a smaller amount.

The polyvinyl alcohol (E) used in the present invention is not particularly limited as long as it is a normal polyvinyl alcohol, but a modified polyvinyl alcohol having an alkyl group at a terminal is particularly preferably used. And to improve the appearance of the obtained conductor.

Specific examples of the modified polyvinyl alcohol having an alkyl group at the terminal are not particularly limited as long as the polyvinyl alcohol has an alkyl group introduced at the terminal. Those having a chain repeating unit of from 100 to 1000 and a degree of suspension of from 85 to 100% are particularly preferable because a smaller amount thereof can provide the effect of improving the stability during blending and storage and the appearance of the conductor.

Although the surfactant (D) and the polyvinyl alcohol (E) can be used alone in the conductive composition, the effect can be obtained. Shows the effect of improving stability.

Next, the method of compounding the conductive composition of the present invention will be specifically described. The method of compounding the conductive composition of the present invention is not particularly limited. For example, after adding the solvent (C) to the vinyl polymer emulsion (B), the powder or solution of the water-soluble conductive polymer (A) is added. Addition method, or powder of water-soluble conductive polymer (A) to vinyl polymer emulsion (B) containing surfactant (D) and / or polyvinyl alcohol (E) and solvent (C) in advance. A method of adding a solution may, for example, be mentioned.

The method of adding the surfactant (D) to the vinyl polymer emulsion (B) is not particularly limited, either.
It may be added as a surfactant for emulsion polymerization at the time of producing the vinyl polymer emulsion (B), or may be added at the end of emulsion polymerization.

Similarly, the method of adding the polyvinyl alcohol (E) to the vinyl polymer emulsion (B) is not particularly limited, and is added as a surfactant for emulsion polymerization during the production of the vinyl polymer emulsion (B). And may be added at the end of the emulsion polymerization.

The mass (a) of the water-soluble conductive polymer (A) used in the present invention is a ratio (a) to the mass (b) of the vinyl polymer in the vinyl polymer emulsion (B).
/ (B) is preferably added so as to be in the range of 0.05 to 4, more preferably in the range of 0.01 to 3. If (a) / (b) is less than 0.05, the conductivity of the obtained conductor may be poor, and if it exceeds 4, the stability during storage of the conductive composition may be deteriorated when compounding the conductive composition. The water resistance and moisture resistance of the conductor may decrease.

The mass (c) of the solvent (C) used in the present invention is such that the ratio (a) / (c) to the mass (a) of the water-soluble conductive polymer (A) is 0.0001-5. It is preferable to add so as to be within the range. If the ratio of (a) / (c) is less than 0.0001, the conductivity of the obtained conductor may be poor, and if it exceeds 5, when the conductive composition is blended,
The stability during storage may be deteriorated, and the water resistance, moisture resistance, and smoothness of the obtained conductor may decrease.

The mass (d) of the surfactant (D) blended in the conductive composition of the present invention is the ratio (b) of the mass (b) of the vinyl polymer in the vinyl polymer emulsion (B). It is preferable to add d) / (b) so as to be in the range of 0.001 to 0.1. When (d) / (b) is less than 0.001, the stability at the time of blending or storage is deteriorated, and the appearance of the obtained conductor may be poor.
If it exceeds 0.1, the water resistance and moisture resistance of the conductor may be adversely affected.

Similarly, the mass (e) of the polyvinyl alcohol (E) blended in the conductive composition of the present invention is different from the mass (b) of the vinyl polymer in the vinyl polymer emulsion (B). The ratio (e) / (b) is 0.001 to 0.1
It is preferable to add so as to be within the range. (E) / (b)
Is less than 0.001, the stability during blending and storage is poor, and the appearance of the resulting conductor may be poor. May adversely affect water resistance and moisture resistance. Further, it is also preferable to use the surfactant (D) and the polyvinyl alcohol (E) in combination within the above-mentioned range.

As the substrate on which the conductive composition is applied, polymer compounds, wood, paper, ceramics and films thereof, foams, elastomers or glass plates are used. For example, as polymer compounds and films, foams, elastomers, 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, polyether sulfone, polysulfone, Examples include polyetherimide, polybutylene terephthalate and its films, foams, and elastomers.

In order to form a transparent conductive polymer film on at least one surface of these polymer films, the film surface is subjected to a corona surface treatment or a plasma treatment for the purpose of improving the adhesion of the polymer film. Is preferred.

The conductive composition used to form the conductor of the present invention is processed on the surface of a substrate by a method generally used for coating. For example, gravure coater, roll coater, curtain flow coater, spin coater, bar coater, reverse coater, kiss coater,
A coating method such as a fountain coater, a rod coater, an air doctor coater, a knife coater, a blade coater, a cast coater, and a screen coater, a spraying method such as spray coating, and a dipping method such as dip are used. After processing on the surface of the substrate, the substrate may be dried at room temperature to 250 ° C. if necessary. As a drying method, an arbitrary method such as standing at normal temperature, hot air drying, and drying under reduced pressure can be selected.

When the composition is applied to a plastic substrate such as polypropylene, it is mixed with an emulsion of another resin such as chlorinated polyolefin or a water-soluble resin to improve the adhesion of the conductor to the substrate. Is also good. Furthermore, the conductive composition of the present invention may contain a pigment, an antifoaming agent, a film forming aid, an ultraviolet absorber, an antioxidant, a heat resistance improver, a leveling agent, an anti-sagging agent, a matting agent, if necessary. And various additives such as preservatives.

[0053]

The present invention will be described below in more detail with reference to examples. In the examples, “parts” are “parts by mass” and “%”.
Indicates "% by mass".

Production Example 1, Synthesis of conductive polymer (A-1) poly (2-sulfo-5-methoxy-1,4-iminophenylene) (A-1) 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 then 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.
cm.

Production Example 2, conductive polymer (A-2) poly (2-sulfo-1,4-iminophenylene) (A-
Synthesis of 2) 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. The volume resistance of this polymer is 50Ω.
Cm.

Production Example 3, Synthesis of Conductive Polymer (A-3) Poly (2-sulfopropyl-1,4-iminophenylene) (A-3) Poly (2-sulfo-1,4-iminophenylene) By a known method "J. Chem. Soc., Chem. Com.
mun. , (1990), 180 ".

Production Example 4, conductive polymer (A-4) poly (2-sulfopropyl-2,5-thienylene) (A
-4) Synthesis of poly (2-sulfopropyl-2,5-thienylene) by a known method "39th Preprints of the Society of Polymer Science, 1990, 56
No. 1).

Production Example 5, conductive polymer (A-5) poly (2-carbonyl-1,4-iminophenylene)
Synthesis of (A-5) 2-aminoanisole-4-carboxylic acid 100 mmol
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 10 g of a polymer powder.

Production Example 6, Vinyl polymer emulsion (B-1) 233 parts of deionized water, Adecaria soap SE-10N
(Asahi Denka Kogyo) 3 parts, Emulgen 985 (Kao nonionic surfactant, HLB = 18.9) 6 parts by a stirrer,
The mixture was charged into a flask equipped with a condenser, a temperature controller, a dropping pump, and a nitrogen inlet tube, and stirred and mixed. Further, a mixture 100 comprising 40 parts of methyl methacrylate (hereinafter, MMA), 28 parts of n-butyl acrylate (hereinafter, BA), 30 parts of 2-ethylhexyl acrylate (hereinafter, EHA), and 2 parts of methacrylic acid (hereinafter, MAA). After charging 20 parts of the mixture and raising the temperature to 80 ° C. while stirring, 0.5 part of potassium persulfate (KPS) was added under a nitrogen atmosphere. After reacting for 30 minutes, the above monomer mixture 10
The remaining 80 parts out of 0 parts were polymerized dropwise over 2 hours. After the completion of the dropwise addition, the mixture was kept at 80 ° C. for 1 hour to obtain a vinyl polymer emulsion (B-1). The solid content of the obtained emulsion was 32%.

Preparation Example 7, Vinyl polymer emulsion (B-2 and B-3) Preparation Example 6 (B-1) except that the monomer composition and the surfactant were changed as shown in Table 1. Was carried out in the same manner as in Example 1 to obtain vinyl polymer emulsions (B-2 and B-3).

Production Example 8, vinyl polymer emulsion (B-4), 200 parts of deionized water, Adecaria Soap SE-10N
3 parts (manufactured by Asahi Denka Kogyo) were charged into a flask equipped with a stirrer, a condenser and a temperature controller, and completely dissolved.
Once stirring was stopped, 30 parts of MMA, 10 parts of EHA, B
A44 parts, 16 parts of MAA, 0.5 parts of azobisisobutyronitrile, 5 parts of n-dodecylmercaptan were added, stirring was started again, and the temperature was raised to 75 ° C.
The reaction was performed for 3 hours while maintaining the temperature at 80 ° C. Then 9
The temperature was raised to 0 ° C. and maintained for 1 hour. 80 μm
m, and then dried to obtain a vinyl polymer (I). Table 2 shows the properties of the obtained vinyl polymer (I).

100 parts of the vinyl polymer (I) and 410 parts of deionized water were charged into a flask equipped with a stirrer, a condenser, a temperature controller, a dropping pump and a nitrogen inlet tube. While stirring, 10 parts of 28% aqueous ammonia was added, stirring was continued for 30 minutes, and the temperature was further raised to 80 ° C. and stirred for 1 hour to obtain an aqueous liquid of the vinyl polymer (I). While maintaining the temperature at 80 ° C., under a nitrogen atmosphere, 0.5 part of KPS was added.
, A pre-emulsion prepared by stirring a mixture of 10 parts of glycidyl methacrylate (hereinafter referred to as GMA), 5 parts of Adecaria Soap SE-10N (manufactured by Asahi Denka Kogyo) and 50 parts of deionized water was dropped and polymerized over 1 hour. . After dropping, 80
C. for 1 hour to obtain a vinyl polymer emulsion (B-3). The solid content of the obtained emulsion was 31%.

Preparation Example 9, Vinyl Polymer Emulsions (B-5 and B-6) The same procedure as in Preparation Example 8 (B-4) was carried out except that the monomer composition was changed as shown in Table 2. Polymerization was performed to obtain vinyl polymer emulsions (B-5 and B-6).

Examples 1 to 5 While stirring 30 parts of a vinyl polymer emulsion, 10 parts of a 10% aqueous solution of a water-soluble conductive polymer was added to obtain a conductive composition (solid content of the conductive polymer). / Solid content of vinyl polymer {10/90). Table 3 shows the properties of the obtained conductive composition.

Examples 6 to 10 Emulgen 985 in the amount shown in Table 3 was added to 30 parts of the vinyl polymer emulsion (solid content of the vinyl polymer ≒ 9 parts).
(Non-surfactant manufactured by Kao, HLB = 18.9) and / or modified PVA MP-103 (modified PVA manufactured by Kuraray Co., Ltd.) were added and stirred for 1 hour. With further stirring, 10 parts of a 10% aqueous solution of the conductive polymer (A-1) (solid content of the conductive polymer = 1 part) was added to obtain a conductive composition. Table 3 shows the properties of the obtained conductive composition.

Comparative Examples 1 and 3 While stirring 30 parts of the vinyl polymer emulsion, 10 parts of a 10% aqueous solution of the conductive polymer (A-1) was added.
A conductive composition was obtained (solid content of conductive polymer / solid content of vinyl polymer 系 10/90). Table 3 shows the properties of the obtained conductive composition.

Comparative Examples 2 and 4 Emulgen 985 in the amount shown in Table 3 was added to 30 parts of the vinyl polymer emulsion (solid content of the vinyl polymer ≒ 9 parts).
(Non-surfactant manufactured by Kao, HLB = 18.9) and / or modified PVA MP-103 (modified PVA manufactured by Kuraray Co., Ltd.) were added and stirred for 1 hour. With further stirring, 10 parts of a 10% aqueous solution of the conductive polymer (A-2) (solid content of the conductive polymer = 1 part) was added to obtain a conductive composition. Table 3 shows the properties of the obtained conductive composition.

The evaluation of the performance in the examples and comparative examples was performed using the following method. (1) Blending stability: The stability of the conductive composition immediately after blending was visually evaluated. ○ No aggregates △ Aggregate formation × Coagulation during addition of conductive polymer aqueous solution (2) Conductor appearance: The compounded conductive composition was applied on a glass plate by bar coating, dried at room temperature for 1 hour, and then dried.
By heating at 0 ° C. for 1 hour, a test conductor having a film thickness of 10 μm was prepared. The appearance of the test conductor was visually evaluated. ○ Smooth and good transparency × Surface is uneven and opaque

(3) Conductivity: The surface resistance of the conductive coating surface was measured using Hiresta “MCP-TEST manufactured by Mitsubishi Chemical Corporation”.
The measurement was made at two terminals using "ER". (4) Flexibility: The compounded conductive composition was impregnated and applied to foamed polyethylene, and heated at 80 ° C. for 2 hours to prepare a test piece. The test piece was contracted by a load of 1 kg, and the conductivity was measured after repeating the expansion and contraction of 100 times after the load was stopped and extended. ○ No change in conductivity × Loss of conductivity

[0070]

[Table 1]

[0071]

[Table 2]

[0072]

[Table 3]

[0073]

The conductive composition of the present invention is excellent in stability during blending and storage, and can form a flexible conductor having good transparency, smoothness, conductivity and the like. A flexible conductor that does not cause a decrease in conductivity due to cracks even when the base material is expanded or contracted or deformed after the formation of the conductor on a suitable base material is obtained, which is extremely useful in industry.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08L 65/00 C08L 65/00 71/02 71/02 79/00 79/00 Z 101/00 101/00 101/14 101/14 H01B 1/12 H01B 1/12 Z 5/14 5/14 A F-term (reference) 4J002 BC02X BE02Z BG01X BG04X BG05X BG10X BG12X BG13X BH00X BN11X CD19X CE00W CH05Y CM00W CM05W DE026 EC026 EC036 EC046 FD206 FD31Y GH00 GQ02 HA07 4J011 AA05 AA07 BA04 BA05 DA01 KA20 KA29 KB14 KB29 KB30 PA69 PB40 PC02 4J026 AA43 AA45 AA53 AC23 BA26 BA27 BA30 BB02 DA03 DA12 DB04 DB14 FA04 GA06 GA08 GA09 GA10 5G301 FC02 DA02 DA10

Claims (10)

[Claims] 1. A water-soluble conductive polymer having a sulfonic acid group and / or a carboxyl group (A), a vinyl polymer emulsion having a glass transition temperature of 40 ° C. or lower (B), and a solvent (C). The conductive composition characterized by the above. 2. The conductive composition according to claim 1, wherein the conductive composition contains a surfactant (D). 3. The conductive composition according to claim 1, wherein the conductive composition contains polyvinyl alcohol (E). 4. A solvent in which a vinyl polymer emulsion (B) having a glass transition temperature of 40 ° C. or lower is prepared by dissolving or dispersing an acidic group-containing vinyl polymer (F) using a basic compound, An emulsion obtained by emulsion polymerization of a vinyl polymerizable monomer (G), and the acid group-containing vinyl polymer (F) has an acid value of a solid content of 50 to 200 mg KO.
The conductive composition according to any one of claims 1 to 3, wherein H / g and the weight average molecular weight are in the range of 5,000 to 50,000. 5. The method according to claim 1, wherein the water-soluble conductive polymer (A) is(R in the above formula₁~ R₂Are each independently H, -SO₃ ⁻,
-SO₃H, -R₃₅SO₃ ⁻, -R₃₅SO₃H,-
OCH₃, -CH₃, -C₂H₅, -F, -Cl, -B
r, -I, -N (R₃₅)₂, -NHCOR₃₅, -O
H, -O⁻, -SR₃₅, -OR₃₅, -OCO
R₃₅, -NO₂, -COO⁻, -R₃₅COO ⁻, −
COOH, -R₃₅COOH, -COOR₃₅, -CO
R₃₅, -CHO and -CN.
Where R₃₅Is the carbon number C₁~ C₂₄The alkyl, ally
Or aralkyl group or alkylene or arylene
Or an aralkylene group, and R₁, R₂Within
At least one is -SO₃ ⁻, -SO₃H, -R₃₅S
O₃ ⁻, -R₃₅SO₃H, -COOH, -COO⁻,
-R ₃₅COO⁻And -R₃₅From the group consisting of COOH
The group of choice. )(R in the above formula₃, R₄Are each independently H, -SO₃ ⁻,
-SO₃H, -R₃₅SO₃ ⁻, -R₃₅SO₃H,-
OCH₃, -CH₃, -C₂H₅, -F, -Cl, -B
r, -I, -N (R₃₅)₂, -NHCOR₃₅, -O
H, -O⁻, -SR₃₅, -OR₃₅, -OCO
R₃₅, -NO₂, -COO⁻, -R₃₅COO ⁻, −
COOH, -R₃₅COOH, -COOR₃₅, -CO
R₃₅, -CHO and -CN.
Where R₃₅Is the carbon number C₁~ C₂₄The alkyl, ally
Or aralkyl group or alkylene or arylene
Or an aralkylene group, and R₃, R₄Out of
At least one is -SO₃ ⁻, -SO₃H, -R₃₅S
O₃ ⁻, -R₃₅SO₃H, -COOH, -COO⁻,
-R ₃₅COO⁻And -R₃₅From the group consisting of COOH
The group of choice. )(R in the above formula₅~ R₈Are each independently H, -SO₃ ⁻,
-SO₃H, -R₃₅SO₃ ⁻, -R₃₅SO₃H,-
OCH₃, -CH₃, -C₂H₅, -F, -Cl, -B
r, -I, -N (R₃₅)₂, -NHCOR₃₅, -O
H, -O⁻, -SR₃₅, -OR₃₅, -OCO
R₃₅, -NO₂, -COO⁻, -R₃₅COO ⁻, −
COOH, -R₃₅COOH, -COOR₃₅, -CO
R₃₅, -CHO and -CN.
Where R₃₅Is the carbon number C₁~ C₂₄The alkyl, ally
Or aralkyl group or alkylene or arylene
Or an aralkylene group, and R₅~ R₈Out of
At least one is -SO₃ ⁻, -SO₃H, -R₃₅S
O₃ ⁻, -R₃₅SO₃H, -COOH, -COO⁻,
-R ₃₅COO⁻And -R₃₅From the group consisting of COOH
The group of choice. )(R in the above formula₉~ R₁₃Are 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, -COO⁻, -R₃₅CO
O⁻, -COOH, -R₃₅COOH, -COO
R₃₅, -COR₃₅, -CHO and -CN
Where R₃₅Is the carbon number C₁~ C₂₄No
Alkyl, aryl or aralkyl or alkyl
An arylene or aralkylene group;
₉~ R₁₃At least one of which is -SO₃ ⁻, -SO
₃H, -R₃₅SO₃ ⁻, -R₃₅SO₃H, -COO
H, -COO⁻, -R₃₅COO⁻And -R₃₅COO
H is a group selected from the group consisting of )(R in the above formula₁₄Is -SO₃ ⁻, -SO₃H, -R₃₆
SO₃ ⁻, -R₃₆SO ₃H, -COOH, -CO
O⁻, -R₃₅COO⁻And -R₃₆COOH
Selected from the group₃₆Is the carbon number C₁~ C₂₄
Alkylene, arylene or aralkylene group
You. At least one group selected from the group consisting of
The repeating unit is 20 to 1 in the repeating unit of the whole polymer.
Contains 00% and has a molecular weight of 2000 to 1,000,000
The guide according to any one of claims 1 to 4, characterized in that:
Electrically conductive composition. 6. The water-soluble conductive polymer (A) is represented by the following formula:(In the above formula, y represents any 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,
-COO⁻, -R₃₅COO⁻, -COOH, -R₃₅
COOH, -COOR₃₅, -COR₃₅, -CHO and
And -CN, where R₃₅Is carbon
Number C₁~ C₂₄Alkyl, aryl or aralkyl of
Group or alkylene, arylene or aralkylene
And R_Fifteen~ R ₃₂At least one of
Is -SO₃ ⁻, -SO₃H, -R₃₅SO₃ ⁻, -R
₃₅SO₃H, -COOH, -COO⁻, -R₃₅CO
O⁻And -R₃₅A group selected from the group consisting of COOH
is there. ) Is the repeating unit of the entire polymer
20 to 100% of the total number of repeating units, and mass average
Characterized by an average molecular weight of 2,000 to 1,000,000
The conductive composition according to claim 1. 7. The method according to claim 1, wherein the water-soluble conductive polymer (A) is (In the above formula, R ₃₃ represents a sulfonic acid group, a carboxyl group,
Showing one group selected from the group consisting of alkali metal salts, ammonium salts and substituted ammonium salts thereof,
R ₃₄ represents a methyl group, an ethyl group, an n-propyl group,
-Propyl group, n-butyl group, iso-butyl group, se
c-butyl group, tert-butyl group, dodecyl group, tetracosyl group, methoxy group, ethoxy group, n-propoxy group, iso-butoxy group, sec-butoxy group, ter
a single group selected from the group consisting of a t-butoxy group, a heptoxy group, a hexoxy group, an octoxy group, a dodecoxy group, a tetracosoxy group, a fluoro group, a chloro group, and a bromo group, wherein X is 0 <X <1 Indicating the number, n indicates the degree of polymerization and is 3 or more. The conductive composition according to any one of claims 1 to 4, wherein 8. A conductive material containing a water-soluble conductive polymer (A) having a sulfonic acid group and / or a carboxyl group, a vinyl polymer emulsion (B) having a glass transition temperature of 40 ° C. or lower, and a solvent (C). A flexible conductor having a transparent conductive polymer film formed by applying a composition to a substrate. 9. The method according to claim 8, wherein the transparent conductive polymer film is a surfactant (D).
9. The flexible conductor according to claim 8, which comprises: 10. The flexible conductor according to claim 8, wherein the transparent conductive polymer film contains polyvinyl alcohol (E).