JP3037547B2 - Conductive composition, conductor and method of forming the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a conductive composition, a conductor formed from the conductive composition, and a method for producing the same. The conductive composition of the present invention can be applied to various antistatic applications by a simple method such as coating, spraying, casting, and dipping. Further, the conductor of the present invention obtained from the composition, semiconductors, industrial packaging materials such as electrical and electronic parts, films for overhead projectors, antistatic films such as electrophotographic recording materials such as slide films, audio tape, video Antistatic of magnetic recording tapes such as tapes, tapes for computers and floppy disks, and transparent conductive films used as antistatic and transparent electrodes for input and display devices such as transparent touch panels, electroluminescent displays and liquid crystal displays or It can be used as a transparent conductive glass or the like.

[0002]

2. Description of the Related Art Conventionally, 7,7,8,8-tetracyanoquinodimethane (T
Known are CNQ) complex salts, conductive polymers such as polyaniline, metal-based powders and carbon powders, surfactants, and combinations of these components with polymer compounds. Further, as the conductor, a conductor formed on a base material using a conductive paint made of the above composition is known. For example, a method of forming a metal thin film such as gold or platinum or a metal oxide thin film such as indium tin oxide (ITO) on a base material such as a plastic film or glass using an ion beam sputtering device or a vacuum evaporation device is known. It is known that a conductor excellent in transparency and conductivity can be obtained. However, since the equipment used to form the thin film is expensive, and the noble metals such as gold and platinum used as materials and ITO are also expensive, the resulting conductor is also expensive. is there. As an electron conductive polymer conductor using TCNQ, a polymer conductor composed of a polymer compound having a quaternary nitrogen cationic group and TCNQ is known, but the solubility in a solvent is very poor. Many of them are soluble only in special solvents such as dimethylformamide and the like, and it is hard to say that they are suitable as varnish. In addition, T
A method of making a conductive polymer composition containing an organic low molecular complex of CNQ into a transparent conductive material by forming this compound on the surface of an electrically insulating polymer film (Japanese Patent Laid-Open No. 63-2)
No. 76815, Japanese Patent Application Laid-Open No. Hei 1-210470) have been proposed. The conductor obtained by this method is
It is thought that the conductivity of the TCNQ complex salt crystal grows in the polymer compound and the more they overlap, the more the crystal growth state is easily affected by the evaporation rate of the solvent and the temperature distribution during drying. Since the number of conductive paths per unit area becomes non-uniform, the variation in surface resistance is large,
Uniform surface resistance cannot be obtained. In addition, high temperatures (for example, 1
40 ° C heating) or high temperature and high humidity (eg, 60 ° C, 95% R)
Under the condition of H), even if the bonding point of the crystal is slightly deteriorated, there is a problem that the conductive path is significantly reduced and the conductivity is significantly reduced.

[0003] Doped polyaniline (conductive polymer) is well known, but is insoluble in almost all solvents and has difficulty in molding and processing. Further, a method of electrolytic oxidation polymerization of aniline [JP-A-60-235831,
J. Polymer Sci. , Polymer
Chem. Ed. , 26 , 1531 (198
8)] can form a polyaniline film on the electrode, but has problems in that the isolation operation is complicated and mass synthesis is difficult. On the other hand, a conductive composition comprising undoped polyaniline obtained by chemical oxidative polymerization of aniline and an ammonium salt of a protonic acid having an acid dissociation constant pKa of 4.8 or less (Japanese Unexamined Patent Application Publication No.
No. 85983), but it is hard to say that undoped polyaniline is suitable as a varnish because it is soluble only in a special solvent such as N-methyl-2-pyrrolidone. In addition, in recent years, a conductive composition comprising an alkali-soluble sulfonated polyaniline and a polymer compound that exhibits conductivity without adding a dopant (US Pat.
0) has been reported. However, the polymer compound used is a poly (1,4-benzoamide) resin or a polyimide resin having extremely low solubility in an organic solvent, and a large problem remains as a varnish because sulfuric acid or the like is used as a solvent.

Furthermore, the above-mentioned conductive composition and the like use an organic solvent. However, when these are dangerous substances having properties such as flammability and explosiveness, there is a problem such as safety of the working environment. Furthermore, the safety of the human body due to toxicity and the global environmental problem are increasing, and regulations on various organic solvents that affect the human body and the environment are increasing, and the safety of the conductive composition is also an important issue.

Further, a conductor formed from a conductive composition comprising a carbon powder or a metal powder and a polymer compound has a problem in that the coating film has excellent durability but lacks transparency.
In addition, anionic, cationic, nonionic, amphoteric or other translucent surfactants are kneaded into the plastic film or coated on the plastic film surface to impart hydrophilicity and ionicity to the film surface. The one provided with conductivity is known. But,
Since the conductor obtained by this method is ionic conductivity, its conductivity is easily affected by humidity in the atmosphere, and the surface resistance per unit area can be 10 ⁸ Ω / □ or less. There is a problem that can not be.

[0006]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned various problems of the prior art. Water can be used as a solvent, and high conductivity without humidity dependence can be obtained. Developed and film-forming properties, moldability, conductive composition with excellent transparency, and high conductivity without humidity dependence using this composition, small variation in surface resistance,
An object of the present invention is to provide a conductor obtained by forming a conductive polymer film having excellent film-forming properties, moldability, and transparency, and a method for forming the same.

[0007]

A first feature of the present invention is as follows.
It is selected from the group consisting of aniline-based conductive polymers (a) containing a sulfone group at a ratio of 15 to 80% based on the total aromatic ring, water-soluble polymer compounds, and polymer compounds that form an emulsion in an aqueous system. A conductive emulsion comprising at least one polymer compound (b), water (c), and at least one nitrogen-containing compound (d) selected from the group consisting of amines and quaternary ammonium salts. In the composition.

A second feature of the present invention is that at least one compound (A) selected from the group consisting of aniline, N-alkylaniline and phenylenediamine, and an alkoxy-substituted aminobenzenesulfonic acid (B) The aniline-based conductive polymer (f) containing a sulfone group obtained by copolymerizing the sulfone group at a ratio of 15 to 80% with respect to the total aromatic ring, a water-soluble polymer compound, and a water-based polymer. Contains at least one polymer compound (b) selected from the group consisting of molecular compounds, water (c) and at least one nitrogen-containing compound (d) selected from the group consisting of amines and quaternary ammonium salts A conductive composition. Further, a third feature of the present invention is that the first or second conductive composition is formed into a film, or is coated on at least one surface of a base material to form a film of the conductive polymer composition. A conductor obtained by leaving or heating at room temperature to volatilize and remove the components (c) and (d), and a method for producing the same.

The treatment of the transparent conductive polymer film includes:
Although it can be carried out by leaving it at room temperature, the amount of the components (c) and (d) remaining by the heat treatment can be further reduced, so that the conductivity is further improved (resistance value is reduced), which is preferable. . The amount of the component (d) remaining in the conductor is preferably 2 parts by weight or less, more preferably 1 part by weight or less, based on 10 parts by weight of the conductive film, although it varies depending on the intended use. Further, it is better that the component (c) does not substantially exist. As the heat treatment, 250 ° C. or less, preferably 4 ° C.
Heating in the range of 0-200C is preferred. If the temperature is higher than 250 ° C., the conductivity may decrease due to the deterioration of the component (a).

Hereinafter, the conductive composition of the present invention, a conductor formed from the conductive composition, and a method for producing the same will be described in detail. Examples of the aniline-based conductive polymers (a) or (f) containing a sulfone group constituting the conductive composition and the conductor of the present invention include compounds represented by the following structural formula (I): Or a compound having this repeating unit as a partial structure.

[0011]

Embedded image (Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ or R ⁸ are each selected from the group consisting of hydrogen, sulfonic acid group and alkoxy group, and R ′ is hydrogen or carbon It is selected from the group consisting of alkyl groups of formulas 1 to 4, benzenesulfonic acid groups and benzenecarboxylic acid groups, and x represents an arbitrary number of 0 to 1.)

Specific examples of the compound represented by the structural formula of the above formula (I) include, for example, the journal of the Chemical Society of Japan, 1985 , 11
24, JP-A 61-197633, JP-A 1-3
01714, J.P. Am. Chem. Soc. , 1
990 , 122, 2800. J. Am. Chem. S
oc. , 1991 , 113, 2665-2666. And WO. Various sulfonated polyanilines described in 9106887 can be used. Further, as the polyaniline compound, those obtained by various synthesis methods can be used. For example, at least one compound selected from the group consisting of aniline, N-alkylaniline and phenylenediamines, and aminoanisolesulfonic acid A copolymer obtained by copolymerizing with an alkoxy group-substituted aminobenzenesulfonic acid (hereinafter referred to as the former copolymer), or at least one compound selected from the group consisting of aniline, N-alkylaniline and phenylenediamines And o-, m-, and / or p-
A copolymer obtained by copolymerizing an aminobenzenesulfonic acid and then sulfonating with a sulfonating agent and adjusting the sulfonation degree (hereinafter referred to as the latter copolymer) is preferably used.

As the N-alkylaniline, N-alkylaniline
Methyl aniline, N-ethyl aniline, N-n propyl aniline, N-iso propyl aniline, N-butyl aniline and the like can be mentioned. Examples of phenylenediamines include phenylenediamine, N-phenylphenylenediamine, N, N ' -Diphenylphenylenediamine,
N-aminophenyl-N'-phenylphenylenediamine and the like can be mentioned. Aniline, N-alkylaniline and phenylenediamines are used alone or in combination. The ratio (weight) used for aniline and / or phenylenediamine of N-alkylaniline is such that the total amount of aniline and / or phenylenediamine is 100 and N-alkylaniline is 0%.
~ 30 is convenient. If the proportion of the N-alkylaniline is too large, the solubility in water is reduced and the conductivity tends to be poor. The aniline and the phenylenediamine are used alone or in a mixture at an arbitrary ratio.

In the aniline-based conductive polymers (a) containing a sulfone group, the sulfone group has 15
It is preferably in the range of from 80% to 80%, and more preferably in the range of from 20% to 75%, in which an aromatic ring containing a sulfone group and an aromatic ring having no sulfone group are appropriately mixed and bonded, and have an alternately arranged structure. Are more preferred. Here, when the content of the sulfone group is less than 15%, the solubility of the obtained film is insufficient because the solubility is insufficient. On the other hand, when the content exceeds 80%, the conductivity tends to decrease. .

Hereinafter, the former copolymerization will be described. In the former copolymerization, the most representative of the alkoxy-substituted aminobenzenesulfonic acids (B) are aminoanisolesulfonic acids, and the aminoanisolesulfonic acids are 2-aminoanisole-3-sulfonic acid and 2-aminoanisole. Anisole-4-sulfonic acid, 2-aminoanisole-5-sulfonic acid, 2-aminoanisole-6-sulfonic acid, 3-aminoanisole-2-sulfonic acid, 3-aminoanisole-4-sulfonic acid, 3-amino Examples thereof include anisole-5-sulfonic acid, 3-aminoanisole-6-sulfonic acid, 4-aminoanisole-2-sulfonic acid, and 4-aminoanisole-3-sulfonic acid. In addition, those in which the methoxy group of anisole is substituted with another alkoxy group such as an ethoxy group or a propoxy group can also be used. However, 2-aminoanisole-3-sulfonic acid, 2-aminoanisole-4-sulfonic acid, 2-aminoanisole-6-sulfonic acid, 3-aminoanisole-2-sulfonic acid, 3-aminoanisole-4-sulfonic acid Acids and 3-aminoanisole-5-sulfonic acid are particularly preferably used.

The weight ratio of the (A) group monomer composed of aniline, N-alkylaniline and phenylenediamine used in the polymerization to the (B) group monomer composed of alkoxy-substituted aminobenzenesulfonic acids represented by aminoanisolesulfonic acids. Is A: B = 8: 2
１ ： 1: 9, preferably A: B = 7: 3 to 2: 8. The alkoxy group-substituted aminobenzenesulfonic acids (B) represented by aminoanisolesulfonic acids may be used alone or in a mixture of isomers at an arbitrary ratio. Here, when the ratio of the alkoxy group-substituted aminobenzenesulfonic acids (B) is small, the introduction ratio of the alkoxy group-substituted aminobenzenesulfonic acids tends to decrease, and the solubility in a solvent tends to decrease. There is a tendency that the introduction ratio of the substituted aminobenzenesulfonic acids increases and the conductivity decreases.

The copolymerization can be carried out by oxidative polymerization with an oxidizing agent in an acidic solvent. The polymerization operation is -5 to
It is preferably carried out in a temperature range of 70 ° C, more preferably in a range of 0 to 60 ° C. Here, below -5 ° C, the solubility of the copolymer in the solvent tends to decrease, and above 70 ° C, the conductivity tends to decrease.

The solvent used for the reaction is water, methanol,
Ethanol, isopropanol, acetonitrile, methyl isobutyl ketone, dimethylformamide, dimethylacetamide and the like are preferably used.

As the oxidizing agent, ammonium peroxodisulfate, hydrogen peroxide or the like is used, and it is used in an amount of 0.1 to 5 mol, preferably 0.5 to 5 mol, per 1 mol of the monomer. As the acid, sulfuric acid, hydrochloric acid, p-toluenesulfonic acid or the like or a mixture thereof is used, and the concentration of the acid is 0.1 to
It is used in an amount of 3 mol / l, preferably in the range of 0.2 to 2 mol / l. At this time, it is also effective to add a transition metal such as iron or copper as a catalyst.

Here, the copolymer of aniline and / or N-alkylaniline with an alkoxy-substituted aminobenzenesulfonic acid has a sulfonic acid group introduction ratio of 25 to 40% based on the aromatic ring, and phenylenediamine. , N-
Compared to the case where phenylenediamines such as phenylenediamine are used, the introduction ratio of sulfone groups is generally lower but the conductivity tends to be better. On the other hand, copolymers of phenylenediamines such as phenylenediamine and N-phenylenediamine and alkoxy-substituted aminobenzenesulfonic acids have a sulfone group introduction ratio of 2 to the aromatic ring.
It is as high as 5 to 50% and tends to have good solubility.

The thus obtained aniline-based conductive polymer having an alkoxy group and a sulfonic acid group on the same aromatic ring has an average weight molecular weight of 300 to 500,000. Further, the alkoxy group and the sulfonic acid group are 2
It has a content of 5 to 50% and can be dissolved in water or an organic solvent containing a base such as ammonia and an alkylamine or a mixture thereof without further performing a sulfonation operation.

Hereinafter, the latter copolymerization will be described. In the latter copolymerization, any of o-, m- and p- can be used as the aminobenzenesulfonic acid (C). Copolymers of o-aminobenzenesulfonic acid or m-aminobenzenesulfonic acid with aniline have already been described in J. Am. Am. Chem. Soc. , 1991, 1
As described in JP-A-13,2667 and JP-A-1-301714, the present inventors have found that p-aminobenzenesulfonic acid and aniline also copolymerize.
As the copolymer of p-aminobenzenesulfonic acid and aniline, a polymer different from a conventionally known linear polymer (repeated bonding at the p-position) can be obtained.

The molar ratio of the A group monomer composed of aniline, N-alkylaniline and phenylenediamine to the C group monomer composed of aminobenzenesulfonic acids used in the polymerization is as follows. Group monomer 10 to 500
Parts by weight are used. Aminobenzenesulfonic acids are
o-, m-, and p- may be used alone or as a mixture at an arbitrary ratio.

The copolymer can be obtained by oxidative polymerization with an oxidizing agent in an acidic solvent. As the solvent, water, methanol, ethanol, isopropanol, acetonitrile, methyl isobutyl ketone, methyl ethyl ketone, dimethylformamide, dimethylacetamide and the like are preferably used. The oxidizing agent is ammonium persulfate,
Hydrogen peroxide and the like are preferably used, and 0.1 to 10 mol, preferably 0.5 to 5 mol, per 1 mol of the monomer is used. As the acid, sulfuric acid, hydrochloric acid, p-toluenesulfonic acid or the like or a mixture thereof is preferably used, and the concentration of the acid is used in a range of 0.1 to 5 mol / l, preferably 0.2 to 3 mol / l. . The reaction temperature is 70 ° C
It is preferably carried out in the following, more preferably in the range of −20 ° C. to 50 ° C. Here, the copolymer of aniline and / or N-alkylaniline and aminobenzenesulfonic acid generally has a low sulfone group introduction ratio of 10 to 25% with respect to the aromatic ring, and has poor conductivity and solubility. Not enough. However, copolymers of phenylenediamines and aminobenzenesulfonic acids tend to have a sulfone group introduction ratio as high as 25 to 40% with respect to the aromatic ring, and have good conductivity and solubility in sulfonated polyaniline. Is obtained.

The obtained copolymer is sulfonated with a sulfonating agent without a solvent or in a solvent. Not only copolymers of phenylenediamines and aminobenzenesulfonic acids, but also copolymers of aniline and / or N-alkylaniline and aminobenzenesulfonic acid,
Alcohol already has a sulfone group in part of the aromatic ring, so it has higher solubility in sulfonating agents and solvents than polyaniline, improves operability, and promotes the reaction smoothly. There is an advantage that the ratio increases. As the sulfonating agent, concentrated sulfuric acid, fuming sulfuric acid, sulfur trioxide, a sulfur trioxide complex, or the like is preferably used. The reaction is preferably carried out in the absence of a solvent when sulfonating using concentrated sulfuric acid and fuming sulfuric acid, and in a solvent when using sulfur trioxide and a sulfur trioxide complex. The solvent is dimethylformamide,
Dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, pyridine and the like are preferably used. Concentrated sulfuric acid and fuming sulfuric acid are 10 to 20 with respect to 1 g of the copolymer.
0 g, preferably in the range of 20 to 100 g.
The sulfur trioxide and the sulfur trioxide complex are 1 g of the copolymer.
1 to 100 g, preferably 5 to 50 g. The solvent is used in an amount of 10 to 300 g, preferably 20 to 200 g, per 1 g of the copolymer. The reaction temperature is 20
The temperature is preferably 0 ° C or lower, more preferably 0 to 100 ° C. In the obtained sulfonated product, the introduction ratio of the sulfone group is increased to 40 to 80% with respect to the aromatic ring.

The sulfonated polyaniline thus obtained has an average molecular weight of 300 to 500,000,
It can be dissolved in water containing a cation of a base such as ammonia and alkylamine or the above-mentioned base such as ammonium acetate and ammonium oxalate, a solvent such as methyl alcohol, ethyl alcohol and isopropyl alcohol, or a mixture thereof.

The ratio of the aniline-based conductive polymers (a) or (f) containing a sulfone group in the conductor to the polymer compound (b) is (a) or (f) / (b) = 0.0
25/100 to 100 / 0.5, preferably
(A) or (f) / (b) = 0.15 / 100-1
00/1. When the ratio of the aniline-based conductive polymers (a) or (f) is other than this ratio, the conductivity decreases, and the flatness and the transparency deteriorate. If the proportion of the polymer compound (b) is other than this ratio, the hardness, abrasion resistance, conductivity and the like of the film are reduced, and the adhesion to the substrate is deteriorated. The proportion of the components (a) and (c) used is as follows:
(C) 0.1 to 20 parts by weight, preferably 0.5 to 15 parts by weight, per 100 parts by weight. Component (a)
If the ratio is less than 0.1 part by weight, the conductivity will be inferior. On the other hand, if it exceeds 20 parts by weight, the solubility, flatness and transparency will deteriorate, and the conductivity will peak and will not increase.

The water component (c) of the composition used in the present invention may be used alone, but may be used by mixing at least one kind of an organic solvent compatible with water at an arbitrary ratio. Organic solvents include alcohols such as methanol, ethanol, propanol and isopropanol; ketones such as acetone and methyl isobutyl ketone; cellosolves such as methyl cellosolve and ethyl cellosolve; propylene glycols such as methyl propylene glycol and ethyl propylene glycol; Examples include amides such as formamide and dimethylacetamide, and pyrrolidones such as N-methylpyrrolidone and N-ethylpyrrolidone. The ratio used is preferably water / organic solvent = 1/100 to 100/0.

The component (b) of the conductive composition and the conductor of the present invention may be used alone or in combination of two or more in any ratio. Water-soluble polymer compounds include polyvinyl alcohols such as polyvinyl alcohol, polyvinyl formal and polyvinyl butyral, polyacrylamides, poly (Nt-butylacrylamide), polyacrylamides such as polyacrylamide methylpropanesulfonic acid, Polyvinyl pyrrolidone, water soluble alkyd resin, water soluble melamine resin, 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 Polymer resins, water-soluble vinyl acetate / acrylic copolymer resins, water-soluble polyester resins, water-soluble styrene / maleic acid copolymer resins, and copolymers thereof are used. Aqueous polymer compounds that form emulsions include aqueous alkyd resins, aqueous melamine resins, aqueous urea resins, aqueous phenol resins, aqueous epoxy resins, aqueous polybutadiene resins, aqueous acrylic resins, aqueous urethane resins, and aqueous acrylic / styrene copolymer resins. Water-based vinyl acetate / acrylic copolymer resins, water-based polyester resins, water-based styrene / maleic acid copolymer resins, water-based acrylic / silica resins, and copolymers thereof are used.

The proportion of the polymer compound (b) used is 0.1 to 400 parts by weight, preferably 0.5 to 300 parts by weight, per 100 parts by weight of the component (c) water. 0.1
If the amount is less than part by weight, the film formability, moldability, and strength will be inferior, while if it exceeds 400 parts by weight, the solubility of the aniline-based conductive polymer containing a sulfone group of the component (a) or (f) will decrease. Or poor conductivity.

The nitrogen-containing compound as the component (d) of the composition used in the present invention is, for example, a compound represented by the formula (II) or (III)
The compound represented by is used. The structural formula of the amines used is shown in formula (II).

[0032]

Embedded image In the formula, R _{1 to} R ₃ each independently represent hydrogen, carbon number 1 to 4
(C ₁ -C ₄ ) alkyl group, CH ₂ OH, CH ₂ CH ₂ O
Represents H, CONH ₂ or NH ₂ . Further, the structural formula of the quaternary ammonium salts used is shown in formula (III).

[0033]

Embedded image In the formula, R _{1 to} R ₄ each independently represent hydrogen, carbon number 1 to 4
(C ₁ -C ₄ ) alkyl group, CH ₂ OH, CH ₂ CH ₂ O
H, CONH ₂ or NH ₂ ; X ⁻ is OH ⁻ , 1/2 ·
SO ₄ ²⁻ , NO ₃ ⁻ , 1 / 2CO ₃ ²⁻ , HCO ₃ ⁻ , 1/2 ·
(COO) ₂ ²⁻ or R′COO ⁻ , wherein R ′ is an alkyl group having 1 to 3 carbon atoms (C _{1 to} C ₃ ).

The conductivity of the nitrogen-containing compound component (d) can be further improved by using a mixture of these amines and ammonium salts. In particular,
NH ₃ / (NH ₄ ) ₂ CO ₃ , NH ₃ / (NH ₄ ) HCO ₃ ,
NH ₃ / (NH ₄ ) HCO ₃ , NH ₃ / CH ₃ COONH ₄ ,
NH ₃ / (NH ₄ ) ₂ SO ₄ , N (CH ₃ ) ₃ / (NH ₄ ) H
CO ₃ , N (CH ₃ ) ₃ / CH ₃ COONH ₄ , N (CH ₃ )
₃ / (NH ₄ ) ₂ SO _{4 and the} like. The mixing ratio of these may be any ratio, but it is preferable that amines / ammonium salts = 1/10 to 10/0.

The proportion of the nitrogen-containing compound component (d) is 0.01 to 30 parts by weight, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the component (c). When the proportion of the component (d) is less than 0.01 part by weight, the solubility of the component (a) is not sufficient. On the other hand, when the proportion exceeds 30 parts by weight, the solution shows strong basicity, and the decomposition of the component (a) is accelerated. Therefore, the conductivity is inferior. The pH of the solution is determined by the concentration of the nitrogen-containing compound,
PH and pH can be arbitrarily adjusted by the type and mixing ratio.
It can be used in the range of ~ 12.

The conductive composition of the present invention comprises the component (a)
Alternatively, a film with good performance can be formed only by the components (f), (b), (c) and (d). However, when the surfactant (e) is added, flatness, coatability and the like are further improved. The conductivity and the like are improved. Surfactant (e) includes anionic surfactants such as alkyl sulfonic acid, alkyl benzene sulfonic acid and alkyl carboxylic acid, cationic surfactants such as alkyl amine and alkyl quaternary amine, carboxybendaine, amino carboxylic acid and the like. Amphoteric surfactants, nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene sorbitan fatty acid esters, and fluoroalkyl carboxylic acids, perfluoroalkyl carboxylic acids, perfluoroalkyl benzene sulfonic acids, perfluoroalkyl polyoxyethylene ethanol A fluorine-based surfactant such as In addition, even if it uses two or more surfactants, there is no problem.

The proportion of component (e) used is determined by the proportion of component (c)
0 to 10 parts by weight, preferably 0 to 100 parts by weight of water
-5 parts by weight. When the proportion of the component (e) exceeds 10 parts by weight, the coating properties are improved, but the flatness is reduced, and the flatness is improved, but phenomena such as poor conductivity are caused. Further, a storage stabilizer, an adhesion aid, and the like can be added to the conductive composition used in the present invention, if necessary.

The conductive composition according to the present invention comprises an aniline-based conductive polymer (a) or (f) containing a sulfone group in water (c) at a ratio of 15 to 80% based on the total aromatic ring; At least one polymer compound (b) selected from a water-soluble polymer compound and a polymer compound that forms an emulsion in an aqueous system, and at least one nitrogen-containing compound (d) selected from amines and quaternary ammonium salts. Add and mix completely at room temperature or with heating and stirring, or prepare by mixing. If solids precipitate at room temperature, they are filtered and used. The conductor of the present invention can be formed by applying the conductive composition prepared as described above to a substrate. When mixing these components, a blade-type stirring and kneading device such as a spiral mixer, a planetary mixer, a disperser, or a hybrid mixer is preferably used. After this, it is desirable to further thoroughly disperse and dissolve using a ball-type kneading apparatus such as a ball mill, a vibration mill, a sand mill, and a roll mill.

The conductive composition used as a method for forming a conductor according to the present invention is processed on the surface of a substrate by a method used for general paints. For example, gravure coater,
Roll coater, curtain flow coater, spin coater, bar coater, reverse coater, kiss coater, fountain coater, rod coater, air doctor coater, knife coater, blade coater, cast coating, coating method such as screen coating, spraying such as spray coating A dipping method such as a dipping method is used.

The transparent conductive polymer film formed from the conductive composition can be formed to a thickness of 0.01 to 1000 μm, but if the film thickness is large, the transparency of the transparent conductive polymer film becomes poor. Therefore, it is required to be as thin as possible, preferably in the range of 0.01 to 500 μm, more preferably in the range of 0.02 to 100 μm. Further, in order to obtain a transparent conductive polymer film having the above thickness, the viscosity of the conductive composition is 1000 cp or less, preferably 1 to 50 cp.
It is preferably in the range of 0 cp and the solid content is in the range of 0.1 to 80% by weight.

As a substrate on which the conductive composition is applied, a polymer compound, wood, paper, ceramics, a film thereof, a glass plate, or the like is used. For example, as the polymer compound and the film, polyethylene, polyvinyl chloride, polypropylene, polystyrene, polyester, A
BS resin, AS resin, methacrylic resin, polybutadiene, polycarbonate, polyarylate, polyvinylidene fluoride, polyamide, polyimide, polyaramid, polyphenylene sulfide, polyetheretherketone, polyphenyleneether, polyethernitrile,
Examples include polyamide imide, polyether sulfone, polysulfone, polyether imide, polybutylene terephthalate, and films thereof. For these polymer films, in order to form a transparent conductive polymer film on at least one surface thereof, it is preferable to perform a corona surface treatment or a plasma treatment on the film surface for the purpose of improving the adhesion of the polymer film. . The heat treatment after forming the transparent conductive polymer film on the base material is performed at 250 ° C. or lower, preferably in the range of 40 to 200 ° C., to form the conductor.

[0042]

EXAMPLES Example 1 10 parts by weight of aniline and m-aminobenzenesulfonic acid 1
Eight parts by weight was polymerized with ammonium peroxodisulfate under acidic conditions of hydrochloric acid to synthesize a copolymer. This copolymer was further sulfonated with 640 parts by weight of fuming sulfuric acid to synthesize a sulfonated polyaniline. This compound IR spectrum (FIG 2,1500Cm ^-1 vicinity: backbone of the sulfonated polyaniline, 1100 cm ^-1 vicinity Sulfonated absorption of group) sulfonated polyaniline-specific absorption was observed in. In addition, the content of the sulfone group of the obtained sulfonated polyaniline was 48%. The above sulfonated polyaniline 2
Urethane resin "Adekabon Titer 232" which forms an emulsion in parts by weight and water system (Asahi Denka Kogyo Co., Ltd.)
50 parts by weight and 0.3 parts by weight of ammonia were stirred and mixed with 100 parts by weight of water at room temperature to prepare a conductive emulsion composition. The solution thus obtained was applied on a glass substrate having a thickness of 1 mm by a dipping method, and dried at 100 ° C. for 2 minutes. The component (d) remaining in the formed film is 1% or less based on the weight of the film. A film having a smooth surface resistance of 1.5 × 10 ⁶ Ω / □ with a thickness of 3 μm was obtained.

Example 2 10 parts by weight of aniline, 1.3 parts by weight of N-methylaniline and 20 parts by weight of m-aminobenzenesulfonic acid were polymerized with ammonium peroxodisulfate under acidic conditions of sulfuric acid to synthesize a copolymer. This copolymer was further sulfonated with 1530 parts by weight of concentrated sulfuric acid to synthesize a sulfonated polyaniline. This compound has an IR spectrum (FIG. 4, 1500 cm
Around ^-1 : Sulfonated polyaniline skeleton, 1100cm
Around ^-1 : absorption of sulfone group), absorption specific to sulfonated polyaniline was observed. In addition, the content of the sulfone group of the obtained sulfonated polyaniline was 49%. Acrylic / styrene resin "Nicazole RX-832A" (Nippon Carbide Industrial Co., Ltd.) 7 which forms an emulsion with 5 parts by weight of the above-mentioned sulfonated polyaniline and water system.
0 parts by weight and 1.0 parts by weight of ammonia were stirred and mixed at room temperature with 100 parts by weight of water / isopropyl alcohol (1/1) to prepare a conductive emulsion composition. The solution thus obtained was applied on the PET film by a casting method, and dried at 100 ° C. for 2 minutes. The component (d) remaining in the formed film is 1% or less based on the weight of the film. Smooth surface resistance of 3.5 μm thick surface 2.5 ×
A film of 10 ⁶ Ω / □ was obtained.

Example 3 10 parts by weight of aniline and 20 parts by weight of 2-aminoanisole-4-sulfonic acid were copolymerized with ammonium peroxodisulfate under sulfuric acid conditions to synthesize polyaniline having a sulfone group on an aromatic ring. This compound IR spectrum (FIG 5,1500Cm ^-1 vicinity: backbone of the sulfonated polyaniline, 1100 cm ^-1 vicinity Sulfonated absorption of group) sulfonated polyaniline-specific absorption was observed in.
In addition, the content of the sulfone group of the obtained polyaniline having a sulfone group in the aromatic ring was 48%. The epoxy resin “Adekaresin E” which forms an emulsion with 2 parts by weight of the polyaniline having a sulfone group in the aromatic ring and an aqueous system
PE-0410 "(manufactured by Asahi Denka Kogyo KK) 50 parts by weight,
0.5 part by weight of ammonia was stirred and mixed with 100 parts by weight of water at room temperature to prepare a conductive emulsion composition. The solution thus obtained was applied on a glass substrate having a thickness of 1 mm by spin coating, and dried at 100 ° C. for 2 minutes. The component (d) remaining in the formed film is 1% or less based on the weight of the film. As a result, a film having a smooth surface resistance of 1.5 × 10 ⁶ Ω / □ having a thickness of 2.0 μm was obtained.

Example 4 With respect to the sulfonated polyaniline synthesized in Example 2, 2 parts by weight of the sulfonated polyaniline, a urethane resin "Adekabon Titer 232" which forms an emulsion in an aqueous system
50 parts by weight (manufactured by Asahi Denka Kogyo KK) and 40 parts by weight of triethylamine were stirred and mixed at room temperature with 100 parts by weight of water to prepare a conductive emulsion composition. The solution thus obtained is applied on a glass substrate by a spin coating method,
Dried at 100 ° C. A film having a smooth surface resistance of 6.5 × 10 ⁹ Ω / □ on the surface having a thickness of 3 μm was obtained.

Comparative Example 1 With respect to the sulfonated polyaniline synthesized in Example 3, 3 parts by weight of the sulfonated polyaniline and trimethylamine 1.
3 parts by weight, 0.05 parts by weight of perfluoroalkylbenzenesulfonic acid were dissolved in 100 parts by weight of water at room temperature with stirring.
A conductive composition was prepared. The solution thus obtained was applied on a glass substrate by spin coating,
Dry at ℃. A film having a smooth surface resistance of 1.5 × 10 ⁶ Ω / □ on the surface having a thickness of 0.3 μm was obtained, but Example 3 was obtained using a composition to which a water-soluble polymer compound was added. The adhesiveness to the glass substrate was remarkably deteriorated, and the abrasion resistance was lowered as compared with the film No.

Comparative Example 2 With respect to the sulfonated polyaniline synthesized in Example 2, 2 parts by weight of the sulfonated polyaniline, an urethane resin “Adekabon titer 232” forming an emulsion in an aqueous system
[Asahi Denka Kogyo Co., Ltd.] 50 parts by weight and 1.5 parts by weight of sodium hydroxide were stirred and mixed at room temperature with 100 parts by weight of water to prepare a conductive emulsion composition. The solution thus obtained was applied on a glass substrate by a spin coating method, and dried at 100 ° C. Although a 0.3 μm thick film having a smooth surface was obtained, the surface resistance was increased as compared with the film obtained in Example 2 using ammonia, and was 1.0 × 10 ¹² Ω / □ or more. Having a surface resistance value of

Hereinafter, embodiments of the present invention will be described. 1. It is selected from the group consisting of aniline-based conductive polymers (a) containing a sulfone group at a ratio of 15 to 80% with respect to the total aromatic ring, water-soluble polymer compounds, and polymer compounds forming an emulsion in an aqueous system. An emulsion comprising at least one polymer compound (b), water (c) and at least one nitrogen-containing compound (d) selected from the group consisting of ammonia, amines and quaternary ammonium salts. Conductive composition. 2. The aniline-based conductive polymer (a) is at least one compound (A) selected from the group consisting of aniline, N-alkylaniline and phenylenediamines
The conductive composition according to 1 above, which is a sulfonated aniline-based copolymer, which is a sulfonated product of a copolymer of aniline-based copolymer and aminobenzenesulfonic acid (C). 3. The conductive composition according to the above 2, wherein the weight ratio of the (A) group monomer to the (C) group monomer is 10 to 500 parts by weight of the C group monomer with respect to 100 parts by weight of the (A) group monomer. 4. The aniline-based conductive polymer (a) is at least one compound (A) selected from the group consisting of aniline, N-alkylaniline and phenylenediamines
The conductive composition according to any one of the above items 1 to 3, which is a sulfonated aniline-based copolymer, which is a sulfonated product of a copolymer of aniline-based copolymer with aminobenzenesulfonic acid (C). 5. A sulfone group obtained by copolymerizing at least one compound (A) selected from the group consisting of aniline, N-alkylaniline and phenylenediamines with an alkoxy-substituted aminobenzenesulfonic acid (B) At least one selected from the group consisting of an aniline-based conductive polymer (f) containing 15 to 80% of a total aromatic ring, a water-soluble polymer compound, and a polymer compound which forms an emulsion in an aqueous system. A conductive composition comprising a polymer compound (b), water (c), and at least one nitrogen-containing compound (d) selected from the group consisting of amines and quaternary ammonium salts. 6. The weight ratio of the (A) group monomer to the (B) group monomer is A: B = 8: 2-1: 9, preferably A: B = 7: 3-2: 8. Stuff. 7. The conductive composition according to any one of the above 1 to 5, further comprising a surfactant (e).

8. The use ratio (weight ratio) of the component (a) or (f) and the component (b) is (a) or (f)
/(B)=0.025/100 to 100 / 0.5, preferably (a) or (f) / (b) = 0.15 / 100
The conductive composition according to any one of the above items 1 to 7, which is 100 to 100/1. 9. Component (a) or (f) and component (c) are used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 15 parts by weight, per 100 parts by weight of component (c). ~ 8
A conductive composition. 10. Component (b) and component (c) are used in an amount of 0.1 to 4 based on 100 parts by weight of component (b).
The conductive composition according to 1 to 9 above, which is 00 parts by weight, preferably 0.5 to 300 parts by weight. 11. Component (d) and component (c) are used in an amount of 0.01 to 100 parts by weight of component (c).
The conductive composition according to any one of the above 1 to 10, which is 30 parts by weight, preferably 0.5 to 20 parts by weight. 12. Component (e) and component (c) are used in an amount of 0 to 10 parts by weight, preferably 0 to 5 parts by weight, based on 100 parts by weight of component (c). Composition.

13. A conductor or an antistatic body, which is formed from the conductive polymer film of 1 to 12 above. 14． 12. The conductor or antistatic body of 12 produced by forming a transparent conductive polymer film formed by forming a film of the conductive composition of 1 to 12, and then leaving or heating at normal temperature. 15. The aniline-based conductive polymer is aniline, N
An aniline-based conductive polymer obtained by copolymerizing at least one compound (A) selected from the group consisting of alkyl anilines and phenylenediamines with an alkoxy-substituted aminobenzenesulfonic acid (B) 13. The conductor or antistatic body of 13 to 14 above. 16. 15. The conductor or antistatic body according to the above 15, wherein the weight ratio of the (A) group monomer to the (C) group monomer is 10 to 500 parts by weight of the C group monomer with respect to 100 parts by weight of the (A) group monomer. 17． The aniline-based conductive polymer is aniline, N
A sulfone group obtained by copolymerizing at least one compound (A) selected from the group consisting of alkyl anilines and phenylenediamines and an alkoxy-substituted aminobenzenesulfonic acid (B) with a wholly aromatic compound; 13. The conductor or antistatic body according to 13 to 14, which is an aniline-based conductive polymer contained at a ratio of 15 to 80% with respect to the ring. 18. The weight ratio of the group monomer (A) to the group monomer (B) is A: B = 8: 2 to 1: 9, preferably A: B = 7: 3 to 2: 8, or 17 Antistatic body. 19. The conductor or antistatic body according to 13 to 18, wherein the conductor or the antistatic body is an industrial packaging material. 20. Conductors are antistatic film, audio tape,
The above 13 to 13, which are antistatic magnetic recording tapes such as video tapes, computer tapes, floppy disks, etc.
18 conductors or antistatic bodies.

21. A conductive or antistatic body comprising a conductive polymer film formed by forming a film of the conductive composition of 1 to 12 on at least one surface of a substrate. 22. After forming the conductive polymer film by applying the conductive composition of 1 to 12, on at least one surface of the substrate,
21. The conductor or antistatic body according to 21 above, which is produced by standing or heating at room temperature. 23. The heat treatment is performed in a temperature range of 40 to 250 ° C. to remove the component (c) and the component (d).
1 to 22 conductors or antistatic bodies. 24. The aniline-based conductive polymers, aniline,
At least one compound (A) selected from the group consisting of N-alkylanilines and phenyleneamines;
21. The conductor or antistatic of the above-mentioned 21 to 23, which is a sulfonated product of a copolymer with aminobenzenesulfonic acid (C). 25. The conductor or antistatic body according to the above item 24, wherein the weight ratio of the (A) group monomer to the (C) group monomer is 10 to 500 parts by weight of the C group monomer per 100 parts by weight of the (A) group monomer. 26. The aniline-based conductive polymers, aniline,
Aniline-based conductivity obtained by copolymerizing at least one compound (A) selected from the group consisting of N-alkylaniline and phenylenamine with an alkoxy-substituted aminobenzenesulfonic acid (B) 21. The conductor or antistatic body of the above 21 to 23 which is a polymer. 27. The weight ratio of (A) group monomer to (B) group monomer is A: B = 8: 2 to 19, preferably A: B = 7: 3 to 2: 8. body. 28. The conductor or antistatic member according to any one of the items 21 to 27, wherein the substrate is a polymer film. 29. The conductor or antistatic body according to any one of the items 21 to 28, wherein the base material is an industrial packaging material. 30. The conductor or antistatic body of 21 to 28, wherein the base material is an antistatic magnetic recording tape such as an audio tape, a videotape, a computer tape, a floppy disk and the like. 31. Substrate is film for overhead projector,
The above-mentioned 21 which is an electrophotographic recording material such as a slide film;
To 28 conductors or antistatic bodies. 32. The conductor or antistatic body according to any one of the items 21 to 28, wherein the base material is an input and display device such as a transparent touch panel, an electroluminescent display, or a liquid crystal display.

33. The conductor or antistatic body of 21 to 27, wherein the substrate is a glass plate. 34. An antistatic method comprising forming a film of the conductive composition of 1 to 12 above on a substrate, and then leaving the film at room temperature or heating. 35. Performing a heat treatment in a temperature range of 40 to 250 ° C.,
(34) for removing the components (c) and (d)
Antistatic method. 36. The antistatic method according to any of the above items 34 to 35, wherein the base material is an industrial packaging material. 37. The antistatic method according to any one of the above items 34 to 35, wherein the base material is a magnetic recording tape such as an audio tape, a video tape, a computer tape, and a floppy disk. 38. Substrate is film for overhead projector,
34, which is an electrophotographic recording material such as a slide film.
To 35 antistatic methods.

[0053]

[Effect] 1. Water can be used as a solvent for the conductive composition according to the present invention, and the composition is applied to an appropriate substrate, sprayed, cast, dipped, and exhibits high conductivity without humidity dependence only by heat treatment. A conductive thin film having excellent film-forming properties, moldability, and transparency can be obtained. 2. In the present invention, a transparent conductive polymer film having excellent film formability, moldability, and transparency comprising an aniline-based conductive polymer containing a sulfone group and a polymer compound is applied to an appropriate substrate. After forming by a process such as spraying, casting, or dipping, it is possible to obtain a conductor which exhibits high conductivity without humidity dependency and has a small variation in surface resistance only by being left at room temperature or subjected only to heat treatment.

[Brief description of the drawings]

FIG. 1 shows the I of the sulfonated polyaniline in Example 1.
It is an R spectrum figure.

FIG. 2 shows I of sulfonated polyaniline in Example 2.
It is an R spectrum figure.

FIG. 3 shows the I of the sulfonated polyaniline in Example 3.
It is an R spectrum figure.

FIG. 4 shows the I of the sulfonated polyaniline in Example 4.
It is an R spectrum figure.

FIG. 5 shows I of sulfonated polyaniline in Example 5.
It is an R spectrum figure.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References WO 92/18987 (WO, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 79/00

Claims (7)

(57) [Claims] 1. The method according to claim 1, wherein the sulfonic acid group is 15 to
At least one polymer compound (b) selected from the group consisting of an aniline-based conductive polymer (a), a water-soluble polymer compound, and a polymer compound that forms an emulsion in an aqueous system; (C) and the above
1 to 30 times the total number of moles of the repeating unit (a)
At least one nitrogen-containing compound (d) selected from the group consisting of amines and quaternary ammonium salts of (a) , wherein (a) is uniformly dissolved in the solution. Emulsion composition. 2. The aniline-based conductive polymers (a)
Is a sulfonated product of a copolymer of at least one compound (A) selected from the group consisting of aniline, N-alkylaniline and phenylenediamines and aminobenzenesulfonic acid (C). 2. The conductive emulsion composition according to claim 1, which is a sulfonated aniline copolymer. 3. A method of copolymerizing at least one compound (A) selected from the group consisting of aniline, N-alkylaniline and phenylenediamines with an alkoxy-substituted aminobenzenesulfonic acid (B). Group consisting of an aniline-based conductive polymer (f) containing the sulfone group obtained by the above at a ratio of 15 to 80% based on the total aromatic ring, a water-soluble polymer compound, and a polymer compound which forms an emulsion in an aqueous system. At least one polymer compound (b) selected from the group consisting of water (c) and a repeating unit (f)
At least one nitrogen-containing compound (d) selected from the group consisting of amines and quaternary ammonium salts in an amount of 1 to 30 moles with respect to the total number of moles of (f).
A conductive composition characterized by being uniformly dissolved in water. 4. A conductor formed from a transparent conductive polymer film formed by forming the conductive composition according to claim 1, 2 or 3. 5. A transparent conductive polymer film formed by forming the conductive composition according to claim 1, 2 or 3 on at least one surface of a substrate. Conductor. 6. A transparent conductive polymer film is formed on at least one surface of a substrate by applying the conductive composition according to claim 1, 2, or 3, and then left at room temperature or heated. 6. The method according to claim 5, wherein the solvent and the nitrogen-containing compound are removed . 7. The method for producing a conductor according to claim 6, wherein the heat treatment is performed in a temperature range of 40 to 250 ° C. to remove the components (c) and (d).