JPH08143662A - Conductive composition, conductor and method for forming the same - Google Patents

Abstract

(57) [Abstract] [Purpose] Aqueous solutions showing all pH values of alkaline, neutral (especially water) and acidic can be used as a solvent, exhibiting high conductivity without humidity dependency, film-forming property, A conductive composition having excellent moldability and transparency, and a conductive polymer film formed from the composition, which exhibits high conductivity without humidity dependency and has excellent film formability, moldability, and transparency. Provided are a conductor including the method and a method for forming the conductor. [Configuration] 1. Soluble aniline-based conductive polymers having a weight average molecular weight of 10,000 to 3240000 and solid at room temperature, which are polymers having acidic group-substituted aniline, alkali metal salts, ammonium salts and / or substituted ammonium salts thereof as repeating units ( 1. A conductive composition containing a) and a solvent (b);
A polymer having an acidic group-substituted aniline, its alkali metal salt, ammonium salt and / or substituted ammonium salt as a repeating unit, and having a weight average molecular weight of 1,000.
A conductor formed from a transparent conductive polymer film containing 0 to 3240000 soluble aniline-based conductive polymers (a) that are solid at room temperature.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD 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, dipping and the like.

The conductor of the present invention obtained from the above-mentioned conductive composition is an antistatic film for industrial packaging materials such as semiconductors and electric / electronic parts, films for overhead projectors, electrophotographic recording materials such as slide films and the like. , Anti-static of magnetic recording tapes such as audio tapes, video tapes, computer tapes, floppy disks, etc., and also used as transparent electrodes for input and display device surface prevention of transparent touch panels, electroluminescent displays, liquid crystal displays, etc. It can be used as a transparent conductive film, transparent conductive glass, various sensors, or the like.

[0003]

2. Description of the Related Art Conventionally, 7,7,8,8-tetracyanoquinodimethane (TCNQ) complex salt, a conductive polymer such as polyaniline, a metal-based powder or a carbon powder as a conductive component of a conductive composition, Those using a surfactant and those using a combination of these components and a polymer compound are known. Further, as the conductor, a conductor formed on a base material by using a conductive coating material composed of the above composition is known.

For example, a metal thin film such as gold or platinum or a metal oxide thin film such as indium tin oxide (ITO) is formed on a substrate such as a plastic film or glass by using an ion beam sputtering device or a vacuum deposition device. It is known that the method described above can provide a conductor having excellent transparency and conductivity. However, since the apparatus used for forming the thin film is expensive, and the precious 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-conducting polymer conductor using TCNQ, a polymer conductor comprising a polymer having a quaternary nitrogen cationic group and TCNQ is known, but its solubility in a solvent is extremely high. However, many of them are soluble only in special solvents such as dimethylformamide, and it is hard to say that they are suitable as varnishes. Further, a conductive polymer composition comprising a polymer compound and an organic low-molecular complex salt of TCNQ (Japanese Patent Publication No. 44-16499, Japanese Patent Publication No. 50-123750, Japanese Patent Publication No. 54-130651, Japanese Patent Laid-Open Publication No. 54-130651). 1-2
No. 10470) is proposed. The conductor obtained by this method is believed to have higher conductivity as the crystals of TCNQ complex salts grow in the polymer compound, and the more they overlap, the more the state of this crystal growth depends on the solvent volatilization rate and the time of drying. Is easily affected by the temperature distribution and the number of conductive paths per unit area is non-uniform, so that the surface resistance varies greatly and uniform surface resistance cannot be obtained. In addition, even if the crystal bonding point deteriorates even under a condition of high temperature (for example, heating at 140 ° C.) or high temperature and high humidity (for example, 60 ° C., 95% RH), the conductive path is significantly reduced and the conductivity is significantly increased. There is a problem of decrease.

[0006] Doped polyaniline (conductive polymer) is well known, but it is insoluble in almost all solvents and has a problem in molding and processing. In addition, a method of electrolytically oxidatively polymerizing aniline (JP-A-60-235831,
J. Polymer Sci. , Polymer Ch
em. Ed. , 26 , 1531 (1988)) is capable of forming a polyaniline film on an electrode, but has a problem that the isolation operation is complicated and mass synthesis is difficult.

On the other hand, undoped polyaniline obtained by chemical oxidative polymerization of aniline and acid dissociation constant pKa
A conductive composition composed of an ammonium salt of a protonic acid having a ratio of 4.8 or less (JP-A-3-285983) has been reported. However, polyaniline in a dedoped state is a special composition such as N-methyl-2-pyrrolidone. It is difficult to say that it is suitable as a varnish because it is soluble only in various solvents.

Further, although an organic solvent is used in the method of forming the conductor, when these are dangerous substances having properties such as flammability and explosiveness, there is a problem in safety of working environment. Further, with the increase of safety to human body due to toxicity and global environmental problems, regulations on various organic solvents affecting human body and environment are increasing, and safety of conductive composition is also an important issue.

In recent years, alkali-soluble sulfonated polyaniline which exhibits conductivity without adding a doping agent and its synthesis method, and carboxylated polyaniline and its synthesis method have been proposed, and a conductive composition using them is proposed. Have also been reported.

For example, as a conductive composition using sulfonated polyaniline, a conductive composition comprising alkali-soluble sulfonated polyaniline and a polymer compound (US
510970) has been reported. However, the polymer compound used is a poly (1,4-benzamide) resin, a polyimide resin, or the like having extremely low solubility in an organic solvent, and since sulfuric acid or the like is used as a solvent, a big problem remains as a varnish.

In addition to the above, sulfonated polyanilines, a synthetic method and a conductive composition using them are also known. The synthetic method of the polymer is obtained by polymerizing chemically or electrochemically. The emeraldine type polymer (polyaniline) thus obtained is sulfonated with concentrated sulfuric acid (Japanese Patent Laid-Open No. 58-210902), and a method of sulfonation using a sulfuric anhydride / triethyl phosphate complex (Japanese Laid-Open Patent Publication No.
1-197633), a method of sulfonating with fuming sulfuric acid (J. Am. Chem. Soc., (1991) 11
3, 2665-2671, J. Am. Chem. So
c., (1990) 112, 2800, WO91-068.
87, JP-A-6-145386), a method of chemically or electrochemically polymerizing aniline and aminobenzenesulfonic acid (Journal of the Chemical Society of Japan, 1985, 1124, JP-A-2-166165, JP-A-1-301714).
No.), a method for electrochemically polymerizing aminobenzene sulfonic acids (Proceedings of the 64th Autumn Meeting of the Chemical Society of Japan)
II 706 (1992)), a method of chemically oxidatively polymerizing an aminobenzenesulfonic acid compound or a monomer containing an aminobenzenesulfonic acid compound and an aniline compound (JP-A-6-56987), diphenylamine-4-sulfonic acid. (Sodium salt) is chemically polymerized to produce N
-Method for synthesizing substituted sulfonated polyaniline (Po
Lymer, (1993) 34, 158-162) and the like are known.

J. Am. Chem. Soc., (199
1) 113, 2665-2671, J. Am. Che
m. Soc., (1990) 112, 2800,
It is noted that when polyaniline is sulfonated with fuming sulfuric acid, about 1 sulfone group is introduced into 2 aromatic rings.
However, when it is attempted to sufficiently sulfonate polyaniline by this method, since the solubility of polyaniline in fuming sulfuric acid is not sufficient, fuming sulfuric acid is required in a large excess. In addition, when polyaniline is added to fuming sulfuric acid, the polymer tends to solidify, which complicates the manufacturing process, and also increases the cost as a conductive component constituting the conductive composition. Further, the sulfonated product of the polymer synthesized by the above method has insufficient conductivity, and is soluble in an aqueous solution containing a base such as ammonia and alkylamine but not soluble in water alone. As for the problem remains.

In the method of electrochemically polymerizing aniline and m-aminobenzenesulfonic acid to synthesize a sulfonated polyaniline (Journal of the Chemical Society of Japan, 1985, 1124, JP-A-2-166165), the product is on the electrode. Therefore, it is not suitable as a conductive composition because it has a manufacturing problem that the isolation operation becomes complicated and mass synthesis is difficult.

The inventors of the present invention additionally tried a method of chemically polymerizing aniline and m-aminobenzenesulfonic acid with ammonium peroxodisulfate, which is described in JP-A-1-301714. Since only one sulfone group is introduced, there is a problem that conductivity and solubility are not sufficient.

Also, in the proceedings of the 64th Autumn Meeting of the Chemical Society of Japan, II 706 (1992), a method for synthesizing a soluble conductive polymer by electrolytic oxidation of aminobenzenesulfonic acid is explained. It is hard to say that it is suitable for synthesis, and there is a problem in performance. Further, it is described that no product was obtained when aminobenzenesulfonic acid was chemically oxidatively polymerized using ammonium peroxodisulfate as an oxidizing agent. Also, J. Am. Chem. So
c. , (1991) 113, 2665-2671, it was noted that attempts were made to chemically and electrochemically polymerize o-, m-aminobenzenesulfonic acid, but were unsuccessful.

Further, the inventors of the present invention attempted polymerization in an aqueous solution containing a protonic acid using ammonium peroxodisulfate as an oxidizing agent, and similarly obtained a product suitable for a conductive component of a conductive composition. I couldn't.

In JP-A-6-56987, there is disclosed a water-soluble conductive polymer obtained by chemically oxidatively polymerizing an aminobenzenesulfonic acid compound or a monomer containing an aminobenzenesulfonic acid compound and an aniline compound. Although the production method has been described, when the present inventors conducted an aqueous solution containing a protonic acid and polymerization in an aqueous solution using ammonium peroxodisulfate as an oxidizing agent, a water-soluble polymer was obtained. However, a practical polymer capable of forming a film could not be obtained because of its low molecular weight.

Also, when sulfonation is carried out by the method disclosed in JP-A-61-197633, the solubility of polyaniline in a sulfonation solvent is not sufficient and the reaction is carried out in a dispersed state as described on page 7 of the publication. Therefore, aromatic ring 5
Only about one sulfone group is introduced into each. The thus-obtained sulfonated polyaniline having a small introduction ratio of sulfone groups has a problem that the conductivity and the solubility are not sufficient.

Also, Polymer, (1993) 3
According to 4,158-162, diphenylamine-4-
When sulfonic acid (sodium salt) is polymerized, N having one benzenesulfonic acid group introduced into the aniline skeleton
Although a position-substituted sulfonated polyaniline is obtained and is soluble in water alone, it is described that an ultracentrifugation operation is necessary for isolation of the polymer. When the present inventors retested, the acquisition yield of the polymer from the polymerization solvent is low due to its high solubility, and when the high-speed centrifugation operation is not performed, the polymer cannot be isolated, It is difficult to use as a conductive component of a general-purpose conductive composition. In addition, since the N-position substitution type, J. Am. Chem. Soc. , (1991) 11
As compared with the polymer synthesized by the method of 3,2665-2671, the conductivity is low and the composition is insufficient.

Further, for example, as a method for synthesizing a carboxylated polyaniline, 2- or 3-carboxyaniline or a salt thereof is oxidatively polymerized and then treated with a basic substance to obtain a carboxyl group in a salt form (a special method). Kaihei 4
No. 268331) has been proposed, but the amount of the oxidizer used is required to be at least twice the amount of the raw material, and the conductivity is low, and it is not suitable as a conductive composition. In addition, it is considered that the reactivity of the monomer is low and a low molecular weight polymer is produced.

Further, a synthetic method in which methylanthranilate (anthranilic acid methyl ester) is polymerized in the presence of ammonium peroxodisulfate in an aqueous acidic medium and then the methyl ester is saponified with alcoholic potassium hydroxide No. 5-226238) has been proposed, but the operation is very complicated because the reaction has two stages.

Further, when the present inventors tried polymerization of 2-carboxyaniline with ammonium peroxodisulfate as an oxidizing agent in an aqueous solution containing a protic acid, the product could not be obtained. Further, the inventors of the present invention tried to polymerize aniline and 2-carboxyaniline with ammonium peroxodisulfate as an oxidizing agent in an aqueous solution containing a protic acid. The sex was also low. The copolymer obtained from this is considered to have a low copolymerization ratio of 2-carboxyaniline, and there is a problem in terms of performance as a conductive composition.

Therefore, the conductive component constituting the conductive composition is a polymer which is easy to synthesize and exhibits conductivity without adding a doping agent, and more components are required to improve the solubility. It is expected that a sulfone group or a carboxyl group needs to be introduced into the aromatic ring of the main chain.

In consideration of moldability such as film formation by coating, it should be soluble in both water and an organic solvent in order to be able to coat particularly hydrophilic or hydrophobic substrates. Is desired. However, although the sulfonated product of polyaniline has solubility in alkaline water, its solubility in organic solvents is not sufficient, and it cannot be said that it is suitable as a constituent component of a conductive composition.

As a method for solving these various problems,
The present inventors have found that the sulfone group is 15 to 80 relative to the total aromatic ring.
% Of at least one polymer compound (a) selected from the group consisting of aniline-based conductive polymers (a), a water-soluble polymer compound and a polymer compound that forms an emulsion in a water system, and water (c). A conductive composition characterized by containing at least one nitrogen-containing compound (d) selected from amines and quaternary ammonium salts (Japanese Patent Application No. 5-269407) was proposed.

The aniline-based conductive polymers (a) containing the sulfone group in the conductive composition in a proportion of 15 to 80% based on all aromatic rings include aniline, N-alkylaniline and phenylenediamines. At least one compound (A) selected from the group consisting of (A) and aminobenzene sulfonic acid (B) are copolymerized and further sulfonated with a sulfonating agent, to produce a sulfonated aniline copolymer. Proposed by method
No. 178989), at least one compound (A) selected from the group consisting of aniline, N-alkylaniline, and phenylenediamines, and aminoanisolesulfonic acid (B). The method for producing an aniline-based copolymer, characterized in that the sulfonation operation for generating a large amount of waste is omitted by copolymerizing
The polymer proposed by No. 0) (hereinafter referred to as the latter copolymer) is preferably used.

The former copolymer is presumed to have the structure of the following formula (5),

Embedded image (In the formula, R ₁₆ , R ₁₇ , R ₁₈ , and R ₁₉ are each selected from the group consisting of hydrogen and a sulfonic acid group, and the proportion of the sulfonic acid group is 40 to 80% with respect to the aromatic ring. R'is selected from the group consisting of hydrogen or an alkyl group having 1 to 4 carbon atoms, x represents an arbitrary number of 0 to 1, and n represents a degree of polymerization of 2 to 1500. is there.)

The latter copolymer is presumed to have the structure of the following formula (6).

[Chemical 6] (In the formula, R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ ,
R _{26 and} R ₂₇ are each selected from the group consisting of hydrogen, an alkoxy group and a sulfone group, and the proportion of the sulfonic acid group is 25 to 50% of the content of the sulfonic acid group with respect to the aromatic ring. The aromatic ring contains an alkoxy group and a sulfonic acid group. R'is selected from the group consisting of hydrogen or an alkyl group having 1 to 4 carbon atoms. x represents an arbitrary number of 0 to 1. n is a number from 2 to 1500 indicating the degree of polymerization. )

However, even in the case of these copolymers, the former copolymer requires an operation of sulfonation in concentrated sulfuric acid in the production method, and the treatment of waste acid remains a big problem. Both of them are not dissolved in water alone, and thus are not sufficient as a conductive composition.

Further, a conductor composed of a carbon powder or a metal powder and a polymer compound has a problem that the coating film is excellent in durability but lacks in transparency. Anion type, cation type,
A non-ionic or amphoteric semitransparent surfactant is kneaded into a plastic film or coated on the surface of the plastic film to impart hydrophilicity and ionicity to give conductivity to the film surface. Are known. However, since the conductor obtained by this method is ionic conductive, its conductivity is easily affected by humidity in the atmosphere, and the surface resistance value per unit area is 10 ⁸
There is a problem that it is not possible to obtain conductivity of Ω / □ or less.

[0031]

The present invention has been made in order to solve the above-mentioned problems, and an aqueous solution having all pHs of alkaline, neutral (especially water) and acidic is used as a solvent. A conductive composition that can be used and exhibits high conductivity without humidity dependency and has excellent film formability, moldability, and transparency, and high conductivity without humidity dependency using the composition. Manifested, the variation in surface resistance is small,
An object of the present invention is to provide a conductor obtained by forming a conductive polymer film having excellent film formability, moldability, and transparency, and a method for forming the conductor.

[0032]

The conductive composition according to the present invention comprises: [I] a soluble aniline-based conductive polymer (a).
And a solvent (b), [II] at least one polymer compound (c) selected from a water-soluble polymer compound and a polymer compound which forms an emulsion in an aqueous system, in these components (a) and (b), and / Or at least one nitrogen-containing compound (d) selected from amines and quaternary ammonium salts, [III] The composition of the above [I] or [II] is further allowed to coexist with a surfactant (e). Characterize.

The conductor of the present invention is a soluble aniline-based conductive polymer (a) or a soluble aniline-based conductive polymer (a) which is a water-soluble polymer compound and a polymer compound which forms an emulsion in an aqueous system. It is characterized by comprising a transparent conductive polymer film containing at least one polymer compound (c) selected from the above and / or a surfactant (e).

The conductor of the present invention is, for example, a conductive composition containing [I] a soluble aniline-based conductive polymer (a) and a solvent (b) on at least one surface of a substrate, II] At least one polymer compound (c) selected from water-soluble polymer compounds and polymer compounds forming an emulsion in an aqueous system, and / or amines and quaternary compounds in addition to these components (a) and (b) At least one nitrogen-containing compound (d) selected from ammonium salts
A conductive composition containing [III], said [I] or [II]
The composition (1) is further coated with a conductive composition in which a surfactant (e) is coexisted to form a transparent conductive polymer film, which is then left at room temperature or heat treated to remove components (b) and (d). It is a manufacturing method characterized by removing by volatilization.

The conductive composition of the present invention, the conductor formed from the conductive composition, and the method for producing the same will be described below.

As examples of the component-soluble aniline-based conductive polymers (a) constituting the conductive composition and the conductor of the present invention, the present inventors have proposed (Japanese Patent Application No. 6-1).
No. 83882), which is a compound represented by the structural formula of the following formula (1), or a repeating unit of which 70
% Or more is preferable.

[0037]

[Chemical 7] (In the formula, A is one group selected from a sulfone group, a carboxyl group, an alkali metal salt thereof, an ammonium salt and a substituted ammonium salt, and B is hydrogen, a methyl group, an ethyl group, an n-propyl group, iso- Alkyl group such as propyl group, n-butyl group, sec-butyl group, t-butyl group, hydroxy group, nitro group, fluoro group, chloro group,
One group selected from halogen groups such as a bromine group is shown. x represents an arbitrary number of 0 to 1, n represents a degree of polymerization,
A polymer having an acidic group-substituted aniline represented by the formula (10 to 5,000), its alkali metal salt, ammonium salt, or substituted ammonium salt as a repeating unit, and having a weight average molecular weight of 10,000 to 3,240, 000
Are soluble aniline-based conductive polymers that are solids at room temperature.

Examples of alkali metal salts include lithium, sodium and potassium.

Examples of the substituted ammonium include aliphatic ammonium, cyclic saturated ammonium, cyclic unsaturated ammonium and the like.

The lipophilic ammoniums are represented by the following formula (7)

Embedded image (In the formula, R _{28 to} R ₃₁ are groups independently selected from the group consisting of hydrogen, an alkyl group having 1 to 4 carbon atoms, CH ₃ OH and CH ₃ CH ₂ OH.). For example, methyl ammonium, dimethyl ammonium, trimethyl ammonium, ethyl ammonium, diethyl ammonium, triethyl ammonium, methyl ethyl ammonium, diethyl methyl ammonium, dimethyl ethyl ammonium, propyl ammonium, dipropyl ammonium, isopropyl ammonium, diisopropyl ammonium, butyl ammonium, dibutyl ammonium. , Methylpropyl ammonium, ethyl propyl ammonium, methyl isopropyl ammonium, ethyl isopropyl ammonium, methyl butyl ammonium,
Ethylbutylammonium, tetramethylammonium, tetramethylammonium, tetraethylammonium, tetra-n-butylammonium, tetrase
Examples thereof include c-butyl ammonium and tetra t-butyl ammonium. Among them, R _{28 to} R ₃₁
Most preferably, one of them is hydrogen, the other three are alkyl groups having 1 to 4 carbon atoms, then two of R _{29 to} R ₃₂ are hydrogen, and the other two are alkyl groups having 1 to 4 carbon atoms. Is preferred.

Examples of cyclic saturated ammoniums include piperidinium, pyrrolidinium, morpholinium, piperazinium and derivatives having these skeletons.

The cyclic unsaturated ammonium compounds include pyridinium, α-picolinium, β-picolinium, γ-.
Examples thereof include picolinium, quinolinium, isoquinolinium, pyrrolinium, and derivatives having these skeletons.

As the component (a), those obtained by various synthetic methods can be used. For example, the production method proposed by the present inventors (Japanese Patent Application No. 6-183882) is used.
General formula (2)

[Chemical 9] (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are selected from the group consisting of hydrogen, a linear or branched alkyl group having 1 to 4 carbon atoms, an acidic group, a hydroxyl group, a nitro group, and halogen. , At least one of which represents an acidic group, and the acidic group represents a sulfone group or a carboxyl group.) At least one of an acidic group-substituted aniline, an alkali metal salt, an ammonium salt, and a substituted ammonium salt thereof. A soluble aniline-based conductive polymer (a) obtained by polymerizing one compound (a) with an oxidizing agent in a solution containing a basic compound (b) is preferably used.

In this method, at least one compound (a) selected from acidic group-substituted aniline, its alkali metal salt, ammonium salt and substituted ammonium salt is used as a monomer in a solution containing a basic compound (b) and an oxidizing agent. When polymerized using, the reactivity is remarkably improved and
Alternatively, anilines having an acidic group such as a carboxyl group can be polymerized by itself, contrary to the theory that it is difficult to chemically oxidize and polymerize. Moreover, the obtained soluble aniline-based conductive polymer has an acidic group in all of the benzene nuclei, so that it is highly conductive and has an alkaline, neutral (particularly mere water) and acidic aqueous solution having all pH. It has excellent solubility in organic solvents such as alcohol.

Further, in the compound (a) such as the acidic group-substituted aniline of the general formula (2), the one in which the acidic group is bonded to the o-position or the m-position with respect to the amino group has a higher conductivity of the polymer, Excellent performance such as solubility.

The most representative of the acidic group-substituted anilines (a) is a sulfone group-substituted aniline or a carboxyl group-substituted aniline. Preferred is a sulfo group-substituted aniline, which tends to have higher conductivity than a carboxyl group-substituted aniline.

The most representative sulfone group-substituted anilines are aminobenzenesulfonic acids, specifically, o-, m-, p-aminobenzenesulfonic acid, aniline-2,6-disulfonic acid and aniline-. 2,5-Disulfonic acid, aniline-3,5-disulfonic acid, aniline-2,4-disulfonic acid and aniline-3,4-disulfonic acid are preferably used.

Other sulfo group-substituted anilines include methylaminobenzenesulfonic acid, ethylaminobenzenesulfonic acid, n-propylaminobenzenesulfonic acid, iso-propylaminobenzenesulfonic acid, n.
-Butylaminobenzenesulfonic acid, sec-butylaminobenzenesulfonic acid, t-butylaminobenzenesulfonic acid, and other alkyl group-substituted aminobenzenesulfonic acids, hydroxy group-substituted aminobenzenesulfonic acids,
Examples thereof include nitro group-substituted aminobenzenesulfonic acid, fluoroaminobenzenesulfonic acid, chloroaminobenzenesulfonic acid, bromoaminobenzenesulfonic acid, and other halogen group-substituted aminobenzenesulfonic acid. These sulfone group-substituted anilines may be used alone, or the isomers may be mixed in an arbitrary ratio.

The most representative ones of carboxyl group-substituted anilines are aminobenzenecarboxylic acids, specifically o-, m-, p-aminobenzenecarboxylic acids,
Aniline-2,6-dicarboxylic acid, aniline-2,5-
Dicarboxylic acid, aniline-3,5-dicarboxylic acid, aniline-2,4-dicarboxylic acid and aniline-3,4-dicarboxylic acid are preferably used.

Other carboxyl group-substituted anilines include methylaminobenzenecarboxylic acid, ethylaminobenzenecarboxylic acid, n-propylaminobenzenecarboxylic acid, iso-propylaminobenzenecarboxylic acid,
Alkyl group-substituted aminobenzenecarboxylic acids such as n-butylaminobenzenecarboxylic acid, sec-butylaminobenzenecarboxylic acid and t-butylaminobenzenecarboxylic acid, hydroxy group-substituted aminobenzenecarboxylic acid, nitro group-substituted aminobenzenecarboxylic acid, fluoro Examples thereof include halogen group-substituted aminobenzenecarboxylic acids such as aminobenzenecarboxylic acid, chloroaminobenzenecarboxylic acid and bromoaminobenzenecarboxylic acid. These carboxyl group-substituted anilines may be used alone, or the isomers may be mixed in an arbitrary ratio.

More specifically, specific examples of the acidic group-substituted aniline of the general formula (2) include sulfone group-substituted alkylaniline, carboxyl group-substituted alkylaniline, sulfone group-substituted hydroxyaniline, carboxyl group-substituted hydroxyaniline, sulfone group-substituted nitroaniline, carboxyl group-substituted. Examples include nitroaniline, sulfone group-substituted fluoroaniline, carboxyl group-substituted fluoroaniline, sulfone group-substituted chloroaniline, carboxyl group-substituted chloroaniline, sulfone group-substituted bromaniline, and carboxyl group-substituted alkylaniline. An example is shown in Table 1.

[0052]

[Table 1]

Here, A: one group selected from a sulfone group or a carboxyl group, its alkali metal salt, ammonium salt, and substituted ammonium salt, B: methyl group, ethyl group, n-propyl group, iso -One group selected from alkyl groups such as propyl group, n-butyl group, sec-butyl group and t-butyl group, and halogen groups such as hydroxy group, nitro group, fluoro group, chloro group and bromine group. , H: indicates hydrogen.

Acidic group-substituted anilines (a) shown above
Among them, general formula (3)

[Chemical 10] (In the formula, R ₆ , R ₇ , R ₈ , R ₉ , and R ₁₀ are selected from the group consisting of hydrogen, a linear or branched alkyl group having 1 to 4 carbon atoms, and an acidic group, and two of them are An acidic group and an alkyl group, wherein the acidic group represents a sulfone group or a carboxyl group), and at least one of an acidic group-substituted alkylaniline, an alkali metal salt thereof, an ammonium salt, and a substituted ammonium salt Compound of

Alternatively, the general formula (4)

[Chemical 11] (In the formula, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , and R ₁₅ are selected from the group consisting of hydrogen, a hydroxyl group, and an acidic group, and two of them represent an acidic group and a hydroxyl group. Is a sulfone group or a carboxyl group), and at least one compound selected from the group consisting of hydroxyaniline having an acidic group, an alkali metal salt, an ammonium salt, and a substituted ammonium salt thereof is most preferable in practice.

Next, as the basic compound (b) used when synthesizing the soluble aniline-based conductive polymer (a) used in the conductive composition of the present invention, the acidic group-substituted aniline (a) is used. Any compound can be used as long as it forms a salt with), but ammonia, aliphatic amines, cyclic saturated amines, cyclic unsaturated amines, inorganic bases and the like are preferably used. Especially, aliphatic amines, cyclic saturated amines, cyclic unsaturated amines and the like are preferable.

The fatty amines are represented by the following formula (8)

[Chemical 12] (In the formula, each of R _{32 to} R ₃₄ is a group independently selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, CH ₃ OH and CH ₃ CH ₂ OH.) ,

Alternatively, the general formula (9)

[Chemical 13] (In the formula, each of R _{35 to} R ₃₈ is a group independently selected from the group consisting of hydrogen, an alkyl group having 1 to 4 carbon atoms, CH ₃ OH and CH ₃ CH ₂ OH.). A side compound may be mentioned.

The cyclic saturated amines include piperidine,
Pyrrolidine, morpholine, piperazine, derivatives having these skeletons, and ammonium hydroxide compounds thereof are preferably used.

Examples of the cyclic unsaturated amines include pyridine,
α-picoline, β-picoline, γ-picoline, quinoline, isoquinoline, pyrroline, derivatives having these skeletons, and ammonium hydroxide compounds thereof are preferably used.

As the inorganic base, salts of hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and the like are preferably used. The above-mentioned aliphatic amines,
The conductivity tends to be inferior to cyclic saturated amines and cyclic unsaturated amines.

The concentration of these basic compounds (b) is 0.1
mol / l or more, preferably 0.1 to 10.0 mol /
1 and more preferably in the range of 0.2 to 8.0 mol / l. At this time, when the amount is 0.1 mol / l or less, the yield of the obtained polymer tends to decrease, and when it is 10.0 mol / l or more, the conductivity tends to decrease. The basic compound (b) can be mixed and used at an arbitrary ratio.

The weight ratio of the compound (a) such as aniline substituted with an acidic group and the basic compound (b) is (a):
(B) = 1: 100 to 100: 1, preferably 10: 9
0 to 90:10 is used. Here, if the ratio of the basic compound is low, the reactivity decreases and the conductivity also decreases. On the other hand, when the ratio is high, the ratio of forming the salt of the basic compound and the acidic group in the obtained polymer is high and the conductivity tends to be lowered.

The equivalent ratio of the acidic group (c) and the basic compound (b) in the compound (a) such as the acidic group-substituted aniline is (c) :( b) = 1: 100 to 100: 1. , Preferably 1: 0.25 to 1:20, more preferably 1:
It can be used at 0.5 to 1:15. Here, if the ratio of the basic compound is low, the reactivity decreases and the conductivity also decreases. On the contrary, when the ratio is high, the ratio of the acidic group and the basic compound in the obtained polymer to form a salt is high and the conductivity tends to be lowered.

Polymerization or copolymerization is carried out by oxidative polymerization with an oxidizing agent in a solution containing these basic compounds. 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 has a standard electrode potential of 0.6 V.
The oxidizing agent is not particularly limited as long as it is the above-mentioned oxidizing agent, but peroxodisulfates such as peroxodisulfate, ammonium peroxodisulfate, sodium peroxodisulfate and potassium peroxodisulfate, hydrogen peroxide and the like are preferably used, and 1 mol of the monomer is used. On the other hand, it is used in an amount of 0.1 to 5 mol, preferably 0.5 to 5 mol. At this time, it is also effective to add a transition metal compound such as iron or copper as a catalyst.

The reaction temperature is preferably in the temperature range of -15 to 70 ° C, more preferably -5 to -5 ° C.
A range of 60 ° C applies. Here, if the temperature is -15 ° C or lower, or 70 ° C or higher, the conductivity tends to decrease.

The above-mentioned x can be obtained in the range of 0.2 to 0.8 in the case of the one synthesized by the present method. However, an oxidizing agent such as benzoyl peroxide, ammonium peroxodisulfate and hydrogen peroxide can be obtained. When x is oxidized, a small x is obtained, and when reduced with a reducing agent such as hydrazine, phenylhydrazine, sodium borohydride or sodium hydride, a large x is obtained.

A in the general formula (1) of the component-soluble aniline-based conductive polymer (a) constituting the conductive composition of the present invention and the conductor formed from the conductive composition is
It is a group independently selected from the group consisting of a sulfone group and / or a carboxyl group, an alkali metal thereof, ammonium and a substituted ammonium, that is, these groups can be obtained in a mixed state rather than alone.

Specifically, when polymerized in the presence of sodium hydroxide, most of the hydrogen of the sulfonic group or the carboxyl group in the isolated polymer is in the state of being replaced with sodium.

Similarly, the hydrogen in the sulfone group or carboxyl group in the polymer is mostly ammonium when polymerized in the presence of ammonia, and mostly trimethylammonium when polymerized in the presence of trimethylamine. When polymerized, the majority is obtained with quinolinium.

When basic compounds are mixed and used, they are obtained in a mixed state. Specifically, when polymerized with sodium hydroxide in the presence of ammonia, hydrogen at a sulfone group or a carboxyl group in the isolated polymer is obtained in the presence of both sodium and ammonium. Also, when the obtained polymer is treated with a solution in which both sodium hydroxide and ammonia are present, hydrogen in the sulfone group or carboxyl group in the polymer is similarly obtained in the presence of both sodium and ammonium.

Thus, the polymer in which the sulfone group or the carboxyl group in the polymer forms a salt is a polymer in which most of the sulfone group or the carboxyl group in the polymer is desalted and replaced with hydrogen when treated in an acid solution. Can be Acidic solutions include hydrochloric acid, sulfuric acid, p
-Toluenesulfonic acid, nitric acid and the like. However, even if the acid substitution is sufficiently carried out, it is difficult to obtain the one completely replaced with hydrogen. However, the polymer produced by this method can be a practical soluble aniline-based conductive polymer having high conductivity without desalting by such an acid treatment.

The thus obtained soluble aniline-based conductive polymer having a sulfone group and / or a carboxyl group on all aromatic rings has a degree of polymerization of 10 to 5,000,
It is preferably from 20 to 5,000 and has a molecular weight of about 10.0.
00-3,240,000, preferably 20,000-
3,240,000, more preferably 50,000
It is 0 to 3,240,000. This polymer is not further subjected to sulfonation operation, but is simply water, a base such as ammonia and an alkylamine or water containing a base and a basic salt such as ammonium acetate and ammonium oxalate, a water containing an acid such as hydrochloric acid and sulfuric acid, or It can be dissolved in a solvent such as methyl alcohol, ethyl alcohol, isopropyl alcohol or a mixture thereof.

In the soluble aniline-based conductive polymers (a) constituting the conductive composition and the conductive material in the present invention, the sulfone groups described in Japanese Patent Application No. 5-269407 are used in an amount of 15 to 15 with respect to all aromatic rings. It is also possible to use the aniline-based conductive polymers contained at a ratio of 80%.

As the component (b) solvent of the conductive composition used in the present invention, water or an organic solvent is used, but a mixed system of water or an organic solvent compatible with water is more preferable, Particularly, water alone is more preferable.

Specific examples of the organic solvent include methanol,
Alcohols such as 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, dimethyl formamide, dimethyl acetamide and the like. Amides, pyrrolidones such as N-methylpyrrolidone and N-ethylpyrrolidone, ethyl lactate, methyl lactate, methyl β-methoxyisobutyrate, methyl α-hydroxyisobutyrate,
Examples thereof include hydroxy esters such as ethyl α-hydroxyisobutyrate and methyl α-methoxyisobutyrate. Alcohols, propylene glycols, amides and pyrrolidones are preferably used, and alcohols are more preferably used. By using the organic solvent or the solvent containing the organic solvent, the coating property of the conductive composition on the substrate to be coated can be improved. The ratio used as a mixed system with water is preferably water / organic solvent = 1/100 to 100/1.

By adding an acidic compound to the solvent (b), the conductivity can be improved by the doping effect of the acidic compound. Examples of the acidic solvent include inorganic acids such as sulfuric acid, hydrochloric acid and nitric acid, organic acids such as p-toluenesulfonic acid, acetic acid and methanesulfonic acid. The ratio of the weight ratio added to the solvent (b) is as follows: solvent: acidic compound = 70:30 to 100: 0.0.
1 is preferred. It is also possible to mix and use one or more of the above-mentioned respective solvents and acidic compounds in an arbitrary ratio.

The ratio of the component (a) and the solvent (b) used is 0.1 to 20 with respect to 100 parts by weight of the solvent (b).
Parts by weight, preferably 0.5 to 15 parts by weight.
If the proportion of component (a) is less than 0.1 parts by weight, the conductivity will be poor, while if it exceeds 20 parts by weight, the solubility, flatness, and transparency will be poor and the conductivity will reach a peak. Does not increase.

As the polymer compound (c) which is a constituent of the composition used in the present invention, a water-soluble polymer compound and a polymer compound which forms an emulsion in a water system are used.

Specific examples of the water-soluble polymer compound include polyvinyl alcohols such as polyvinyl alcohol, polyvinyl formal, and polyvinyl butyral, polyacrylic amide, poly (Nt-butyl acrylic amide), polyacrylic amide methylpropane sulfonic acid. Such as polyacrylic amides, polyvinylpyrrolidones, 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 copolymer resin, water-soluble vinyl acetate / acrylic copolymer resin, water-soluble polyester resin, water-soluble styrene / maleic acid copolymer resin, water-soluble fluororesin and their copolymers, etc. Is mentioned. Specific examples of the polymer compound that forms an emulsion in an aqueous system include an aqueous alkyd resin, an aqueous melamine resin, an aqueous urea resin, an aqueous phenolic resin, an aqueous epoxy resin, an aqueous polybutadiene resin, an aqueous acrylic resin, an aqueous urethane resin, and an aqueous acrylic / Styrene copolymer resin,
Examples thereof include water-based vinyl acetate resin, water-based vinyl acetate / acrylic copolymer resin, water-based polyester resin, water-based styrene / maleic acid copolymer resin, water-based acrylic / silica resin, water-based fluororesin, and copolymers thereof. Each of these polymer compounds may be used alone, or two or more kinds may be mixed and used at an arbitrary ratio.

Polymer compound (c) in conductive composition
The use ratio is 0.1 to 100 parts by weight of the solvent (b).
It is 400 parts by weight, preferably 0.5 to 300 parts by weight. If it is less than 0.1 part by weight, the film formability, moldability and strength will be inferior, while if it exceeds 400 parts by weight, the solubility of the soluble aniline-based conductive polymer (a) will be reduced or the conductivity will be inferior. It will be.

For the transparent conductive polymer film of the conductor, the soluble aniline-based conductive polymer (a) can be used alone, but by incorporating the polymer compound (c), the hardness and abrasion resistance of the film can be improved. And the adhesion to the substrate can be improved. The ratio of the soluble aniline-based conductive polymers (a) to the polymer compound (c) is (a) :( c) = 0.025: 100 to 100: 0.5.
And preferably (a) :( c) = 0.15 / 100 to 100/1.
Is. When the soluble aniline-based conductive polymer (a) has a ratio other than this, the conductivity is lowered and the flatness and transparency are deteriorated. When the polymer compound (c) has a ratio other than this,
The hardness, abrasion resistance, conductivity, etc. of the film are lowered, and the adhesiveness with the substrate is deteriorated.

Further, the nitrogen-containing compound (d), which is a constituent of the composition used in the present invention, has the formula (10) and the formula (1)
The compound represented by 1) is used. The structural formula of the amines used is shown in formula (10).

[0085]

Embedded image (In the formula, R _{39 to} R ₄₁ are independently of each other hydrogen, carbon 1
To 4 alkyl _{group, CH 2 OH, CH 2 CH} 2 OH, C
Represents ONH ₂ or NH ₂ . )

Further, the structural formula of the quaternary ammonium salt used is shown in formula (11).

[0087]

[Chemical 15] (In the formula, R _{42 to} R ₄₅ are each independently hydrogen and a carbon number of 1
To 4 alkyl _{group, CH 2 OH, CH 2 CH} 2 OH, C
Represents ONH ₂ or NH ₂ , X ⁻ is OH ⁻ , 1/2 · SO
^{_{4 2-, NO 3 -, 1}} / 2CO 3 2-, HCO 3 -, 1/2 ·
(COO) ₂ ²⁻ or R′COO ⁻ (in the formula, R ′ is an alkyl group having 1 to 3 carbon atoms). )

The nitrogen-containing compound (d) can be further improved in conductivity by using a mixture of these amines and ammonium salts. Specifically, NH
₃ / (NH ₄ ) ₂ CO ₃ , NH ₃ / (NH ₄ ) HC
O ₃ , NH ₃ / (NH ₄ ) HCO ₃ , NH ₃ / CH ₃ C
OONH ₄ , NH ₃ / (NH ₄ ) ₂ SO ₄ , N (C
_{H 3) 3 / (NH 4} ) HCO 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 amines / ammonium salts = 1/10 to 10/0 are preferable.

The proportion of the nitrogen-containing compound (d) used as a constituent component is 0 to 30 parts by weight, preferably 0 to 20 parts by weight, per 100 parts by weight of the component (b). If the amount exceeds 20 parts by weight, the solution exhibits strong basicity, resulting in poor conductivity. The pH of the solution can be arbitrarily adjusted by adjusting the concentration, type and mixing ratio of the nitrogen-containing compound.
It can be used in a range of 12.

The conductive composition of the present invention comprises the component (a),
(B); (a), (b), (c); or (a),
By using the components (b), (c), and (d), it is possible to form a film with good performance, but it is more flat when a surfactant (e) is added to each conductive composition. Property, coating property, and conductivity are improved.

Examples of the surfactant (e) include alkylsulfonic acid, alkylbenzenesulfonic acid, alkylcarboxylic acid, alkylnaphthalenesulfonic acid, α-olefinsulfonic acid, dialkylsulfosuccinic acid, α-sulfonated fatty acid, N-methyl-N. -Oleyl taurine, petroleum sulfonic acid, alkyl sulfuric acid, sulfated oil, polyoxyethylene alkyl ether sulfuric acid, polyoxyethylene styrenated phenyl ether sulfuric acid, alkyl phosphoric acid, polyoxyethylene alkyl ether phosphoric acid, polyoxyethylene alkylphenyl ether phosphorus Anionic surfactants such as acid, naphthalenesulfonic acid formaldehyde condensate and salts thereof, primary to tertiary fatty amines, quaternary ammonium, tetraalkylammonium, trialkylbenzylammonium Mualkylpyridinium, 2-alkyl-1-alkyl-1-hydroxyethylimidazolinium, N, N-dialkylmorpholinium, polyethylene polyamine fatty acid amide, polyethylene polyamine fatty acid amide urea condensation product, polyethylene polyamine fatty acid amide urea condensation Cationic surfactants such as quaternary ammonium compounds and salts thereof, N, N-dimethyl-N-alkyl-N-carboxymethylammonium betaines, N, N, N-trialkyl-N-sulfoalkyleneammonium betaines , N, N-dialkyl-
N, N-bispolyoxyethylene ammonium sulfate betaine, 2-alkyl-1-carboxymethyl-
Betaines such as 1-hydroxyethylimidazolinium betaine, amphoteric surfactants such as aminocarboxylic acids such as N, N-dialkylaminoalkylenecarboxylic acid salts, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxy Ethylene polystyryl phenyl ether, polyoxyethylene-polyoxypropylene glycol, polyoxyethylene-polyoxypropylene alkyl ether, polyhydric alcohol fatty acid partial ester, polyoxyethylene polyhydric alcohol fatty acid partial ester, polyoxyethylene fatty acid ester, polyglycerin Fatty acid ester, polyoxyethylenated castor oil, fatty acid diethanolamide, polyoxyethylene alkylamine, triethanolamine fatty acid partial ester Le, nonionic surfactants and fluoroalkyl carboxylic acids, such as trialkyl amine oxides, perfluoroalkyl carboxylic acids, perfluoroalkyl benzene sulfonic acids, fluorine-based surfactants such as perfluoroalkyl polyoxyethylene ethanol is used. Here, the alkyl group has 1 to 24 carbon atoms.
Are preferred, and those having 3 to 18 carbon atoms are more preferred.

In the present invention, in the case of the conductive composition containing the component (c), among these surfactants, a nonionic surfactant is particularly preferably used, and among them, the general formula (12),

Embedded image HO (CH ₂ CH ₂ O) _n R (12) (wherein, R is a linear or branched alkyl group having 1 to 24 carbon atoms, a linear or branched alkyl group having 1 to 24 carbon atoms) Is an alkyl group-substituted phenyl group, n is the degree of polymerization of an oxyethylene group, and is a number from 1 to 100.) is preferably used. As the polyoxyethylenes, polyoxyethylene alkyl ether and polyoxyethylene alkylphenyl ether are preferably used, and more preferably polyoxyethylene alkylphenyl ether is used. The degree of polymerization n of the oxyethylene chain is preferably 5 to 100, more preferably 10 to
100 is preferably used. Further, in the case of a conductive composition containing no component (c), an anionic surfactant is particularly preferably used among these surfactants, and among them, an anion such as a sulfone group or a carboxyl group is included in the molecule. A surfactant having a group is more preferably used. It should be noted that two or more kinds of surfactants may be used without any problem.

The ratio of the constituent component (e) to be used depends on the solvent (b).
0 to 10 parts by weight, preferably 0 to 100 parts by weight
5 parts by weight. When the ratio of the component (e) exceeds 10 parts by weight, the coating property is improved but the flatness is lowered, or the flatness is improved but the conductivity is deteriorated.

Further, the conductive composition used in the present invention may be added with storage stability, an adhesion aid and the like, if necessary.

The conductive composition according to the present invention comprises a solvent (b).
(A) Soluble aniline-based conductive polymer (a) alone; (b) (a) and (c); (c) (a), (c)
And (d); (d) a combination of any of (i), (b), and (c) with (e) further coexisting;
(B), (C), or (D) is added, and completely dissolved by mixing at room temperature or with heating, or mixed to prepare. If solids precipitate at room temperature, they are filtered off before use.
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 by using a ball-type kneading device such as a ball mill, a vibration mill, a sand mill or a roll mill.

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

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

The treatment after forming the transparent conductive polymer film on the substrate can be carried out by leaving it at room temperature, but the amount of the components (b) and (d) remaining after the heat treatment can be adjusted. Since it can be further lowered, the conductivity is further improved (the 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, and more preferably 1 part by weight or less, based on 100 parts by weight of the conductive film, although it depends on the intended use. Further, it is preferable that the component (b) does not substantially exist. As heat treatment, 25
Heating in the range of 0 ° C or lower, preferably 40 to 200 ° C is preferable. When the temperature is higher than 250 ° C, the conductivity may decrease due to the deterioration of the component (a).

As the base material to which the conductive composition is applied, polymer compounds, wood, paper materials, ceramics and their films or glass plates, etc. are used. For example, as the polymer compound and film, polyethylene, polyvinyl chloride, polypropylene, polystyrene, polyester, A
BS 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, polyether imide, polybutylene terephthalate and films thereof. These polymer films form a transparent conductive polymer film on at least one surface thereof, and therefore it is preferable to subject the film surface to corona surface treatment or plasma treatment for the purpose of improving the adhesion of the polymer film. .

[0100]

EXAMPLES Examples will be described below. The IR spectrum was measured by using a model 1600 apparatus manufactured by Perkin Elmer. For the measurement of the molecular weight distribution and the molecular weight, GPC measurement (polystyrene conversion) was performed using a GPC column for N, N-dimethylformamide. As the column, three types of columns for N, N-dimethylformamide were connected and used. As the eluent, 0.01 mol / liter of triethylamine and 0.1 mol / liter of lithium bromide in N, N-dimethylformamide were used. Regarding the conductivity, the 4-terminal method was used for measuring the conductivity, and the 2-terminal method was used for measuring the surface resistance.

Example 1 100 mmol of o-aminobenzenesulfonic acid was added at 25 ° C.
Dissolve with stirring in 4 mol / liter ammonia aqueous solution,
An aqueous solution of 100 mmol of ammonium peroxodisulfate was added dropwise. After completion of dropping, the mixture was further stirred at 25 ° C. for 12 hours, and the reaction product was separated by filtration, washed and dried to obtain a polymer powder
g was obtained. The volume resistance value of this polymer is 12.0 Ωcm,
As a result of molecular weight measurement, the number average molecular weight was 150,000, the weight average molecular weight was 190,000, and the Z average molecular weight was 210,00.
0, dispersity MW / MN1.5, MZ / MW1.3. Water, 0.1 mol / liter sulfuric acid aqueous solution or 0.1
The polymer was added little by little to 10 ml of ammonia water of 1 mol / liter, and when the polymer became insoluble, it was filtered, and the dissolved amount was determined. The solubility of the conductive polymer synthesized in Example 1 was 230 mg / ml of water. It was 225 mg / ml of 1 mol / l sulfuric acid aqueous solution and 200 mg / ml of 0.1 mol / l ammonia water.

The IR spectrum of the conductive polymer is shown in FIG. Assignment of IR spectrum is as follows. Sulfone group: Absorption near 1120,1020 cm ^-1 Ammonium salt of sulfo group: Absorption near 1400 cm ^-1 Polymer skeleton: Absorption near 1500 cm ^-1

3 parts by weight of the above polymer was dissolved in 100 parts by weight of a 0.2 mol / liter sulfuric acid aqueous solution with stirring at room temperature to prepare a conductive composition (solvent was an aqueous sulfuric acid solution). The solution [(a) + (b) type] thus obtained was applied onto a glass substrate by spin coating and dried at 100 ° C. A smooth surface resistance value of 2.5 x
A film of 10 ⁷ Ω / □ was obtained.

Example 2 3-Methyl-6-aminobenzenesulfonic acid 100 mm
is dissolved in a 4 mol / liter trimethylamine aqueous solution with stirring at 4 ° C., and ammonium peroxodisulfate 100 is added.
An aqueous solution of mmol was added dropwise. After the dropwise addition was completed, the mixture was further stirred at 25 ° C. for 6 hours, and then the reaction product was separated by filtration, washed and dried,
10 g of polymer powder was obtained. The polymer was stirred in an acetone solution of 1 mol / liter p-toluenesulfonic acid (PTS) for 1 hour, separated by filtration, washed and dried to obtain 18 g of a polymer powder having a free sulfo group. The volume resistance value of this polymer was 12.5 Ωcm.

1 part by weight of the above polymer was dissolved in 100 parts by weight of water with stirring at room temperature to prepare a conductive composition. P of the composition
Since H was about 3.5, it is estimated that about 80% or more of the sulfone groups in the polymer are free.
The thus obtained solution (simply using water as a solvent) [(a) + (b) type] was applied on a glass substrate by a casting method and dried at 100 ° C. Film thickness 0.
A film having a smooth surface resistance value of 5.0 × 10 ⁶ Ω / □ having a 1 μm surface was obtained.

Further, 0.05 part by weight of PTS (p-toluenesulfonic acid), which is an acidic compound, was dissolved in the conductive composition by stirring to prepare a conductive composition. The solution thus obtained (using an acidic aqueous solution as a solvent) [(a) +
Type (b)] was applied onto a glass substrate by a casting method and dried at 100 ° C. A film having a smooth surface resistance value of 3.8 × 10 ⁶ Ω / □ having a film thickness of 0.1 μm was obtained.

Example 3 2-Carboxylaniline (anthranilic acid) 100 m
mol at 4 ° C. with stirring in a 4 mol / liter aqueous quinoline solution, and ammonium peroxodisulfate 100 mmo
l of aqueous solution was added dropwise. After the dropwise addition was completed, the mixture was further stirred at 25 ° C. for 12 hours, the reaction product was separated by filtration, washed and dried to obtain 11 g of a polymer powder. The volume resistance value of this polymer is 45Ω.
It was cm.

Urethane resin "Adekabon titer 232" which forms an emulsion with 3 parts by weight of the above polymer and an aqueous system.
30 parts by weight (manufactured by Asahi Denka Kogyo Co., Ltd.) was dissolved in 100 parts by weight of water with stirring at room temperature to prepare a conductive composition. Since the pH of the composition was about 6.0, it is estimated that about 20% or more of the sulfonic acid groups in the polymer form a salt.

The solution thus obtained [(a) +
(B) + (c) type] was applied on a PET film by a spin coating method and dried at 80 ° C. Smooth surface resistance of 0.2 μm film thickness 5.0 × 10 ⁷ Ω /
A film of □ was obtained.

Example 4 100 mmol of 3-hydroxyanthranilic acid was added at 25 ° C.
Was dissolved in a 3 mol / liter 2-methylpyridine (α-picoline) aqueous solution with stirring, and an aqueous solution of 100 mmol of ammonium peroxodisulfate was added dropwise. 25 after dropping
After stirring at 12 ° C. for 12 hours, the reaction product was separated by filtration, washed and dried to obtain 11 g of polymer powder. The volume resistance value of this polymer was 37 Ωcm.

Acrylic resin "Nicazole RX-301c" which forms an emulsion with 3 parts by weight of the above polymer and an aqueous system.
(Manufactured by Nippon Carbide Industry Co., Ltd.) 10 parts by weight and 1.0 part by weight of ammonia are added to water / isopropyl alcohol (7 /
3) A conductive composition was prepared by dissolving in 100 parts by weight at room temperature with stirring (using an alkaline alcohol aqueous solution as a solvent).
The solution thus obtained [(a) + (b) + (c)
+ (D) type] was applied onto a glass substrate by a spin coating method and dried at 100 ° C. The amount of the component (d) remaining in the formed film is 1% or less based on the weight of the film.
A smooth surface resistance value of 0.25 × 10 ⁶
A film of Ω / □ was obtained.

Example 5 100 mmol of 4-nitroanthranilic acid was added at 4 ° C at 4 ° C.
The solution was stirred and dissolved in a mol / liter aqueous solution of triethanolamine, and an aqueous solution of 100 mmol of ammonium peroxodisulfate was added dropwise. After the dropping was completed, the mixture was further stirred at 25 ° C. for 12 hours, and the reaction product was separated by filtration, washed and dried to obtain 9.5 g of polymer powder. The volume resistance value of this polymer is 50 Ωc.
It was m.

3 parts by weight of the above-mentioned polymer, water-soluble polyester resin "Alastar 300" (manufactured by Arakawa Chemical Industry Co., Ltd.) 8
0 parts by weight was dissolved in 100 parts by weight of water with stirring at room temperature to prepare a conductive composition (simple water as a solvent). The solution [(a) + (b) + (c) type] thus obtained was treated with PE.
It was applied on a T film by a casting method and dried at 70 ° C. Smooth surface resistance value of 0.5 μm surface
A film of × 10 ⁷ Ω / □ was obtained.

Further, 0.05 parts by weight of polyoxyethylene nonyl phenyl ether was dissolved in the conductive composition by stirring to prepare a conductive composition. The solution [(a) + (b) + (c) + (e) type] thus obtained was treated with PE.
It was applied on a T film by a casting method and dried at 70 ° C. Smooth surface resistance value of 0.5 μm surface
A film of × 10 ⁷ Ω / □ was obtained.

Example 6 100 mmol of m-nitroanilinesulfonic acid was added at 25 ° C.
Dissolve with stirring in a 4 mol / liter piperidine aqueous solution,
An aqueous solution of 100 mmol of ammonium peroxodisulfate was added dropwise. After the dropping was completed, the mixture was further stirred at 25 ° C. for 12 hours, and the reaction product was separated by filtration, washed and dried to obtain 6 g of polymer powder.
I got The volume resistance value of this polymer was 15 Ωcm.

An acrylic resin "Cybinol EK-100" which forms an emulsion with 2 parts by weight of the above polymer and an aqueous system.
5 "(manufactured by Saiden Chemical Co., Ltd.) is dissolved in 100 parts by weight of 0.2 mol / liter ammonia water by stirring with a high-speed disperser at room temperature, followed by sand mill treatment, and then filter paper (Whatman filter No. 5). 3) was filtered to prepare a conductive composition having a viscosity of 10 cp (solvent is simply water). This viscosity was measured using an Ubbelohde viscometer.

The solution thus obtained [(a) +
(B) + (c) + (d) type] is 180 mesh,
75μm thickness by gravure coater with 35μm depth
The polyester film "Lumirror T type" (manufactured by Toray Industries, Inc.) is coated on one surface, and the dry coating film has a thickness of O.I. A 4 μm transparent conductive polymer film was formed. The obtained film was aged by heating (60 ° C., 72 hours), and then the surface resistance was measured. The average value was 2.5 × 10 ^7.
Ω / □, maximum value 3.0 × 10 ⁷ Ω / □, minimum value 1.7 ×
It was 10 ⁷ Ω / □, and the variation was small, and the light transmittance was 90% or more and the haze was 15 or less. In addition, this film is exposed to a high temperature and high humidity atmosphere of 60 ° C and 95% RH.
The surface resistance was measured for 20 hours, then 2.8 x 1
It was 0 ⁷ Ω / □, and the conductivity was maintained.

Example 7 2-Chloro-5-aminobenzenesulfonic acid 100 mm
is dissolved in a 3 mol / liter sodium hydroxide aqueous solution with stirring at 4 ° C., and ammonium peroxodisulfate 100 is added.
An aqueous solution of mmol was added dropwise. After completion of dropping, the mixture was further stirred at 25 ° C. for 6 hours, and then the reaction product was washed by filtration and dried,
6 g of polymer powder was obtained. The volume resistance value of this polymer is 20.
It was Ωcm. 1 mol / l of p-
The mixture was stirred in an acetone solution of toluenesulfonic acid (PTS) for 1 hour, washed by filtration, and dried to obtain 4 g of a polymer powder having a free sulfonic acid group.

3 parts by weight of the above polymer and 0.05 parts by weight of dodecylbenzenesulfonic acid were dissolved in 100 parts by weight of water with stirring at room temperature to prepare a conductive composition (the solvent was an acidic aqueous solution of an organic acid). The viscosity of the composition is 4.7 cp (25 ° C.)
Met. This viscosity was measured using an Ubbelohde viscometer. Since the pH of the composition was about 3.8, it is estimated that about 80% or more of the sulfonic acid groups in the polymer are free.

The solution thus obtained [(a) +
[Type of (b) + (e)] was applied onto a glass substrate by spin coating and dried at 80 ° C. Film thickness 0.1μ
A film having a smooth surface resistance value of 8.5 × 10 ⁶ Ω / □ was obtained.

Example 8 3 parts by weight of the polymer synthesized in Example 2 and 0.5 parts by weight of triethylamine were dissolved in 100 parts by weight of isopropyl alcohol with stirring at room temperature to prepare a conductive composition (organic solvent alone). The solution [(a) + (b) thus obtained
+ (D) type] was applied onto a glass substrate by a spin coating method and dried at 120 ° C. A film having a smooth surface resistance value of 1.6 × 10 ⁷ Ω / □ having a film thickness of 0.1 μm was obtained.

Example 9 3 parts by weight of the polymer synthesized in Example 4, ammonia.
3 parts by weight of an alkylnaphthalenesulfonic acid “Perex NB” (manufactured by Kao Corporation) was dissolved in 100 parts by weight of water with stirring at room temperature to prepare a conductive composition. The solution [(a) + (b) + (d) + (e) type] thus obtained was applied onto a glass substrate by spin coating and dried at 100 ° C. A film having a smooth surface resistance value of 1.4 × 10 ⁷ Ω / □ having a film thickness of 0.1 μm was obtained.

Example 10 3 parts by weight of the polymer synthesized in Example 2, 50 parts by weight of a polyester resin "AY241W" (manufactured by Hoechst Japan Ltd.) which forms an emulsion in an aqueous system, and 0.5 parts of ammonia.
By weight, 0.1 part by weight of polyoxyethylene octyl phenyl ether was dissolved in 100 parts by weight of water at room temperature with stirring to prepare a conductive composition. Solution thus obtained [(a) + (b) + (c) + (d) + (e) type]
Is applied onto a glass substrate by spin coating, and 120
It was dried at ° C. A film having a smooth surface resistance value of 9.2 × 10 ⁶ Ω / □ having a film thickness of 0.1 μm was obtained.

Comparative Example 1 Sulfonated polyaniline was used as an aniline-based conductive polymer by a known method [J. Am. Chem. Soc. ,
(1991), 113, 2665-2666]. The content of the obtained sulfone group was 52% based on the aromatic ring. 3 parts by weight of the sulfonated polyaniline was mixed with 100 parts by weight of a 0.2 mol / liter sulfuric acid aqueous solution at room temperature to prepare a conductive composition. The solution thus obtained was applied onto a glass substrate by a spin coating method, but no film was formed because the sulfonated polyaniline was insoluble in a 0.2 mol / l sulfuric acid aqueous solution. The solubility of the conductive polymer synthesized in Comparative Example 1 (conventional method) was 0 mg / ml water, 0.1 mol / liter sulfuric acid aqueous solution 0 mg / ml, 0.1 mol / liter ammonia water 50 mg / ml. .

Comparative Example 2 Sulfonated polyaniline was used as an aniline-based conductive polymer by a known method [J. Am. Chem. Soc. ,
(1991), 113, 2665-2666]. The content of the obtained sulfone group was 52% based on the aromatic ring. 3 parts by weight of the sulfonated polyaniline, a water-soluble polyester resin "Alastar 30"
0 "(manufactured by Arakawa Chemical Industry Co., Ltd.) was dissolved in 100 parts by weight of water with stirring at room temperature to prepare a conductive composition. The solution thus obtained was applied onto a glass substrate by a spin coating method, but the film was not formed because the sulfonated polyaniline was insoluble in the aqueous solution.

Comparative Example 3 As an aniline-based conductive polymer, polyaniline having a sulfone group on an aromatic ring was used as a known method (Japanese Patent Application No. 5-485).
No. 40) and synthesized as follows. Aniline 10
20 parts by weight of 2-aminoanisole-4-sulfonic acid was copolymerized with ammonium peroxodisulfate under sulfuric acid acidic conditions to synthesize polyaniline having a sulfone group in the aromatic ring. The content of the sulfone group in the polyaniline having the sulfone group was 48%. 3 parts by weight of polyaniline having a sulfone group in the aromatic ring, water-soluble polyester resin "Alaster 300" (manufactured by Arakawa Chemical Industry Co., Ltd.)
80 parts by weight of water was stirred and dissolved in 100 parts by weight of water at room temperature to prepare a conductive composition. The solution thus obtained was applied onto a glass substrate by spin coating, but the film was not formed because the polyaniline having a sulfone group in the aromatic ring was insoluble in the aqueous solution.

Comparative Example 4 100 mmol of o-aminobenzenesulfonic acid and 40 mmol of aniline were mixed with stirring in a 1 mol / liter sulfuric acid aqueous solution at 4 ° C., and 140 m of ammonium peroxodisulfate was added.
A 1 mol / liter sulfuric acid aqueous solution was added dropwise. After the dropwise addition was completed, the mixture was stirred at 25 ° C. for 12 hours, the reaction product was separated by filtration, washed and dried to obtain 4.6 g of a polymer powder. The volume resistance value of this polymer was 15 Ωcm. The content of sulfone group of polyaniline having this sulfone group is 17%
Met. 3 parts by weight of polyaniline having a sulfone group in the aromatic ring, a water-soluble polyester resin "Alastar 30"
0 "(manufactured by Arakawa Chemical Industry Co., Ltd.) was dissolved in 100 parts by weight of water with stirring at room temperature to prepare a conductive composition. The solution thus obtained was applied onto a glass substrate by spin coating, but the film was not formed because the polyaniline having a sulfone group in the aromatic ring was insoluble in the aqueous solution. The solubility of the conductive polymer synthesized in Comparative Example 4 (conventional method) was as follows: water 0 mg / ml 0.1 mol / liter sulfuric acid aqueous solution 0 mg / ml 0.1 mol / liter ammonia water 3 mg / ml. .

[0128]

[Effect] 1. The conductive composition of the present invention has a conductive aniline-based conductive polymer, which is a conductive component thereof, in which all of the benzene nuclei have an acidic group such as a sulfone group and / or a carboxyl group, so that the solvent is alkaline or neutral. (Especially just water), all acidic pH
It is possible to use an aqueous solution having the following properties: coating the composition on a suitable substrate, spraying, casting, dipping, and heat treatment to develop high conductivity without humidity dependency and form a film,
A conductive thin film having excellent moldability and transparency can be obtained. 2. In the present invention, a transparent conductive film comprising a soluble aniline-based conductive polymer or a soluble aniline-based conductive polymer and a polymer compound, which is excellent in film formability, moldability, and transparency, is applied to a suitable substrate. After being formed by processing such as spraying, casting, dipping, etc., it can be left at room temperature or only by heat treatment to exhibit high conductivity without humidity dependency and to obtain a conductor with small variation in surface resistance.

[Brief description of drawings]

FIG. 1 shows an IR spectrum of a conductive polymer synthesized in Example 1.

Front page continuation (72) Inventor Yasuyuki Takayanagi 10-1 Daikokucho, Tsurumi-ku, Yokohama-shi, Kanagawa Nitto Chemical Industry Co., Ltd.

Claims (17)

[Claims] 1. A polymer having an acidic group-substituted aniline, an alkali metal salt, an ammonium salt and / or a substituted ammonium salt thereof as a repeating unit, which is a room-temperature solid having a weight average molecular weight of 10,000 to 3,240,000. 2. A conductive composition containing the soluble aniline-based conductive polymer (a) and the solvent (b). 2. The soluble aniline-based conductive polymer (a) has the general formula (1): (In the formula, A is one group selected from a sulfone group, a carboxyl group, an alkali metal salt thereof, an ammonium salt and a substituted ammonium salt, and B is hydrogen, a methyl group, an ethyl group, an n-propyl group, an iso- group. Propyl group, sec-
Propyl group, n-butyl group, iso-butyl group, sec
It represents one group selected from an alkyl group such as -butyl group and t-butyl group, a hydroxy group, a nitro group, and a halogen group such as a fluoro group, a chloro group and a bromo group. x represents an arbitrary number of 0 to 1, n represents a degree of polymerization, and 10 to 5
The number is 000. ) An acidic group-substituted aniline represented by
A polymer having the alkali metal salt, ammonium salt and / or substituted ammonium salt as a repeating unit, the weight average molecular weight of which is 10,000 to 3,240,
2. The conductive composition according to claim 1, which is a soluble aniline type conductive polymer which is a solid at room temperature of 000. 3. The soluble aniline-based conductive polymer (a) is an acidic group-substituted aniline, an alkali metal salt thereof,
A soluble aniline-based conductive polymer obtained by polymerizing at least one compound (a) of an ammonium salt and a substituted ammonium salt in a solution containing a basic compound (b) with an oxidizing agent. Or the conductive composition according to 2. 4. The compound (a) has the general formula (2): (In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are selected from the group consisting of hydrogen, a linear or branched alkyl group having 1 to 4 carbon atoms, an acidic group, a hydroxyl group, a nitro group and halogen. , At least one of which represents an acidic group, and the acidic group represents a sulfone group or a carboxyl group.) At least one of an acidic group-substituted aniline, an alkali metal salt, an ammonium salt and a substituted ammonium salt thereof. The conductive composition according to claim 3, which is a kind of compound. 5. The compound (a) has the general formula (3): (In the formula, R ₆ , R ₇ , R ₈ , R ₉ , and R ₁₀ are selected from the group consisting of hydrogen, a linear or branched alkyl group having 1 to 4 carbon atoms, and an acidic group, and two of them are An acidic group and an alkyl group, wherein the acidic group represents a sulfone group or a carboxyl group), and at least one of an acidic group-substituted alkylaniline, an alkali metal salt, an ammonium salt and a substituted ammonium salt thereof. The electrically conductive composition according to claim 3, which is a compound of 6. The compound (a) has the general formula (4): (In the formula, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , and R ₁₅ are selected from the group consisting of hydrogen, a hydroxyl group, and an acidic group, and two of them represent an acidic group and a hydroxyl group. Is an acid group-substituted hydroxyaniline represented by a sulfone group or a carboxyl group, and its compound is at least one compound selected from the group consisting of alkali metal salts, ammonium salts and substituted ammonium salts thereof. 7. The method according to claim 1, wherein at least one polymer compound (c) selected from a water-soluble polymer compound and a polymer compound forming an emulsion in an aqueous system is contained.
The electrically conductive composition according to 3, 4, 5 or 6. 8. A conductive composition according to claim 1, which contains at least one nitrogen-containing compound (d) selected from amines and quaternary ammonium salts. . 9. The conductive composition according to claim 1, which contains a surfactant (e). 10. A polymer having an acidic group-substituted aniline, its alkali metal salt, ammonium salt and / or substituted ammonium salt as a repeating unit and having a weight average molecular weight of 10,000 to 3,240,000 at room temperature. And a soluble aniline-based conductive polymer (a), which is a transparent conductive polymer film. 11. A polymer having an acidic group-substituted aniline, its alkali metal salt, ammonium salt and / or substituted ammonium salt as a repeating unit, which is a room temperature solid having a weight average molecular weight of 10,000 to 3,240,000. A water-soluble aniline-based conductive polymer (a), a water-soluble polymer compound, and at least one polymer compound (c) selected from polymer compounds that form an emulsion in an aqueous system. A conductor formed from a transparent conductive polymer film. 12. The conductor according to claim 10, wherein the transparent conductive polymer film contains a surfactant (e). 13. A polymer having a repeating unit of an acidic group-substituted aniline, an alkali metal salt, an ammonium salt and / or a substituted ammonium salt on at least one surface of a substrate, the weight average molecular weight of which is 10,000.
After forming a transparent conductive polymer film by applying a conductive composition consisting of 0 to 3,240,000 water-soluble aniline-based conductive polymers (a) and a solvent (b) that are solid at room temperature,
A method for producing an electric conductor, which is characterized in that it is formed by leaving it at room temperature or heating it. 14. A polymer having acidic group-substituted aniline, its alkali metal salt, ammonium salt and / or substituted ammonium salt as a repeating unit on at least one surface of a substrate, and having a weight average molecular weight of 10,000.
At least one selected from water-soluble aniline-based electrically conductive polymers (a), solvents (b), water-soluble polymer compounds, and polymer compounds that form an emulsion in an aqueous system, which are solids at room temperature of 0 to 3,240,000 Polymer compound (c) of
A method for producing a conductor, which comprises forming a transparent conductive polymer film by applying a conductive composition containing the above, and then forming the transparent conductive polymer film by allowing it to stand at room temperature or heat treatment. 15. A polymer having acidic group-substituted aniline, its alkali metal salt, ammonium salt and / or substituted ammonium salt as a repeating unit on at least one surface of a substrate, and having a weight average molecular weight of 10,000.
At least one selected from water-soluble aniline-based electrically conductive polymers (a), solvents (b), water-soluble polymer compounds, and polymer compounds that form an emulsion in an aqueous system, which are solids at room temperature of 0 to 3,240,000 Polymer compound (c) of
Formed by applying a conductive composition consisting of at least one nitrogen-containing compound (d) selected from amines and quaternary ammonium salts to form a transparent conductive polymer film, and then leaving it at room temperature or heat treatment. A method for producing an electric conductor, comprising: 16. The electroconductive composition contains a surfactant (e), claim 13, 14 or 1.
5. The method for producing a conductor according to 5. 17. The method for producing a conductor according to claim 13, 14, 15 or 16, wherein the heat treatment is carried out in a temperature range of 40 to 250 ° C. to remove the components (b) and (d).